TW201120084A - Curable resin composition and cured products thereof - Google Patents

Abstract

Provided is a curable resin composition which, after being heat-cured, does not suffer from depression and which exhibits excellent corrosive gas resistance and excellent optical characteristics such as discoloration resistance. Also provided are cured products of the curable resin composition. The curable resin composition is characterized by comprising an epoxy resin obtained by oxidizing an olefin compound represented by general formula (1), and either a curing agent which is reactive with the epoxy resin and/or a cure accelerator. In general formula (1), multiple R1s and R2 are each independently a hydrogen atom or C1-6 alkyl.

Description

201120084 VI. Description of the Invention: [Technical Field] The present invention relates to a curable resin composition and a cured product which are suitable for use in electrical and electronic materials, particularly for use in optical semiconductor applications. [Prior Art] A method for hardening an epoxy resin using an acid anhydride has hitherto been used for various insulating materials and materials. Especially in the field where optical characteristics are required, such as LED products, etc., an acid anhydride hardened material of an epoxy resin is often used. A glycidyl ether type epoxy resin composition represented by a bisphenol A type epoxy resin excellent in heat resistance, transparency, and mechanical properties has been widely used as a sealing ring for optical semiconductor elements such as the above-mentioned LED products. Oxygen resin. However, the development of the short wavelength of the LED light-emitting wavelength (mainly the following blue light) indicates that the LED material is colored on the LED wafer due to the influence of short-wavelength light, which ultimately leads to LED products. reduce. Here, in terms of transparency, 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexyl"曰" jin represents an alicyclic epoxy resin which is more fragrant than glycoside (4) Since the epoxy resin composition is excellent, it is actively studied as an LED sealing material (Patent Document i. • Another aspect) The alicyclic epoxy resin is indicated to have a low viscosity and is volatile when thermally hardened. When the soldier uses the anhydride in the case of a hardener, it is volatilized in most cases. The amount of flattening has become a pollution hardening furnace. 0 201120084 The above-mentioned hardening resin composition such as a surface mount type in a led product (surface) In the case of packaging, since the amount of resin to be cast is extremely small (for example, about 10 mg), when a curable resin composition containing the alicyclic epoxy resin and an acid anhydride is used, it is generated during heat curing. As a result, there is a case where the sealing portion of the surface mount type LED product is recessed to cause an abnormality. Further, depending on the degree of the recess, the lead portion for supplying the wafer current is exposed, and this has become the case. The function as a sealing material cannot be exerted. As described above, the alicyclic epoxy resin still has problems in volatilization during heat curing. In recent years, LED products have been further developed to be brighter in order to be suitable for illumination or backlighting of τν. Therefore, when the LED is lit, it is accompanied by a large amount of heat. Therefore, even if the resin composition using the alicyclic epoxy resin is colored on the LED wafer, the illuminance of the LED product is lowered, and the durability is also present. (Patent Document 3) Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 】

For the problem of the property, the resin which is introduced into the skeleton of the Si-ruthenium bond represented by the following epoxy resin is known. It is generally known that the introduction of the azide skeleton is more stable to heat and light. Therefore, the resin of the breast shelf is more resistant than the epoxy resin to the sealing material used for the LED product. The durability of the resin is higher than that of the 201120084 oxyalkyl skeleton. Resin type is similar to ring 2: fat: different. However, this introduction is therefore inferior in gas permeability resistance by using a polyvalency resin or a polyoxyl resin. In the case of sealing materials, although the LED ring resin as the LED dense still has the following problems: the mineral is applied to the problem, but the silver component on the metal lead frame (, the component is colored or blackened, and finally the coffee σ In addition, the performance of the gamma ray rate is reduced, and the performance of the β mouth is reduced.

In the case of the city, an epoxy resin composition of a sealing material and a problem of I is sought, and the depression caused by volatilization during heating is suppressed as compared with the permeation resistance of the body: 曰 = epoxy resin is higher. Durability of ED products The present invention has been made in view of the above-described actual circumstances.曰岍9, the result is completed, ie, the invention relates to: (1) (wherein or carbon number 1,

There are a plurality of alkyl groups of R1 and 6); R independently represents a hydrogen atom 201120084 (2) The hardening of the above item (1) of Gekou, /,,,,,,,,,,,,,, ΑΛ All R1, "p 2 inferior κ is the olefin compound j (3) of the mouse atom, wherein the epoxy resin is a raw material; the hardening resin composition of the above item (1) or (2) is the following formula (2) One or more compounds shown: wherein the hardener

(wherein R3 represents a hydrogen atom, a mercapto group or a slow group); (4) The hardener in the curable resin composition according to any one of the above items (1) to (3) is the following formula (3) More than one compound shown:

(In the formula, a plurality of R3 independently represent a hydrogen atom, a fluorenyl group having a carbon number of 2 to 20 or a cyclic aliphatic group); (5) the above-mentioned (4) hardening resin composition In the formula (1), p 201120084 is a branched chain ring structure (6) The curable resin composition of i as shown in the following formula (1), wherein the curing agent contains more than one kind of the hardening agent. Compound

(wherein R3 represents a hydrogen atom, a fluorenyl group or an enantiomer group) and a compound of the above formula (3)

(wherein a plurality of r3 independently represent a nitrogen atom, a methyl group or a thiol 'p represents a chain or a cyclic aliphatic group having 2 to 20 carbon atoms), and the use ratio thereof is the following range: W2 / (W2 + W3) = 0.30 ~ 〇, 95 parts by weight, W3 means (where 'W2 represents the blended parts by weight of the compound of formula (2)); (7) a hardening The material is obtained by hardening the hard 201120084 chemical resin composition according to any one of the above items (1) to (6); (8) an optical semiconductor device by the above (1)~ The curable resin composition according to any one of the items (6) is obtained by sealing. The curable resin composition of the present invention is excellent in heat resistance, prevention of depression after heat curing, corrosion resistance, and excellent coloring resistance, and is therefore highly useful for optical materials, particularly for optical semiconductors (LED products, etc.). Materials, sealing materials. [Embodiment] The curable resin group of the present invention is described below. The curable resin composition of the present invention is required to contain an epoxy resin having an epoxy compound represented by the following formula (4) as a main component (hereinafter referred to as an epoxy epoxide of the present invention). Obtained by epoxidizing the olefin compound of the above formula (1):

(In the formula, a plurality of R'r2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). The olefin compound of the above formula (1) can be produced by a known method, for example, by reacting a cyclohexene carboxylic acid with cyclohexene dimethanol. The cyclohexenecarboxylic acid derivative can be exemplified by the following formula (5): 201120084

