TW201207043A - Curable resin composition and cured product thereof - Google Patents

Abstract

The aim of the present invention is to provide a novel curable resin composition which provides a cured product having superior light-fast colouring properties, heat-resistant colouring properties, and corrosive-gas resistant properties. The curable resin composition of the present invention contains an organopolysiloxane (A), a polyvalent carboxylic acid (B), an organic metal salt and/or an organic metal complex (C), and a light stabiliser (D). The organopolysiloxane (A), the polyvalent carboxylic acid (B), and the light stabiliser (D) meet the following conditions. Organopolysiloxane (A): An organopolysiloxane having at least a glycidil group and/or an epoxycyclohexyl group in the molecules thereof. Polyvalent carboxylic acid (B): A polyvalent carboxylic acid having at least two carboxyl groups, and an aliphatic hydrocarbon group as the main skeleton. Light stabiliser (D): A compound represented by structural formula (1).

Description

201207043 A resin in which a siloxane skeleton (specifically, a skeleton having a si_0 bond) is introduced as a sealing material, which is represented by a polyoxyxylene resin or a polyoxymethylene-modified epoxy resin (Patent Document 3). It is known that a resin in which a decane skeleton is usually introduced is more stable to light than an epoxy resin, and (4) is insufficient, and further improvement is becoming a problem. As a method for solving the above problems, a method of adding a light stabilizer is known (Patent Document 4). However, although light resistance is improved by adding a light stabilizer, the resin is deteriorated by heat or the like emitted from the LED wafer. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION An object of the present invention is to provide a new curable resin which provides a cured product which is excellent in time coloring property, heat-resistant coloring property, and corrosion-resistant gas property. The inventors of the present invention have completed the present invention in view of the above results. That is, the above-mentioned actual circumstances have been made in an effort to study: the present invention relates to: a curable resin composition comprising cerium: an organic polyfluorene polycarboxylic acid (B), an organic metal salt and/or an organometallic complex ^ : Light stabilizer (D) 'where, right; ^ # μ g / , ' T organopolyoxane (A) with multiple, light stabilizer (D) meets the following conditions: Organic polyoxane (A): An organopolyoxopolycarboxylic acid (B) having at least two epoxy groups and/or 4 201207043 epoxy cyclohexyl groups: a compound light stabilizer having at least two carboxyl groups and having a main skeleton aliphatic hydrocarbon group (D): as shown in Structural Formula (1) [Chemical 1]

(1) (wherein, X X and X 2 are a hydrogen atom, an alkyl group having a carbon number of 1 to 5 Å, an aromatic earth, a square group, an aryl group having an alkyl group having a carbon number of 120, an alkoxy group or a structural formula v, At least one of J in 1 and X2 is structural formula (2):

C?) (In the formula (2), the structural formula (2) is bonded to the structural formula (1) # oxygen atom at the * mark, and γ represents a hydrogen atom, an alkyl group having a carbon number of 1 to 5 Å, and a aryl group. (2) The curable resin composition according to the above (1), which comprises the compound (2) of the structural formula (1) having a structural formula of a pitoxy group having a carbon number of 1 to 2 Å. 201207043 The curable resin composition according to the above (1) or (2), wherein the organometallic salt and/or the organometallic complex (C) is a phosphate ester of zinc phosphate and/or has the same acid or (4) The curable resin composition according to any one of the above (1) to (3), wherein X1 and Χ2 of the structural formula (1) are both structural formulas (2) And (5) a curable resin composition according to any one of the above (1) to (4), which contains an acid anhydride; (6) as described above (1) i (5) The curable resin composition according to any one of the invention, wherein the polyvalent carboxylic acid (B) is a compound obtained by a reaction of a 2 to 6-functional polyol having a carbon number of 5 or more and a saturated aliphatic cyclic acid anhydride. (7) It contains == to (6) The curable resin composition according to any one of the above, wherein the cured product is obtained by curing the π-based resin composition. ^The hardening of the curable resin composition of the present invention is due to the color and the resistance of the """""""""""""""""""""""""""" The material is extremely useful. (Connected to LED products, etc.) 201207043 [Configuration] The following describes the curable resin composition of the present invention. The curable resin composition of the present invention contains organic = (?, an organic metal salt and / or organic metal mismatch: two and light stabilizer (D). Organic polyoxane (A) is the use of its molecular | or epoxy cyclohexyl organic polyoxetane. / The above-mentioned organopolyoxane is characterized by its organic polymerization of molecular oxygen cyclohexyl groups, and usually by:::: (4) the second base of the substrate should be cut (four) in the melting of the raw material - the specificity of the Japanese Patent Laid-Open No. Hei 2__25(10) No. 9, Japanese Patent Laid-Open No. Hei 2__3461441, International Publication No. 2004/07215G, Japanese Patent Laid-Open No. _8747, International Publication No. 2__399(), Japanese Patent Special Drawings Bulletin, International Publication No. 2007/135909, Japan Three-dimensional expansion is described in the Japanese Patent Publication No. 359933, the International Publication No. 2005/100445, and the Japanese Patent Laid-Open Publication No. Hei. No. Hei. In the present invention, the structure is not particularly limited, but since it is simply three-dimensional, blinking, "the structure of the oxirane compound is too hard" And a structure which is expected to relax the hardness in the present invention, and is particularly preferable as a block structure having a bond-like poly-oxygen sheet, k, and the above sesquiterpene oxide structure (hereinafter referred to as Block type 201207043 siloxane compound (E)). The enemy type oxalate compound (E) is not a compound having a repeating unit in a straight chain like a usual block copolymer, but has the following structure: The mesh-like structure of the dimensional expansion, with the sesquiterpene oxide structure as the core, the chain polyoxynene fragment extends and is connected to the next sesquiterpene oxide structure. The structure is hardened by the hardening composition of the present invention. The meaning of the balance between hardness and softness The saponin-type oxoxane compound (E) can be produced, for example, from a oxy-oxyl group U represented by the following formula (3) and a poly 11 oxy-oil represented by the formula (4). And, if necessary, the pyrochlore Xiyuan (7) represented by the formula (5) can be used as a raw material. The bond-shaped Xiyang oxygen fragment of the block type money-burning compound (ε) is formed by the poly-stone oxygen (1), three-dimensional The mesh-shaped double-cut oxygen sheet is formed of alkoxy decane (a) (and an alkoxy oxime added as needed. Hereinafter, each raw material will be described in detail. The oxy-stone pit (a) is composed of The above formula (1) represents: XSi(OR丨)3 (3) As the organic group of the γ^.A hexyl group in the formula (3), there is no particular one containing a glycidyl group and/or a epoxy group. Ethyl, "glycidoxypropane", for example, exemplified by the number of carbon atoms substituted by epoxy oxypropoxy group = alkyl group of epoxycyclohexyl)ethyl ' 4 such as phenyloxypropyl butyl group 'Epoxypropyl, p-(3, cyclodextrose ethyloxycyclohexyl)propyl...cyclopentyl)butyl 'wan-(3,4-epoxydi-yl)propyl, Η3'4· The epoxy group is substituted with a carbon number of 丨~5. Cycloalkyl group appearance of epoxy groups. In the above, it is preferred that the carbon number substituted by 8 201207043 oxy is the alkyl group of ^ 3 ^ ^ ^. The cyclohexyl group having a clothing base is taken, and the base of the base 3 is, for example, a point-glycidoxy Ethyl ethyl, r-cyclopropoxypropyl, "3,4_epoxycyclohexyl epoxycyclohexyl)ethyl. ^ (3,4 In the general formula (3), the plurality of cores may be the same or may not represent a linear chain having a carbon number of 1 to 1 Å, and examples thereof include a mercapto group, an ethyl group, a n-propyl group, and a filling- Butyl I, propyl, n-butyl, isobutyl, mono-, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, etc. These R are compatible, reactive and other reactions 'ethyl, special Preferably, the methyl group is exemplified as a preferred example of methyl or epoxy = oxygen-oxygen-oxime, which may be exemplified by: /3_I Shixi/ylethyldimethoxy(tetra)glycidoxy Ethyl triethoxy: group: ethoxypropyltrimethoxy (tetra), 7·epoxypropoxylate; lyoxycyclohexyl)ethyltrimethoxy(tetra) m cyclohexyl)ethyltriethoxy Particularly preferred is β-(3,4-epoxycyclohexyl)ethyltrimethoxy group which can be used alone or in combination with two kinds of (c) ) and use it together. 』』一 alkoxy decane + oxime oil (b) has the following general formula (4) H〇 Y I ~~~Si*-〇 4

m 9 (4) 201207043 Household /^ -.. 2: The chain end of the structure contains a sterol-based chain polyoxylate. ^ ^( ( A \ is different, in the form of the table - mountain, there are a plurality of squares 2 which are identical to each other, or the number of ore is 2 W number is 1~]0, and the aryl group having a carbon number of 6 to 14 Further, (7) indicates the number of repeating units. 1乍 is an alkyl group having a carbon number of 1 to a chain shape and eight ± 10, and a straight knife branch or ring having a carbon number of 1 to 丨 0 can be cited. a base such as n-propyl, isopropyl, n-r A s τ 1 Uethyl 'n-pentyl, isoprene A, second butyl, tert-butyl, hexyl, odor 2 The group, the cyclopentyl group, the cyclohexyl group, the octyl group, the 2-ethyl group are a methyl group, and the group 1 is a group. In these cases, in view of light resistance, a fluorenyl group or a cyclohexyl group is preferred. Examples of the phenyl group, the m-methyl group, the p-methyl group, the xylyl group, and the like are exemplified as the phenyl group and the phenyl group. Examples of the heat resistance of the base, such as ethylene, butyl, and hexenyl, etc. It is a methyl group, a stupid group, a % hexyl group, a n-propyl group, and is preferably a ketone group or a phenyl group. 4) The compound ~200, A, the repeated number of early digits of the substance m is represented by an average value of 3, preferably 3 to (10)', and it is more preferable that the cured product becomes too hard and the low elastic modulus characteristic is lowered. However, there is a tendency for the mechanical properties of the cured product to deteriorate, so it is not preferable. The weight of the polyoxygenated oil (b) is Λ 〜1M00 (gpc h is preferably 300 knives (MW)

