TW201111407A - Curable resin composition for encapsulating optical semiconductor and cured article thereof - Google Patents

Abstract

Provided is a curable resin composition and a cured article thereof, the curable resin composition prevents the cave formation after cured, and has an excellent resistance to corrosiveness gas, as well as an excellent resistance to coloration. The curable resin composition comprising an epoxy resin represented by the following formula (1), a hardening agent and/or a hardening promoting agent. The curable resin composition of this application preferably uses cyclohexane -1, 3, 4-tricarboxylic acid-3, 4-anhydride and methylhexahydrophathalic acid anhydride as hardening agent, and obtains a especial effect of preventing the cave formation after cured. (wherein, the plurality of R1 are same or different, respectively independently represents a hydrogen atom or a methyl group).

Description

201111407 VI. Description of the Invention: [Technical Field] The present invention relates to a curable resin composition suitable for use in an electric and electronic material, particularly an optical semiconductor, a cured product thereof, and an optical semiconductor containing the cured product Device. [Prior Art] Conventionally, a sealed material of an optical semiconductor element such as an LED product is an epoxy resin composition based on the balance between performance and economy. In particular, an epoxy resin composition represented by a double-type a-type epoxy resin, which is excellent in balance of heat, transparency, and mechanical properties, has been widely used. However, some people refer to ----- sigh tribute into the wavelength of the girl (mainly for blue LED products, the wavelength of gamma (10) or less) the result of the short-wavelength light, the above packaging materials will be led The wafer is dyed, and at the end the illumination of the LED article is lowered. In this regard, an alicyclic epoxy resin represented by 3,4-epoxycyclohexylmethyl_3,4, an epoxycyclohexyl W is used as an epoxy type epoxy having an aromatic ring. Since the resin composition is superior in transparency, it is currently being actively studied as an LED package (Patent Documents i and 2). On the other hand, it has been pointed out that the alicyclic epoxy resin has a low viscosity, and there is a problem in the heat-hardening reaction. Among the LED products, when the S-body is a surface-assembled type, the amount of green resin is extremely small (for example, about ton). Therefore, if the alicyclic epoxy tree is used, it will volatilize during heat curing. As a result, the package portion of the surface group X 322191 4 201111407 product is sometimes sunken. In this case, a current is supplied to the lead portion of the LED chip to be exposed and recessed 1 to function as a package. As described above, there is still a problem in the volatilization of the wax ring type in the case of heat curing. . Oxygen resin, in addition, in recent years, the product is more southerly due to the illumination and the back of the TV, so that the LED illumination is accompanied by σ = the resin group of the alicyclic epoxy resin is used = 2 after 3 == _ The LED product has a low degree, and there are also problems on both sides (Patent Document 3). [Patent Document 1] Japanese Patent Laid-Open No. Hei 9-213997 (Patent Document 3): Japanese Patent No. 3,618,238, No. [Patent Document 3]: Japanese Patent Laid-Open No. 2005-10〇445 I SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The problem of the long-term nature of epoxy resin is currently being studied using a deer that is represented by a derivative of the Wei-cut epoxy ageing material as a skeleton with a Si-〇 bond. Fish I $ is known to be introduced into the stagnation of the stagnation of the stagnation of the squid, and the sap of the tree is more than the epoxy tree. Durability of the oxy-resin type disk. However, the use of the tree having the stone-oxygen-fired skeleton was not as good as the gas permeability. Therefore, when the LED package gas corrugated or Shixi oxygen modified epoxy resin does not cause the dyeing problem on the LED crystal 322191 5 201111407, it will cause the silver component on the lead frame of the LED package (for The metal hard knife c is silver-plated in order to reflect the reflectivity and discoloration or ... s after the performance of the LED product is lowered to leave a problem. At present, a package material is being sought on the market, which is composed of an epoxy resin composition with a helmet problem, and is more conventional; 2, a depression caused by volatilization during heating, and further, a means for solving the problem The inventors have made diligent research in view of the above-mentioned current conditions, and as a result, the present invention has been made. ° The invention of the present invention is as follows: (1) The curable resin composition 'is a compound represented by the following formula (1): a latex resin, and a hardening reaction with the epoxy resin Agent and / or hardening accelerator;

D c

(2) The curable resin composition according to (1) above, wherein all of the oximes in the formula (1) are hydrogen atoms. (3) The hardening resin composition according to (1) or (2) above, wherein the hardening agent which can be hardened with the epoxy resin of 322191 6 201111407 is a compound represented by the following formula (2) and/or a compound represented by the formula (3);

(wherein R2 represents a hydrogen atom or a fluorenyl group). (4) The curable resin composition according to (3), wherein the hardener comprises both the compound of the formula (2) and the compound of the formula (3), and the ratio is in the following range: W2/(W2+W3)= 0. 2 to 0.9 (wherein, W2 represents a part by weight of the compound of the formula (2); and W3 represents a part by weight of the compound of the formula (3)). (5) A cured product obtained by curing the curable resin composition according to any one of the above (1) to (4). (6) An optical semiconductor device comprising an optical semiconductor and the cured product of the above (5) encapsulating the optical semiconductor. Advantageous Effects of Invention The curable resin composition of the present invention is excellent in corrosion resistance, excellent in corrosion resistance, and excellent in dyeing resistance. Therefore, it is highly suitable for use in optical materials, such as optical semiconductors (LED products, etc.). [Substrate and Package] [Embodiment] The curable resin composition of the present invention is described below. The curable resin composition of the present invention contains the rabbit of the formula (1) as an essential component. * Resin The epoxy resin represented by the formula (1) can be synthesized by oxidizing a diene compound represented by the following (a) as a raw material.

(a)

R (wherein, a plurality of R1s present may be the same or different, each having an atom or a sulfhydryl group). The present hydrocarbon-baked hydrocarbon compound, for example, a compound in which R1 is a gas atom, has been disclosed in the specification of 曰 ==Γ772, and the structure of the substituent can be produced in the same manner. The method of oxidizing includes an oxidation method using a peracid such as peracetic acid, an oxidation method using an aqueous hydrogen peroxide solution, and the like, and is not limited. The method of oxidizing by the use of peracid is oxidized by the method of oxidizing by a peracid, and the method of epoxidation of an aqueous solution of nitric oxide is disclosed in Japanese Patent Laid-Open No. 2006-52187. In the Japanese Patent Application Laid-Open No. Sho 59-108793, JP-A-62-234550, JP-A No. 5-213919, and JP-A No. 1-349579 In the present invention, the method described in the Japanese Patent Publication No. Hei. No. Hei. No. Hei. It is preferable to use hydrogen peroxide. An example of a method of performing epoxidation using hydrogen peroxide is described below. The epoxy resin represented by the formula (1) used in the present invention may be produced by any method, and is not limited. The following methods: The specific method of epoxidation using hydrogen peroxide is carried out by using tungstic acid as a catalyst for epoxidation. Examples of the tungstic acid include tungsten acid such as tungstic acid, tungstophosphoric acid, and tungstic acid. Examples of the counter cation of the salt include a quaternary cation, a soil-measuring metal ion, a metal ion, etc. Specific examples thereof include tetraammonium ion, benzyltriethylammonium ion, and thirteen base. Ammonium ion, dilauryldimethylammonium ion, trioctylammonium ion, trialkylammonium (mixture of octyl and nonenyl) ions, tris(hexadecyl)phosphonium ion, trimethyl a quaternary ammonium ion such as stearyl ammonium ion, tetraammonium ion, trimethyl cetyl ammonium ion, benzoyl tributylammonium ion, trioctyl ammonium ion, dicetyl diammonium ion; calcium The alkaline earth metal ions such as ions and magnesium ions; metal ions such as sodium, traita, and strontium are not particularly limited. The above-mentioned relative cations in the present invention are particularly preferably quaternary ammonium ions, especially for phase-dissolving epoxy. The resin is preferably a quaternary ammonium ion having a long-chain alkane 9 322191 201111407 as a relative cation. A specific method for producing a quaternary ammonium ion having a long-chain alkyl group as a relative cation tungstic acid can be exemplified as a tungstic acid. Cation with a quaternary ammonium salt The method of changing the reaction. The quaternary ammonium salt used at this time is preferably a long-chain alkyl group as described above, and a quaternary ammonium salt having a total carbon number of 10 or more, preferably 25 to 10 0 may be used. In particular, it is preferred that the alkyl chain is an aliphatic chain. The reaction of the tungstic acid with the quaternary ammonium salt is preferably carried out in a two-layer system of water or a water-organic layer. Further, tungsten is known. Since the acid changes its structure depending on its pH, it is preferred to adjust the pH of the aqueous layer to between 2 and 6. A buffer solution can be used for adjusting the pH of the aqueous layer, and various buffers such as a phosphate or tartaric acid can be used. However, as long as the pH can be adjusted, a buffer solution such as a general one can be used. In the preparation method, in particular, the pH adjustment convenience and the compatibility with the metal salt of the phosphorus atom are preferably buffered with scaly acid. liquid. Specifically, an aqueous solution in which tungstic acid is dissolved is added to the quaternary ammonium salt while stirring. Heating (40 to 90 ° C) can promote the reaction when the reaction is slow. The resulting organotungsten-based catalyst is chromatographed from water. The precipitated salt is filtered or extracted with an organic solvent and liquid-separated to obtain a desired tungsten-based catalyst. The shape is crystallized, and there are various shapes of the resin. Further, at this time, in order to simplify the step, the obtained catalyst may be directly subjected to an epoxidation reaction by adding a diolefin compound as a raw material without separation. Although the structure of the tungsten-based catalyst obtained by this method is not clear, the framework of the relative cations of the tungstic acid is hydrogen ion (proton) and quaternary ammonium cation 10 322191