(wherein R represents a hydrogen atom or a carbon number of 1 to 6

The alkyl group, X represents a compound having no hydroxyl group, and specific examples thereof include cyclohexenecarboxylic acid, propylcyclohexene decanoate, cyclohexene methacrylate, cyclohexene decanoate, cyclohexene. Formic acid (cyclohexenyl decyl) ester, cyclohexene decanoate octyl ester, cyclohexene methyl hydrazine gas, cyclohexene hydrazine bromine, methylcyclohexane carboxylic acid, methyl cyclohexene decanoate methyl ester, A Ethyl cyclohexenecarboxylate, propyl decyl cyclohexene decanoate, nonylcyclohexene decanoic acid (methylcyclohexenyl decyl) ester, decyl cyclohexene oxime, etc., but not Limited to these. These may be used alone or in combination of two or more. Further, '% hexene dimethanol can be subjected to a cross Cannizzaro reaction by subjecting the cyclic olefin carbon age to furfural (or its synthetic isotope, dimeric decanoic acid, etc.) followed by a ketolization reaction. generate. The reaction of the % hexanoic acid derivative with cyclohexanol can be applied to the usual esterification method. Specifically, a general esterification reaction can be applied, and examples thereof include Fischer esterification using an acid catalyst, bubbling of an alcohol under an alkaline condition, reaction of an alcohol, condensation reaction using various condensing agents, and the like (ADVANCEDORGANIC CHEMISTRY PartB : Reaction and Synthesis pi35, 145 — 147, 151, etc.). Further, as a specific example, an esterification reaction of an alcohol with a carboxylic acid can be used (Tetrahedr〇n vol. 36 201120084 ρ·2409 (1980), Tetrahedron Letter p_4475 (1980)), and further, a formate is used. It is produced by a transesterification reaction (Japanese Patent Publication No. 2-5-〇52i87). The olefin compound of the above formula synthesized in the above manner is preferably a compound of the above formula (1) wherein R1 is a hydrogen methyl group or an ethyl 'butyl group, particularly when the substituent R1 is bonded to a carbon atom constituting an olefin bond. In order to enhance the reactivity, R丨 is preferably any one of a hydrogen atom and a methyl group, particularly an atom. The epoxy resin of the present invention is obtained by epoxidizing the compound of the above formula (1) by oxidation. Examples of the method of oxidizing include a method of oxidizing by a peracid such as peracetic acid, a method of oxidizing by using hydrogen peroxide water, a method of oxidizing by air (oxygen), and the like, but are not limited thereto. In the method of epoxidation of a peracid, the method of epoxidation of the hydrogen peroxide water described in the Japanese Patent Publication No. 7, No. 7, No. 7, No. 2, No. =二^本特开平" 本特开平平----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- In the invention of the Japanese Patent Publication No. 3-5, the low viscosity of the product is more preferably used as follows, and an example of a method of epoxidation using peroxidation gas is described. The epoxy resin represented by the formula (1) may not be limited to the following methods. Uncle, this. Under the latex state of organic solvent and hydrogen peroxide, make the temple "() olefinic compound, polyacid or its salt and quaternary ammonium should be. In addition, π should be used The polyacid or a salt thereof to be used in the present invention is not particularly limited as long as it is a compound having a polyacid structure, and it is preferably a polyacid or a salt thereof which contains a crane or a stalk, and particularly preferably a sulphate.吏佳 is 3 acids." Unless otherwise specified, the polyacetic acid or its salt is abbreviated as "poly polyacid, 5 丨 and · 酸 2: · / 2, acid, 12, .. Tungsten 矽 文, molybdic acid, disc molybdate, molybdenum citrate, etc.. Contrast cations of the salt of k4, cesium, etc. (caffe eatiGn), for example, money, alkaline earth metal ions, alkali metal ions, etc. In terms of material: (4) sub-1 ions and other soil-measuring metal nano-ions, potassium ions, and 10" μ #金四离子$, but not limited to «Hai 4. The preferred contrast cation is ^ ion. + is the amount of nano-ion, potassium ion, about ion, recorded =, relative to the compound of formula (1) 丨 metal element conversion (if it is tartaric acid, the main ear is «mole, more preferably 2.5~15 mm For the 1.0 to 20 four-level (four), it is preferable to make the total carbon number to be 'perfectively 25 201120084 ~ 100, more preferably 25 to 55 of the four-level salt, especially for the base bond Specific examples of the aliphatic chain include: trimethyl ketone, dilauryl dimethyl salt, trioctylmethyl sulphate, trialkylmethyl (a compound based on octyl) Mixed with sulfhydryl compounds) ammonium salt, tri-hexadecylmethylammonium salt, trimethyl stearyl salt, tetrapentyl salt, chlorpyrifos trimethyl sulphate, nodal base Butyl salt, dioxin dimethyl sulphate, sulphate methyl sulphate salt, dihardened tallow alkyl dimethyl ammonium salt, etc., but are not limited thereto. The anion species is not particularly limited, and specific examples thereof include a chiral ion "chaotic acid ion, & acid ion, hydrogen sulfate ion, acetate ion, carbonate ion, etc., but not If the carbon number is increased by 100, the hydrophobicity becomes too strong, and the solubility of the quaternary ammonium salt in the organic layer is deteriorated. If the carbon number is less than 10, the hydrophilicity becomes strong, and the same The amount of the quaternary ammonium salt in the organic layer is preferably the valence of the polyacid used: 0:01 to 0.8 times equivalent or UM0 times equivalent. More preferably 〇〇 5 to 〇 7 times equivalent or 1.2 to 6.0 times equivalent 'better 〇 〇 5 〇 5 times equivalent or i field equivalent. For example, if it is tungstic acid, it is 2 valence in h2W 〇 4, so relative Preferably, the toluic acid 1 Moer 'four-grade naphthoate is a G.02H.6 molar or a 2.2 to 2 molar range. Also, if it is a tungsten phosphate, it is a trivalent, so the same = Preferably, it is 0.03~2.4 moor or 3.3~3G moule. If it is acid, it is 4 valence, so it is preferably 0.04~3.2 moor or 4·4~4 〇 Mo. The amount of salt is less than a multiple of the price of the polyacid. 12 201120084 Equivalent case, the following problems occur: the epoxidation reaction is difficult to carry out (as the case may be, the reaction proceeds), and further, by-products are easily formed. 1〇 In the case of ^, not only the subsequent treatment is troublesome, but also the effect of suppressing the reaction is unsatisfactory. As the buffer solution, a known buffer solution can be arbitrarily used, but in the present reaction, it is preferred to use an aqueous phosphate solution. Preferably, it is adjusted to be between 4 and 10', more preferably PH5 to 9. When the pH is less than 4, the hydrolysis reaction and polymerization of the epoxy group are easily carried out. Further, in the case of pH (four) iq, The reaction becomes extremely slow and the reaction time is too long. Especially in the case of dissolving the polyacid as a catalyst in the present invention, it is preferred to adjust the pH to between 5 and 9. The method of using the buffer is, for example, used as a comparison. In the case of a phosphate-phosphate aqueous solution of a good buffer, 'the following method is used: 0.1 to 10 mol% of phosphoric acid (or phosphate such as sodium dihydrogen phosphate) is used with respect to hydrogen peroxide, and a basic compound is used ( For example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium carbonate, carbonated, etc. are used for pH adjustment. Here, in terms of pH, when hydrogen peroxide is added, it is preferably added so as to have the above pH. Further, adjustment may be carried out using sodium dihydrogen hydride or disodium hydrogen citrate. Preferably, the concentration of the phosphate is 〇, 丨~6〇% by weight, preferably i~45% by weight. Further, in the present reaction, it is also possible to directly add disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, sodium tripolyphosphate or the like without using a buffer and without pH adjustment - in the sense of simplification, it is particularly preferable The trouble of pH adjustment is added and added directly. The amount of phosphate used at this time is usually G1 to 5 #耳% equivalent, preferably 0.2 to 4 13 201120084 mole equivalent, more preferably 0.3 to 3, more than 5 mole % of hydrogen peroxide. , / ° equivalent. At this time, if it is relative to the excess of the ear, the pH of the epoxy compound which is generated by the tolerance is adjusted, and the epoxy compound which is formed in the case where the reaction is not reached, or the reaction becomes slow is used. Hydrogen peroxide was <butyl peroxide. The hydrogen peroxide acting on wood and strontium is simple in its operation. _ & The hydrazine used in the reaction is preferably an aqueous solution (4) having a hydrogen peroxide concentration of 10 to 40% by weight. In the case where the degree of work exceeds 40% by weight, in addition to the difficulty in handling, it is also difficult to carry out the decomposition reaction of the produced epoxy resin, which is unsatisfactory. This reaction uses an organic solvent. The organic used is humanized for the dilute hydrocarbonization as a reaction substrate. The substance 1 is 〇 3 to 10, preferably 0.3 to 5, more preferably 〇 5 5 2.5 by weight. In the case where the weight ratio exceeds 10, the progress of the reaction becomes extremely loud, and the Yuling is unsatisfactory. Specific examples of the organic solvent that can be used include an alkane such as an already-rich state, an alkane such as a hexane or a heptane, an aromatic hydrocarbon a to be used such as toluene or diphenylbenzene, and an anthracene, 曱 _ 'ethanol, isopropyl alcohol , butanol, hexanol, cyclohexanol and other alcohols _. Shou shou class and 'optionally use methyl ethyl ketone, methyl isobutyl ketone, ring lion s pentanone, J ketone (an 〇ne) and other ketones, diethyl ether, hydrofuran An ether such as two decane, an acetate such as ethyl acetate, butyl acetate or methyl vinegar, or a nitrile such as acetonitrile (IV). The solvent of Optima is an aromatic hydrocarbon compound such as a burned hydrocarbon such as hexene or cyclohexane, or a benzene or diphenylbenzene. Specific reaction operation method, for example, when the reaction is carried out in a batch reactor, an olefin compound 'hydrogen peroxide (aqueous solution), a polyacid (catalyst), a buffer solution, a quaternary ammonium salt and an organic solvent are added to the double layer. Stir. Stirring speed 14 201120084 degrees is not specified. Since hydrogen peroxide may be added, it may be added slowly after adding each component. In this case, the following method is used: a buffer method is added. After the pH adjustment of the polyacid, the quaternary salt and the phosphate are added, and the mixture is mixed in a double layer, and then the mixture is diluted and diluted. Alternatively, the following method may be used: After ah mixing water, organic solvent, and olefinic handle are added with polyacid and disc acid (or disc acid salt) in 35 steps, a quaternary ammonium salt is added to double-layer in: ... silly drop plus hydrogen halide reaction temperature is not particularly limited, preferably 卜 75 ° C ' Especially good for hunger ~ order better 0 ~ .. „ ^ 夂 should be / when the dish is still too easy to carry out When the hydrolysis reaction is carried out and the temperature is low, the speed of the & is extremely slow. Moreover, the reaction time depends on the reaction temperature, the amount of the catalyst, etc., but from the viewpoint of industrial production, the long-term reaction consumes a large amount of energy. ^ It is not preferable. The preferred range is 48 hours, preferably 3 to 3 minutes, and 4 to 24 hours. After the reaction is completed, the excess hydrogen peroxide is quenched. The quenching treatment preferably uses a basic compound. It is also preferred to use a reducing agent and a basic compound in combination. A preferred method of treatment is as follows: After the pH is neutralized to 6 to 1 Torr by using a basic compound, the residual hydrogen peroxide is quenched with a reducing agent. When the pH is less than 6, the heat generated when the excess hydrogen peroxide is reduced is large, and there is a possibility that a decomposition product is generated. Examples of the reducing agent include sodium sulfite, sodium thiosulfate, hydrazine, oxalic acid, vitamin C, and the like. Reducing agent usage, relative The excess part of the peroxidation 15 201120084 ίο nitrogen molar number 'usually 0. 01~20 times Moule, more preferably 〇〇 5 Mo, more preferably 1 〇 5~3 times Mo. 30 重It is preferably added as an aqueous solution at a concentration of % by weight. Examples of the basic compound include sodium hydroxide, potassium hydroxide, metal hydroxide, sodium carbonate, potassium carbonate, and the like. Phosphate such as sodium hydrogen phosphate, ion exchange resin in L-specific solids. ^ Its use, if it is in water or organic solvent (for example: 曱, dimethyl W = aromatic hydrocarbon compound 'methyl isobutyl ketone , mercaptoethyl net, etc.: such as pentane, gamma, octyl, and other solvents, such as alcohols such as methanol, ethanol, and isopropanol, etc., the amount of use is relative to the excess portion of peroxidation. : Moir number, usually 0.01~20 times Mo's better 〇〇5~1〇 times machine I,, enter! ^佳为(四)5~3倍莫耳^etc can be used as water or above The addition of the agent solution can also be carried out by using a monomer. When using a solid solution insoluble in water or an organic solvent, For the amount of hydrogen peroxide remaining in the system, (4) the amount by weight of the leaves is 1 to 1 times, more preferably 10 to· times, and even more preferably 1 to 1.00 times. In the case of solid solution in water or organic solvent, it can also be treated after separation of the aqueous layer and the organic layer described below. μ = organic layer and water after quenching of hydrogen peroxide (or before quenching) : not: separation or when the organic solvent is not used, the above organic solvent is added to carry out the extraction operation. The extraction of the reaction product is carried out from the aqueous layer. The organic solvent used at this time is compared with the raw material olefin compound by weight ratio 〇 .5~1〇16 201120084 times 'preferably 0.5 to 5 times. The organic layer separated after several times of the above operation is repeated as needed, and washed with water if necessary. The known organic layer is made by ion exchange resin or metal oxide (especially tannin, alumina, etc.), activated carbon (in particular, chemically activated carbon (Chmical reaCtlvation active carb〇n)), composite ^ is a salt (particularly an alkaline composite metal salt), clay minerals (especially for the layer: clay minerals such as stone) to remove impurities, and then washed with water, after the distillation to remove the solvent to obtain the target ring Oxygen compound. ~ Depending on the situation, it can be further purified by the technique of p s column chromatography or distillation. The epoxy oxime & resin obtained in the above manner is a compound having the following formula and mixed with a compound of various structures represented by the formula: U)

(wherein a plurality of, or a carbon number of 1 to 烷基 alkyl groups) independently represent a hydrogen atom, 17 201120084