Chr〇m, gel permeation chromatography, Gel Permeaiion

Chromatography))). In these cases, if we consider the elastic modulus of the low 10 201207043, it is better to be 3〇〇~1〇〇〇〇, if we consider the composition of the cymbal and the amp; Exciting' is better for 3〇〇~5, the best, especially good for 500~3, the best. When * θ repeats the average molecular weight of 300 or less, 曰"1" 'has a characteristic that it is difficult to express the chain-like polyoxyl moiety of the surname from the temple, as a characteristic of the block type + _ 才贝The possibility 'if it exceeds i 8, 〇〇〇, it has a steep layer separation structure, and Chuntiantian is difficult to use when it is used for optical materials. In the present invention, the weight average molecular weight (Mw) in terms of polyethylene measured by GPC (gel permeation chromatography) under the following conditions is taken as the molecular weight of the polyoxyxane oil (1). GPC various conditions Manufacturer: Shimadzu Manufacturing Bureau column · Protection tube _ S mad bH 〇 DEX GPC LF-GLF-804 (3) Flow rate: 1.0 ml / min Column temperature: 4 〇 used 'mixture. Ding HF ( Tetrahydrofuran, butyl etrahydrofuran) Detector: RI (differential refraction detector) The dynamic viscosity of the polyoxyl oil (b) is preferably 1 〇 to 2 〇〇 range of dynamic reduction 'more preferably 30 to 9 〇 (3) Viscosity. The viscosity of the block type siloxane compound (E) in the clear V τ of (4) (5) or less is too low. In the case of the optical semiconductor sealing agent, when the viscosity is 200 cSt or more, the viscosity of the block type calcined compound (E) increases, which tends to adversely affect the workability, which is not preferable. As a preferable specific example of the oxygen-absorbing oil (b), the following product name 201207043 can be cited. For example, D0w Corning Toray Silicone's PRX413, BY16-873, Shin-Etsu Chemical Co., Ltd. X-21-5 84, KF-9701, Momentive's XC96-723, TSR160, YR3370 'YF3800, XF3905 , YF3057, YF3807, YF3802 'YF3897, YF3804, XF3905, DMS-S12 'DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S3 1, DMS-S32, DMS-S33, manufactured by Gelest DMS-S35, DMS-S42, DMS-S45, DMS-S5, PDS_0332, PDS-1615, PDS-9931, etc. In the above, from the viewpoint of molecular weight and dynamic viscosity, it is preferably PRX4 1 3 , BY 16-873, X-21-5841, KF-9701, XC96-723 'YF3800, YF3804, DMS-S12, DMS-S14. , DMS-S15, DMS-S21, PDS-1615. In the above, in order to have the characteristics of the flexibility of the polyoxynene fragment, from the viewpoint of molecular weight, x_21_584bXc96723, YF3800, YF3804, dms_sm, and pDS161 5 are particularly preferable. These polyoxygenated oils (匕) may be used singly or in combination of two or more. Then, 'the oxidant of the cerium is exemplified. The cerium oxide (c) has the structure of the following formula (5). R3Si(〇R4)3 (5) R3 in the formula (5) The methyl group or the phenyl group is represented by a plurality of groups in the formula (5) which are carbon-chain-like, branched or cyclic, and may be the same as each other: J is different. Example, tributyl, n-pentyl I, butyl, isobutylpentyl, n-hexyl 'cyclopentyl, compatibility, anti-shore cage; 5 I® At base, etc. From the viewpoint of the biosynthesis reaction conditions, the homing 4 is preferably 曱12 201207043 or ethyl.

Preferred examples of the preferred embodiment of the present invention include: A A = methoxy: burned, phenyl trimethoxy money, methyl triethoxy money: the base diethoxy sulphur Wait. In the above, it is preferably methyltrimethoxy decane or benzyltrimethoxydecane. In the present invention, in order to adjust the molecular weight of the block type oxalate compound (8), the compatibility at the time of forming a composition, the heat resistance of a cured product, light resistance, low moisture permeability, low gas permeability, etc., (4) (1) . "Qi Qian (1) Keisaki = alkoxy (4) (1) When used in combination with decyloxy (1), it is preferably burned in the base of Oxygen (a) and Oxygen in the base (5) It is used within the range of % of ear, more preferably 5~5&quot; ear n bucket right is greater than 70 mol. Then the father of hardened material decreases in degree, the mechanical strength decreases, so it is not good. The anti-base material (4), jujube oil (b), the amount of the hospital's oxygen (the reaction ratio of 〇 and τ, preferably in the case of the base of the sulphuric acid (b), ...... butyl reaction relative to the poly: = oxy #") For the alkoxy group (1) and the alkoxy group in the earthworm (e), it is 虱~, especially good... Μ1.5~2°°' is preferably 2 hard = !!Γ2 〇°, the block type compound (1) is used. The cross-linking is too hard, and the low elastic modulus property of the target is lowered. The following is a description of the block type shixi compound (E). The Ik method 13 201207043 is used as a block. The oxoxane compound is subjected to the production step (丨) of the following (丨), (2), and the sterol-terminated polyoxyl oil and the alkoxy group-containing hydrazine compound are subjected to the sterolization. Steps of Combining 疋 Manufacturing Steps (2) The step of hydrolyzing and condensing alkoxy groups of a fluorene compound having an alkoxy group by adding water is carried out, and the steps (1) and (2) can be sequentially carried out by the steps of the steps. The preferred production method is specifically the following three methods: "Production method (1) &gt; '° The production method (1) is a method for producing a oxalate compound (E) by the following steps: 1 First, The following steps are carried out as the production step (1): the de-alcohol (b) of the alcohol-based group (b) and the de-alcoholic compound having the compound of the oxygen group W, oxygen = calcination (1) (addition of the alkoxy group (4) (c) if necessary) Human =, the silk-based money is modified on the end of the poly-wei oil, and the di-mercapto-decane is modified (d). Then, the following steps are carried out as the basis of the production step, namely alkoxy oxalate (a) (The visual acuity is obtained by the alkoxylation (1)), and the obtained in the production step (1), and the addition of water to the alkoxylated calcined modified body (4) is carried out in the same manner as in the above, and the production method (2) &gt; ° ^ The manufacturing method (2) is by alkylation Method of the substance (E): ''Making the block type 14 201207043 First, the step of performing the alkoxy group is carried out as the step of the production step (7): #1 from the direction to the base stone (c)) ^ p alkoxy Shi Xiyuan (a) (additional oxygen is added as needed to obtain intramolecular water to carry out hydrolysis and condensation reaction of alkoxy groups with each other, and then to carry out an oxy double (house. The alcohol-based polysulfide oxygen, rrb is used as the production step (1): the reaction is carried out by the reaction of the terminal with a half-time operation and the halophilic (° reaction. The residual alkoxy group and the sterol group are removed. Alcohol condensation <Manufacturing method (3)&gt; The manufacturing method f = _ morphological compound (E) side:: The block type oxime oxygen generation first b is produced by the following method: for the production step (1) , by the need of a poly(alkyl group) at the end, and the alkoxy oxime compound, alkoxy decane (a) (depending on the added oxy group Wc), is subjected to dealcoholization condensation, and the end is subjected to oxygen burning. The base stone court was upgraded to form the hospital, and then the water was added to the system, and the method was used to sell the water. . In the following steps: in the present invention, it is shortened by the hydrolysis reaction of the oxy group (a) (oxygen (1)) and the alkoxy group (d) From the viewpoint of the production step, it is preferred to use the above production method (2) in which the reaction is gradually carried out by a one-pot method. ‘.·· Hereinafter, the manufacturing method (3) will be described more specifically. When the reaction is carried out by the one-pot method, if the reaction is carried out in the reverse order of the above-mentioned production method (c), that is, the manufacturing step (1) is carried out after the manufacturing step (1) of 15 201207043 as in the production method (2), The oxy-octogenated oligo-oligomer formed by the step-by-step method is not incompatible with the poly-coin. In the subsequent manufacturing step (1), the alcohol-free condensation is not carried out, and the unreacted polysulfuric acid residue remains. The possibility is higher. The other party is: if the method of manufacturing step (2) is carried out by a crane method as in the manufacturing method (3), then the polyoxygen oil (b) and the oxygenated money (1) or alkoxylate are used. The compatibility of the base stone (1) is relatively high, so that the problem of incompatibility as described above without reacting can be avoided. Further, since the low molecular alkoxydecane which does not undergo a condensation reaction with the alkoxy austenite is present in a large amount with respect to the sterol group, it is also preferable from the viewpoint of reactivity. The manufacturing step 〇) in the case where the reaction is carried out by the one-pot method is referred to as the second-stage reaction, and the production step (2) is referred to as the second-stage reaction, which is first performed in the first-stage reaction (manufacturing step (1) In the)), the polyoxyxane oil (b) and the alkoxy decane (a) (addition of the alkoxy decane as needed (the dealcoholization condensation of cd causes the alkoxy sulfonyl group to be modified at the end of the polyoxyxanic oil) The alkoxydecane modified product (d) is obtained. Since no water is added in the first-stage reaction, hydrolysis and condensation of the alkoxy groups are not caused, and 3 equivalents or more are used with respect to 1 equivalent of the sterol group. When the alkoxy group is reacted, the alkoxydecane modified body (d) is considered to have a structure represented by the following formula (6).

(6) In the formula (6), r2 and m represent the same meaning as described above, and r5 represents X or R3 in the above 16 201207043.

Re is represented by the case where Rs is the above X, and R4 is represented when Rs is the above L. In the first-stage reaction, if the alkoxy group is reacted in an amount of less than 1.0 equivalent based on the oxime oxime equivalent, the alkoxy group is not present at the end of the second-stage reaction, so the second alkoxy group is not introduced. In the stage reaction, if the alkoxy group is reacted in an amount of from 1.0 to 1.5 equivalents, two or more of the alkoxydecane (a) (alkoxydecane (c) to be added) The alkoxy group reacts with the sterol group of the polyoxyxane oil (b), and at the end of the reaction at the second stage, it becomes a polymer and gelatinizes. Therefore, it is necessary to carry out the reaction with respect to the sterol group 1 and to make the alkoxy group in an amount of 1.5 equivalent or more. From the viewpoint of controlling the reaction, it is preferably 2 〇 or more, more preferably 3 〇 equivalent or more. After the completion of the reaction in the hydrazine stage, the second-stage reaction is carried out (in the production step, water is directly added to carry out hydrolysis and condensation of the alkoxy groups. In the reaction in the stage, the following (I) to (III) are produced. Step (2)), and, in the first reaction. (I) The alkoxy groups of the alkoxydecane (a) (optionally added alkoxydecane (c)) remaining in the system are condensed with each other. (Π) condensation of the alkoxydecane modified body (d) obtained in the first-stage reaction with the alkoxy group of the alkanoyldecane (a) (optionally added alkoxydecane (c)) reaction. (ΙΠ) a portion of the alkoxydecane modified product obtained in the first-stage reaction (with the alkoxydecane (a) (added alkoxy 17 201207043 decane (c )) as required in (1) The condensation reaction of the alkoxy groups of the condensate. In the second-stage reaction, the above reaction is produced in a composite manner, the formation of the sesquiterpene gas-fired fragment, and further, the bond-like polystone derived from the polysulfate The condensation of the oxy-oxygen moiety is carried out simultaneously. The production of the block-type oxoxane compound (E) can also be carried out without a catalyst, but if the reaction is not carried out slowly, the reaction time is shortened. It is preferably carried out in the presence of a catalyst. It can be used as a catalyst which can be used as an acidic or basic compound. Examples of the compound which exhibits acidity (acidic catalyst) can be exemplified by hydrochloric acid. An inorganic acid such as sulfuric acid or acid, or an organic acid such as citric acid, acetic acid or oxalic acid. Further, as an example of a compound exhibiting inertness (basic catalyst), sodium hydroxide, potassium oxynitride, lithium hydroxide or hydrogen can be used. An alkali metal hydroxide such as cerium oxide, An inorganic base such as an alkali metal carbonate such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate, ammonia, triethylamine, diamethylenetriamine, or butyl is a worker, 丞月女, dimethylhydrazine An organic base such as triethanolamine or tetradecyl ammonium hydroxide. In particular, it is easy to remove the catalyst from the product, and the weight is to be a base, particularly preferably sodium hydroxide or potassium hydroxide. The total amount of the catalyst added is usually from 1 to 75 〇·01 to 5% by weight based on the total weight of the alkoxy decane (a) (and optionally condensed (c)) in the reaction system. c)) The weight of the alkoxylated oxime added. /. ' is preferably or is, *f i at this time, as described above,