201111407 Sub-metal ion correlation for pH adjustment buffer. This reaction is epoxidized using hydrogen peroxide. Among them, in particular, the concentration of hydrogen peroxide in the reaction system is preferably 40% by weight or less. When the concentration exceeds 40% by weight, the decomposition reaction of the resulting epoxy compound becomes easy to carry out, which is not preferable. This reaction uses a phosphoric acid-phosphate aqueous solution to adjust the pH. In terms of its pH, it is preferably adjusted to a pH of from 2 to 7, more preferably from pH 3 to 7, in the stage of mixing the hydrogen peroxide used in the reaction. When the pH is 2 or less, the hydrolysis reaction and the polymerization reaction of the epoxy group are facilitated. In addition, if it exceeds pH 7, the reaction becomes extremely slow, causing a problem that the reaction time is too long. It is generally considered that a phosphoric acid-phosphate aqueous solution is generally thought to have an effect as a buffer, but in the present reaction, it is considered to have no buffering effect by adding a phosphate-phosphate to an excess of an acid (aqueous hydrogen peroxide solution). Not as a buffer. The phosphoric acid-phosphate aqueous solution used can be obtained by the following method: 0.1 to 10 mol equivalents of phosphoric acid (or a phosphate such as sodium dihydrogen phosphate) relative to the hydrogen peroxide used, and a basic compound (Methods such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, etc.) to adjust the pH, but are not limited thereto. Here, the pH is preferably added to the pH as described above when hydrogen peroxide is added. 0至6. 0。 The preferred pH range is 3. 5 to 6. 5, the best is 4. 0 to 6. 0.至重量重量和〇。。 The concentration of the phosphate is from 0.1 to 20% by weight, preferably from 0.1 to 10 weight ° / 〇. An organic solvent can also be used in the reaction. The amount of the organic solvent used is relatively 11.3 to 1 〇, and is preferably from 3. 3 to 5, more preferably 至. 5 to 2.5, based on the weight ratio of the diene compound to the reaction substrate of 11 322191 201111407. If the weight ratio exceeds 1 ,, the reaction progresses extremely slowly, which is not preferable. Specific examples of organic materials that can be used include hexanyl, cyclohexane, and heptane (four); f stupid, di-benzene; aromatic hydrocarbon compounds such as benzene; decyl alcohol, ethanol, isopropanol, butanol, hexanol, cyclohexanol, etc. Alcohols. In addition, ketones such as methyl ethyl ketone, methyl acetobutyl ketone, cyclopentanone, and cyclohexanone may be used as appropriate; triethyl ether, tetrahydrofuran, di: hospital, etc.; acetic acid ethyl acetate, acetic acid butyl vinegar, f A acid such as acetonitrile or the like is a compound such as a nitrile compound such as acetonitrile. Stirring a specific reaction operation method, for example, adding a di-hydrocarbon compound as a raw material, hydrogen peroxide, a crane catalyst: pH adjustment money, if necessary (4) on the second floor when the reaction is carried out in a batch reaction Take a ride. The speed of the lining is not particularly specified, and it is preferred that the degree of emulsification of the reaction system is greater than that. In addition, hydrogen peroxide is often exothermic due to the addition, so that it may be added slowly after the addition of each component. Or you can add the peroxide gas, the crane catalyst, the PH adjustment button, and the _, and then slowly add the method of adding a compound. In addition, the crane catalyst can be added to the pre-formation, or it can be directly used in the reaction after being prepared in the reaction system. The reaction temperature is not particularly limited, and is preferably 0 to 9 CTC, more preferably 0 to 75. (: 'The optimum is 15 to 75t. When the acidity in the aqueous solution is high, specifically, when the pH is 4. G, and further 3. G or less, the reaction temperature is preferably 60 ° C or lower. 322191 12 201111407 In addition, 'reaction time varies with the && production industry's point of view - the county neck varies in amount, but the reaction between work,,,, &"& The preferred range is ... 〇〇 hours, more preferably café hours, most preferably 5 to 48 hours. After the reaction is over, 'overcapacity; two preparations & and ruthenium peroxide are subjected to a quench treatment. The hydrogen capture method can be carried out by using a basic compound in addition to a reducing agent. The present invention is particularly preferably carried out in the same manner. The reducing agent can be used as a sulfurous acid or a sodium thiosulfate. , hydrazine, oxalic acid, etc. Use of reducing agent I, (d) excess peroxide of 0.01 to 20. megamolar, preferably 〇〇5 hopper number U to 3 times mole. ° 5 to 10 times Mo The ear, more preferably 〇·〇5 Basic compounds may be exemplified by metal hydroxides such as sodium hydroxide and water hydroxide; sodium carbonate: gold, =, « _Hydrogen scales; salt; potassium / metal carbonate; in terms of its use, as long as it is aromatic hydrocarbons such as toluene, xylene, etc.; methyl iso-, or organic solvents (such as;   院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院 院Excessive peroxidation 10 times Mo, more preferably om material ear. 2 is preferably added in the form of a solution of U5 to organic solvent (the above), or 1 can be water, or if it is insoluble in water or organic solvent It can be added in the form of the early body. The amount of hydrogen peroxide remaining in the system is more than the ratio of the weight of the reaction to the reaction.] to 1〇〇〇 times 322191 13 201111407, more preferably 10 to 500 times, most It is preferably 10 to 300 times. If a solid base which is insoluble in water or an organic solvent is used, it can be treated after separation of the aqueous layer and the organic layer described later. After capturing hydrogen peroxide (or before capturing), organic The layer is separated from the water layer. At this time, when the organic layer and the water layer are not separated or the organic solvent is not used, the layer is added. The organic solvent is washed with water, and the weight ratio of the organic solvent to the raw material diolefin compound obtained is 0.5 to 10 times, more preferably 0.5 to 5 times, and the operation is repeated several times as needed. Then, the separated organic layer is purified by washing with water as needed. The obtained organic layer may be purified by adding an ion exchange resin, a metal oxide, activated carbon, montmorillonite, acid white clay, activated clay, and Shixia. These may be natural or synthetic, and one type may be used or a plurality of types may be used in combination. This treatment can effectively reduce the amount of the catalyst remaining in the organic solvent. After the obtained organic layer is washed as needed, the solvent can be distilled off to obtain the intended epoxy compound. The epoxy resin obtained as described above has a structure represented by the formula (1) as a main structure, and is a mixture of compounds having various structures represented by the formula (4):

14 322191 3 (4) 201111407 R,

(In the formula, / the so-called "〇C> (B) (D) P = H or CH3〇〇 to D combination can be any combination.) The structure shown in formula (1) is used as the main structure: Jing In the fat composition, the above epoxy resin can be used separately/other epoxy resin.