(wherein, the combination of A to D may be any combination). The curable resin composition of the present invention can be used alone or in combination with other epoxy resins. When used in combination, the ratio of the epoxy resin to the total epoxy resin is preferably 5% or more, more preferably 40% by weight or more. Among them, in the case where the epoxy resin of the present invention is used as a modifier of a curable resin composition, it is! Add a ratio of ~30% by weight. The other epoxy resin which can be used for the curable resin composition tf? of the present invention is exemplified by a novolac type epoxy resin, a bisphenol A type epoxy resin, a biphenyl type epoxy resin, and a triphenyldecane type ring. Oxygen resin, phenol aralkyl type epoxy resin, and the like. Specific examples thereof include bisphenol A, bisphenol S, thiophenol, bisphenol, stilbene, 4,4, monophenol, 2,2'-diphenol, 3,3,5,5. , a tetradecyl group ~~[1,1,biphenyl]-4,4,monodiol, hydroquinone, resorcinol, naphthalenediol, tris(4-hydroxyphenyl)decane 1,1,2,2-tetra(4-hydroxyphenyl)ethane, phenols (phenol's alkyl substituted phenol, naphthol, alkyl group 18 201120084 generation 4 years old, two _ loans For the base group, the acid is based on the base /;: via the base, etc.) with formic acid, B road, stupid road, T test, o-hydroxybenzaldehyde, + acetamidine, dicyclopentane m4, 4, - double (gas vm O-based benzoquinone-bis(methoxy A..." bis (gas P-based)-1, bisbiphenyl, - bis (methoxymethacene, biphenyl, M-bis (gas methyl) stupid, Μ A" Double: the second type of polycondensate, these modified substances, _ 氧 oxygen tree ^ ^ raw glycidol (four), alicyclic diglycidyl amine epoxy resin, glycidol coffee resin ^ Oxygen resin (in the structure of chain, ring, ladder, or the like, at least the structure of the oxygen-producing structure Solid or liquid epoxy resin such as water glyceryl and/or epoxy resin, but especially for the use of the curable resin composition of the present invention for optical purposes: preferably in the form of an alicyclic mixture Epoxy resin and doubling (tetra) oxygen crater structure: milk resin. Especially in the case of alicyclic epoxy resin, it is preferable to 'in the bone ' ', the compound with % oxime structure is especially good An epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure. The epoxy resin is exemplified by a compound oxidation which can be produced by the following method, etc. cyclohexenecarboxylic acid and Esterification of alcohols or esterification of cyclohexene sterols with carboxylic acids (5) ―yd % ρ 24〇9 ◦ 980), Tetrahedr〇n as described in ρ. 4475 ο·), etc. Or the cyclohexene reaction of the cyclohexene road (Tishchenk. reacti〇n) (曰本特开 2003 - 170059 f tiger bulletin, Japanese special (5) 2〇〇4_ 262871 citizens, etc.), and then cyclohexene carboxylate The transesterification reaction of an acid ester (method described in JP-A-2006-052187, etc.). 19 201120084 As the alcohol _, # Α θi, it can be mentioned that the compound of ethylene glycol: propylene 'diyl group is not particularly limited ... butylene glycol, ... glutarylene: propylene propylene. One: diol, 2〆-diethylpentanediol, 2_ethyl-~%-hexan, A-alcohol, di-s-butyl-1,3-propanediol, neodecyl alcohol曱二曱醇,降,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Kedi, 2, triols such as ketones, ketones, ketones, alcohols, pentaerythritols, hexamethylene methacrylates, etc. ^ ^ ιε Illustrative: oxalic acid, maleic acid, anti-butene-Xiyiwen, phthalic acid, isophthalic acid, adipic acid 1 hexanedicarboxylic acid, etc., but is not limited thereto. Other examples of the compound having a ring-ring-fired structure in the lunar frame include an acetal compound obtained by reacting a cyclohexene with a acetal. The reaction method can be produced by applying a usual acetalization reaction. For example, it is disclosed that: 庠 庠 哲 哲 amp 愿 质 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用Method (U.S. Patent No. 2945008); a method of performing a reaction while slowly adding an aldehyde after dissolving a polyhydric alcohol in a concentrated solution of hydrochloric acid, f 特 特 48 48 48 48-96590); Method (U.S. Patent No. 3,092, 640); a method of using an organic solvent in a reaction medium (Equ. (U.S. Patent No. 7-215979); a method using a solid acid catalyst (Japanese yy moto open 2 〇 〇7_23〇992 Bulletin), etc. In terms of structural stability, 舾杜达 is preferably a cyclic acetal structure. Specific examples of such epoxy resins are available. J Γ List: ERL-4221 , UVR~ 6105, ERL-4299 (both are σ 々 々 同 0 名 '' by Dow Chemical (D〇w

Chemical), CELLOXide β2〇2ΐΡ, EPOLEAD GT401, 20 201120084 ΕΗΡΕ 3150.EHPE 3150CE (i^^〇^, industrial manufacturing) and dicyclopentadienyl epoxide = 丨 丨 chemistry (Reference: General The epoxy resin basic article Ιρ76=^ is limited to these, and may be used alone or in combination with two or more kinds of oxygen resins, preferably in a proportion of 6% by weight or less, particularly preferably: :/ If it exceeds 6. wt%, it will be used in combination with the situation. Volatilization #bad", oxygen-based epoxy resin (in chain, ring, ladder, or "mixture structure of temple to mx" The solid or liquid liquid such as the water structure of the structure and/or the epoxy resin of the epoxy ring structure is preferably used in the range which does not affect the gas resistance of the corrosion resistance. (4) In the case of the oxygen-cutting epoxy resin, the proportion of the total epoxy resin is preferably 7% by weight or less, and particularly preferably the weight is less than or equal to or less than %. If a large amount of the sesquifer-oxygenated epoxy resin is used in combination, The gas resistance is lowered. The curable resin composition of the present invention contains the above epoxy resin. Reactive hardener and/or hardening accelerator. Hereinafter, the curing agent which can be used in the present invention will be described. Examples of the curing agent include an amine compound, an acid anhydride compound, a guanamine compound, and a phenol compound. A carboxylic acid-based compound, etc. Specific examples of the hardener which can be used include diaminodiphenyl decane, diethylene ethylamine, tri-ethyltetramine, diaminodiphenyl sulfone, and the like. a nitrogen-containing compound (amine, guanamine compound) such as a sulfonamide diamine, a cyanodiamine, a polyamine resin synthesized from a dimer of linolenic acid and ethylenediamine; 21 201120084 trimellitic anhydride, pyromellitic dianhydride, maleic anhydride 'tetrahydrophthalic anhydride, decyl tetrahydrophthalic anhydride, methyl anhydride, ceric anhydride, hexahydrogen O-phthalic anhydride, mercapto hexahydrophthalic anhydride, butyl phthalic anhydride, bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, fluorenylbicyclo[2,2,1 ]Geng Shao - 2,3 - dicarboxylic anhydride, cyclohexan ~ ι, 2,4 - tricarboxylic acid _ 1 2 - anhydride and other anhydride; by various alcohols, hydrazine A carboxylic acid resin obtained by an addition reaction of an alcohol (carbin〇i) modified polyfluorene oxide with the above acid anhydride; bisphenol A, double age F, bisphenol S'diphenol, stilbene, 4, 4, _ Biphenol, 2,2,-biphenol, 3,3,,5,5,-tetramethyl-[1,1'-biphenyl]-4,4,monodiol, hydroquinone Diphenol, naphthalenediol, tris-(4-hydroxyphenyl)decane, anthracene, 12,2-tetrakis(4-hydroxyphenyl)ethane, phenols (phenols, alkyl-substituted phenols, naphthols) , alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with formaldehyde, acetaldehyde, benzofural 'p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone , dicyclopentadiene, furfural, 4,4,-bis(gas methyl)_丨,丨,-biphenyl, 4,4-bis(decyloxymethyl)-1,1'- a polycondensate of 1,4,-bis(gas methyl) stupid, 1,4 bis(decyloxyindenyl)benzene, and the like, and a modified substance such as tetrabromophenol A and the like Polyphenols such as condensates with phenols; compounds such as imidazole, boron trifluoride-amine complex, and hydrazine derivatives, but are not limited Such. The materials may be used singly or in combination of two or more. In the present invention, it is particularly preferred to use a compound having the acid liver structure represented by the above-mentioned sour liver and/or a compound having a carboxylic acid structure represented by the above carboxylic acid resin as a curing agent. A compound having an acid needle structure, particularly preferably: methyltetrahydrophthalic anhydride, methylic acid anhydride, ceric anhydride, hexahydrophthalic anhydride, hydrazine 22 201120084 hexahydro phthalate Butane tetraphthalic anhydride, bicyclo[2Ί]heptane-2,3-diphthalic anhydride, indenylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, cyclohexane-1,2 , 4 - tridecanoic acid - 1, 2-anhydride and the like. Among them, 'espeth is hexahydrophthalic anhydride, mercaptohexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid _ 1,2- anhydride represented by the following formula (2) :

〇 (2) (wherein R3 represents a hydrogen atom, a thiol group or a carboxyl group). a compound having a carboxylic acid structure (hereinafter referred to as a polycarboxylic acid), particularly preferably a 2~ minute B-based carboxylic acid, more preferably an addition reaction of a 2~4 functional polyol with an acid anhydride And the polycarboxylic acid obtained. The polyol having 2 to 4 g of the energy group is not particularly limited as long as it is an alcoholic hydroxyl group. Examples thereof include ethylene glycol, propylene glycol, hydrazine, and 3-propanediol: polybutylene glycol and M-butanediol. , hydrazine, 5-pentanediol, 1,6-hexanediol, guangjiyuan dimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butylene, etc. Alcohol, dicyclopentadialdehyde dimethanol diethanol, glycerol, :r silk® ψ « — # f ethane, trimethylolpropane, trimethylolbutane, 2-hydroxyl _ 14 ^ Alcohol, _ ", - butanediol and other triols, tetraols such as pentaerythritol-to-dimethylpropane. Alcohol, neopentyl glycol, norbornenediol, propanol/alcohol are cycloheximide dimethanol, 2,4-diethylpentyl 2- 2 -butyl-anthracene, 3 ^ methanol, etc. Cyclic aliphatic alcohol dicyclopentadiene 23 201120084 /, is an acid anhydride for the production of poly(tetra), preferably methyl tetrahydro ortho-acid anhydride, ceric acid anhydride, hexahydro phthalic anhydride Phthaphthalic anhydride, butane tetracarboxylic anhydride, bicyclo [Hi] heptane-dicarboxylic acid needle, methyl bicycloheptane - 2,3-dicarboxylic acid needle, hexane- 1,2,4-tricarboxylic acid _ Hey, 〗 - Anhydride, etc. The conditions of the addition reaction are not specifically specified. The specific reaction strip is such that the acid needle and the polyol are reacted at a temperature of from 1.5 to 15 ° C under the conditions of no catalyst or solvent, and the reaction is directly after the reaction. The method of taking out. However, ^ is not limited to the reaction conditions.疋' compound: obtained by the above method _, particularly preferably represented by the following formula (3)