The addition method of the catalyst is carried out in a direct addition, a solvent such as a solvent, and is unilaterally dissolved in the condensation of decyl alcohol and ethanol 18 201207043 decane (a) (addition of alkoxy decane (c) as needed). The sesquiterpene oxide oligomer thus formed may be incompatible with polyoxyxane oil (匕) to cause white turbidity. The production of the oxime-type oxane compound (E) can be carried out without a solvent or in a solvent. Further, a solvent may be added in the middle of the production step. The solvent in the case of using a solvent is a mixture of an alkoxy group (4) (1) (alkoxydecane (c) added as needed), a polyoxyxane (b), an alkoxy decane (d), a mixture, There are no special restrictions. As such a solvent, for example, methylcaramine, dimethylacetamide or tetrahydrogen can be exemplified. Aprotic polar solvents such as ketone, such as methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone, are derived from 'acetic acid B', acetic acid butyl vinegar, lactic acid ethyl acetate, and butyric acid isopropyl alcohol. Such as vinegars such as 曱 _, ethanol, propanol, butanol and other alcohols, hexane, cyclohexane, toluene, hydrocarbons such as dioxane. In the present invention, from the viewpoint of controlling the reaction, t is preferably a reaction in an alcohol, more preferably decyl alcohol or ethanol. If the amount of the solvent used is smoothly carried out in the reaction (4), then the benefit (4) limits 'relative to the oxy group (4) (a) (and the smoldering base stone (c) added as needed), polyoxime oil The total weight part of the compound of (b) is usually about 0 to 900 parts by weight. The reaction temperature depends on the amount of the catalyst, but it is usually 2G to 16Gt, preferably 4G to i4Qt, and particularly preferably 5 to 15 generations. The reaction time is usually in each manufacturing step. It is preferably 5 to 30 hours. After the reaction is completed, the catalyst is removed by quenching and/or water washing as needed. When water washing is carried out, it is preferred to add a bathing agent to the water knife depending on the kind of the solvent to be used. Preferred examples of the solvent include methyl ketone 19 201207043 ketone, keto isobutyl ketone, and ketones such as cyclopentanone, ethyl acetate, butyl acetate, ethyl lactate, and isopropyl butyrate. Equivalent esters, hydrocarbons such as hexane, cyclohexane, hydrazine, xylene, and the like. In this reaction, the catalyst can be removed only by washing with water. However, since the reaction is carried out under any conditions of acidic or qualitative conditions, it is preferably subjected to quenching by a neutralization reaction, followed by water washing, or use. After the adsorbent adsorbs the catalyst, the adsorbent is removed by the reaction. If it is an acidic or basic compound, it can be used for the neutralization reaction. Examples of the compound which exhibits acidity include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as capric acid, acetic acid, and grass mash. Further, as an example of a compound showing basicity, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide or hydroxide can be used, sodium carbonate, potassium carbonate, sodium hydrogencarbonate or hydrogen carbonate. An alkali metal carbonate such as potassium, an inorganic base such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, polyphosphoric acid or sodium tripolyphosphate, ammonia 'triethylamine, two extensions An organic base such as ethylenetriamine, n-butylamine, dinonylamine ethanol, triethanolamine or tetramethylammonium hydroxide. In the case of the ruthenium or the like, in particular, from the viewpoint of easy removal from the product, it is preferably an inorganic test or an inorganic acid, and more preferably a phosphate which is more easily adjusted to the vicinity of neutrality. Examples of the adsorbent include activated clay, activated carbon, zeolite, inorganic/organic synthetic adsorbent, and ion exchange resin. Specific examples thereof include the following products. As the activated clay, for example, activated clay SA35, SA Bu T, R_15, E, Nikkante G-36, G_153, 20 201207043 G-168 manufactured by Toshinaga Chemical Co., Ltd., Galleon made by Mizusawa Industrial Chemicals Co., Ltd. Earth, Mizuka Ace, etc. As the activated carbon, for example, CL, Y, FC, DP, SA1000, K, A, manufactured by Ajinomoto Fine-Techno Co., Ltd., CL-H, Y-1 OS, Y-1OSF, Futamura Chemical Co., Ltd. KA, M, CW13 0BR, CW130AR, GM130A, etc. Examples of the zeolite include Molecular Sieve 3A, 4A, 5A, and 13X manufactured by Union Showa. Examples of the synthetic adsorbent include Kyoward 100, 200, 300, 400, 500, 600, 700, 1000, 2000 manufactured by Kyowa Chemical Co., Ltd., or Amberlystl 5 JWET, 15DRY, 16 WET, 31 WET manufactured by Röhm & A21 'Amberlite IRA400JCM, IRA403BLC IRA404JC1, or Dowex66, HCR-S, HCR-W2, MAC-3, etc. manufactured by Dow Chemical Company. The adsorbent is added to the reaction liquid, and is subjected to a treatment such as stirring or heating. After the catalyst is adsorbed, the adsorbent is filtered, and the residue is washed with water, whereby the catalyst and the adsorbent can be removed. After completion of the reaction or after quenching, in addition to washing with water and filtration, it may be purified by a conventional separation and purification method. As the purification method, for example, a column chromatography method, a concentration under reduced pressure, distillation, extraction, or the like can be used. These purification methods may be carried out singly or in combination of plural kinds. ^When the reaction is carried out using a solvent mixed with water as a reaction solvent, = the reaction enthalpy mixed with water is removed from the system by steaming or concentration under reduced pressure after quenching, and then water and water are used. The separated solvent is washed with water. After the good washing, the solvent is removed by concentration under reduced pressure or the like, whereby a block 21 201207043 type oxoxane compound (E) can be obtained. The block type siloxane compound (E) obtained in the above manner is usually in the form of a liquid which is colorless and transparent and has fluidity at 25 °C. Further, the molecular weight thereof is preferably from 8 〇〇 to 20,000 1,000 to 10,000, and the weight average molecular weight is 800 or less in terms of the weight average molecular weight measured by GPC, and there is a possibility that the heat resistance is lowered. When the temperature is 20,000 or more, the viscosity rises and the workability is adversely affected. ' Weight average molecular weight is a polystyrene-equivalent weight average molecular weight (Μ*) measured by GPC (gel permeation chromatography) under the following conditions. Manufacturer: Shimadzu Pipeline: Protection column SHODEX GPC LF-GLF-m c 3 roots) Flow rate · 1 · 〇rn 1 / mi η · Column temperature: 4 〇. (: Solvent used: THF (tetrahydrofuran) detector · RI (differential refraction detector) and epoxy equivalent of '4 block type Oxygen compound (E) (determined by the method described in Xenopus 7236) Preferably, it is 3〇〇~丨, the cap (10) is more preferably 4〇0~1, _1, especially preferably 450~900 g/eq. The epoxy equivalent is less than 300 g/eq, and there is The hardened material is hard, and the elastic modulus becomes too late. When it is more than L600 g/eq, the mechanical properties of the cured product tend to deteriorate, so it is not preferable. 22 201207043 The viscosity of the segmented siloxane compound (E) (E-type viscosity meter, measured at 25 C) is preferably 5 〇 2 〇〇〇〇 mpa · s, more preferably $ (10) ~ lO'OOOmPa.s 'Specially good is 800 to 5 〇〇〇 mPa.s. When the viscosity is 5 〇 mPa· s X at the clear/on time, there is a possibility that the viscosity is too low and it is not suitable for use as an optical semiconductor sealing material. In the case of _mpa·s or more, there is a case where the viscosity is too high and the workability is poor. The block of the block/stone compound (8) is derived from the bond of the sesquitertes. The ratio of the three daisy's Shi Xi atom to all the Shi Xi atom is better: two: 8 to 30 mol%, especially good... Moer %. If the source ratio is 5 ^ key ^ in 3 The oxygen-free ceremonial atom tends to be too soft in the hardened material with respect to all of the ceremonial atoms, and if it is 50 mol% or more, the surface is wrinkled or damaged. The hardened material becomes too hard, so欠 又 又 又 又 又 又 又 又 又 又 又 所 所 所 所 所 所 所 所 所 所 所 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 特征 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Carboxyl group and χ 'compound: at least two corpses and U aliphatic hydrocarbon-based polybasic acid include not only a single one. In the present invention, the position of the substituent is different, or the compound of the acid compound is also included. The compound is a polybasic acid-reducing composition, and a polycarboxylic acid of a plurality of compounds. In the middle of the month, these are collectively referred to as polybasic decanoic acid (Β), particularly preferably 2 to 6~ acid (Β) if carbon If the number is small, then the solidified acid is also the enemy acid. The polycarboxylic acid ~ 曰 strong 'as a sealing material, 23 201207043 Since the property is lowered, it is preferably a compound obtained by a reaction of a hydroxyl group having a carbon number of <2 to 6 functional groups and an acid anhydride. When the carbon number is 4 or more, the workability can be ensured as a Miller'. From the viewpoint of durability, in order to improve the heat resistance, it is preferable that the above-mentioned acid is a polycarboxylic acid which is a saturated aliphatic cyclic acid anhydride. Diversified brewing, ο Φ ^ a. Intoxicated/, is an alcoholic compound having an alcoholic hydroxyl group, and is not particularly limited, \ j 幻 罕 . 6 _ alcohol, propylene glycol, 丨 3 · propylene glycol, 1, 2 _butanediol, t 4 1 - drunk I5 · pentyl leaven, 1,6-hexanediol, hexane hexane dimethanol, 2 4- - 7 a 丄, Λ ▲, monoethylpentyl fermentation, 2- Ethyl 2, butyl, ι, 3 propylene glycol, neopentyl glycol, tricyclic hydrazine __田# 二醇 a clothing, alkane-methyl fermentation, diol and other glycols, propylene glycol, trishydroxyl Ethyl ethane, tri-&amp;methanine, trimethyl butyl ketone, 2- thiol-1,4-butanediol, etc. = % with meter s ^ , pentaerythritol, di-trishydroxyl Methylpropane-conducting tetraols, dipentaerythritol and other hexaols . Particularly preferred alcohols are alcohols having a carbon number of s μ ^ times double horses, in particular 1,6-hexanediol, 1,4-hexane-methanol, 1,3_j hexane hexanediol, I, 〗  Cyclohexane dimercaptan, 2, : ethyl decanediol, 2-ethyl I butyl-U propylene glycol, neopentyl glycol, Sanzhi · 癸 曱 曱 、 、 降A compound such as an alcohol (n〇rb〇rnene diol) is preferred, and in view of imparting stagnation resistance, soil resistance, and maintaining a high illuminance retention rate, the fee &lt;go me 9 7 # 2 is more preferably 2-ethyl 2 -butyl-U-propanediol, neopentyl glycol, diethyl decanediol, 1,4-cyclohexane dimethanol, tricyclodecane dimethanol, human alcohol An alcohol having a branched structure or a cyclic structure. As an acid needle, it is specifically an I mtj Λ a methyl phthalate, a methyl phthalic anhydride, a methyl sulphate, a sulphuric acid anhydride, a squid, a scorpion Benzoic anhydride, methylhexahydrophthalic acid, butane tetracarboxylic anhydride, hydrazine "9 % 1_2, 2, 1] heptane 2, 3 - dicarboxylic anhydride, methyl 24 201207043 Bicyclo[2,2,1]heptane_2 3_dicarboxymethane 巳 巳 三 tricarboxylic acid _ι, 2-needle, etc., 'Methylhexahydrophthalic acid needle, cyclohexene appearance', 2,4_tri-hyal acid-1,2-anhydride is preferred because of high transparency. The addition reaction material is not specifically specified, but specifically One of the reaction conditions is a method in which the polyol is reacted under a condition of no catalyst or solvent, and is reacted at 40 to 1 Torr 5 Torr C, and is heated immediately after the completion of the reaction. However, it is not limited thereto. The present reaction conditions. As the polyacid to be obtained in the above manner, a compound represented by the following formula (7) is particularly preferred:

(7) In the formula, a plurality of Qs represent a hydrogen atom, a methyl group, or a carboxyl group; and P is a chain-like, cyclic aliphatic group derived from the above polyol having a carbon number of 2 to 20 Em is the functional group number of the polyol, which is an integer of 2 to 6 in the horse. The curable resin composition of the invention preferably contains an acid needle. The viscosity as a hardener can be arbitrarily adjusted by including I. =Acidate' specific examples: o-benzene di-acid needle, stupid triacid needle, tetra-two:: two-needle, cis-butane diacid needle, four-gas phthalate needle, f-dicarboxylic anhydride, methyl-resistant Geoanhydride, phthalic anhydride, hexahydroortylene 25 201207043 dicarboxylic acid needle, methyl hexahydro phthalic acid wild, butyl (tetra) acid needle. [2,2,1]^^-2,3-needle, ring院院-1,2,4-three enemy Jun], 2·anhydride and so on. Particularly preferred are methyltetrahydrophthalic acid anhydride, methyl benzoic acid anhydride, hexahydrophthalic acid, methyl hexahydrophthalic acid, needle bicyclic carboxylic acid, and tetrabutyl sulfonate. , double ring [2, 2, 1] geological appearance _2, 3 · two resouric anhydride 'mercapto double ring [2, m Gengyuan-2, 3_: m acid needle: ring hexadium ΐ 52, 4 _ three enemy acid _ I2_ rape and so on. Particularly preferred is hexahydro-o-p- phthalic acid anhydride represented by the following formula (8), fluorenyl hexahydro-o-indole phthalic anhydride, and cyclohexanone hydrazine. 4 _ Lower | Human 疋 1,2,4-dicarboxylic acid ", 2 - anhydride, wherein decyl hexahydro phthalic acid is folded, cyclohexene], 2, tri-hyal acid _u2_ needle is better because of transparency :

When the methyl group and the base are used at least in combination (Z in the formula represents one or more hydrogen atoms). The polycarboxylic acid (B) and the acid anhydride are preferably used in combination, and the use ratio thereof is preferably in the following range. WJ/(W1 + W2)=〇.〇5^〇.65 In the middle, the weight of the W1 main-equipment 不 兀 carboxylic acid (B), the acid Xuan's tone tongue @八2表矛- Seriously hurt. As the range of W 〗 / (WI + W2), it is estimated to be ~0.65, #占* Λ 闽 佳 佳 4 O.Oi is better than 0.10~〇65, especially good is 〇3~ Right is 〇.〇5 to 26 201207043 The next 'in the hardening of the acid anhydride when the discovery of the eve of the night ... ..., the higher two = (four) 'is therefore poor. Anhydride (except for the case where a small amount remains, it is difficult to handle it. In the case of no shape or near solid form, or crystallization, = the shape becomes a solid day without problems. 'When using multiple (four) (8) and acid ox, operate In terms of simplicity, it is produced in an excess of an acid anhydride in the production of a polycarboxylic acid (B), and a method of reading the acid (B) and an acid anhydride is also preferred. The curable resin composition of the present invention is a metal complex (C). "Organic metal salts and / or organic as organic metal salts and / or organic metals are wrong in Shao, Meng, iron, Shi, Jin, steel, and m. Metals are used as the above organic metal salts and / or money metal. T: 2-ethylhexanoic acid &quot;, 2-ethylhexylethylhexanoate, ethyl 2-hexanoate, 2-ethylhexanoic acid, 2-ethylhexanoic acid steel, 2-ethylhexyl Acidic, _ 2-ethylhexanoic acid, tin 2-ethylhexanoate, 2-ethylhexanoic acid ship, Huanyuan 醆 New, Γ Γ 酸 acid, ring iron acid, ring burning acid drill, ring Hyun acid record, · ring acid copper, (four) acid word, Huanyuan acid error, cyclodextrin tin, Huanji acid record, hard acetic acid, hard manganese, hard iron acetate, hard _ ancient, hard nickel acetate, Hard vinegar, steel, hard S, acid, stone, acetic acid, acid, tin, hard g, acid, zinc, bay, zinc, twenty-six acid, four-character, four-word, brown, zinc, meat Ugly, sour, brown, sour, ring acid, #酸酸,辛酸辞^ Aluminium-acetamidineacetate complex, manganese_acetamidineacetate complex, iron-acetamidineacetate complex -Acetylpyrene complex, nickel·acetamidineacetate complex, copper-acetamidineacetate complex, zinc· Acetylacetone complex, zinc (2-ethylhexyl) zinc malt= 27 201207043 Tin-acetamidineacetate complex, lead-acetamidine, oxime-acetophenone complex, ketone mismatch Here, the corrosion-resistant 泠/style button is given to the singularity of the singularity, 5, preferably zinc salt and/or zinc 516, specifically 2_ethylhexyl zinc, Phosphoric acid (2-ethylhexyl) zinc complex and / Λ. Λ ρ ,, .. times 1 hard know I zinc, undecylenic acid lauric acid words, two 4 ~ 々-^ - several - knock Zinc, zinc 12-hydroxystearate, zinc montanate, zinc myristate, yttrium, yttrium zinc, zinc naphthenate, zinc hexanoate, zinc octoate. More preferably, it is a zinc complex of 2_ethylhexanoate, a wall bismuth (2-ethylhexyl) and/or a salt thereof, zinc hard acid, and zinc decanoate, considering transparency, A zinc complex of zinc 2-ethylhexanoate or bismuth (2-ethylhexyl) and/or a salt thereof is preferred. As such a commercially available product, Zn-St,

Zn-ST, 602, Zn-St' NZ, ZS-3, ZS-6, ZS-8, ZS-7, ZS-lo, ZS-5, ZS-14, ZS-16 (made by Nitto Chemical Industrial Co., Ltd.), χΚ_614 (by 叩

Made by Industries), ΐ8〇/. Then ctope ζη, 12% of Octope Ζη, 8% of Octope Ζη (made by Hope Chemical), as a phosphate ester and/or a zinc phosphate body, may be exemplified by LBT-2000B (manufactured by SC Organic Chemicals), XC-9206 (King) Made by Industries). Here, the ratio of the organometallic salt and/or the organometallic complex (C) is from 0. 01 to 8 wt%, more preferably from 0.05 to 5 by weight based on the organopolyoxane (A). The weight % is more preferably 0.1 to 4% by weight. Further, it is particularly preferably 0 · 1 to 2% by weight. The curable resin composition of the present invention contains a light stabilizer (D). The light stabilizer (D) is preferably a compound represented by the following formula (1). 28 201207043 (1) X "〇JL0—x2 VIII I, X2 are the same or different, and the alkyl group, the aryl group, the aryl group have a carbon number of two atoms, a carbon number of 1 to 50, or a structural formula ( 2), X1 horse 1 ~ base aryl ' at least - the structural formula (2):

(2) In the above formula, an oxygen atom is bonded. Base, alkoxy group. Wherein, the structural formula (2) # Ψ ^ ; is at the * mark and the formula (1) and the 'Y table is not a nitrogen atom, the nitrate age c rv ^ is an alkyl group having an inverse number of 1 to 50, and the aryl is a formula ( 1) Preferred specific examples of the compound shown are: The structural formula (2) of the hydrogen atom is set to X(2,6,6-tetramethylpiperidin-4-yl) of X丨 and χ2. Carbonate, the structural formula (2) of Υ = fluorenyl group is set to Χ| and X2 double (1,2,2,6,6-pentamethyl-based base-4-yl) carbonate The structural formula (2) of γ = propoxy is set to bis(2,2,6,6-tetradecyl-propoxypiperidin-4-yl) carbonate of Χι and I, and Y = undecane The structural formula (2) of the oxy group is a diindole-undecyloxy-2,2,6,6-tetradecylpiperidine-4·yl)carbonate of the substituents Χι and X2, and Y=曱The structural formula (2) is Χι and the third pentyloxy group is set to X2, 1,2,2,6,6-pentamethylenepiperidin-4-yl-tert-amylcarbonyl. 29 201207043 Oxyacid Ester and the like. As a particularly preferable compound, the structural formula (2) in which γ = undecyloxy group is a substituent Χ| and bismuth (1 - undecyloxytetramethyl succinyl) is exemplified. Carbonic acid. Here, the ratio of the light stabilizer (D) is 0.005 to 5% by weight, more preferably 〇〇丨4 to 4% by weight, still more preferably 0.1 to 2 by weight based on the weight of the organopolyoxane (A). weight%. When the ratio of the light stabilizer (D) is less than 0.005% by weight based on the organopolysiloxane (A), the effect of improving light resistance is insufficient. On the other hand, when it is more than 5% by weight, the cured resin is colored to cause a decrease in illuminance, which is not preferable. The light stabilizer (D) can be used to significantly enhance the cured resin by using it in combination with the organopolyoxane (A), the polycarboxylic acid (B), and the organometallic salt and/or the organometallic complex (c). The characteristics, in particular, as the organic metal salt and/or the organometallic complex (C), preferably a zinc salt and/or a zinc complex, as the light stabilizer (D), preferably a biguanide_ten Monoalkoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate is preferably used in combination. The reason for this is that when it is used in the above-described combination, it is excellent in light resistance and heat resistance, is hard to be colored by light or heat, and is excellent in corrosion resistance gas. The light stabilizer (D) may also be used in combination with other light stabilizers. As a light stabilizer which can be used, for example, tetrakis(12,2,6,6•pentamethyl-4 piperazine) 1, 2,3,4·butane tetracarboxylic acid vinegar, four (2) , 2,M•Tetramethyl-heartpiperidinyl)=1,2,3,4-butane tetracarboxylate, hydrazine, 2,3,4•butanetetracarboxylic acid and pentamethyl-4- Mixed esterified product of piperidinol and 3,9-bis(2-hydroxy], indenyldiethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, azelaic acid 30 201207043 (2,2,6,6-tetradecyl-4-pylon) adipic acid ester, mercaptopropionic acid 2,2,6,6-tetradecyl-4-piperidinyl lipid, Bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate Ester, 4-phenylhydrazineoxy-2,2,6,6-tetramethylpiperidine, 1-[2-[3-(3,5-di-t-butyl-4-hydroxyphenyl) Propyloxy]ethyl]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoxy]-2,2,6,6-tetradecyl Pyridinium, 1,2,2,6,6-pentamethyl-4-piperidinyl-mercaptoacrylate 'malonate bis(1,2,2,6,6-pentamethylene-4-piperidine) ()[[3,5-bis(l5l-didecylethyl)-4-hydroxyphenyl]indolyl]butyl ester, azelaic acid bis(2,2,6,6_four -1(octyloxy)-4-piperidinyl) ester; 1, 1, dimethyl-ethyl hydroxyhydroperoxide and cincinating reaction product, hydrazine, hydrazine, hydrazine, |, hydrazine, -tetrakis-(4,6-bis(butyl-(N-methyl-2,2,6'6-tetradecylpiperidine-4-yl)amino)_三〇井_2_ base) 4,7-diazadecane-ι, ι〇-diamine, dibutylamino _13 5_三〇井_N,N,• bis(2,2,6,6 tetradecyl-dehydropiperidinyl a poly(1,6-hexanediamine) complex with N_(2,2,6,6-tetradecyl-4-pyridinyl)butylamine, poly[[6-(1,1,3,3) _ tetradecyl butyl)amino-1,3,5-trisole-2,4-diyl][(2,2,6_6-tetradecyl-4-piperidinyl)imido] Amidino [(2,2,6,6-tetradecyl-4-piperidyl)imino]], dimethyl succinate and 4-hydroxy-mb tetradecyl 丨 哌 piperidine ethanol Polymer, 2,2,4,4-tetradecyl-20-(0-dodecanelacylcarbyl)ethyl-7-oxa-3,20-diazadispiro[5,1,11 , 2] behenyl 21 ketone cold. Alanine, 〜(2,2,6,6-tetradecyl-4-piperidyl)-dodecyl ester / tetradecyl ester, N-ethyl fluorenyl _3 ·Dodecanetetramethyl-4(piperidinyl)pyrrolidine-2,5-dione, 2,2,4,4-tetradecyl-7-oxalate-3,2-diazide disulfide [5 , 1,11,2]hexadecane_21•ketone, 2 2,4 4•tetramethyl_21•oxadiazepine pepper_[5,1,1 1,2]-fecosane_ 2〇_D-propionate/tetradecyl ester, malonic acid-[(cardiomethylphenyl)-indenyl]•bis(丨,2,2,6,6•pentamethyl_4· Piperidinyl) 31 201207043 Ester, 2,2,6'6-tetraf-based higher fatty acid esters such as decyl alcohol', 3_ abbreviated amine 'N,N-double (2,2,6,6 - tetramethyl- 4-pyro-based group, etc. hindered galenic, diphenyl fluorene compound such as octanone, 2_(2H_benzotriene). Sitting _2 base) ice (1,1 3 tetramethylbutyl) benzene, 2_(2. thiol-5-methylphenyl) benzotris, hydrazino, 4, 5, 6. Hydrogen o-xylylene imine·methyl)_5_methylbenzoic acid. Sitting, 2. (3-tert-butyl.2_hydroxy_5•methylphenyl)·5' is stupid and three. Sitting, 2-(2-carbyl-3,5•di-p-pentylphenyl) is stupid. Sit, Jiayi 3: (3-(2Η-本开三嗤_2_yl)·5·t-butyl-(p-phenyl)propionic acid to produce polyethylene glycol reaction product ' 2·( 2Η·benzotriene. Sit·2_base)_6_dodecyl·4_methylphenol and other benzodiazole-based compounds '2, di-t-butylphenyl group_3,5_ first butyl_4 Benzoic acid esters such as -hydroxybenzoic acid esters, two well systems such as 2_(4,6·diphenyl-Ι'3'5·three wells_2_yl)_5_[(hexyl)oxy]benzene When the curable resin composition of the present invention is used for an optical material, particularly a photo-semiconductor encapsulant, a particularly preferred component is a phosphorus-based compound containing an antioxidant material. The compound is not particularly limited, and examples thereof include: 'mono(2methyl-4-monotridecylphosphite_5_t-butylphenyl)butane,-stearylsulfonium pentaerythritol II Yadis vinegar 'bis(2,4_di-t-butanthyl)-pivalaerythritol diphosphite, bis(2,6·di-t-butyl-4-methyl-based) quaternary tetraol Diar yuric acid, phenyl double expectant pentaerythritol di arsenic acid &quot;t hexyl pentaerythritol II Phosphite, tris(diethylphenyl)phosphite = tris(di-isopropylphenyl) phosphite, tris(di-n-butylphenyl) phosphite, first phosphite , 4_di-t-butylphenyl) ester, tris(2,6-di-butylphenyl)phosphoric acid, tris(2,6-di-t-butylphenyl) SI phosphite ' 2,2,- 32 201207043 Amidino bis (4'6-a. second butyl styl) (2,4_di-t-butylphenyl)-parite η鲅酉曰, 2,2 - Yttrium-bis(4,6-di-t-butylphenyl]-t-butyl-4-mercaptophenyl) sub-acidic acid, 2,2,_-indenyl bis (4_曱Base_6_t-butylphenyl)(2-t-butyl-4-methylphenyl)phosphite, 2,2,-ethylenebis(4-fluorenyl-6-t-butyl Stupid base) (2_t-butyl-4-yl-nonylphenyl) phosphite, tetrakis(2,4-one-t-butylphenyl)·4,4,·biphenyl diphosphoric acid Ester, tetrakis(2,4-mono-t-butylphenyl)·4,3,_biphenyl diphosphite, tetrakis(2,4-di-t-butylphenyl)_3,3' - extended biphenyl diphosphite, tetrakis(2,6-di-t-butylphenyl)-4,4'-extended biphenyl diphosphorus Acid ester, tetrakis(2,6-di-t-butylphenyl)-4,3'-extended stearyl diphosphite, tetrakis(2,6-di-t-butylphenyl)-3 , 3'-Exbiphenyl bisphosphite, bis(2,4-di-tert-butylphenyl)_4_phenyl-phenyl phosphite, bis(2,4-di-t-butyl Phenyl)-3-phenyl-phenyl sub-allate, bis(2,6-di-n-butylphenyl)_3_phenyl-phenylphosphite, bis(2,6-di- Tributylphenyl)_4_phenyl-phenylphosphite, bis(2,6-di-t-butylphenyl)-3-phenyl-phenylphosphite, tetra (2,4- Di-t-butyl-5-mercaptophenyl)-4,4'-extended biphenyl diphosphite, tributyl phosphate, tridecyl phosphate, tridecyl phosphate, phosphoric acid Phenyl ester, tristearyl phosphate, triethyl phosphate, diphenylphosphonium phosphate, mono-o-phenyl diphenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate Ester, dioctyl phosphate, diisopropyl phosphate, and the like.