== The ratio of the oxygen resin is preferably 30% C ΜίΓ. However, when the epoxy resin of the present invention is used as a curing agent for a curable tree or a substance, it is added in a ratio of illusion to weight (four). Other epoxy trees which can be used in the curable resin composition of the invention are: a secret epoxy resin, a fine A _ fat reduction, a biphenyl, a triphenyl styrene epoxy resin, a ph_larakyl resin, and the like. Specifically, 'double enzyme A, double test s, and sulfur secondary age can be mentioned. , ^ 卞 卞 屮丄 联 联 联 联 二醇 二醇 二醇 二醇 氯 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ Test (age, age of substituted base, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with furfural, acetaldehyde, benzofural, p-hydroxybenzaldehyde, O-hydroxybenzaldehyde, p-hydroxyacetophenone, o-p-ethylidene, monocyclopentadiene, sulphate, 4,4-bis (gas sulfhydryl)-i,; , a polycondensate composed of bis(indolyl)-1, fluorene-biphenyl, 1,4-bis(carbomethoxy)benzene, anthracene, 4-bis(methoxyindolyl)benzene, etc. Such as modified materials, four desert bisphenols, such as epoxy propyl ether compounds derived from alcohols, alicyclic epoxy resins, epoxy propylamine epoxy resins, propylene acrylate epoxy resins ^ Fatty disesquioxane-based epoxy resin (in the form of a chain, a ring, a ladder, or a mixture of at least two or more of these kinds) (4) The towel has an epoxy propyl group, and/or an epoxy ring. Solid or liquid epoxy resin such as epoxy resin) herein. l r into μ ....' machine example I am a bit of oxenoxane epoxy tree difficult. The alicyclic epoxy resin specifically includes 3,4-epoxycyclohexyl, -3''4,-epoxycyclohexyl-g, etc., and the secondary ratio in the total epoxy resin is preferably 60. When the weight is less than or equal to 4% by weight, particularly preferably 4% by weight or more, there are defects such as volatilization. In addition, the system = epoxy resin (in the form of a bond, a ring, a ladder, or the like, at least two of which have an epoxy propyl group in the structure of ==5:=, and/or an epoxy ring to resist the charm ^ The resin of the genus of the genus is preferably used in the range of the influence of the inferiority. When the weight of the bismuth is used in combination, the ratio of the total epoxy resin is preferably "the following, particularly preferably 4." "The following. If the oxy-resin is used in the 322191 16 201111407, the corrosion-resistant gas composition is reduced. The curable resin composition of the present invention contains reactivity with the above epoxy resin. The curing agent is, in particular, a curing agent capable of undergoing a thermosetting reaction. Examples of the hard U include an amine compound, an acid group compound, a guanamine compound, a expectant compound, a kinetic compound, and the like. Specific examples thereof include diaminobenzophenone, di-extension ethyltriamine, tri-ethylidenetetraamine, diamine diphenylsulfone, isophoronediamine, dicyanamide, and linseed oil. Polyamide resin, phthalic anhydride, ^, synthesized by acid diploid and ethylene diamine Benzoic anhydride, 1'2,4,5-benzenetetracarboxylic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic acid Anhydride), nadic anhydride, hexahydrophthalic anhydride, gamma hexahydrophthalic anhydride, butyl sulphate, bicyclo [2, 2, 1] Gengyuan-2, 3-dicarboxylate Anhydride methylbicyclo[2,2,1]heptane-2,3- bis-anhydride, cyclohexane: 1'3'4-tricarboxylic acid-3,4-anhydride, bisphenol oxime, bisphenol F, Bisphenol s, bisphenol, stilbene, 4, 4'-biphenol, 2, 2'-biphenol, 3, 3, 5, 5,-tetramethyl-D, i, biphenyl] -4, 4'-diol, hydrogen brewing, isophthalic acid, naphthalenediol, tris-(4-phenylene)methane, 1,1,2,2-tetrakis(4-phenylene)ethene , test class (, hope, substituted by the base of phenol, naphthol, alkyl substituted naphthol, dihydroxy stupid, dihydroxy naphthalene, etc.) and formaldehyde, acetic acid, benzene disk, p-benzoic acid, orthophthalic acid Disc, p-acetophenone, o-hydroxyacetophenone, dicyclopentadiene, furanal, 4,4,-bis(chloromethyl)-1'1-biphenyl, 4,4'-bis (a Oxymethyl group ;)_1,1,_ Polycondensate composed of 1,4,_bis(gasmethyl)benzene, 1,4,-bis(methoxymethyl)benzene, and the like, and the modified product of the four deserts A and the like Age, taste, and gas 322191 17 201111407 Boron-amine complex, anthraquinone derivative, box and phenol are limited to this. These may be used alone or 2 = upper #' but not in addition, If it is used for transparent encapsulation such as LED, an acid anhydride excellent in transparency after hardening is used, and for example, methyl tetragas = dicarboxylic acid needle, quinamic acid needle, nadic acid field, hexahydroortho anhydride , Yinji hexahydrophthalic acid anhydride, butane tetracarboxylic anhydride, bicyclo [2, diheptane^-dicarboxylic anhydride~methylbicyclo^^^heptane^-"' anhydride, cyclohexan-1, 3, 4-tri-hysonic acid-3, 4-anhydride (a compound of the formula (2)) and the like having an alicyclic skeleton. These acid livers having an alicyclic skeleton can be used; for example, in the h_TMa series manufactured by Mitsubishi Gas Chemical Co., Ltd., "the product can be obtained (although it is a surplus product, but it is in a solid state, The workability is very poor.) In addition, when using cyclohexane-13,4-tricarboxylic acid _3,4, it is sometimes used because it is a solid state or a high viscosity semi-solid state. It may become extremely bad. Therefore, it is desirable to be able to use other hardeners, and it is preferable to use a bribe with an alicyclic f. In this case, the hardener which can be used in combination is not limited as long as it is liquid and has a low viscosity, for example, A commercially available hardener and S' may be a ship containing a methyl nadic anhydride or a nadic anhydride, a vessel (100 manufactured by Nippon Chemical and Chemical Co., Ltd.), or a needle containing a hexahydrophthalic acid (a formula (3)). , R2 is a hydrogen atom), fluorenyl hexanitrophthalic acid field (the compound of the formula (3), and R2 is a methyl group) RIKACID MH700 (manufactured by Nippon Chemical and Chemical Co., Ltd.)