(wherein, a plurality of R3 independently represent a hydrogen atom, a methyl group or a thiol 'P represents a chain or cyclic aliphatic group derived from a polyhydric alcohol having 2 to 20 carbon atoms). The acid anhydride of the above formula (7) and the y acid component of the above formula (3) may be used singly or two or more kinds thereof may be used. Preferably, one or more compounds of the formula (2) are used in combination with the compound of the formula (3). More than one species. In the case of use in combination, the use ratio is preferably in the following range. W2/(W2 + W3)=0.30 〜0.95 24 201120084 (There is a blending weight of the compound of the formula (2), which indicates the blended parts by weight of the compound of the formula (3)) W2/(W2 The range of + W3) is more preferably 〇4〇~〇%, and further preferably (10)~(4), especially better as G.6~G.85. When it exceeds Q 95, the tendency of the volatile component to increase becomes strong, and if it is less than 0.30, the viscosity becomes high and the operation becomes difficult. In the curable resin composition of the present invention, the curing agent is used in an amount of 1 equivalent to the epoxy group of the epoxy resin, preferably 5 to 15 equivalents. More preferably, it is 0.7 to 1.2 equivalents, and particularly preferably 〇8 to M equivalent. With respect to the epoxy group i equivalent, when the amount of the hardener used is less than 5 equivalents, or when i5 is exceeded, the case where S is incomplete, the hardening is incomplete and good hardening properties are not obtained. In the curable resin composition of the present invention, a curing accelerator (curing catalyst) may be used in combination with the curing agent, or a curing accelerator may be used alone without using a curing agent. Specific examples of the hardening accelerator which can be used include 2-nonyl imidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 2-phenyl-tetradecyl group. Imidazole, 1-benzyl-2-phenylene. Sodium, 1-benzyl-2-mercaptoimidazole, 1-cyanoethyl-2-methylimidazole, cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl Sodium saliva, 2,4 -amino- 6 (2'-indolyl (1')) ethyl-all three wells, 2,4-diamino- 6 (2'-undecylimidazole Ethyl-all three wells, 2,4-diamine- 6 (2'-ethyl-1,4-mercaptoimidazole (1,)) ethyl--three wells, 2,4-diamine- 6 ( 2'-nonyl imidazole (1,)) ethyl one uniform three wells - iso-cyanuric acid adduct, 2-mercaptoimidazole isocyanuric acid 2: 3 adduct, 25 201120084 2 - stupid Imidazolyl isocyanurate adduct, 2-phenyl-1,3-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxyindole-5-nonylimidazole, 1-cyanoethyl one Various imidazoles such as 2-phenyl-; 3,5-dicyanoethoxymethylimidazole, and the imidazoles and phthalic acid, meta-dicarboxylic acid, terephthalic acid, and benzoic acid a salt of a polycarboxylic acid such as pyromellitic acid, naphthalene dicarboxylic acid, maleic acid or oxalic acid, or a guanamine such as dicyanodiamine. a salt of diaza, 8-dioxabicyclo(5.4.0) undecene-7, and salts of such tetrasuccinates, phenol novolacs, and the like, and the above polycarboxylic acids or a salt of a phosphinic acid, an ammonium salt such as tetrabutylammonium bromide, cetyltrimethylphosphonium bromide, dioctylmethylammonium bromide or cetyltrimethylammonium hydroxide, or a phenylphosphine a phosphine or a scaly compound such as bis(indolyl)phosphine, tetraphenylphosphonium bromide, tetraphenylboronic acid tetraphenyl scale, or a phenol such as 2,4,6-triaminononylphenol, amine plus a compound such as a metal compound such as tin octylate or the like, and a microcapsule-type hardening accelerator for forming the curing accelerator into microcapsules. In the present invention, it is preferred to contain a zinc salt and/or a zinc complex. The salt and/or the complex compound function as a hardening accelerator for an epoxy resin and a hardener in the present invention. The salt and/or zinc complex is a salt and/or a mixture of zinc ions as a central element. The article 'preferably contains at least one of a carboxylic acid, a phosphate, and a phosphoric acid selected from the group consisting of a comparative ion and/or an alkyl group having a carbon number of 1 to 30 as a ligand. In the present invention, zinc carboxylate or zinc phosphate is preferred. The alkyl group may, for example, be methyl, isopropyl, butyl, 2-ethylhexyl, octyl-isodecyl or isostearyl. The carboxylic acid body of the present invention is preferably a carboxylic acid body having a chain branch structure of 26 201120084, or an alkyl group having a functional group such as an olefin, more preferably 3~ A carbon number of 3 。, particularly preferably a carbon number of 5 to 20. This is preferably equivalent to a case where the carbon number is too large (the carbon number is 30 or more) or has no structure such as a branched structure or a functional group. The compatibility with the resin is inferior, and therefore it is not preferable. Specific examples thereof include zinc 2-ethylhexanoate, zinc isostearate, and zinc 10-carbenoate. Particularly preferred in the present invention is a acid, preferably a salt of acid or citric acid (single base ester, dialkyl ester, trialkyl ester, or a mixture thereof) / or zinc complex, may also contain a plurality of phosphate bodies. Specifically, among the phosphates contained, the molar ratio of the monoalkyl ester, the dialkyl ester, and the trialkyl ester is replaced by the purity of gas chromatography, wherein three In the stage of performing the tridecyl decylation treatment, the amount of the monoalkyl ester body is preferably 50% by area or more. The zinc salt and/or zinc complex of zinc phosphate described above is obtained, for example, by reacting a phosphate with, for example, zinc carbonate, zinc hydroxide or the like to obtain a zinc salt and/or a zinc complex used in the present invention (patent Document: EP 699708). In the case of the zinc salt and/or the zinc complex of the above phosphate, the ratio of the phosphorus atom to the zinc atom (P/Zn) is preferably from 12 to 2 3, more preferably 13"2". ^佳为"~... That is, in the form of Yu Jia, it is preferred that the phosphate (or phosphoric acid derived from phosphate) is less than 2 moles, and the simple ion structure is relative to the deviation of 1 mole. Rather, it has a structure in which several molecules are linked by ionic bonds (or 2). The above-mentioned zinc salt and/or zinc complex compound is also obtained, for example, by the method described in Japanese Patent No. 51495. 27 201120084 The above compounds, commercially available m acid words can be cited: zn-la —

St 602, Zn- St NZ, ZS-3' Zs A ZS-6, zs-8, zs-8, zs-7, ZS-l〇, ZS-5, zs-14 (made by Nitto Kasei Industrial Co., Ltd.), 4 (Manufactured by Klng), _ Q_pe Zn, 12% 〇ct〇pe ~, 8% 0ctope Zn (manufactured by H〇pe Pharmaceuticals); phosphoric acid vinegar and/or dish acid, which can be cited as: LBT-2000B (Manufactured by SC Organic Chemicals) , _92 〇 6 (five) called Industry manufacturing). Which one of these hardening accelerators is used is appropriately selected depending on the properties required for the transparent resin composition obtained by, for example, the transparency 'hardening rate and the working condition (four). The hardening accelerator is usually used in an amount of from 0.001 to 15 parts by weight, more preferably from 1 to 5 parts by weight, even more preferably from 1 to 3 parts by weight, based on 1 part by weight of the epoxy resin. In the present reaction, the curing may be carried out under the conditions of no catalyst, but it is preferable to add a catalyst from the viewpoint of preventing coloration upon hardening. Particularly, from the viewpoint of preventing coloration and improving corrosion-resistant gas characteristics, it is preferred to use a zinc salt and/or a zinc complex. In the curable resin composition of the present invention, an inhibitory compound may be contained as a flame retardancy imparting component. The phosphorus-containing compound may be of a reactive type or an additive type. Specific examples of the phosphorus-containing compound include trimethyl ester, triethyl phosphate, triamyl phosphate, trixylenyl phosphate, toluene diphenyl ester, and acid. Ere sy 1-2,6-dixy lenyl phosphate, 1,3 -phenylene bis(di(biphenyl)phosphate), 1,4 a phenyl bis(di(xylylene) phosphate), 4,4'-biphenyl (dixylenyl phosphate) (4,4'-biphenyl (dixylenyl phosphate) and other phosphates; 9, 10 —Dihydro-9-oxa-10-phosphine-128 2011 20114 4 10 Oxide (9,1〇-dihydro-9-〇xa-l〇_ph〇spha

Phenanthrene-1〇_oxide), 1〇(2,5-dihydroxyphenyl)_i〇h-9-oxa-1-phosphonium- 1〇-phosphine and other phosphanes; a phosphorus-containing epoxy compound, red phosphorus or the like obtained by reacting an oxygen resin with active hydrogen of the above phosphine; preferably a phosphate ester, a phosphine or a phosphorus-containing epoxy compound, particularly preferably a 1,3-phenylene double (bis(diphenylene) phosphate), hydrazine, 4-phenylphenyl bis(di(diphenylene) phosphate), 4,4·-biphenyl (bis(xylene) phosphate) or phosphorus-containing epoxy Compound. The content of the phosphorus-containing compound is preferably a phosphorus-containing compound/epoxy resin ~ 〇.6 (weight ratio). When it is less than ι·ι, the flame retardancy is insufficient; if it exceeds 〇 6 ′, it has an adverse effect on the hygroscopicity and conductive properties of the cured product. Further, in the curable resin composition of the present invention, a binder resin may be blended as needed. Examples of the binder resin include a butyraldehyde resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, an NBR-phenol resin, an epoxy-NBR resin, a polyamide resin, and a polyimine. The resin is a polyoxyphthalic resin or the like, but is not limited thereto. The blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually used in an amount of 5 to 5 parts by weight, preferably 〇〇, per 100 parts by weight of the resin component. 5 to 20 parts by weight. In the curable resin composition of the present invention, an inorganic filler may be added as needed. Examples of the inorganic filler include crystal oxidizing, sulphur dioxide, alumina, bismuth, calcium silicate, calcium carbonate, strontium carbide, tantalum nitride, boron nitride, cerium oxide, forsterite. A powder such as talc, spinel, titanium dioxide or talc, or particles obtained by spheroidizing the particles, etc., but is not limited thereto. These filler materials may be used singly or in the form of 2 29 201120084 = top: the contents of the inorganic fillers are used in the curable di-halide of the present invention. ~95% by weight. Further, in the curable resin composition of the present invention, π $ i ^ ^ is added with an oxalate coupling agent, stearic acid, palmitic acid, zinc stearate, stearin &# 驮 calcium 4 release agent Various pigments such as pigments, and various thermosetting trees. / /: The curing resin composition of this month is used for optical materials, especially (4) of the photo-semiconductor (4) agent, by using the inorganic filler material used in the above-mentioned inorganic filler material to have a nanometer-level filling material. It does not inhibit the mechanical strength of the top 4 and the like. From the viewpoint of transparency, the standard for the nano-level is preferably a filler having an average particle diameter of 500 nm or less; and Doujia is a filler having an average particle diameter of 200 nm or less. When the curable resin composition of the present invention is used for an optical material, particularly a calendered semiconductor encapsulant, a phosphor may be added as needed. The phosphor is, for example, a person who absorbs a portion of the blue light emitted from the blue LED element and emits wavelength-converted yellow light to thereby form white light. The phosphor is preliminarily dispersed in the curable resin composition, and the photo-semiconductor is sealed. The phosphor is not particularly limited, and a phosphor of the above-mentioned type can be used. For example, a rare earth element acid salt, a thiogallate, or a protoporate can be exemplified. More specifically, a phosphor such as a YAG phosphor ' TAG phosphor, a protonate phosphor, a thiogallate, or a sulfide phosphor can be exemplified, and YAl〇3 : Ce is exemplified. γ3Α15012 : ce, γ4Α12〇9 : Ce, Y202S : Eu, Sr5(P04)3Cl : Eu, (Si"Eu)〇-Al2〇3, and the like. The particle diameter of the phosphor is a particle diameter well known in the art, and the average particle diameter is preferably from 1 to 25 Å to the claw, particularly preferably from 2 to 30, 2011, 2008, and 50. In the case of using such a phosphor, the amount thereof is preferably 8 parts by weight, more preferably Η, based on the weight of the resin component (10). Parts by weight. The hardening of the present invention is used for the use of optical materials, especially in the case of optical semiconductor encapsulants, for the purpose of preventing the hardening of various phosphors. When it settles, it is possible to add a shake denature imparting agent represented by a white oxide powder (also referred to as eight (10) or A (10) 〇!). Examples of the above-mentioned dioxygen fine powder include A(10)chuan 50, Aerosil 90, Aer〇sU 13〇, Α_διΐ 2〇〇, 八(10)州300^ Aerosil 380 ^ AerosU 0X50 . Aerosil TT600 > Aerosi, R972, Aerosil R974 , Aerosil R2〇2, Α_π R8i2, 丨 s s, Aerosll R805, RY2 〇〇, RX2 〇〇 (曰本—Manufactured by the company). The use of the curable resin M of the present invention for optical materials, in particular