A commercially available product can be used for the above phosphorus compound. The commercially available phosphorus-based compound is not particularly limited, and examples thereof include: ADEKASTAB manufactured by Adeka

PEP-4C, ADEKASTAB PEP-8, ADEKASTAB PEP-24G, ADEKASTAB PEP-36, ADEKASTAB HP-10, ADEKASTAB 33 201207043 2112, ADEKASTAB 260 'ADEKASTAB 522A, ADEKASTAB 1178, ADEKASTAB 1500 'ADEKASTAB C, ADEKASTAB 135A, ADEKASTAB 3010, ADEKASTAB TPP. Here, the ratio of the phosphide is 0.005 to 5% by weight, more preferably 0.001 to 4% by weight, still more preferably 〇2 to 2% by weight, based on the weight of the organopolysiloxane (A). The curable resin composition of the present invention contains an organic polysiloxane (A) as an epoxy resin, a polycarboxylic acid (B) as a curing agent, an organic metal salt as an additive, and/or an organic metal complex (c). And the light stabilizer (d), as an essential component, contains an acid anhydride as a curing agent and an antioxidant as an additive as a preferable optional component, and these may be used in combination with other epoxy resins, hardeners, and various additives. In the oxyresin, the organopolyoxane (A) may be used singly or in combination with other epoxy resins. When used in combination, the organopolysiloxane (A) accounts for all of the epoxy resin. The ratio is preferably 6% by weight or more, particularly preferably 70% by weight or more. As another epoxy resin which can be used in combination with the organic polysiloxane (A), a novolac type epoxy resin 'bisphenol A Epoxy resin 'Lianbu ^ ring resin, triptycene type decene type epoxy resin, phenol aralkyl type epoxy 4 grease, etc. Specific examples include: double A, double bismuth s, sulfur Two hopes, although double anticipating diphenols, 4,4'-biphenol, 2,2 -biphenol, 3,3,5,5'-tetramethyl i-stupid]-4,4·-diol, p-diphenol, isophthalic acid, cage_不一一' three- (4 -i base group) decane, hydrazine, 2,2-tetrakis(4-hydroxyphenyl)ethane phenols (phenols, alkyl substituted phenols, naphthols, alkyl substituted naphthols, — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — Dilutex, hydrazine, 4,4, _ bis (gas methyl) 丨, biphenyl, 4, 4, _ bis (methoxy yl) 丨, 匕 biphenyl, 1,4- bis (gas a polycondensate of methyl)benzene, bismuth-bis[methoxymethyl)benzene, and the like, and a modified bisphenol, such as a bisphenol bisphenol, a glycidyl derivative derived from an alcohol. , glycidylamine-based epoxy resin, alicyclic core, resin, glycidol vinegar-based epoxy resin, sesquiterate, epoxy tree, sapphire (in chain, ring, ladder, or such An arm having at least two or more mixed-dissolved W-oxygen I structures having a glycidyl group and/or an epoxy ring-burning structure: The liquid or liquid epoxy resin is not limited to these. The "Xi Temple" can be used alone or in combination of two or more. ^ The curable resin composition of the present invention is used for optical purposes and for optical use. In the case of a lipocyclic ring, it is preferred to use it together. When used in combination with an alicyclic epoxy resin, it is preferred that the compound having an epoxy ring structure in the bone 1 is: An epoxy resin obtained by emulsification reaction of cyclohexane with θ θ 4 as an epoxidized epoxy resin, which can be exemplified by an esterification anti-corridor of a carboxylic acid and an alcohol. Cyclohexene rTf , % hex # methanol and several acids of the reductive anti-godling et-v〇丨·36ρ 24〇9 (198 (a) reaction Ρ · 4475 (1980) and other methods described in the edron Letter reaction Special (five) ΝΟΒ-ΠΟ. "No.: hexene hexazone 2_-262871" in the middle of the μ, / /, Japanese patent special ... exchange reaction (method described in the method described in this patent) oxidation of the compound _ = 7 on the bulletin, etc. Illustrator 35 201207043 is not particularly limited as long as it is a compound having an alcoholic hydroxyl group. τ Lists ethylene glycol, propylene glycol, U3_propylene glycol, butyl diol, and 1 '4 butyl alcohol 丨, 5_ Pentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, n-ethylpentyl glycol, 2-ethyl-2-butyl-1,3·propylene glycol, neopentyl glycol, tricyclic a diol such as decane dimethanol or a diol, a glycerol or the like, glycerol, trishydroxy ethane dimethylolpropane, trishydroxybutane, 2-hydroxymethyl-1,4-butanediol Examples include diols, tetraols such as pentaerythritol 'di-trimethylolpropane, and the like. In addition, : carboxylic acid, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid 'cyclohexane dicarboxylic acid, etc., but not limited In these. Further, an acetal compound obtained by a reaction of a cyclohexenal derivative with an acetal of an alcohol may be mentioned. Specific examples of such epoxy resins include ERL_422丨' UVR-6105 and ERL-4299 (all of which are trade names, all manufactured by D〇w Chemical), CELL〇XIDE 2021Ρ' EP〇LEAD GT4〇1. EHpE3i5〇, EHPE3150CE (all are trade names, all manufactured by Xinyi Chemical Industry) and: Dicyclopentadiene oxide, etc., but not limited to this reference, General Principles of Epoxy Resin, Basic Section I, p 7 6 _ 8 5 ). These may be used singly or in combination of two or more kinds as a curing agent. The polycarboxylic acid (B) may be used alone or in combination with an acid anhydride, or may be used in combination with other curing agents. In the case where the polybasic acid compound (8) is used together with The ratio of the total amount of the acid if to the total amount of the hardener is preferably 30% by weight or more, particularly preferably 4% by weight. the above. Amine-based compound and acid As the curing agent which can be used in combination, for example, 36 i 201207043 ^ compound, a guanamine compound, a phenol compound, or a carboxylic acid compound =. Specific examples of the hardener which can be used include amines or polyamidoximes (by diaminobenzophenone, diethylenetriamine, tri-ethylidene, and amino groups). Diphenyl sulfone, isophorone diamine, dicyanodiamine, linoleic acid dimer and polyamidene resin synthesized by stretching ethyl diamine, etc.) 'Anthraquinone anhydride and polyfluorene oxide system Alcohol reactants (o-dodecanoic anhydride, benzoic anhydride anhydride pyrofluoric acid dianhydride, maleic anhydride, tetrahydrophthalic anhydride methyltetrahydrophthalic anhydride, thiol resistance Geoanhydride, benzoic acid anhydride, hydrazine hydrogen o-benzoic anhydride, mercapto hexahydrophthalic anhydride, butane tetracarboxylic anhydride, bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, Anthracene bicyclo[m]heptane=, 3-diphthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and the like, and methanol-modified polyoxyl alcohol Class of reactants, etc.); polyphenols (bisphenol A, phenol F, double hope S, double g points, blessing g, 4, 4, _ cumbersome, 2, 2, _ _ _ § '3,3,5,5'-tetramethyl·(1) widebiphenyl]·4,4,_diol, hydroquinone, m-phenol phenol, di- (4-hydroxyphenyl)decane, mi tetra(4-hydroxyphenyl)ethane, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, two Hydroxynaphthalene, etc.) with furfural, acetaldehyde, benzoquinone, p-butyric acid, o-benzyl benzoyl, p-acetophenone, o-decyl acetophenone, dicyclopentadiene, furfural , 4,4, · bis (gas sulfhydryl) _ 丨, broad as benzene 4,4 _ bis (decyloxymethylbiphenyl, 1,4,-bis (gas methyl) benzene, two 4-double ( a polycondensate of methoxymethyl)benzene or the like, and a modified substance thereof, a functionalized bisphenol such as tetrabromoX phenolphthalein, a condensate of styrene and a phenol; and other compounds (imidazole, boron difluoride) - an amine complex, an anthracene derivative, etc.), etc., but not limited to these. These may be used alone or in combination of two or more. 37 201207043 In the curable resin composition of the present invention, it is preferably used. The compounding ratio of the organopolyoxane (A) to the above-mentioned polybasic acid (.&quot; hardener] is 1 equivalent to the organic polysulfide, and the number of functional groups in the polybasic acid (1) is 〇.7 U s amount Particularly preferred is 〇-75~hl() equivalent. When the amount of the functional group in the polybasic acid (8) is less than 〇·7 equivalent relative to the epoxy group I, the hardness is more than Κ2 equivalent. Incompletely, the possibility of obtaining a good hardening property is not obtained. In the curable resin composition of the present invention, the organometallic salt and/or the organometallic complex (c) as an essential component directly exhibits the function of the hardening catalyst. However, other curing catalysts may not be added, but other curing catalysts may be used in combination. As a specific example of a curing accelerator which can be used, exemplified are: 2_ mercapthylimid, 2-phenyl oxazole, and 2-undecyl imidazole. 