And other hardeners. When used in combination, the solid or semi-solid cyclohexane-1 '3,4-diphthalic acid-3,4-anhydride and the lower viscosity hardener can be pre-conditioned at room temperature or heated (in warming conditions) On the other hand, in order to prevent the volatilization of the hardener, it is preferable to mix it until it is uniform under the condition of 15 (TC 322191 18 201111407, more preferably 120C), thereby achieving a workability. From the viewpoint of the concave portion of the encapsulant, 5 'cyclohexene H, 3, 4-trisole, 4 - anhydride is used in the total hardener in a ratio of 5 to 90% by weight, more preferably 1 to 9 % by weight. It is preferably in the range of 30 to 80% by weight. If the mixing ratio exceeds 9% by weight, the workability as a hardener may be extremely poor. Further, if it is less than 5% by weight, there is an improvement in the depression of the packaging material. The amount of the hardener to be used in the curable resin composition of the present invention is preferably from 5 to 5 equivalents, more preferably from 0.7 to 1.2, based on the epoxy group equivalent of the epoxy resin. Equivalent. If the equivalent of the epoxy group is less than 〇5 when 1, or more than 1.5 equivalents, the hardening is not complete. In the curable resin composition of the present invention, a curing accelerator (also referred to as a curing catalyst) may be used together with the curing agent or a curing accelerator may be used alone without using a curing agent. Specific examples of the hardening accelerator to be used include 2-methylmeridene, 2-phenylmethane sigma, 2-base 11-mw, 2-septyl-salt, 2-phenyl-4- Methylimidazole, 1-phenylhydrazino-2-phenylimidazole, 1-phenylhydrazino-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, cyanoethyl 2-phenylimidazole , 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6(2'-mercaptoimidazole (Γ)) ethyl-symmetric tri-D well, 2,4-diamino- 6(2,-11-hydroxypyrene (Γ)) ethyl-symmetric tri-D well, 2,4-diamino-6(2'-ethyl-4-mercaptoimidazole (1')) - Symmetric triterpene, 2, 4-diamino-6 (2'-methylimidazolium (Γ)) ethyl-symmetric tri-farming, iso-cyanuric acid adduct, 2-mercaptoimidazole isotrimerization 2:3 adduct of cyanate, adduct of 2-phenylimidazolium isocyanurate, 2-phenyl-3,5-dihydroxyindole 19 322191 201111407 imidazole, 2-phenyl-4-hydroxyl曱-5-methylimidazole, 1-cyanoethyl-2-phenyl-3-, 5-dicyanoacetoxyimidazole, various imidazoles; and the likes and sulphonic acid, isophthalic acid Formed by polycarboxylic acids such as capric acid, terephthalic acid, 1,2,4-benzenetridecanoic acid, 1,2' 4, 5-tetracarboxylic acid, naphthalene dicarboxylic acid, maleic acid, oxalic acid a salt; a guanamine such as dicyandiamide, an anthracene, an anthracene, a bismuth-bis-bicyclic ring (5.4.0), an eleven -7, etc., an anthracene compound, and a tetracene-based acid ester, a pan varnish a salt of a resin or the like, a salt formed of the above polybasic phthalic acid or a phosphonic acid; an ammonium salt such as tetrabutylammonium bromide, cetyltrimethylammonium bromide or octyltrimonium bromide; triphenylphosphine; a phosphine or a scaly compound such as a phthalocyanine or a fluorinated compound such as a tetraphenylphosphonium bromide or a tetraphenylphosphonium tetraphenylborate; a phenol such as 2,4,6-triamine cresol; A metal compound such as a compound or a stannic acid; and a microcapsule-type hardening accelerator or the like which is a microcapsule. Which kind of hardening accelerator is used is appropriately selected depending on the characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions. The hardening accelerator is usually used in an amount of from 1 to 15 parts by weight based on 1 part by weight of the epoxy resin. The curable resin composition of the present invention may further contain a phosphorus-containing compound as a component imparting flame retardancy. The phosphorus-containing compound may be either a reactive type or an additive type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, xylenol squarate, tris-phenylene dimethyl sulphate, cresol diphenyl phosphate, and cresol -2,6-diphenylene phosphate, 1,3_phenylene bis(diphenylene phosphate), hydrazine, 4-phenylene bis(diphenylene dimethyl phosphate) , 4, 4'-linked phenyl (diphenylene phosphate) and other phosphates; 9, 10-dihydro-9-oxa-ίο-phosphaphenanthrene oxime, 1 〇 (2,5_ 322191 20 201111407 dihydroxy phenyl)-1〇Η-9-oxa _ι〇-Phosphane; Phosphorus, red structure, etc. Reaction yield =; a particularly good diphenyl: = benzene:: base called 酉曰), Shen Stupi bis (diphenylene biphenyl (diextended dimethylphosphine or containing compound = object) The content of the product is lower than (4) containing the compound/county = () 丨 to 〇 6 (reset ratio). If it is below 0. i, the flame retardancy will be insufficient, and if it is 〇, it may be hygroscopic to the hardened material. , dielectric properties have an adverse effect. · Into the hardening composition of the present invention can also be used as needed (4) The binder resin may be exemplified by: Ding Yue resin, BJ resin, acrylic resin, epoxy-nylon, etc., resin, epoxy grade resin, polyamine resin The polyimine-based resin or the sulphur-based resin is not limited thereto. The blending amount of the adhesive is preferably used within the range of the flame retardancy and heat resistance of the 曰σ-cured material, as opposed to two. The component parts by weight is usually 0.05 to 50 parts by weight, more than '^20 parts by weight. 々u.ub to the curable resin composition of the present invention may be added as needed. The inorganic filler may be exemplified by crystalline silica. The smelting of the sulphur dioxide, the sulphuric acid, the smelting, the sulphur, the sulphur, the carbonation, the nitriding: the fossil, the boron, the cerium oxide, the strontium silicate, the talc, the spinel, the second gas, the nitrite The powder or the spheroidized beads or the like may be used alone or in combination, and may be used singly or in combination of two or more kinds. The content of the material may constitute the curability of the present invention. In the resin composition, q, 'machine is filled to the amount of 9 5 weight 322191 21 201111407%. The curable resin composition of the present invention may be added with various components such as a decane coupling agent, a stearic acid, a palmitic acid zinc stearate, a calcium stearate, a release agent such as a pigment, and various thermosetting resins. When the curable resin composition of the present invention is used for an optical semiconductor encapsulant, the particle size of the inorganic filler used as described above can be used to reinforce mechanical strength and the like without using transparency by using a nano-sized filler. The standard of the rice grade is an average particle diameter of 500 nm or less, and particularly, a filler having an average particle diameter of 20 Å or less is preferable for transparency. When the curable resin composition of the present invention is used for an optical semiconductor package. , you can add a fluorescent body as needed. The fluorescent system has a function of, for example, absorbing a part of the blue light emitted from the blue lED element to emit a yellow light having a changed wavelength, thereby forming white light. The fluorescent system is previously dispersed in the curable resin composition, and then the photo-semiconductor is encapsulated. The phosphor is not particularly limited, and a conventionally known phosphor can be used, and examples thereof include an aluminate of a rare earth element and a thiogallate acid salt. More specifically, a phosphor such as a YAG phosphor, a TAG phosphor, a strontium silicate phosphor, a thiogallate phosphor, a sulfide phosphor, or a CASN phosphor can be used. For example, YAl〇3: Ce, Y3Al5〇12: Ce, Y4Al2〇9: ce, y2〇2S: Eu, Sr5(P〇4)3Cl: Eu, (SrEu)O. AW, CaA1SiN3, and the like. The particle size of the glare body is a particle size which is conventionally known in the art, and is preferably from 丄 to 250 # m' in terms of the average particle diameter, particularly preferably from 2 to 50/zm. When these phosphors are used, the amount thereof is from i to 8 parts by weight, preferably from 5 to 60 parts by weight, per part by weight of the resin component. When the curable resin composition of the present invention is used for the optical semiconductor package 322191 22 201111407, in order to prevent sedimentation of various phosphors during hardening, for example, a shake such as cerium oxide micropowder (also referred to as Aer〇sil) may be added. The agent is given. The above-mentioned ceria micropowder may, for example, be: Aerosil 50, Aer〇sil 9〇, Aer〇sii 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil 〇X50 ^ Aerosil TT600 ^ Aerosil R972 > Aerosil R974 ^ Aerosil R202 ' Aerosil R812> Aerosil R812S > Aerosi1 R805, RY200, RX2〇〇 (manufactured by Japan Aerosil Co., Ltd.). The curable resin composition of the present invention can be used as a light stabilizer, a wall compound, and an age-based compound as an antioxidant for the purpose of preventing dyeing. The above amine compound may, for example, be tetra(1,2,2,6,6-pentamethyl-4-piperidinyl)=1,2,3,4-butanetetracarboxylate or tetra(2, 2) , 6, 6-tetramethyl-4-0 bottom bite) = 1,2,3,4-butane tetracarboxylic acid ester, ι,2,3,4-butane sulphuric acid and 1,2, 2' 6, 6-penta-f--4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2, 4, 8, 10-tetraoxaspiro[ 5. 5] Mixed esterified compound of undecane, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate of decanedioic acid, double (1_11 entertainment •oxy-2, 2, 6, 6-tetradecyl dentate-4-yl)carbonate, 2, 2, 6, 6-tetradecyl-4-piperidine methacrylate, bis (2 , 2, 6, 6_tetramethyl-4-piperidinyl) sebacate, bis(;[,2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate, 4-phenylhydrazineoxy-2, 2, 6, 6-tetramethylpiperidine, 1-{2-[3-(3, 5-di-t-butyl-4-hydroxyphenyl)propanoid Oxy]•ethyl b 4_[3_(3,5-di-t-butyl-4-hydroxyphenyl)propenyloxy]_2, 2, 6, 6-tetradecylpiperidine, 1,2 , 2, 6, 6-pentamethyl-4-piperidinyl-methacrylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl){ [3, 5_ double g, bisdimethylethyl) 23 322191 201111407 _4 hydroxyphenyl] methyl butyl butyl malonate 'decane diacid bis (2, 2, 6, 6 ~ four 曱Reaction product of keto-1 (octyloxy)_4_piperidinyl) ester, bismuthylethyl hydrogen pervaporate and octane, ^^^,,,^,,- four gas orders ^ Bis(butyl-(N-fluorenyl 2,2,6,6-tetramethylpiperidin-4-yl)amino)__Sansui-2-yl)-4,7-diaza癸 癸 -1, 丨〇 _ diamine, dibutylamine · 1,3 卜 trimorph. Ν, Ν '-bis (2, 2, 6, 6-tetramethyl-4-piperidinyl)-1 , a polycondensate of 6-hexamethylenediamine and Ν-(2, 2, 6, 6-tetramethyl-4-piperidyl)butylamine, poly{[6-(1,1,3, 3-tetramethylbutylamine amine 1,3,5-trinyl-2,4-diyl][(2, 2, 6, 6-tetramethyl-4-piperidinyl)imido] Hexamethylene[(2,2 6,6-tetramethyl-4-piperidinyl)imido]}>dimethyl succinate with 4_hydroxy-2, 2, 6' 6-tetra Polymer of keto-1-piperidineethanol, 2, 2, 4, 4-tetramethyl-20-(0-lauroyloxycarbonyl)ethyl-7-oxa-3, 2〇-diazaspiro [5. 1. 11. 2] Behenyl-21-one, yg-alanine, hydrazine, one (2) , 2, 6, 6_tetramethyl-4-piperidinyl)-dodecyl ester/tetradecyl ethionyl _3_dodecyl-1-(2, 2, 6, 6-four Methyl-4-Brigade bite) "; bite 2, 5-dione, 2, 2' 4, 4-tetramethyl-7-oxa-3, 20-diazabispiro[ 5. 1. 11. 2 2] behen-2-one, 2, 2, 4, 4-tetradecyl-21-oxa-3, 20-diazabicyclo-[5. 1. 11 . 2]-Tetradecane-20-propanoic acid dodecyl ester/tetradecyl ester, malonic acid [(4-methoxyphenyl)-methylene]-bis (1,2, 2, a higher fatty acid ester of 6,6-pentamethyl- 4-pyridyl) 3⁄4, 2, 2, 6, 6-tetradecyl-4-brazidin; 1,3-benzoammine, hydrazine,受'-bis(2, 2, 6, 6-tetramethyl-4-α-bottom base) and other hindered amines such as dioxobenzone and other diphenyl ketone compounds; 2-(2H-stupid Andoxazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, (2-hydroxy-5-nonylphenyl)benzotriazole, 2-[2- Hydroxy-3-(3, 4, 5, 6- 322191 24 201111407 tetrahydrophthalimido-methyl)-5-methylphenyl]benzotriazole, 2-(3-third 2-yl-2-carbyl-5-tolyl)-5-chlorobenzotrienyl, 2-(2-propionyl-3, 5-di-third Phenyl)benzotriazole, methyl 3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionate and polyethylene glycol a reaction product, a benzotriazole compound such as 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol; 2,4-di-t-butylphenyl a benzoate ester such as -3,5-di-t-butyl-4-hydroxybenzoate or 2-(4,6-diphenyl-1,3,5-trin-2-yl) A triterpenoid compound such as -5-[(hexyl)oxy]phenol, and the like, and a hindered amine compound is particularly preferable. As the amine compound of the above light stabilizer, a commercially available product shown below can be used. The commercially available amine-based compound is not particularly limited, and examples thereof include THINUVIN 765, THINUVIN 770DF > THINUVIN 144 'THINUVIN 123 ' THINUVIN 622LD ' THINUVIN 152, CHIMASSORB 944 manufactured by C i ba Specialty Chemicals, Inc.; LA manufactured by ADEKA Corporation -52, LA-57, LA-62, LA-63P, LA-77Y, LA-81, LA-82, LA-87, etc. The phosphorus compound is not particularly limited, and examples thereof include 1,1,3-tris(2-mercapto-4-bis(tridecane)phosphite-5-tert-butylphenyl)butane, and Stearyl neopentyl alcohol diphosphite, bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-t-butyl-4- Tolyl) neopentyl alcohol diphosphite, phenyl bisphenol A neopentyl alcohol diphosphite, dicyclohexyl neopentyl alcohol diphosphite, tris(diethylphenyl) phosphite, three (di-isopropylphenyl) phosphite, tris(di-n-butylphenyl) phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(2,6-di -T-butylene) 25 322191 201111407 Phosphite, tris(2,6-di-t-buttyl) phosphite, 2, 2,-fluorenylene bis (4,6-di-third Butyl phenyl) (2,4-di-t-butylphenyl) phosphite sorbate, 2' 2'-fluorenylene bis(4,6-di-t-butylphenyl) (2-tert-butyl 4-曱phenyl)phosphite, 2,2'-fluorenylene bis(4-mercapto-6-tert-butylphenyl) (2-tert-butyl-4-anthracenephenyl) subwall Acid ester, 2, 2'-Asia Bis(4-mercapto-6-t-butylphenyl)(2-t-butyl-4-tolyl)phosphite, tetrakis(2,4-di-t-butylphenyl)-4, 4'-Extended biphenyl diphosphinate, tetrakis(2,4-di-tert-butylphenyl)-4,3'-extended biphenyl diphosphinate, tetrakis (2, 4-di -Third butyl)-3,3'-Extended biphenyl diphosphinate, tetrakis(2,6-di-t-butylidene)-4,4'-extended biphenylphosphonium diphosphine Acid ester, tetrakis(2,6-di-t-butylidene)-3,3'-extension of phenyldiphosphinate, bis(2,4-di-t-butylphenyl)-4- Phenyl-phenylphosphinate, bis(2,4-di-t-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-n-butyl) -3-styl-phenylphosphinic acid vinegar, bis(2,6-di-t-butylphenyl)-4-phenyl-phenylphosphinate, bis (2, 6- _ second Butyl)-3-phenyl-phenylphosphinic acid g, tetrakis(2,4-di-tert-butyl-5-fluorenylphenyl)-4,4'-extended biphenyl diphosphine Acid ester, tributyl phosphate, tridecyl phosphate, tridecyl phenylate, triphenyl phosphate, trichlorophenyl phthalate, triethyl phosphate, diphenyl decyl phenyl phosphate Biphenyl diphenyl phosphate esters, tris butoxyethyl acrylate broken, broken dibutyl fill dioctyl phosphate and 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 ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK manufactured by ADEKA Corporation. STAB 2112, ADK STAB 260, 26 322191