In the case of a photo-semiconductor sealant, in order to prevent coloring, it may contain a female compound which is a stable compound of I or a phosphorus-based compound and a phenolic compound which are antioxidant materials. The above amine compound may, for example, be 1,2,3,4-butanetetradecanoic acid tetraruthenium, 2,2,6,6-pentamethyl-4. bottom.定)), 1, 2, 3, 4 - butyl tetracarboxylic acid tetra (2, 2, 6, 6 - tetramethyl - 4 ~ ° Chen mouth base) S, 1, 2, 3, 4 - D Alkanoic acid and 1,2,2,6,6-pentamethyl-4"-decyl alcohol and 39-bis(2-hydroxy-indolylethyl)-2'4'8,1〇~ Mixed esterified product of tetraoxaspiro[5 5]undecane; bis(2,2,6,6'tetramethyl-4-.sub.2) azelaic acid citrate, carbonated double (1- Tetra- 6-oxy-2,2,6,6-tetramethyl(tetra)-4-yl)acetate, methyl acrylate 2,2,66_tetramethyl. u 'T-based piperidyl ester, Sebacic acid bis(2,2,6,6 31 201120084-tetramethyl-4-piperidyl) g, azelaic acid bis(mGj-pentamethyl-4piperidinyl) ester, 4-benzene Methoxyoxy-2,2,6,6-tetramethylpiperidine, work-[2-[3—(3,5-a mono-t-butyl-4-phenyl-phenyl)propenyloxy] Ethyl]—4 — [3 —(3,5—di-tert-butyl-4-hydroxyphenyl)propenyloxy]-2,2,6,6-tetramethylpiperidine, methacrylic acid ι,2,2,6,6-penta-yl- 4-a. Base vinegar, {[3,5-bis(ι,ι-dimethylethyl)-4-pyridylphenyl]methyl} Butylmalonic acid bis(1,2,2,6,6-pentamethyl- 4-strand), the purpose of bismuth, bismuth (2,2,6,6-tetradecyl-l-(辛 氧基 oxy) 一 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 One (4,6-bis(butyl-(N-fluorenyl-2,2,6,6-tetradecylpiperidine-4-yl)amino)-three wells 2-base)-4,7 - diazepine - 1,10 - diamine, dibutylamine ~ 1,3,5 - three wells - N, N, one pair (2,2,6,6-tetramethyl- 4-piperidyl a polycondensate of ι,6-hexanediamine and N-(2,2,6,6-tetradecyl-4-piperidinyl)butylamine, poly{[6—(1,1,3,3— Tetramethylbutyl)amino-1,3,5 - three wells - 2,4-diyl][(2,2,6,6-tetradecyl-4-piperidyl)imine] Methylene [(2,2,6,6-tetramethyl-4-cyclopiperidyl)imido]]' didecyl succinate and 4-hydroxy-2,2,6,6_tetra Base-1 - piperidine ethanol polymer '2,2,4,4-tetramethyl- 2 〇-(calling a lauryloxy)ethyl-7-oxa-3,20-two Aza-bispiro[5丄11_2]diazine--burning a 21-ketone,/5-alanine, ν-(2,2,6,6-tetradecyl- 4-0 base)12 Hyun • Base Although/14-burning vinegar, Ν-acetamido- 3--di-burning one-one one (2,2,6,6-tetradecyl-4--sigma-based base) 2,5-dione, 2,2,4,4 _tetradecyl~7-oxa-3,20-diazabispiro[5,1,11,2]octadecane- 21-one , 2,2,4,4-tetramethyl-21-oxa 32 201120084- 3,20-diazabicyclo-[",丨丨"-tetradecane-(10)-dodecyl propionate /Tetradecyl ester, malonic acid, [(4-methoxyphenyl)-fluorenylene]-bis(1,2,2,6,6-pentamethyl-4piperidinyl) vinegar , 2,2,6,ό_tetramethyl-4_piperidinol, higher fatty acid vinegar, phthalicinamine, N,N,-bis(2,2,6,6-tetramethyl-4_ A pipecyanyl compound such as piperidinyl) is a bismuthone compound such as octaphenylfluorene, 2-(2H-benzotriazol-2-yl)-4-yl (Ul 3 3_tetramethylbutyl)phenol, 2- (2-hydroxy-5-methylphenyl)benzotriazole, 2 [2 hydroxy-3-(3,4,5,6-tetrahydroortylene) A (PEI) - Yue-yl) -5 - Yue phenyl] benzotriazole, a 2 (3-tert-butyl _2 - $ hydroxy-methyl substantially yl) -5 - chaos present Bian III. Sit, 2-(2 - via base 3, 5 - 2nd second pentyl base) benzotriazine, 3-(3 - (2H - benzotrisin-2-yl)-5 - third The reaction product of butyl 4-hydroxyphenyl) propionate and polyethylene glycol, 2-(2Η-benzotriazol-2-yl)-6--}dialkyl- 4__methylbenzene Benzene and other benzotriazole-based compounds '2,4-di-tert-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, etc., 2 - (4,6-diphenyl- 1,3,5-three wells-one-one base) _5-[(hexyl)oxy]phenol and the like are three well compounds, and particularly preferred are hindered amine compounds. As the amine compound of the above light-stable material, a commercially available product as shown below can be used. The commercially available amine-based compound is not particularly limited, and examples thereof include TINUVIN 765, TINUVIN 770DF, TINUVIN 144, TINUVIN 123, TINUVIN 622LD, TINUVIN 152, CHIMASSORB 944, Adeca manufactured by Ciba Specialty Chemicals. LA-52, LA-57, LA-62, LA-63P, LA-77Y, 33 201120084 LA-81, LA-82, LA-87, etc. are manufactured. The phosphorus-based compound is not particularly limited, and examples thereof include ruthenium 3 -tris(2-methyl-tetra-di(tridecyl)phosphite-5-t-butylphenyl) butadiene. Distearyl pentaerythritol di arsenic acid vinegar, bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis(2,6 di-t-butyl n-methylphenyl)pentaerythritol Diammonium citrate, phenyl bis(10)a quaternary tetraol diphosphite, - earned p 1 ^ one cyclohexyl quinone quinone di bis phosphite tributite tris(diphenylphenyl) vinegar, sub Tris(di-isopropylphenyl)S phosphate, tris(di-n-butylphenyl)tetraphosphate, tris(2,4-di-t-butylphenyl)phosphoric acid, triphosphoric acid 2 6_二—第=乐一乙基基) S, sub-acid three (2,6-a second butylphenyl) vinegar, 2,2, monomethylene double (4,6 - two a tributylphenyl)(2,4~di-t-butylphenyl)phosphite sorbate, 2,2,-indenylene group (4,6-di-tert-butylphenyl) 2 —T-butyl-methylphenyl% t-shirt, 2,2,... bis(4-methyl-6_t-butylphenyl) (2 — 4-methyl-based linoleic acid vinegar, 2,2--ethylene bis(4 曱^6 second butyl phenyl) (2-t-butyl-4~~methylphenyl)phosphorous acid Ester, tetrakis (2,4__-indole-butanol, try,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, -biphenylenephosphoni te), tetrakis(2,4~two-t-butyl butyl) - 4,3,_stranded phenyldiphosphinic acid enriched ester S-ester four (2,4 four (2,6 four (2,6 four (2,6 two one third butyl styl) one 3,3, one extended biphenyl diphosphinic acid di-tert-butylphenyl) - 4,4' one extended biphenyl Phosphonic acid--t-butylphenyl)- 4,3'-extended biphenyldiphosphinic acid di-t-butylphenyl)-3,3,-extended biphenyldiphosphinic acid 34 201120084 Ester, bis(2,41-2 dibutylphenyl)-4-phenyl-phenylphosphinate, bis(2,4-di-t-butylphenyl)-3-phenyl —Phenylphosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphinate, bis(2,6-di-t-butylphenyl) —4 benzene Benzyl phenylphosphinate, bis(2,6-di-dibutyl butylphenyl)_3-phenylphenylphosphonate, tetrakis(2,4-di-t-butyl- 5 -nonylphenyl)- 4,4,1-biphenyldiphosphinic acid vinegar, dibutyl succinic acid, sodium sulphate, sulphuric acid, sulphuric acid, vinegar, filling The acid is ridiculously vinegar, the acid is filled with triethylene g, the acid is diphenyl benzene, the diphenyl monoorth xenyl phosphate, the tributoxyethyl phosphate, the phosphoric acid Dibutyl ester, dioctyl phthalate, diisopropyl phosphate, and the like. Commercially available products can also be used as the phosphorus compound. The commercially available phosphorus-based compound is not particularly limited, and examples thereof include Adekastab PEP-4C manufactured by Adeca, Adekastab PEP-8, Adekastab PEP-24G, and