2_heptadecylimidazole, 2·pyridyl-4-mercaptoimidazole 'benzyl-2-phenylimidazole, 丨_knotyl-2-methylimidazole, cyanoethyl-2-methylimidazole, cyanide Ethyl-2-phenylimene. Sitting '丨Cyanoethyl·2_ eleven imidazole, 2,4-diamino _6 (2,_methylimidazolium ethyl tributary well, 2,4-diamino-6 (2'-ten一基咪.Sit (丨,)) Ethyl·Equivalent three tillage, 2,4•diamino-6(2'-ethyl-4-methylimidazo(1,))ethyl_all three wells , 2 4 diamino group · 6 (2, · methyl. m. sitting 〇 ')) ethyl - three tillage _ iso-cyanuric acid adduct, 2 • mercapto imidazole isocyanuric acid 2 : 3 adduct, 2-phenylimidazolium isocyanurate adduct, 2·styl-3,5-dimethylolimidazole, 2-phenylhydroxymethyl-5-methylimidazole, 1 - various imidazoles of Hethyl-2-phenyl- 3,5-dicyanoethoxy decyl imidazole, and the imidazoles and o-didecanoic acid, isophthalic acid, terephthalic acid , benzene trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, maleic acid, grass 38 201207043 acid and other salts of polybasic acids, decylamine such as dicyandiamide, 1,8· a salt of diazabiguanide (.4.0), a diazonium compound, and a salt such as a tetraphenylphosphonic acid I phenol phenolic lacquer, and a salt of the above polycarboxylic acid or phosphinic acid Base ammonium, Molybdenum cetyl trimethylammonium, desertification trioctylmethyl recording and other salt, diphenyl lin, three (A * wake base) Lin, Xihua four stupid base, ® phenyl # tetraphenyl a phosphine or a phosphonium such as a rotten acid salt, a metal compound such as a phenolic 'amine adduct' such as tin octylate such as 2,4,6-triaminemethylphenol, or the like, and the like accelerator is formed into a microcapsule Chengzhi microcapsule type hardening accelerator and the like. Which of the hardening accelerators such as hai is used is appropriately selected depending on characteristics required for the transparent resin composition obtained by, for example, transparency, curing speed, operating conditions, etc. The hardening catalyst is used in relation to the epoxy tree. The weight-of-weight suspension is used in the range of 001 to 15 parts by weight. The hardening resin composition of this month may be added with the following various additives: additives, auxiliary materials, for example, added in two liquids. In some cases, it may be added to either or both of the organopolyoxane (A) and the polycarboxylic acid (B), and the organopolyoxane (A) may be mixed with the polycarboxylic acid (B). The curable resin composition of the present invention may further contain a phosphorus-containing compound as a component imparting flame retardancy. The phosphorus-containing compound may be a reactive type, or a = addition type. For example, trimethyl phosphite, triethyl phosphate, trimethyl stearyl phosphate, tris(diphenyl) phosphate, bismuth diphenyl phosphate, bismuth phosphate 2,6 _二(二曱笨基) =, i, 3- extension base double (phosphoric acid ( Phosphonic acid such as phenyl phenyl) ester, hydrazine, 4 phenylene bis(phosphonium hydride), 4,4·-biphenyl (di(diphenyl) phosphate) 39 201207043 Ester; 9,1 0-dihydro-9-oxa-1 - phenanthroline-1 〇-oxide 〇 (2 $ dipyridyl)-1 Ο Η - 9 - oxa-1 0 - a phenanthrene such as a phenanthrene-1 0-oxide; a disc-containing epoxy compound obtained by reacting an epoxy resin with an active hydrogen of the above phosphine; a red phosphorus or the like; preferably a phosphate ester, a phosphine or a phosphorus-containing epoxy compound, particularly preferably a 1,3-phenylene bis(di(diphenyl) vinegar), an anthracene, a 4-phenylene bis(diphenylene phosphate), 4,4'·biphenyl (phosphoric acid) or phosphorus-containing epoxy compound. The content of the filler-containing compound is preferably phosphorus-containing compound/epoxy resin=0·1~0.6 (weight ratio) If it is less than 〇1, the flame retardancy is insufficient, and if it exceeds 0.6, there is a possibility that the hygroscopic property and dielectric properties of the cured product are adversely affected. Further, the curable resin composition of the present invention In the middle, the adhesive resin can also be blended as needed. Examples of the binder resin include butyral resin, acetal resin, acrylic resin, and epoxy-nylon resin NBR (Nitrile-Butadiene Rubber) _ phenol resin, epoxy _NBR resin, and poly The amide-based resin, the polyamidene-based resin, the polyfluorene-based resin, and the like are not limited thereto. The blending amount of the adhesive resin is preferably in the range of the flame retardancy and heat resistance of the hardened product, as opposed to The curable resin component 'm 〇〇 by weight is usually used in an amount of 0.05 to 5 parts by weight, preferably 5 to 20 parts by weight. In the curable resin composition of the present invention, inorganic filling may be added as needed. Agent. Examples of the inorganic filler include crystalline 11 stone, (4) Shi Xi stone, oxidized Shao, wrong stone, Shixi acid mother, carbonated carbon, carbonized stone, nitrided stone, nitrided stone, oxidized, and forsterite. a powder such as a block talc, a spinel, a dioxins, or a talc, or a granule formed by spheroidizing, etc., but is not limited to 40 201207043 in: and the like. "The filler material may be used singly or in combination of two or more. §Hay and other inorganic fillers will be produced; 彳*h from "3,3% of the curable resin used in the present invention 〇~95% by weight The amount. Further, in the curable resin composition of the present invention, (four) coupling agent, hard s acid, brown money, hard brewed acid,

Hard s Calcium acid isolating agent, various pigments such as pigments, various types of thermal grease. J. When the curable resin composition of the present invention is used for an optical material, particularly a photo-semiconductor encapsulant, by using the inorganic filler material used as described above, the particle diameter is a nano-level filler material, and does not inhibit Improves mechanical strength and the like by transparency. The standard of the nano level is preferably a filler having an average particle diameter of 5 () () or less from the viewpoint of transparency, and particularly preferably a filler having an average particle diameter of 2 Å or less. θ When the curable resin composition of the present invention is used for an optical material, particularly a calender semiconductor encapsulant, a phosphor may be added as needed. Fluorescent systems, for example, have the effect of forming white light by absorbing a portion of the blue light emitted from the blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in the curable resin composition in advance, the photo-semiconductor is sealed. The f-light body is not particularly limited, and a conventionally known phosphor can be used, for example, a rare earth element acid salt, a thiogallium salt, or a protoporate. Specifically, it can be listed as YAG (Yttrium aluminum garnet) phosphor, TAG (labium aluminumgarnet) phosphor, ortho phthalate phosphor, thiogallate sulfate Phosphors such as a light body and a sulfide phosphor may also be υαι〇3 : Ce, Y3Al5〇12 : Ce, γ4Αΐ2〇9 : Ce, Y2〇2S : Eu, 41 201207043

Sr5(P04)3Cl : Eu, (SrEu)O . A1丨2〇3 and the like. The particle diameter of the above-mentioned phosphor is a particle diameter known in the art, and the average particle diameter is preferably from 1 to 2 5 〇 M m, particularly preferably from 2 to 50 M m. In the case of using these phosphors, the amount thereof is from i to 8 parts by weight, preferably from 5 to 60 parts by weight, based on 00 parts by weight of the above resin component. When the curable resin composition of the present invention is used for an optical material, particularly a photo-semiconductor encapsulant, in order to prevent various phosphors from sinking during hardening, a fine powder of cerium oxide (also referred to as AER0SIL) may be added. Or AEROSOL) is a representative of the shake-induced imparting agent. As such a fine powder of the oxidized oxidized stone, for example, AEROSIL 50, AEROSIL 90, AER0SIL 130, AEROSIL 200, AEROSIL 300, AEROSIL 380, AEROSIL 0X50, AEROSIL TT600, AEROSIL R972, AEROSIL R974, AEROSIL R202, AEROSIL R8 12 , AEROSIL R812S, AEROSIL R805, RY200, RX200 (manufactured by AEROSIL). The curable resin composition of the present invention may contain a phenolic compound as an antioxidant material. The phenol compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-nonylphenol and n-octadecyl_3_(3,5-di-t-butyl-4- Hydroxyphenyl)propionate, tetrakis[methylene·3·(3 5_di-t-butyl-4-hydroxyphenyl)propionate]methane, 2,4-di-t-butyl _ 6-methylphenol, hydrazine, 6-hexanediol-bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris(3,5-di- Third butyl-4-hydroxybenzyl)-isocyanate, hydrazine, 3,5-trimethyl-2,4,6-di(3,5·di-t-butyl-4- Hydroxybenzyl)benzene, pentaerythritol-tetrakis[3_(3,5-di-t-butyl-4-phenylphenyl)propionate]' 3,9-bis-[2-[3-(3 - Third butyl 42 201207043 -4-hydroxy-5-nonylphenyl)-propenyloxy]-1,1-dimercaptoethyl]-2,4,8,10-tetraoxaspiro[5 , 5] undecane, triethylene glycol-bis[3-(3·t-butyl-5-indenyl-4-hydroxyphenyl)propionate], 2,2'-butylene bis (4 ,6-di-t-butylphenol), 4,4·-butylidene bis(3-indolyl-6-tert-butylphenol), 2,2·-indenylene bis(4-indenyl- 6-tert-butylphenol), 2,2'-arylene di(4- -6-tert-butylphenol), 2-t-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenol acrylate, 2- [1-(2-Hydroxy-3,5-di-third-pentylphenyl)ethyl]-4,6-di-third-pentyl phenyl acrylate, 4,4'-thiobis (3 - mercapto-6-tert-butylphenol), 4,4·-butylenebis(3-mercapto-6-tert-butylphenol), 2-tert-butyl-4-nonylphenol, 2 , 4-di-t-butyl phenol, 2,4-di-third pentyl phenol, 4,4'-thiobis(3-mercapto-6-tert-butyl phenol), 4 , 4·-butylidene bis(3-methyl-6-tert-butylphenol), bis-[3,3-bis-(4·-hydroxy-3, tert-butylphenyl)-butyric acid] - ethylene glycol ester, 2,4-di-tert-butylphenol, hydrazine, 4-di-third amyl phenol, 2-[1-(2-hydroxy-3,5-di-third pentyl) Phenyl)ethyl]-4,6-di-third amyl phenyl acrylate, bis-[3,3-bis-(4^hydroxy-3^th-butylphenyl)-butyric acid]- Ethylene glycol ester and the like.