201111407 ADK STAB 522A, ADK STAB 1178 ' ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, AM STAB ΊΤΡ. The compound is not particularly limited, and examples thereof include 2,6-di-t-butyl-4-methylphenol and n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl). Propionate, tetrakis[rhodecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 2,4-di-t-butyl-6-anthracene Phenol, 1,6-hexanediol_bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris(3,5-di-t-butyl) -4-hydroxybenzyl)-isocyanate, H5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, Neopentyl alcohol-tetrakis[3_(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,9_bis_{2-[3-(3-t-butyl) -4-hydroxy-5-tolyl)-propenyloxy]-li-dimethylethyl}-2, 4, 8,10-tetraoxaspiro[5. 5]undecane, triethylene Alcohol-bis[3-(3-tert-butyl-5-fluorenyl-4-hydroxyphenyl)propionate], 2,2,-butylenebis(4,6-di-t-butylphenol) , 4,4,-butylidene bis(3_fluorenyl-6-tert-butylphenol), 2, 2'-fluorenylene bis(4-mercapto-6-tert-butylphenol), 2, 2' _Alkenylene bis(4_ethyl-6-tributylphenol), 2-tert-butyl_6_(3_t-butyl-2-hydroxy-5 -methylphenylhydrazinyl)-4-cresol acrylate, hydroxy-3,5-di-p-pentylphenyl)ethyl]-4,6-di-t-pentyl phenyl acrylate, 4, 4 , _ thiobis(3-mercapto-6-tert-butylphenol), 4,4,-butylidene bis(3_methyl_6_third butanol), 2-tert-butyl-4-methyl Phenol, 2, 4-di-t-butylphenol ' 2, 4-mono-p-pentanol, bis-[3, 3-bis-(4'-hydroxy-3, a tributylphenyl)-butyl Acid]-ethylene glycol ester, 2,4-di-third butanol, 2,4-di-p-pentanol, and the like. Commercially available products can also be used as the above-mentioned aging compounds. The commercially available phenolic compound is not particularly limited, and examples thereof include Ciba Specialty