Adekastab PEP- 36 ^ Adekastab HP- l〇 > Adekastab 2112^

Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500 ^ Adekastab C ^ Adekastab 135A ^ Adekastab 3010 ^ Adekastab TPP. The phenol compound is not particularly limited, and examples thereof include 2,6-di-t-butyl-4-methylphenol and 3~(3,5-di-t-butyl-4-hydroxyphenyl). N-octadecyl propionate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 2,4-di-t-butyl- 6-nonylphenol, 1,6-hexanediol-bis-[3-indene, 5-di-tert-butyl-4-hydroxyphenyl)propionate], three (3,5-di- Tributyl-4-hydroxy 3 201120084 base) an isocyanuric acid vinegar, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxyl Benzyl) stupid, pentaerythritol-four [3 - (3,5-di-di-tert-butyl-4-hydroxyphenyl)propionate]', 3,9-double one {2—[3—(3— Tributyl- 4-hydroxy-5-methylphenyl)-propanyloxy]-^-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]Eleven Alkane, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 2,2, _butylene bis (4,6-two Third butyl phenol), 4, 4 , -butylidene bis(3_ fluorenyl-6-tert-butyl phenol), 2,2, monomethylene bis(4_fluorenyl-6-tert-butylphenol), 2,2' a Methyl bis(4-ethyl-6-t-butylphenol), 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylindenyl) 4 曱Acrylic acid from the purpose ' 2 — [1 — (2 — via a 3,5-di-second-pentylphenyl)ethyl]- 4,6-di-tridecylphenyl acrylate , 4,V-thio bis(3-indenyl-6-t-butyl phenol), 4,4·-butylidene bis(3-indenyl-6-tert-butylphenol), 2 - Tributyl-4-methyl primary, 2,4-12-t-butylbenzene, 2,4-di-di-p-butyl benzene i, 4,4'-thiobis(3-methyl a 6-tert-butylphenol), 4,4'-butylene bis(3-methyl-6-t-butylphenol), bis[3,3-bis(4'-hydroxy-3-- Tributylphenyl)-butyric acid]-glycol ester, 2,4 1-2 tert-butyl benzene, 2,4-di- 3 decyl benzene, 2-[1 (2) Base one 3,5 - two one third pentyl stupid Ethyl]-4,6-di-p-third amyl phenyl acrylate vinegar, bis[3,3-bis(4,1-hydroxy-3,-tributylphenyl)-butyric acid]- Glycol esters and the like. Commercially available products can also be used as the phenolic compound. The commercially available phenolic compound is not particularly limited, and for example, it can be exemplified by Ciba Specialty Chemicals Co., Ltd. 36 201120084 IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114, IRGANOX 1098, IRGANOX 1520L, Adekastab AO by Adeca — 20, Adekastab AO — 30, Adekastab AO— 40 ' Adekastab AO — 50 ' Adekastab AO — 60, Adekastab AO — 70, Adekastab AO — 80, Adekastab AO 90, Adekastab AO — 3 30. Sumilizer GA — 80, Sumilizer MDP — S, Sumilizer BBM — S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, etc. manufactured by Sumitomo Chemical Industries. In addition to this, a commercially available additive may be used as the anti-coloring agent for the resin. For example, TINUVIN 328, TINUVIN 234, TINUVIN 326, TINUVIN 120, TINUVIN 477'TINUVIN 479' CHIMASSORB 2020 FDL'CHIMASSORB 119FL manufactured by Ciba Specialty Chemicals Co., Ltd., and the like can be cited. It is preferable to contain at least one of the above-mentioned compound, the amine compound, and the conjugate compound, and the amount thereof is not particularly limited, and is in the range of 0.005 to 5.0% by weight based on the curable resin composition. The curable resin composition of the present invention is obtained by uniformly mixing the components. The curable resin composition of the present invention can be easily made into a cured product by the same method as previously known. For example, a method of using an epoxy resin, at least one selected from the group consisting of a curing agent and a curing accelerator, a lining compound, a binder resin, an inorganic filler, and a blending agent, if necessary, using an extruder or a kneader, A roll mill, a planetary mixer, or the like is sufficiently mixed until uniformity is obtained to obtain a curable resin composition, and when the hard resin composition is liquid, perfusion or casting (casting) The curable resin composition is impregnated into the substrate to 'flow into the mold and cast into shape' to be hardened by heating, and in the case of a solid state, it is molded by a melt casting or a transfer molding machine. Further, it is hardened by heating. The hardening temperature is 80 to 200 t, and the hardening time is 2 to 1 Torr. The hardening method 'can be solidified at one time at a high temperature, but it is preferred to gradually increase the temperature to carry out a hardening reaction. Specifically, an initial hardening between & 8〇~15旳 is performed between 100 C and 200 C for post-hardening. In the hardening stage, it is preferably 2 to 8 stages of temperature rise, more preferably 2 to 4 stages. Further, the curable resin composition of the present invention can be dissolved in hydrazine, diphenylbenzene, acetone, methyl ethyl ketone, decyl isobutyl ketone, dimercaptomethylamine, dimethyl acetamide, N-methyl oxime. A curable resin composition varnish is prepared in a solvent such as a ketone to be impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber or paper, and dried by heating. The hot-press forming of the prepreg is used to form the cured product of the curable resin composition of the present invention. The solvent used in this case is usually used in the mixture of the curable resin composition of the present invention and the solvent. The weight %, preferably 15 to 70% by weight. Further, it is also possible to obtain a cured resin containing a carbon fiber by RTM (Resin Transfer MGlding) in a state of a liquid composition. Further, when the curable resin composition of the present invention can be used as a film-type sealing composition, when the film-type tree residue is obtained, the following method can be used: #Firstly, the curable resin composition of the present invention is produced. The composition is varnished as described above, and is applied to a release film, and the solvent is removed by heating under the heat of 38 201120084, and then B-staged; thereby obtaining a film-type seal by means of a sheet-like adhesive. Use the composition. The sheet-like adhesive can be used as an interlayer insulating layer of a multilayer substrate or the like, and an integral film seal of an optical semiconductor. Next, the case where the curable resin composition of the present invention is used as a crucible sealing material or a die bonding material of a photo-semiconductor will be described in detail. When the curable resin composition of the present invention is used as a sealing material or a solid crystal material for a high-intensity white LED or the like, by the epoxy resin of the present invention, a hardener containing a polycarboxylic acid ( An additive such as a hardener composition, a hardening accelerator, a coupling material, an antioxidant, or a light stabilizer is sufficiently mixed to prepare a curable resin composition. The mixing method may be carried out by using a kneader, a three-parent grinder, a universal mixer, a #star mixer, a homomixer, a homodisperser, a bead mill, etc., at a normal temperature or by heating. The resulting curable resin composition can be used for a sealing material, or for both a die bonding material and a sealing material. An optical semiconductor element such as a south-duty white LED is usually made of an adhesive (solid crystal material) so as to be laminated on a substrate such as sapphire, spinel or germanium, and G a A s, G a P, G a A1 Α ς, r·a. A semiconductor wafer such as η uaAlAs, GaAsP, A1Ga, InP, GaN, InN, or N InGaN is then packaged in a lead frame or a heat radiating plate, and a type of a wire such as a metal wire is connected to a current. & ', seal the surrounding with a sealing material such as a gas-resin resin. The sealing material is used to protect the λ m ° semiconductor wafer from heat or moisture, and play the role of lens function ~ & The curable resin composition of the present invention can be used as the above-mentioned sealing material or the material for taking the next day. In terms of steps, it is more suitable for the solidification of the present invention. Crystalline material and sealing material 39 201120084. The method of attaching a semiconductor wafer to an I& substrate using the curable resin composition of the present invention may be exemplified by the method of dispensing the curable resin composition of the present invention by 4 $ Yi / Cui / After the screen printing is applied to the substrate, the semiconductor wafer is placed on the hardened and oxidized tree composition to be heat-hardened. By this method, the semiconductor wafer can be attached to the substrate. A hot air circulation type, an infrared ray, a high frequency wave, etc. can be used. The heating condition is, for example, preferably 8 Torr to 23 Torr: heating for 1 minute to about Μ hours. To reduce the internal stress generated during heat hardening, for example, under the rib C After pre-hardening for 30 minutes to 5 hours, it is post-hardened with 12 〇 to 1 8 〇, and 30 knives for 1 〇 hours. - The sealing material is formed by using: in the above manner After the sealing material is injected into the mold frame of the substrate of the semiconductor wafer, the injection method is further formed, and the sealing material is pre-filled into the mold to impregnate the semiconductor wafer fixed on the substrate and heat the semiconductor wafer. After hardening, the compression molding method is released from the mold, etc. The method can be exemplified by a dispenser, a transfer molding, an injection molding, etc. Heating can be performed using a hot air circulation type, an infrared ray, or a high frequency wave. The heating condition is, for example, preferably ～230° C. for about 1 minute to 24 hours. To reduce the internal stress generated during heat curing, for example, after 8 minutes to 5 hours for 5 minutes and 5 hours for pre-hardening. The post-hardening is carried out under the conditions of 12 〇 to 18 〇, %, and 5% of the time. Further, the use of the curable resin composition of the present invention is not limited to 'the same applies to the use of epoxy resin. For example, the hardening resin is used. For example, for example, ifc & π forming materials (including sheets, J. , RP, etc., insulating materials (including printed substrates, resin compositions, :::, materials, sealing materials, cyanic acid for substrates, and hardeners for acrylic vinegar resins, etc.) Additives in Lunar 4, etc. The following agent, 4·4· m ', civil engineering, construction gas vehicle, medical A, and & affairs, electronic (4) ’ can be cited as an adhesive for electronic materials. Among these, an adhesive for an electronic material, a layer of a substrate, and a plurality of layers such as a bUlld_UP substrate

A semiconductor adhesive such as a Japanese M or a primer, a BGA primer, an anisotropic conductive film (ACf), and the like are used. Conductive bone (ACP) acts as a sealant and can be used as a sealant. Photodiodes, ICs, LSIs, etc.

Tr jin used for perfusion, impregnation and transfer molding seals, ... C0B, C0F, TAB, etc. used for perfusion sealing, flip-chip (fllp chip) and other primers used, QFP, BGA and CSP ic package Seals for packaging (including reinforcement primers). The cured product obtained in the present invention can be used for various purposes represented by optical component materials. The material for optics generally means a material used for the purpose of passing light such as visible light, infrared rays, X-rays, and laser light through the material. More specifically, the following may be mentioned in addition to the coffee sealing material such as a lamp type or an SMD type. A material for a liquid crystal display device such as a substrate material such as a substrate material, a light guide plate, a ruthenium plate 1, a polarizing plate, a phase difference plate, a viewing angle correction film, an adhesive, or a polarizing 7C protective film in the field of a liquid crystal display. In addition, as a next-generation flat panel display, it is expected to be a sealing material for a color PDP (Electrical Resonance 41 201120084), an antireflection film, an optical correction film, a case material, a protective film for a front glass, and a front glass substitute material. , adhesive, and LED molding material used in LED display device, (10) sealing material, protective film for front glass, front glass replacement material, adhesive, and plasma addressed liquid crystal (PALC) display The substrate material, the light guide plate, the cymbal sheet, the polarizing plate, the position difference plate, the viewing angle correction film, the adhesive, the polarizing element, the protective film X organic EL (electroluminescence) display, the protective film of the front plate glass, the J board A glass substitute material, an adhesive, and various enamel substrates in a field emission display (FED), a protective film for a slab glass, a front plate glass substitute material, and a follower. Optical recording field φ, i , ak A 〒 is VD (video CD), CD/CD — ROM, CD-R/RW, DVD — R/DVD_ RAM, m〇/md, p with phase change disc), optics The disc substrate material for the card, the optical lens reading lens, the protective film, the sealing material, the adhesive, and the like. A, the field of word preparation - '. V heart ... ~ set the rules for He Ke, viewfinder prism, target prism, take me cry" brother to take the hall, benefit (fmder cover), light sensor. In addition, the camera lens of the camera, the brothers and sisters take the hall, theft. In addition, the projection lens of the projection TV, the protective film, the sealing material and the mirror are connected to the illusion. The lens of the light sensing machine is made of material, sealing material and adhesive H Μ ^. In the field of optical components, it is a seal (four) and a binder for the fiber material, lens, material, and 2 around the optical switch in the communication system. (10) The ferrule and sealing material # 1 are connected to I 4 . In the passive parts and parts of the light, it is a lens, a waveguide, a TTm ^ special circuit zero anti-conductance, an LED sealing material, a cCD follow-up agent, and the like. Light mine throwing # 4 Si material 枓, ... Temple optoelectronic integrated circuit (0EIC) around the material, component sealing material, girl 4 such as & bamboo, cut-off material. In the field of optical fiber, it is equipped with Han 42 201120084, etc., and it also uses: sensors for industrial applications such as pilots, display/identification, and optical fiber for digital connection for semiconductor construction and home use. The technique used in the 'edge material' is a micro-button for the LSI^LSI material. Yu, squid / · flute recognize the body 丄, reflector, bearing retainer: Γ: Γ, for the car lamp lamp, bow I engine parts, Thunder layer, switch part, before __ ^ pieces , various materials, drive engines, (four) with rust-proof steel, mterior panel, interior mouth '. , protection / bundle bundles, fuel hoses, car lights, glass instead: two-layer rail vehicle laminated glass. The structural material of the X' aircraft, the engine peripheral components, the wiring harness for protection/bundling, and the corrosion resistant coating. =In the field of construction, it is a material for interior/processing, lampshade, sheet, glass shed, glass substitute, solar cell peripheral material. For agricultural use, it is the yuan: the moon mask. As a next-generation optical/electronic functional organic material, it is an organic EL peripheral material, an organic light-refracting element, a fiber-optic member as a light-to-light conversion device, an optical arithmetic element, a substrate material around an organic solar cell, a sense, a quasi-material, 7L piece of sealing material, adhesive, etc. [Examples] Next, the present invention will be more specifically described by way of examples, and hereinafter, σ should be described as "parts by weight". Further, the present invention is not limited to the above, and in the examples, the epoxy equivalent is measured in accordance with JIS Κ ~ 7236, and the viscosity is carried out at 25 t: using a £-type viscometer. Further, the analysis condition of the _ analysis method (hereinafter referred to as GC) is as follows: the separation column uses Hp ^MS (0.25 mm LD.X 15 m, the film thickness is 〇25 ^), and the temperature of the column supply phase is initially set. Temperature voyage 'heats up at a price per minute, 43 201120084 at 300 ° C for 25 minutes. Further, helium gas is used as a carrier gas. Further, the measurement of gel permeation chromatography (hereinafter referred to as Gpc) is as follows. The column was made of Shodex SYSTEM-21 (kf_803l, KF-8〇25 (x2), KF-802), the solution was tetrahydrofuran, the flow rate was 1 mi/min, and the column temperature was 40 °C. The detection was performed in uv (254 nm) and the calibration curve was made using standard polystyrene manufactured by Shodex. Synthesis Example 1 Synthesis of cyclohexenediol Synthesis Example 1 (refer to Patent Document EP 0487035 B1) In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 12 parts of cyclohexene furfural was added while performing nitrogen purge. 6 parts of ethanol, 300 parts of 35% of formalin, and 284 parts of a 30% by weight aqueous solution of potassium carbonate were heated to reflux temperature while stirring, and reacted for 9 hours in this state. After the completion of the reaction, a Dean_stark cooling tube was installed, and the ethanol was distilled off by allowing the bath to stand at a bath temperature of 100 ° C for 4 hours. After cooling to -temperature, it was allowed to stand for 24 hours in this state. The precipitate is precipitated by filtration under reduced pressure: The cyclohexene dimethanol of the color crystal is separated from the solution by filtration, and the blister is blended to obtain the target cyclohexene diol (the following formula (6)) 1〇3 copies. The purity obtained by the gas enthalpy method was 98 area%. Tomography