Commercially available products can also be used as the phenolic compound. The commercially available phenolic compound is not particularly limited, and examples thereof include: IRGANOX 1070, IRGANOX 1 035, IRGANOX 1076 'IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114, IRGANOX 1098, IRGANOX manufactured by Ciba Specialty Chemicals. 1520L, AdekaSTAB AO-20, ADEKASTAB AO-30, ADEKASTAB AO-40 &gt; manufactured by Adeka ADEKASTAB AO-50, ADEKASTAB AO-60, ADEKASTAB AO-70 'ADEKASTAB AO-80 ' ADEKASTAB &amp; 43 201207043 AO-90, ADEKASTAB AO-330, Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, etc. manufactured by Sumitomo Chemical Industries. In addition, a commercially available additive may be used as the anti-coloring agent for the resin. For example, TINUVIN 328 manufactured by Ciba Specialty Chemicals may be mentioned.

TINUVIN234, TINUVIN326, TINUVIN120, TINUVIN477, TINUVIN479' CHIMASSORB2020FDL' CHIMASSORB 119FL, etc. In the case where the above phenolic compound is added, it is limited to a weight of 5 to 5 相对 with respect to the curable resin composition of the present invention. /. The scope. In the curable resin composition of the present invention, the curable resin composition of the present invention is obtained by uniformly mixing σ with each component, and the cured product can be easily formed by the same method as the previously known method. For example, the curable resin composition of the present invention, other epoxy resin, hardener, and, if necessary, a hardening accelerator: an phosphorus-containing compound, bonding, using an extruder, a kneader, a roll, a planetary mixer, etc., as needed. Resin, inorganic filler, and preparation agent = a knife-n to a uniform sentence to obtain a curable resin composition, and when the obtained curable resin composition of the above (4) is in a liquid state, it is poured or washed to make it Immersed in a substrate [or into a mold, into a mold, etc., and then hardened by heating: the hardenability of the obtained invention can be listed as (4) and then cast, cut _ ' Α ^ &amp; or The film is formed by a transfer molding machine or the like, and is hardened by heating. The degree and time are 80 to 44 201207043 00 C, 2 to 10 hours. As the hardening method, it is preferable to make it quick to raise the temperature at a high temperature to carry out a hardening reaction. Specifically, the initial hardening is performed between 80 and 150 C, and is in the range of l〇〇 ° C to 200. (: Post-hardening is carried out. As the stage of hardening, it is preferable to carry out the temperature increase in 2 to 8 stages, more preferably 2 to 4 stages. Further, the hardening resin composition of the present invention is dissolved in a stupid, Composition of sclerotic dendritic quinone in a solvent such as xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, monodecyl acetamide or N-methylpyrrolidone The varnish is impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamine fiber, oxidized |g fiber, paper, etc., and dried by heating to obtain a preform. The preform is hot pressed into a preform. The towel can thereby form a cured product of the curable resin composition of the present invention. In this case, the solvent is usually used in a mixture of the curable resin composition of the present invention and the solvent in an amount of 10 to 70% by weight, preferably The amount of 〇/〇 15 〜 。 。 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又The curable resin composition is used as a film type seal When the film-type resin composition is obtained, first, the curable resin composition of the present invention is applied to the release film as the above-mentioned clear, and after the solvent is removed by heating, the process proceeds to the B stage. This sheet-like adhesive is used as an interlayer insulating layer of a multilayer substrate or the like, and is packaged by an optical semiconductor. The hardening resin composition of the present invention is used as a sealing material or a paste of an optical semiconductor. The case of the crystal material is described in detail. 45 201207043 When the curable resin composition of the present invention is used as a sealing material or a spot material of a high-intensity white LED or the like, by using an organic polyfluorene (A) , polycarboxylic acid (b), right her · organic metal salt and / or organometallic s (C), light stabilizer (〇), depending on the above epoxy resin, hardener, coupling The additive such as a material, an antioxidant, a light stabilizer, or the like is prepared by "making a hardening resin composition" to form a sealing material or for both a die-bonding material and a sealing material. The 怍 von mixing method uses a kneader, a three-roller, a universal mixer, a planetary mixer, a homogenous mixer, a uniform disperser, and a bead mill to mix at room temperature or under heating. It is still subject to the white LED and other main roads -^ The special 7L parts of the special cattle are usually made of adhesive.

(Crystalline material) GaAs, Gap 'Ga A1 Δ ο ^ A laminated on a substrate such as sapphire, spinel, sic, sl, zn0

OaAlAs^ GaAsP, AlGa&gt;InP&gt; GaN ^ (10), Am, InGaN # semiconductor wafer is formed on the lead frame, the demon plate, and the package. Due to the circulation of electricity, there is also a type in which gold wires are connected. In order to prevent the hot gas or moisture from damaging the semiconductor crystal, the lens is subjected to lens work &amp; and the sealing material is sealed with an epoxy resin or the like. : The curable resin composition of the invention can be used as the above-mentioned sealing material or die-bonding material. In terms of the step, it is preferred to use the curable resin composition of the present invention for both the die-bonding material and the sealing material. As a method of adhering a semiconductor wafer to a substrate using the curable resin composition of the present invention, the curable resin composition of the present invention can be applied by a dispenser, infusion, or screen printing, and the semiconductor wafer is placed and processed. Heat hardened' followed by a semiconductor wafer. For heating, hot air loop type, infrared line, south frequency, etc. can be used. 46 201207043 The heating condition is, for example, preferably 8 〇 to 23 〇. 〇, i minutes ~ hour or so to reduce the internal stress generated during heat curing, for example, after pre-hardening under conditions of 80~1 20 〇C 30 minutes ~ 5 hours, at 1 20~1 80 c 30 / knife Subsequent hardening under conditions of ~1 〇 hours. - as a molding method of the sealing material, a method of injecting a sealing material into a mold frame of a substrate on which a semiconductor wafer is inserted in the insertion port, and then heat-hardening and molding the same; The material 'a compression molding method in which a semiconductor wafer fixed on a substrate is immersed and hardened, and released from a mold. Examples of the injection method include a dispenser, transfer molding, injection molding, etc. Heating can be performed by a method such as hot air loop type, infrared ray, or high frequency. The heating condition is preferably, for example, 8 〇 to 23 〇 t, i. Minutes ~ Μ hours or so. To reduce the internal stress generated during heat hardening, for example, after pre-hardening at 80 to 120 °, 30 minutes to 5 hours, at (10) ~ 18 CTC, 30 minutes ~ 1 ( The subsequent hardening is carried out under the conditions of an hour. The H-monthly composition of the present month can be used for the usual use of a curable resin such as an epoxy resin, for example, an adhesive, a coating, a coating agent, a molding material (for example) Including sheets, films, FRP (fiber reinforced plastics, Fiber Wee's as (four), etc.), insulating materials (including printed substrates, wire coatings, etc.), and other sealing materials, may also be listed as sealing materials, substrate with ester resin Additives such as additives for other resins such as acrylic acid vinegar-based resins that are resistant to (four) and hardeners, etc. For construction, automotive, and general use as an adhesive agent, except for civil engineering 47 201207043 In addition to the ll therapeutic adhesive, an adhesive for an electronic material may be used. In the case of "Using Xuan et al." as an adhesive for electronic materials, τ exemplifies an interlayer adhesive of a multilayer substrate such as a build-up substrate, an adhesive, an underfill. Semiconductor adhesive, BGA (Ball Grid Array, BallGrid Array) reinforcing underfill, anisotropic conductive film (ACF, AniS0tr0pic c〇nductive

Fllm), an adhesive for mounting such as an anisotropic conductive paste (ACP), and the like. Examples of the sealant include a capacitor, a transistor, a diode, a light-emitting diode, and an ic (integrated circuit, Iniegrated circui, (3) (large scale integrated circuit, Large Scale Integrati〇n), etc. Transfer molding, IC or LSI (7)B (Chip Board), COF (Chip 〇n Film), ΤΑβ (Tape Automated B〇nding), etc. The underfill used for the potted sealed flip chip, etc., QFp (square is a flat package,

Quad Hat Package), BGA and csp (wafer size package, to 仏

Package" Seals for IC package mounting (including underfill for reinforcement), etc. The cured product obtained by the present invention can be used for various purposes represented by optical member materials. The so-called optical material 'usually refers to the visible light 'infrared, Ultraviolet rays, X-rays, lasers, etc., which are used for the purpose of passing through the material. More specifically, in addition to LED sealing materials such as lamp type and SMD (Surhce Mount Devices) type, The liquid crystal display of the substrate material, the light guide plate, the cymbal sheet, the deflecting plate, the phase difference plate, the viewing angle correction film, and the liquid crystal film such as the polarizing film The material surrounding the device. (4) The sealing material of the color pDp (P1_a Disp丨ay Panel) as a lower-generation flat panel display, the anti-reflection film optical correction film, the outer casing material, the protective film of the front glassy soil, The front glass replaces the material and the subsequent agent', and the LED molding material used for the LED display device, the LED "sealing material, the front glass" The protective film, the front glass substitute material, and the adhesive agent, and the substrate material in the pALc display liquid crystal (PALc) display, the light guide plate prism sheet, the deflecting plate, the phase difference plate, the viewing angle correction film, The adhesive, the polarizer protective film, and the 胄EL (electrically emitted...lectr〇)

LumiTM) The front glass protective film, the front glass replacement material, and the adhesive, as well as various film substrates in the field emission display (coffee, ^mission Dlsplay), the front glass protective film, the face glass replacement material , adhesive. In the field of optical recording, VD (CD) CD/CD-ROM, CD_R/RW, dvd_r/Dvd ram, m〇/md, PD (phase-kCD), optical disc substrate material, CD-ROM reading Take lens, protective film, sealing material, adhesive, etc. In the field of optical devices, a lens material for a static camera, a viewfinder prism, a target mirror, a viewfinder cover, and a light receiving sensor portion can be cited. Further, a camera lens and a viewfinder of a camera can be cited. For example, a projection lens, a protective film, a sealing material, an adhesive, and the like of the projective television can be cited. Examples of X's include a lens material for a light sensing device, a sealing material, an adhesive, a film, and the like. In the field of optical members, a fiber material, a lens, a waveguide, a sealing material for an element, an adhesive, and the like in the vicinity of an optical switch in an optical communication system can be cited. In addition, it can be listed as a ferrule, a sealing material, an adhesive, etc. for the optical fiber material around the optical connector. Examples of the passive member and the optical circuit member include a lens, a &lt; guide, a led ‘, a LY material CCD (charge coupled device) sealing material, an adhesive, and the like. Further, examples thereof include a sealing material, an adhesive, and the like of a substrate material fiber material member around a photoelectron integrated circuit (〇E) C, Optoel Ectronic lntegmed (5) (4). In the field of optical fibers, there are various types of sensors, such as sensors and light guides for industrial use, such as sensors and light guides for industrial use, and digital displays for communication infrastructure and home use. Among the materials surrounding the semiconductor integrated circuit, a resist material for a microetching technique for a super LSI material can be cited. In the automotive · :: machine field ' 彳 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车Drive engine, brake oil tank 'Automotive anti-iron; Interior trim, interior material, protection and end harness, fuel hose, and = glass substitute... The multi-layer glass for railway vehicles can be cited. ° List the structural toughness of the aircraft to give the protection and protection of the society. Bundle, corrosion resistant sleeve. In the field of construction, it can be processed materials, lampshades, gentlemen, + ^ * 4, glass interlayer film, glass substitutes, solar cell peripheral materials. On the way to the Japanese-made purple, the film for house coating can be cited. The edge-and-electron-functional organic material can be cited as an organic £L element month: material.:: machine light-refracting element, light amplification as a light-to-light conversion device: material light-emitting element, substrate material around the organic solar cell, Fiber Wei: Shake the 'sealing material, adhesive, etc.'. The present invention will be described in more detail by way of Synthesis Examples and Examples. Further, the present invention is not limited to the above-described synthesis examples and examples. Further, each physical property value in the examples was measured by the following method. (1) Molecular weight: It was measured by a gel permeation chromatography (GPC, Gel Permeation Chi^matograph) under the following conditions and subjected to polystyrene exchange to give a weight average molecular weight. Various conditions of GPC: Manufacturer: Shimadzu Manufacturing Column: Protection column SHODEX GPC LF-GLF-804 (3) Flow rate 1.1 · 〇 m 1 / m i η