Chemicals 27 322191 201111407 IRGANOX 1010 ' IRGANOX 1035 ' IRGANOX 1076 ' IRGANOX 1135, IRGANOX 245 ' IRGANOX 259, IRGANOX 295 ' IRGANOX 3114 ' IRGAN0X 1098 ' IRGAN0X 1520L ; ADK STAB AO-20, ADK STAB AO -30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330; manufactured by Sumitomo Chemical Industries Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumi1izer GP, etc. In other aspects, commercially available additives may also be used as the anti-staining agent for the resin. For example, THINUVIN 328 'THINUVIN 234 ' THINUVIN 326 ' THINUVIN 120, THINUVIN 477, THINUVIN 479, CHIMASS0RB 2020FDL, CHIMASSORB 119FL, etc., manufactured by Ciba Specialty Chemicals, Inc., may be mentioned. The 5% to 5.0% by weight of the curable resin composition is not particularly limited as long as it is at least one of the above-mentioned phosphorus-based compound, the amine compound, and the ruthenium-based compound. The scope. The curable resin composition of the present invention can be obtained by uniformly mixing the components. The curable resin composition of the present invention can be easily obtained by the same method as the conventional method. For example, the following methods can be used: an epoxy resin and a hardener, and optionally a hardening accelerator, a scaly compound, a binder resin, an inorganic filler, and a compounding agent, and an extruder, a kneader, a roll machine, and a planet are required. The mixer or the like is sufficiently mixed until uniform to obtain a curable resin composition. If the curable resin composition is liquid 28 322191 201111407, the curable resin composition is impregnated into the substrate or cast by a potting method or a casting method. It is then hardened by heating in the mold; if it is solid, it is melted and then cast, or formed by a transfer molding machine or the like, and then hardened by heating. The hardening temperature and time are from 8 200 to 200 t, from 2 to 10 hours. The hardening method can be directly cured at a high temperature, but it is preferred to gradually heat the hardening reaction. Specifically, initial hardening is carried out between 80 and 15 CTC, and post-hardening is carried out between 100 and 200 °C. The hardening stage is preferably carried out in 2 to 8 stages, more preferably 2 to 4 stages. Further, the curable resin composition of the present invention may be dissolved in toluene, diphenylbenzene, acetone, mercaptoethyl ketone, decyl isobutyl ketone, decyl decylamine, dimercaptoacetamide. , 曱 吡 吡 。. A solvent such as a ketone is used as a curable resin composition varnish, and then impregnated with a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and dried by heating, and then the prepaid The cured product of the curable resin composition of the present invention is obtained by hot press molding of the dip. The solvent at this time is usually used in an amount of from 1 to 70% by weight, preferably from 15 to 70% by weight, based on the mixture of the curable resin composition of the present invention and the solvent. Further, the liquid composition can be directly obtained by RTM (Resin Transfer Molding) to obtain a cured epoxy resin containing carbon fibers. Further, the curable resin composition of the present invention can also be used as a film-type encapsulating composition. When the film-type resin composition is obtained, the curable resin composition (the above-mentioned varnish) of the present invention can be applied to a release film, and then the solvent is removed by heating to carry out B_s^age formation to obtain a sheet-like adhesive. . The sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like, and an integral layer of an optical semiconductor. Next, it will be described in detail with respect to the ^, π π of the oxy-resin assembly (4) photo-semiconductor used in the Z _ encapsulation material (IV) of the present invention. Although the epoxy tree of the present invention is t ^ 曰, and the product is used as a high-intensity white LED or the like, and the selenium is also used, when the adhesive crystal is used, the yttrium of the present invention can be used (hardened) Agent composition) and epoxy resin, as well as other hardening accelerators, sputum, θ^^ σ, antioxidants, light stabilizers and other additives filled with 吣 吣 amp 来 裱 裱 裱 裱 裱 θ θ And, as a packaging material, or as both a bonding material and a packaging material. The mixed tlj , . α method is mixed using a kneader, a three-axis roll 'universal mixer, a planetary mixer 几 a few prosperous machines, a homodisper, a bead mill, etc.' at normal temperature or under heating. Optical semiconductor components such as white LEDs, such as GaAs GaP, GaAlAs, GaAsP 'AlGa, InP, and GaN, are laminated on substrates such as sapphire, spinel, SiC, Si, and ZnO. A semiconductor wafer such as InN or AIN InGaN is adhered to a lead frame, a heat release plate, or a package by an adhesive (adhesive material). In order to flow the current, there is also a turn of a wire such as a gold wire. In order to protect the semiconductor W from heat and moisture, and to function as a lens function, a package such as an epoxy resin is packaged. The epoxy resin composition of the present invention can be used as the encapsulant or the adhesive. In the step, the curable resin composition of the present invention is preferably used as both a binder and a package. The method of bonding a semiconductor wafer to a substrate using the curable resin of the present invention can be carried out by using a dispensing method, a potting method, or a job printing method, and then collecting the money (four) W and performing 322191 30 201111407 Heat hardening to bond semiconductor wafers. For heating, hot air circulation, external line, high frequency, etc. can be used. w ^ The heating condition is preferably, for example, 80 to 23 (Tc is carried out for about 丨 minute to hour. The purpose of reducing the internal stress generated during heat hardening may be, for example, 80 to 120 ° C, pre-hardening for 30 minutes to 5 hours, Further, the post-hardening is carried out at 120 to 18 CTC for 30 minutes to 10 hours. The molding method of the package material may be the following: the injection method is to insert the template into the package after the substrate having the semiconductor wafer as described above is inserted. And heat-hardening and forming; compression molding method, pre-injecting the package material onto the mold, and immersing the semiconductor wafer previously fixed on the substrate in the towel's heat-hardening and then separating from the mold. Dispensing method, transfer molding method, injection molding method, etc. Heating can be performed by a hot air circulation type, infrared ray, high frequency, etc. The twisting condition is preferably, for example, 8 G to 23 (rc is performed from ! minutes to 24 hours.) The purpose of reducing the internal stress generated during heat hardening, for example, can be 8 〇 to 1. Grab, pre-harden for 30 minutes to 5 hours, and then 12 〇 to 8 〇 C ' 30 Post-hardening under conditions of 10 minutes to 10 hours. Other uses of the curable resin composition = tree-hardening ribs - (4) way, except H, such as adhesive 'paint' coating (4), forming materials (including sheets , film, :,,, silk material (including printed substrate, wire coating, etc.), encapsulant may also be used as a package material, an acid ester tree wax composition for a substrate, or a photohardening method as an acrylic acid vine tree Other additives such as wax, etc. 322191 31 201111407 The following agents can be used as an adhesive for electronic materials, such as civil, construction, automotive, general-purpose, and medical adhesives. In the case of the adhesive for an electronic material, an interlayer adhesive for a multilayer substrate such as a buiidup substrate, a semiconductor adhesive such as a binder or a primer, a BGA reinforcing primer, and an anisotropic conductive film (ACF) may be used. An adhesive for assembly such as an anisotropic conductive paste (ACP), etc. Examples of the encapsulating material include a filling method for a capacitor, a transistor, a diode, a light-emitting diode, a 1C, an LSI, etc., a dipping method, and a transfer. Forming method ; package for infusion method of 1C, LSI type COB, C0F, TAB, etc.; for flip chip and other primers, QFP, BGA, CSP and other IC assembly packages (reinforcing primer) The cured product obtained by the present invention can be used for various purposes such as optical component materials, etc. Optical materials generally refer to materials used in applications in which visible light, infrared rays, ultraviolet rays, X-rays, lasers, and the like are transmitted through the material. In addition to the sealing material for LEDs such as a lamp type or an SMD type, the following may be mentioned: a substrate material in the field of liquid crystal display, a light guide plate, a prism sheet, a deflector plate, a phase difference plate, and a viewing angle correction. A material for a liquid crystal display device such as a film for a liquid crystal such as a film, an adhesive or a polarizing element protective film. In addition, the package material, the anti-reflection film, the optical correction film, the outer single material, the protective film of the front glass, the glass of the glass, and the LED used for the next generation are shown as the next generation. Mold material 'lED seal' negative without front glass replacement material, adhesive = film, substrate material in the device, light guide plate, edge display double moon, deflection plate, phase difference plate, 322191 32 201111407 viewing angle correction film, then Protective film for polarizing element; or protective film for front glass in organic EL (electroluminescence) display, front glass substitute material, adhesive; or various film substrates in field emission display (FED), protective film for front glass, front Glass substitute materials and adhesives. In the field of optical recording, VD (Vide Disc, VD/CD-ROM, CD-R/RW, DVD-R/DVD-RAM, MO/MD, PD) (phase change optical disc), optical disc substrate material for optical card, reading lens, protective film, encapsulant, adhesive, etc. ~ In the field of optical equipment, the lens material for the camera, the viewfinder 稜鏡, the target rib Mirror, viewfinder housing, section a light-receiving sensor; or a camera lens, a viewfinder; or a projection lens of a projection television, a protective film, a sealing material, an adhesive, etc.; or a translucent material of a photoreceptor n, a packaging material, an adhesive, a film, etc. In the field of optical parts, the fiber material around the optical switch in the optical information system, the lens, the waveguide, the component, the encapsulant of the package, etc.; or the optical fiber material around the optical connector, the coil B package, and the adhesive In the passive parts or optical circuit parts, the substrate, the fiber material, and the α-lens, the waveguide, the LED package, the CCD package, the adhesive, or the optoelectronic integrated circuit (0EIC) may be used. In the field of optical fiber, decorated with display, Zhaori i ^ Buddha-β # ., 'month, light guide, etc.; detectors for industrial use, display, show no class,念 念 汛 汛 汛 汛 汛 o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o In cars, conveyors In the field, the steam and electricity micro-projection reflector lamp, the bearing compliant ring, the gear part, and the silver lacquer 322191 33 201111407 engine: parts, electrical components, various inner and outer parts, drive engines, teaching car oil, ★ ^ Plate, inner n '' brake rust-proof steel plate, internal panel inner material, protective bundling line, burning sputum substitute; or multi-layer broken glass substitute for railway vehicles, engine peripheral parts, insurance ^Fly _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The light of the generations of the second generation of agriculture, can be listed in the right 妩 W - from the generation of the first motor can be organic materials, can be Ε 举 举 organic Ε "parts of peripheral materials, organic light refracting elements of optical amplification components, optical computing亓 Du Jiu first conversion, c ^ yuan connected 70 pieces, organic solar cell peripheral material, fiber materials, components of packaging materials, adhesives and so on. The earthen packaging material can be used for capacitors, transistors, diodes, ί, '1C, LSI type C0B, c〇F, ΤΑβ, etc. CSP I ϊρ h # ja* 襄 (10) Strong primer, etc. For other uses of the CS" IC package, the sealant material may be used in the form of a curable resin composition, in addition to scales such as an adhesive, a coating, a coating agent, and a molding material (including In addition to the sealing of the sheet, the film, the FRP, etc., the insulating material (2 brush substrate, wire coating, etc.), it can also be used as a supplement for other resins, etc. The adhesive can be used for civil, construction, and pneumatic vehicles. In addition to the general-purpose and medical adhesives, it can also be used as an adhesive for electric enamels. Among them, the adhesive for electronic materials can be used as a primer for the laminated substrate layer. Crystal and base semiconductor 322191 34 201111407 An adhesive for assembly such as an adhesive, a BGA reinforcing primer, an anisotropic conductive film (ACF) or an anisotropic conductive paste (ACP), etc. The present invention will be more specifically described, and the following "parts" means "parts by weight" unless otherwise specified. Furthermore, the invention is not limited to the embodiments. In the examples, the epoxy equivalent was measured in accordance with JIS K-7236; the viscosity was measured at 25 ° C using an E-type viscosity agent. The analysis conditions in gas chromatography (hereinafter referred to as GC) were performed using HP5-MS (0.25 mm ID x 15 m, film thickness: 0.25 #m), and the column oven temperature was set to an initial temperature of 100 ° C per minute. The temperature was raised at a rate of 15 ° C and maintained at 300 ° C for 25 minutes. Helium is used as a carrier gas. In addition, the gel permeation chromatography (hereinafter referred to as GPC) is determined as follows: the column is a Shodex SYSTEM-21 column (KF-803L, KF-802. 5 (x2 tube), KF-802); Tetrahydrofuran was used; the flow rate was 1 ml/min; the column temperature was 40 ° C; and it was detected by UV (254 nm); the standard curve was made of standard polystyrene made of Shodex. The percentages, ratios, parts and the like in the present specification are expressed by weight unless otherwise specified. Synthesis Example 1 Synthesis of di-saturated hydrocarbon compound 172 parts of 1,4-cyclohexanedicarboxylic acid and 3-hexane were added while being purged with nitrogen in a flask equipped with a stirrer, a reflux condenser, a stirring device, and a Dean-Stark tube. 448 parts of ene-1-nonanol, 600 parts of hydrazine, 4 parts of p-toluenesulfonic acid, and adjust the degree of vacuum in the system by reflux at 45 ° C to remove water generated by 35 322191 201111407 and perform 12 Hours of reaction. After the completion of the reaction, the reaction solution was washed three times with 120 parts of a 1% by weight aqueous sodium hydroxide solution, and then washed with water 70 times/time until the waste liquid became neutral, and then heated and decompressed by a rotary evaporator. Diluted and unreacted cyclohexane methanol was distilled off, whereby 343 parts of a diene compound which was liquid at normal temperature was obtained. The synthesis of the epoxy resin was carried out in a flask equipped with a stirrer, a reflux condenser, and a stirring device, while adding 15 parts of water, 12-tungsten-disc yttrium, 0.70 parts of wall acid gas, and 2 tallow base. Dimethylacetic acid@@27 parts (LION AKZ0 '50% by weight hexane solution, ARQUAD 2HT acetic acid vinegar), after the formation of the taurine-based catalyst, 180 parts of toluene and the above-mentioned di-hydrocarbon compound are added. 118 parts 'then re-mixed to make it a milky solution. The solution was warmed to 50 ° C', and 70 parts of a 35 wt% aqueous hydrogen peroxide solution was added over 1 hour while vigorously stirring, and then dropped for another 13 hours at 503⁄4. The progress of the reaction was confirmed by GC, and it was found that the peak of the raw material had disappeared. Subsequently, 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 stirred for 30 minutes, followed by standing. The organic layer separated into two layers was taken out, and 10 parts of Wak〇_gel C-300, activated carbon (manufactured by N0RIT, CAP SUPER), 20 parts, bentonite (made by H0JUN 'Bengel SH) 20 were added. The mixture was stirred at room temperature for 1 hour and then subjected to hydrazine. The obtained filtrate and the liquid were washed three times with 10 parts of water, and the benzene was distilled off from the obtained organic layer, thereby obtaining an epoxy resin (EP) of the following formula (1) which was liquid at normal temperature. -1) 119 parts. The epoxy resin obtained had an epoxy equivalent of 217 g/eq. 322191 36 201111407