Synthesis Example 2 44 201120084 In a flask equipped with a stirrer, a reflux cooling tube, a stirring device, and a Ding Stark tube, a nitrogen purge was carried out while adding 15 parts of a compound, 70 parts of the compound of the above formula (6), and a 3-ring. Diluted formic acid 12M, p-toluene, 2 parts, and reacted for 1 hour after removing water under heating and reflux. After the completion of the reaction, the mixture was washed twice with 5 parts by weight of an aqueous solution of sodium hydrogencarbonate in 5 parts of water; the organic (four) obtained was washed twice with water (50 parts), and the organic solvent was concentrated using a rotary evaporator, whereby the olefin compound of the present invention was obtained. (1) - 丨, 173 parts of the following formula (7)). The obtained olefin compound was found to be in a liquid state, the purity obtained by gas chromatography was 92% by area, and the analysis result by gel chromatography was > % area% purity.

Synthesis Example 3 The epoxy resin was synthesized in a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, and a nitrogen flushing-surface addition water (5 parts, i 2 _ 嫣 酸 酸 i. - 5.4 parts of sodium I.6, ditallow alkyl dimethyl ammonium acetate (Lion Akzo made k 5 〇 heavy! / 〇 己 己 ,, Arquad 2HT - Acetate), after the formation of lanthanide catalysts #1 2Q parts, the above-obtained dilute hydrocarbon compound 1 1 9 1 ', and preferably γ-·-r: stirred for a long time to form a latex state solution. The solution is heated to 50 ° C, % The hydrogen peroxide water-surface was stirred vigorously while adding 35 weights of 1 18 parts in one hour, and in this state, at 5 Torr. (: stirring under 1 3 small 45 201120084. Confirmation of the reaction by GC As a result, the peak of the raw material disappeared. Then, after neutralization with a 1% by weight aqueous sodium hydroxide solution, 25 parts of a 20% by weight aqueous sodium thiosulfate solution was added, and the mixture was stirred for 3 minutes, and the mixture was separated and separated into two layers. Layer, adding 10 parts of silicone (Wak〇gelc - 300), activated carbon (manufactured by N0RIT, CAp SUpER) 2 2 parts of bentonite (manufactured by Hojun, Benge 丨 New Zealand), stirred at room temperature for 1 hour, and then filtered. The obtained filtrate was washed 3 times with 100 parts of water, and the obtained organic layer + steamed Gu recorded f#' Thus, 118 parts of the following epoxy resin (EP_1) which was liquid at normal temperature was obtained, and the obtained epoxy resin had an epoxy equivalent of 148 g/eq.

兮 Example 4 - 25 parts of the obtained epoxy resin (ΕΡ-1), using 1 part of 5 parts of Shixi gum (Wak〇geiC and Wako Pure Chemical Industries, Ltd.), and using ethyl acetate: hexane two i: 4~ The developing solvent of 2.3 was purified by f-column chromatography. The oxime resin of the 仵 仵 _2 _2 _2 ) _2 _2 _2 _2 _2 _2 _2 _2 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂It is about 99 area 7°. Further, the epoxy equivalent was 137 g/eq. Synthesis Example 5 46 201120084 Synthetic Synthesis Example 2 The same length of dilute methanol blood tetrahydrous 1 owe to the synthesis example 3 士. The epoxidation is carried out in the same manner, whereby an epoxy resin having the main component of the gentleman shown in the following eight (9) is obtained. Dance

The obtained epoxy resin was further purified in the same manner as in Synthesis Example 4 to obtain an epoxy resin (Ep_3). The purity of the obtained epoxy resin is based on the measurement result of GPC. (IV) The compound which contains the skeleton of the above formula (9) is acetated to produce an olefin compound having a double adjacent area area or more. Further, in the GC measurement, the purity was about % area%. Further, the epoxy equivalent was 137 g/eq_. Synthesis Example 6 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 1 part of dicyclopentadienyldithiol and decyl hexahydrophthalic anhydride were added while nitrogen gas was purged (Nippon Chemical and Chemical Co., Ltd.) The company manufactures, Rikacid ΜΗ 'hereinafter referred to as acid needle H3) 1 〇〇 part, at 6 〇χ: under heating and mixing for * hours (by GPC to confirm the disappearance of dicyclopentadienyl decyl alcohol), thereby obtaining The hardener composition of the polycarboxylic acid (Bl) is in part. The obtained hardener composition (B1) was a colorless liquid resin. The purity obtained by GPC was: the structure of the polyvalent carboxylic acid was 22 area%, and the mercapto hexahydrophthalic anhydride was 78 area%. Further, the functional group equivalent was 188 g/eq. That is, W2/(W2+ W3) = 0.78. 47 201120084 Synthesis Example 7 According to the patent document 3, the amount of the resin is described. That is, 2-(3 4 -epoxy..., 聚聚乳乳化epoxy(, 己己基)ethyltrimethoxydecane 26·6 Α...(4),)-methyl-methoxy oxalate 73·4 parts (the amount of the oxygenated field is (4)), the triethylamine (10) parts, and the decyl isobutyl ketone are added to the reaction vessel, and the mixture is added at room temperature for 3 minutes. The base was saturated with 1 part of water, and after heating to 80 degrees, it was allowed to react for 6 hours. Thereafter, neutralization (4) was repeated with water using a 20% aqueous solution of sodium dihydrogen phosphate for 3 times. Then, the organic phase was removed under reduced pressure, and the solvent was removed to obtain a poly-modified epoxy resin having a reactive functional group (the epoxy equivalent of the EM (10) compound was 561 g/eq, and the appearance was colorless and transparent. Example 1 The epoxy resin (Ep_2) obtained in Synthesis Example 4 was prepared by using a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride (manufactured by New Japan Physical and Chemical Co., Ltd.). , Rlkacid ΜΗ·, hereinafter referred to as hardener, and using 16-fold-based trimethylammonium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd., 25 wt% sterol solution, called C () as hardening The accelerator's blending ratio (parts by weight) shown in the following table was changed, and defoaming was carried out for 20 minutes to obtain a curable age-aged product of the present invention. Further, the amount of the hardener used was calculated as: relative The epoxy group has an epoxy group of 1 equivalent, and the amount of the hardener used is 1 equivalent. Comparative Example 1 H1 is a comparative example shown in the synthesis example (Ep-3), using a hardener, And use c1 as a hardening accelerator, with the following 148201120084

(heat resistance test) defoaming, obtaining the use amount of the hardener of the present invention, the equivalent amount, the use of the hardener

When it was hardened, the chemical resin composition was subjected to 20 bubbles, and then slowly cast in a mold having a width of 7 mm, a length of 5 cm, and a thickness of about 8 Å, and then covered with a polyimide film from above. After pre-hardening for 12 〇 C x 1 hour, a test piece for dynamic viscoelasticity was obtained at 150 ° C x 3 small. Using these test pieces, the dynamic viscoelasticity test was carried out under the conditions described below. Measurement conditions Dynamic viscoelasticity measuring device: manufactured by TA-仪器, DMA-2980 Measuring temperature range: 30. (:~2 8 0. (: Heating rate: 2. (:/min 5 size): Use a test piece cut into 5 mm x 50 mm (thickness, 'spoon 8 〇〇 "claw). Analysis conditions

Tg - The peak of Tan - < 5 in the DMA measurement is set to Tg. (Transmittance test) After the obtained curable resin composition was subjected to vacuum defoaming for 20 minutes,

'The curable resin and the article are slowly cast on a glass substrate made of a heat-resistant tape to form a dam so as to be 30 mmx2〇mmx height of 1 mm. The casting is subjected to 12 (TC X1 hour pre-treatment) After hardening, the transmittance was measured by using 1 5 (TC X 49 201120084 for 3 hours to obtain a transmittance of 1 mm and a test piece using a spectrophotometer). ^ [Table 1] -—-- — Example 1 — ~----- Example 1 Epoxy Resin EP-2 . 2.74 EP-3 Composition -----~~~~2J4__ Hardener H1 3.36 Hardening Catalyst C1 0.01 Heat Resistance Test Results DMA Tan-d (°〇250 ~ u.oi 10/1 transmittance 400 mm 89.0% lo4 〇yo% According to the results, the epoxy resin composition of the present invention is excellent in transparency and excellent in heat resistance. Examples 2, 3 and Comparative Example 2 The epoxy resin (Eh) obtained in Synthesis Example 3 was used as an epoxy resin, and the usual < 3,4-epoxycyclohexylcarboxylic acid 3',4,-epoxycyclohexyl group was used. The ester (ep-5) was used as a comparative example, and the mixture of the acid anhydride obtained in the synthesis example 6 and the multi-repulsive acid, that is, the hardener was used. (referred to as a hardener, and further use C1 as a hardening accelerator, blended in a blending ratio (parts by weight) shown in Table 2 below, and subjected to a 20-minute elimination of the hardening resin group of the present invention. : The hardening resin composition for comparison. Further, the epoxy resin which is hardened in the epoxy resin...TM agent 50 201120084 « (The densification test after curing of the LED package) The curable resin composition obtained in the examples and the comparative examples Filled in a syringe' using a precision injection device, cast into a surface-encapsulated LED package with an outer diameter of 5 mm square (4 4 mm inside diameter and 1 25 mm in outer wall height). The cast is placed in a heating furnace. 2, it was subjected to a hardening treatment for 1 hour, and further hardened at 150 C for 3 hours to obtain an LED package. The depth of the resin was measured using a depth gauge based on the height of the outer wall. The results of Examples 2 and 3 and Comparative Example 2 are shown in Table 2. Measurement conditions