(l) Rt (all Ri in the formula are hydrogen atoms). Example 1 For the epoxy resin (EP-1) obtained in Synthesis Example 1, methylhexahydro-dodecanoic anhydride (manufactured by Nippon Chemical and Chemical Co., Ltd., RIKACID MH700, hereinafter referred to as H1. Anhydride equivalent ι 68) was used. As a curing agent, hexadecyltrimethylammonium hydroxide (manufactured by Toka Chemical Industries, Ltd., 25% by weight of a decyl alcohol solution, hereinafter referred to as d) is used as a curing accelerator, and the mixing ratio shown in Table 1 below is used. The amount of the hardening resin of the present invention is obtained by the combination of 'but' defoaming for 2 minutes, and the amount of the hardener used is the epoxy group for the epoxy resin! It is calculated as 1 equivalent. Comparative Example 1 For 3'4_% oxocyclohexylmethyl-3',4,-epoxycyclohexyl valerate ~2; epoxy equivalent 133) 'Use H1 as a hardener, C1 as a hardening accelerator, and The blending ratio (parts by weight) shown in the following Table 1 was blended, and defoaming was carried out for 20 minutes to obtain a curable resin composition of the ratio (IV) of the present invention. Here, the amount of the hardener used is calculated as 1 equivalent for the epoxy group i of the epoxy resin. The post-hardening depression test of the field CLED package) The curable resin composition obtained in the examples and the comparative examples was filled in a 322191 37 201111407 syringe' and was mounted on a 5_square surface mount type LED package using a precision discharge device. Body (inner diameter 4 4mm, outer wall g 125 coffee). The ink was placed in a heating furnace, and then an LED package was formed by applying a heat treatment at 120 Torr for 15 hours and then for 3 hours. The height of the outer wall of the linometer was used as a reference to measure the depth of the resin after curing. . EXAMPLES (The results of Comparative Example 1 are shown in Table 1. Measurement Condition Depth Gauge: NIKON, DIGIMICRO STAND MS-11C, Depth Depth is an average of three packages. Table 1 Project Example 1 Comparative Example 1 EP -1 100 Composition EP-2 - 100 Hardener (H1) 77.4 126 Hardening catalyst (C1;) 0.4 0.4 Depression amount after hardening 140 /zm 392 β m From the above results, it is known that 'the epoxy obtained by the synthesis example 1 is used. The curable resin composition of the resin can be improved by 65% compared with the (4) u mesh, and the wire for conducting the LED chip in Comparative Example i can be partially floated. Examples 2 to 5 Epoxy resin prepared in Example 1 (EP_n, using hydrazine and cyclohexane-1'2,4-tricarboxylic acid-i, 2-anhydride (Mitsubishi Gas Chemical Co., Ltd.: 322191 38 201111407) 'Η-ΤΜΑη (semi-solid paste, * divided as follows), hereinafter referred to as Η2, anhydride equivalent 64) as a hardener, and according to the following table 2 ^ 9η, _ kg of the mix ratio (parts by weight), and then defoaming 20 Minutes

Ei 7L ^ The curable resin composition of the present invention. Here, the amount of the hardener used is 1 to 1 in terms of 1 equivalent of the epoxy group of the wood-based resin. _, ,; Because H2 is semi-solid, it is mixed with the hardener H1 in the ratio of the ratio of the two in the previous two, and heated to 1 GG 〇 C to become a homogeneous mixture and then hardened _ H2 with the same square wire reuse). Comparative Example 2 For 3,4~epoxycyclohexylmethyl-3,4,-epoxycyclohexylcarboxylate (Ep 2) 'Use H1 and H2 as hardeners, and as shown in Table 2 below. The blending ratio (parts by weight) was blended, and defoaming was further carried out for 2 minutes to obtain a curable resin composition for comparison of the present invention. Here, the amount of the hardener used is calculated as 1 equivalent for 1 equivalent of the epoxy group of the epoxy resin. (Porosion test after curing of LED package) The curable resin composition obtained in the examples and the comparative examples was filled in a >ejector' and cast into a 5 mm square surface mount type LED using a precision discharge device. The package body has an inner diameter of 4. 4 mm and an outer wall height of 1.25 mm. The castable was placed in a heating furnace, and then an LED package was formed by curing at 120 ° C for 1 hour and then at 15 ° for 3 hours. The recess was measured using the depth gauge outer wall as a reference to measure the depth of the resin after the hardening. The results of Examples 2 to 5 and Comparative Example 2 are shown in Table 2. Measurement conditions 39 322191 201111407 Depth gauge: NIKON system, DIGIMICRO STAND MS-11C, recess depth is an average of 3 packages. Table 2 Project implementation Example 2 Example 3 Example 4 Example 5 Comparative Example 2 EP-1 100 100 100 100 ----- EP-2 — — — A 100 composition hardener (H1) 60. 1 36. 7 21. 90 6 80 98. 1 Hardener (H2) 6. 7 15.8 21. 9 27. 2 10. 9 H2/CH1+H2) 0. 1 0. 3 0. 5 0· 8 1 —> Just one 0.1 after hardening The amount of 143 ^ m 12 is m 8 ^ m 3 /Z m 405 β m. From the above results, it is understood that the epoxy resin and the hardener H1 and the hardener H2 obtained in Synthesis Example 1 were simultaneously used, and Comparative Example 2 2, compared with the hardened recess, showing a remarkable effect, and it is also known that the ratio of H2 / (Η1 + H2) is 〇. 3 or more. Example 4, almost no recess after hardening of Example 5. Comparative Example 3 For 3,4-epoxycyclohexyldecyl-3',4'-epoxycyclohexylcarboxylate (ΕΡ-2), Η1 and Η2 were used as hardeners, and as shown in Table 3 below. The blending ratio (parts by weight) was blended, and defoaming was carried out for 20 minutes to obtain a curable resin composition for comparison of the present invention. Here, the amount of the hardener used is calculated as 1 equivalent for 1 equivalent of the epoxy group of the epoxy resin. (LED illumination test) The curable resin composition obtained in Example 4 and Comparative Example 2 was filled in a syringe with 322191 40 201111407, and poured into a 5 mm square equipped with a wafer having a central emission wavelength of 465 nm using a precision discharge device. The surface mount type LED package body has an inner diameter of 4. 4 mm and an outer wall height of 1.25 mm. The castable was placed in a heating furnace, and then hardened at 120 ° C for 1 hour and then at 15 ° C for 3 hours to prepare an LED package. The illuminance retention rate of the LED illumination after 2 hours was measured by the following conditions. The results of Example 4 and Comparative Example 3 are shown in Table 3. Measurement condition LED chip: Center emission wavelength 465nm LED illumination condition: forward current 6〇mA 'series mode simultaneously open 3 illumination LED lighting environment: illumination illumination retention rate in 85°C 85% damp heat machine: (after 200 hours of illumination) Illumination/initial illuminance) χι〇〇 (unit%) Table 3 Project Example 4 Comparative Example 3 EP-1 100 — EP-2 --* 100 Composition Hardener (H1) 21. 9〇35. 6 Hardener ( H2) 21- 9 ________ ～35.6 H2/CH1+H2) Γ 0.5 0.5 illuminance retention after 200 hours lapse of 83 _*---1 73 From the above results, it was found that the epoxy resin obtained in Synthesis Example 1 was used. The curable resin composition was significantly better than the comparative example 3 in its LED illumination test branch 41 32219] 201111407. The hardened tree of epoxy resin (4) knows that the use of (4) 1 is used to represent the alicyclic ring gas of the past: as an LED packaging material, it is 3,4- compared with -3,4,_if Λ Epoxycyclohexylmethyl 'oxime oxocyclohexyl decanoate s long. Μ 级 级 具有 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 。 。 。 。 Xenon stone 々々〇c dry packed with 2~(3,4-epoxycyclohexyl)ethyltrimethoxy oxysulfon 26_6 parts (burning oxygen 旦0 0〇A hole 丞田里82. l), 二曱Dioxa oxane = oxy equivalent _, triethylamine (four) parts, methyl isobutyl oxime 11' at room temperature (four) 'during 30 minutes, add steamed water (10) parts, ^ temperature to age and then react for 6 hours . After completion of the reaction, the mixture was neutralized with an aqueous solution of = = and washed three times with water. Then, the organic phase was reduced ☆ loot: the solvent was removed, whereby 6 g of a reactive epoxy resin (ep-3) was obtained. The obtained compound had a ring allowance of 561 g/eq., and the appearance was colorless and transparent. Comparative Example 4 Ten pairs of the oxime-modified epoxy resin (Ep_3) obtained in Synthesis Example 2 were used, and eight H1 and H2 were used as hardeners, and blended according to the mixing ratio (weight ϋ shown in Table 4 below). #脱泡 2G分钟, and obtain the curable tree day of the present invention, and the amount of the product H hardening class is calculated as 1 equivalent for 1 equivalent of the epoxy resin soil. The curable resin composition prepared in Example 4 and Comparative Example 4 was filled in a syringe with 322191 42 201111407, and was washed with a precision discharge device on a 5-leg 1-square surface of a wafer having a central emission wavelength of 465 nm. The assembled LED sealing body (inner diameter 4·4mm, outer wall height 1.25mm). The pouring material is put into the heating crucible, first 12〇. (: 1 hour, then l5〇°c 3 hours The LED package was formed by hardening treatment, and the LED package was placed in a corrosive gas under the following conditions, and the change in color of the silver-plated lead frame portion inside the package was observed. The results of Example 4 and Comparative Example 3 are shown in Table 4. Determination of Conditional Corrosive Gas: Ammonium Sulfide 20% Aqueous Solution (When Sulfur Component and Silver Counter It should be turned into black.) Contact method: The container of the aqueous solution of ammonium sulfide and the above-mentioned LED package are coexisted in a wide-mouth glass bottle, and then covered with a wide-mouth glass bottle and under the sealed bear to make the vulcanized ammonium sulfide gas and the LED package Contact: Heart's determination of corrosion: Observing the time required for the lead frame inside the LED package to become zero color (blackening), the longer the discoloration time is, the more excellent the corrosion resistance is. - Table 4 Composition of the project example 4 Comparative Example 4 EP-1 ----- 100 _ EP-3 —--- 100 Hardener (H1) 21. 90 8. 5 Hardener (H2) 21.9 8. 5 H2/CH1+H2) 0. 5 0. 5 The discoloration time of the lead frame is 10 hours or more without discoloration for 1 hour. 32219] 43 201111407 From the above results, it is understood that the curable resin composition of the present invention obtained by using the synthesis example is compared with the comparative example "I hour". (4) / 曰 曰 force epoxy resin sclerosing grade composition compared to the second cited = 吏 from this, it can be known that the hair is made of fine gas. The material = oxime resin has more excellent corrosion resistance 2 as L ED Seal 3'4 per oxycyclohexylmethyl _3,, 4, _ epoxy ring' and also compared with W The ring epoxy resin has better durability and the acidity is the representative of the product. = It has been detailed and referenced to the specific implementation form. ^The industry should be able to easily understand that it does not leave the road. Various changes or amendments can still be made under the premise of the encirclement. * The spirit and model application of Ming is based on the application of the main 4 case on July 7, 2009 (special 2_, 16 deletion), and the content of this patent is used. The present invention provides a curable resin composition and a material suitable for use in an electric and electronic material 5 semiconductor application, and in particular, a simple description of a simplified structure. no. [Main component symbol description] None. . 322191 44

Claims (1)

201111407 VII. Patent application scope: 1. A curable resin composition containing an epoxy resin represented by the following formula (丨) and a hardener and a hardening accelerator which can be hardened with the epoxy resin. One or both; ._ , ^ The curable resin composition according to Item 1, wherein all of R1 in (1) are hydrogen atoms. The sclerosing resin composition according to claim 1, wherein the curing agent of the curing reaction is the following formula (2); Any one or two of the compounds shown in the formula (3) (2) 322191 45 201111407 ο (wherein R2 represents a hydrogen atom or a fluorenyl group). 4. The curable resin composition according to claim 3, wherein the ratio of the compound comprising the compound of the formula (2) to the compound of the formula (3) is in a range of the following: W2/(W2 +W3)=〇.2 to 〇.9 (wherein W2 represents a part by weight of the compound of the formula (2); w3 represents a part by weight of the compound of the formula (3): 5. The type of hardened material is determined by the scope of the patent application The curable resin composition according to any one of items 1 to 4 is cured. 6. The optical semiconductor device comprising the optical semiconductor and the fifth aspect of the patent application scope of the optical semiconductor packaged Hardened. 46 322191 201111407 IV. Designation of representative figure: There is no drawing in this case. (―) The representative drawing of this case is: ( ). (2) The symbol of the symbol of this representative is simple: 5. If there is a chemical formula in this case , please reveal the chemical formula that best shows the characteristics of the invention: 3 322191