Depth gauge: manufactured by NIKON, DIGIMTCRO STAND MS ~ 1 1C Depth depth is the average of 3 packages. [Table 2] Item Example 2 Example 3 Comparative Example 2 EP-1 2.96 2.96 EP-5 2.66 Composition Hardener (H1) 3.36 3.36 Hardener Composition (B1) 3.78 Hardening Catalyst (C1) 0.01 0.01 0 01 Hardening After the amount of depression 190 μm 15 ———ν·νΜ um According to the above results, it was found that the cured resin composition of the epoxy resin 51 201120084 obtained in Synthesis Example 3 can be improved compared with the comparative example. Depression. Further, it is understood that this effect is further improved by containing a polycarboxylic acid (W2/(W2+w3)=() 78). Comparative Example 3 The polyfluorene-modified epoxy resin (Ep-4) obtained in Synthesis Example 7 was blended with H1 as a curing agent at a blending ratio (parts by weight) shown in Table 3 below for 20 minutes. The defoaming is carried out to obtain a curable resin composition of the present invention. Further, the amount of the curing agent used was calculated to be 1 equivalent of the epoxy group of the epoxy resin. The amount of the curing agent used was 1 equivalent. (Corrosion gas permeability test) The curable resin composition obtained in Example 2 and Comparative Example 3 was filled in a syringe, and cast to a diameter of 5 mm square of a wafer equipped with a central emission wavelength of 465 nm using a precision discharge device. The surface mount package has an inner diameter of 4_4 mm and an outer wall height of 丨25 mm. The cast product was placed in a heating furnace to be hardened at 120 ° C for 1 hour, and further at 15 ° C. The underside was subjected to a hardening treatment for 3 hours to form an LED package. The LED package was placed in a corrosive gas under the following conditions, and the color change of the silver-plated lead frame portion inside the seal was observed. The results of Example 2 and Comparative Example 3 are shown in Table 3. Determination of the conditional corrosive gas: 20% aqueous solution of ammonium sulfide (the sulfur component turns black when reacting with silver) Contact method: In the wide-mouth glass bottle, the container of the aqueous ammonium sulfide solution is mixed with the above-mentioned LED package, and the lid is covered with a wide mouth. The glass plate is covered and closed. 52 201120084 In the closed state, the volatilized ammonium sulfide gas is brought into contact with the LED package. Corrosion determination: The time during which the lead frame inside the LED package became black (referred to as blackening) was observed. The longer the discoloration time, the more excellent the corrosion resistance was judged. [Table 3] Item Example 2 Comparative Example 3 EP-1 2.96 Composition EP-4 10 Hardener (H1) 3.36 3.36 Hardening Catalyst (C1) 0.08 0.08 Discoloration time of lead frame for more than 10 hours No time in 1 hour The discoloration clearly shows that the curable resin composition of the present invention is compared with the curable resin composition of the polyfluorene-modified epoxy resin used in Comparative Example 3 (discoloration within i hours) of the lead frame. Silver plating was not discolored, and it was found that the corrosion resistance was excellent. According to the above results, it has been found that the curable resin composition of the present invention is superior to the polysulfide resin in corrosion resistance, corrosion resistance, and corrosion resistance. The LED sealing material is superior in durability to the previous alicyclic epoxy resin which is substituted with 3,4 epoxycyclohexyl decanoic acid v ^ soil f 酉夂 3,4 _ % oxocyclohexyl methyl ester. Example 4, Comparative Example 4 Using the strip obtained in Synthesis Example 3, u-emulsion resin (EP-D was used as the epoxy resin, and 3, 4 - epoxy j'p # 轧 hexyl carboxylic acid 3' was used. , 4, an epoxy cyclohexyl group _ 53 201120084 12,4 - cyclohexane tricarboxylic acid-1, 2 (EP-5) as a comparative example, and using m, Η - TMA, hereinafter referred to as mono-anhydride (Mitsubishi Gas Chemistry Co., Ltd. is manufactured as 硬化2) as a curing agent, and the following mixing ratio (parts by weight) of the flow 矣J μ _ ^ is described in Table 4, ts is carried out for 20 4 4 &> package, and the curable resin of the present invention is obtained. Composition: and a comparative hardening resin composition. Further, the amount of the curing agent used was calculated to be 1 equivalent based on the epoxy & i equivalent of the epoxy resin. The curable resin composition obtained in Example 4 and Comparative Example 4 was subjected to vacuum defoaming for 20 minutes, and then slowly cast into a heat-resistant tape in a manner of 3 mm x 2 mm mm > height i claws. On the glass substrate of the barrier, the cast was subjected to 12 〇. 〇 < 1 hour pre-hardening, 15 〇 ≪ tx was hardened for 3 hours to obtain a test piece for transmittance of 1 mm in thickness. Using these test pieces, the transmittance before and after leaving for 96 hr in an oven of 15 〇t was measured by a spectrophotometer (measurement wavelength: 4 〇〇nm), the retention rate of the transmittance was calculated. (LED lighting test) The curable resin composition obtained in Example 4 and Comparative Example 4 was filled in a syringe, and the casting was carried out with a precision discharge device. A surface-encapsulated LED package with an outer diameter of 5 mm square of an illuminating wavelength of 465 nm (with an inner diameter of 4.4 mm and an outer wall height of 1.25). The cast material is placed in a heating furnace at 12 (TC for i-hour hardening treatment, and further 1 and 3 hours of hardening treatment at 50 ° C. The LED package was fabricated. The LED was lit under the following conditions, and the illuminance was measured. The results of Example 4 'Comparative Example 4 are shown in Table 4 2011 20084. [Table 4] Project Example 4 Comparative Example 4 Composition EP-1 2.96 EP-5 2.66 Hardener (H1) 1.94 1.94 Hardener (H2) 0.84 0.84 Transmittance Transmittance 81.4% 73.3% Retention 90.4% 81.2% LED Test Initial Strength 9590 8910 based on the above results It is understood that the heat-resistant transmittance of the curable resin composition of the present invention and the illuminance at the time of lighting are also excellent. Examples 5 and 6 and Comparative Example 5 The epoxy resin 1> 丨) obtained in Synthesis Example 3 was used as a ring. As the oxygen resin, the usual 3,4-epoxycyclohexyl decanoic acid 3,4,monoepoxycyclohexylmethyl ester (10)-5) was used as a comparative example, and m, H2, and the acid obtained in Synthesis Example 6 were used. The hardening agent composition (B1) which is a mixture of a plurality of polyphenols is used as a hardening agent, and an organic scale salt (manufactured by Nippon Chemical Industry Co., Ltd., ρχ-4Mp, hereinafter referred to as C2) is used as a hardening accelerator, as shown in Table 5 below. The blending ratio (parts by weight) was blended, and the foaming resin of the present invention was obtained by adding the foam of the present invention to the foam of the present invention for 20 minutes. Further, the use of the hardener is a one-equivalent to the epoxy I equivalent of the epoxy resin, and the amount of the hardener 55 201120084 is one equivalent. Using the obtained curable resin composition, the LED test was carried out in the following manner. The hardening conditions were 1 40 ° C x 2 hours after pre-hardening at 12 ° C for 2 hours. (LED reflow test) The curable resin composition obtained in the examples and the comparative examples was subjected to vacuum defoaming for 2 minutes, and then filled in a syringe, and washed by a precision discharge device to have an emission wavelength of 465 nm. A surface-mount LED of a light-emitting element. Thereafter, it was hardened under specific hardening conditions, whereby test LEDs were obtained. The obtained test LED was absorbed by a temperature of 3 (TC, 70% x 24 Hr), and then observed using a high-temperature observation apparatus (STM Scope SK-5000, manufactured by Sanyo Seiko Co., Ltd.) to visually observe whether or not it was produced as follows. The LEDs used for the test under reflow conditions were cracked. The test was carried out with η-3, and evaluated by (NG number) / (test number). The condition was 2 at 2 eC/sec from 25. (: warming to 15 (TC, Thereafter, the temperature was maintained at 15 ° C for 2 minutes and further increased to 260 at 2 ° C / sec. (:, after maintaining the temperature for 1 〇 second, it was cooled to room temperature at Ut / sec. " 56 201120084 m [Table 5 Item Example 4 Example 5 Comparative Example 5 Composition EP-1 2.96 2.96 EP-5 2.66 Hardener (H1) 1.94 1.94 Hardener (H2) 0.84 .084 Hardener Composition (B1) 3.76 _ Catalyst (C2) 0.003 0.003 0.003 _-Reflow resistance __ __0/3 0/3 0/3 According to the above results, the curable resin composition of the present invention is excellent in impact resistance. The present invention has been described in detail with reference to specific examples. However, it is obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. 'This application is based on this patent application filed on October 9th, 2009. (Japanese Patent Application 2〇〇9~234846)' By reference, the 1 body is used. Also, all reference systems cited here It is considered as a whole and is incorporated. [Simple description of the diagram] M. [Description of main component symbols] No 57

Claims (1)

201120084 VII. Patent application scope: 1. A curable resin composition comprising: a piano resin, a hardener, and/or a hardening accelerator obtained by oxidizing an olefin compound represented by the following formula (1): (wherein a plurality of R1 and R2 are each independently represented by hydrogen or an alkyl group having 1 to 6 carbon atoms). The sclerosing resin composition of the first aspect of the patent application, wherein the gas tree sorghum is made of a dilute smoke compound in which all of R1 and r2 are nitrogen atoms. The hardening resin composition of the first or second aspect of the invention, wherein the curing agent is one or more compounds represented by the following formula (2): κ represents a ruthenium atom, a field ^ 4 j, λ, a methyl group or a carboxyl group). 4. If the patented product is the first product of the patent, the hardening resin group /, medium, and hardener are one or more compounds as shown in the following A (3): 58 201120084 In f & or carboxyl group f, a plurality of R3 represent a hydrogen atom, and a chain of 2 to 20 or a cyclic aliphatic group). , Shishen is called the curative resin composition of the fourth paragraph of the patent range, in the beans, (3) in the chain branch or ring structure. The sclerosing resin composition of the invention, wherein the compounding agent contains one or more compounds represented by the following formula (2) (wherein R3 represents a hydrogen atom, a methyl group or a carboxyl group), and a compound of the above formula (3) or more a base (wherein a plurality of R3 independently represent a hydrogen atom, a methyl group or a carboxyl group or a chain or a cyclic aliphatic group having a number of 2 to 20), 59 1 201120084 and its use ratio is The range is: W2 / (W2 + W3) = 0.30 to 0.95 (wherein W2 represents a blended part by weight of the compound of the formula (2), and a blended part by weight of the compound of the formula (3)). 7. A cured product obtained by hardening a curable resin composition of claims 1 to 6 of the patent application. 8. An optical semiconductor device which is obtained by sealing a curable resin composition according to any one of the claims of the patent. 8. Drawing: Benefit W3 means any of the tributaries 1 to 6 60