Column temperature: 40 ° C Solvent used: THF (tetrahydrofuran) Detector: RI (differential refractive index detector) (2) Epoxy equivalent: Measured by the method described in JIS k_7236. (3) Viscosity: The E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd. was used at 25. The present invention will be described in more detail by way of Synthesis Examples and Examples. In the synthesis examples and examples, "parts" means parts by weight, and "%" means % by weight. EXAMPLES Synthesis Example 1 As a reaction of the first stage, 4 parts of no-(3,4-epoxycyclohexyl)ethyltrimethoxyacetate U, and a weight average molecular weight of 17 GG (Gpc measured value) 234 phenyl phenyl polyaminium & 234 parts (base equivalent: 51 201207043 850, calculated as one-half of the weight average molecular weight measured by GPC), 0.5% potassium argon oxide (KOH) methanol solution 18 parts (The fraction of KOH was 0.09 parts) was added to the reaction vessel, and the temperature was raised to 75 ° C, and the temperature was raised. After the temperature was raised, the reaction was carried out for 8 hours under reflux. As the second-stage reaction, 305 parts of sterol was added and passed. 86.4 parts of a 50% distilled water sterol solution was added dropwise over 60 minutes, and the reaction was carried out under reflux at 751: for 8 hours. After the reaction was completed, the mixture was neutralized with a 5% aqueous solution of sodium hydrogen hydride, and then methanol was taken at 80 ° C. Distillation recovery. Add methyl isobutyl ketone (Μ IB K ) 380 parts 'repeated water wash 3 times. Then By removing the solvent from the organic phase at 100 ° C under reduced pressure, an organic poly-glycol compound (A - 1 ) 3 3 3 parts having a reactive functional group is obtained. The equivalent weight was 677 g/eq, the weight average molecular weight was 2,200, and the appearance was colorless and transparent. Synthesis Example 2 As the first-stage reaction, s-(3,4-epoxycyclohexyl)ethyltrimethoxy oxalate 257 was used. The weight average molecular weight is 17 〇〇 (GPC measured value), and the fluorenyl phenyl fluorene oil at the end of the phenolic alcohol group is 5 〇 5 parts (the sterol group equivalent is 5 Å, which is calculated as the weight average measured by GPC). 40 parts of the molecular weight of -), 0.5 〇 / 〇 of potassium hydroxide (1 &lt;: 〇 1 ^) methanol solution (1 &lt;: 〇] &quot; [parts of 0.2 parts) was added to the reaction vessel, The bath temperature was set to 75. The temperature was raised. After the temperature was raised, the reaction was carried out for 8 hours under reflux. As the second stage reaction, after adding 5 parts of decyl alcohol, a 50% distillation solution of methanol was added dropwise after 6 minutes. 1 30 parts, reacting at 75 ° C for 8 hours under reflux. After the end of the reaction 'utilizing 5% aqueous sodium dihydrogen phosphate solution 52 201207043 After that, methanol recovery was carried out at 8 (TC). 704 parts of methyl isobutyl _ (ΜIBK) were added, and washed three times with water. Then, by decompression at 100 ° (3 times for organic phase) In addition to the solvent, 663 parts of an organic polyoxo compound (Α-2) having a reactive functional group was obtained. The obtained compound had an epoxy equivalent of 659 g/eq and a weight average molecular weight of 2370. Colorless and transparent. Synthesis Example 3. In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, while performing nitrogen purge on the surface, 20 parts of tricyclodecanedioxanol and methyl hexanitrophthalic anhydride (new hydrazine) were added. 100 parts of this physicochemical (RIKACID MH, hereinafter referred to as anhydride Η]), reacted at 40 ° C for 3 hours, and then heated and stirred at 7 (rc for 1 hour), thereby obtaining (by GPC) It was confirmed that the disappearance of tricyclodecane dimethanol (1 area% or less) 1 20 parts of the hardener composition (τ-1) containing the polycarboxylic acid benzoic acid f Η 1, ', -). The obtained helmet was obtained from the color liquid resin n + ^ in terms of the purity measured by GPC, and the polycarboxylic acid v - 1 t was used. , eight (9)) is 55 area%, and methylhexahydrogen is two blocks of 45 area. /. . — Τ Ω phthalic anhydride ’ S is equivalent to 201 g/eq. Formula (9)

C9) Synthesis Example 4 53 201207043 In a flask equipped with a stirrer and a reflux cooling tube 'stirring device, / 2,4-diethylpentanediol 2 〇 part, acid needle (H-1) was added while flushing with a nitrogen gas. 100 parts, after reacting at 4 (rc for 3 hours, at 7 Torr., heating and stirring for 1 hour under the arm, thereby obtaining (the disappearance of 2,4-ethylpentanediol by GPC (1 area) % or less)) 2 parts of hardener composition (τ_2 ) containing polybasic decanoic acid (6_2) and acid bismuth (H-7). The obtained product is a variegated wave resin, and the purity is measured by GPC. The polyvalent carboxylic acid (B_2; the following formula (10)) was 50% by area, the acid anhydride (H-fluorene) was 5 Å area%, and the functional group equivalent was 201 g/eq.

(10) Example 1, Comparative Example 1, 2 The organopolysiloxane compound (A_丨) obtained in Synthesis Example 1 was used as an epoxy resin, and the hardener composition obtained in Synthesis Example 3 was used. (The ratio of the organopolysiloxane (A) to the hardener composition (B) is 1:0.8 based on the functional group equivalent). As the hardener, the zinc salt (zinc complex) is used (XC-manufactured by Nanben Chemical Co., Ltd.) 9206, hereinafter referred to as 匕丨) as an organometallic complex, using bis(1-undecyloxy-2,2,6,6-tetramethylpiperidine-4-yl)carbonated deer (made by Adeka) ADEKASTABLA-81, hereinafter referred to as ο"), bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (TINUVIN770DF' by Ciba Japan hereinafter referred to as D_2) 'double &amp; Octyloxy-2,2 6 6tetramethyl 54 201207043 -4-piperidinyl) (TINUVIN123, hereinafter referred to as D-3) is used as a light stabilizer, using 4,4, butylene bis ( 3 - mercapto-6-t-butylphenyl-di-tridecyl phosphite) (ADEKASTAB 260 ', manufactured by Adeka hereinafter referred to as E_丨) as a phosphorus-based compound of an antioxidant, in the following manner Match ratio shown Parts by weight) for 20 minutes formulations and defoaming, to obtain the present invention or the curable resin composition for comparison of. Example 2, Comparative Example 3, 4 The organopolysiloxane compound (A-2) obtained in Synthesis Example 2 was used as the epoxy resin' using the hardener composition (τ-2) obtained in Synthesis Example 4 (organic The ratio of the polyoxygen (A) to the hardener composition (b) is 1:0.8 as the hardening agent's use of the zinc salt (zinc complex X Hope)

18% of 〇 〇 〇 Zn manufactured by Chemical, hereinafter referred to as C-2) as an organometallic complex' using bis(1-undecyloxy-2,2,6,6-tetradecylpiperidine -4-yl)carbonic acid vinegar (adekaSTAB LA-81 by Adeka 'hereinafter referred to as D-1), bismuth azelaic acid (2,2,6,6-tetradecyl-4-piperidinyl) Cool [Ciba Manufactured TINUVIN 770DF, hereinafter referred to as D_2), bis (7-octyl, 2,6,6 tetramethyl _4-Brigade. Fixed base) (TINUVIN 丨 23 manufactured by Ciba Japan, hereinafter referred to as D_3) as a light stabilizer, The compounding ratio (parts by weight) shown in the following Table 2 was blended and defoaming was carried out for 20 minutes to obtain a curable resin composition of the present invention or comparatively. (Heat resistance transmittance test) The obtained curable resin composition was gradually cast and molded on a test piece for 1"_L 1 20 CX for 1 hour to pre-harden the cast product at 1 50 C 3 The hardening was carried out under the conditions of an hour to obtain a test hard 55 201207043. The obtained cured product was subjected to a heat resistance transmittance test under the conditions described below and evaluated (the results are shown in Tables 1 and 2 below). Test conditions: Test conditions: at 80 °. (: oven placed 72 hr test piece size: thickness 〇 · 8 mm Evaluation conditions: measured by 400 ° nm transmittance by spectrophotometer. [Table 1] Example 1 Comparative Example 1 Comparative Example 2 Composition of organopolyoxane Α-1 - 100 100 100 __ hardener composition Τ-1 24 24 24 0.5 0.5 Organometallic salt and/or organometallic Compound C-1 0.5 Light stabilizer D-1 0.25 D-2 0.25 D-3 0.25 Hardening inhibitor Ε-1 0.25 0.25 0.25 Hardened physical permeability 400 η Initial 91.6 91.5 91.6 73.5 60.6 South temperature placed 77.5 [Table 2 ] Example 2 Comparative Example 3 Comparative Example 4 Organic Polyoxane A-2 100 100 100 Hardener Composition T-2 24 24 24 Organometallic Salt and/or Organometallic Complex C-2 0.3 0.3 0.3 Light Stabilizer D-1 0.25 D-2 0.25 D-3 0.25 Hardened property 400 nm initial transmittance 91.5 91.4 90.1 68.6 64.0 High-temperature placement 78.7 According to Examples 1 to 2 and Comparative Examples 1 to 4, the heat-resistant coloring property (heat-resistant transmittance test) of the curable resin composition of the present invention is known. Excellent (LED spot test) Filled in a syringe using the obtained curable resin composition' μ 56 201207043 Puncture type with a precision emission device for a wafer with a central emission wavelength of 465 (10) 5 mm square The cast-molded Led package was placed in a heating furnace, and hardened at 12 (rc for 1 hour) and then hardened at (10) for 3 hours to prepare an LED package. The lighting test was performed at 60 mA which was twice the rated current 3 () minus (acceleration test). The measurement was performed using an integrating sphere to measure the illumination rate before and after lighting 丨G (10) hours, and the average of 3 samples was recorded. 4, j value. The conditions of the sheep fine are as follows (the results are shown in Table 3 below). Lighting detailed conditions Luminous wavelength: 465 nm Driving method: fixed current mode, 6 〇 mA (lighting element rated current is 3 0 m A ) Drive environment: 85 ° C, 85% : Table 3]

According to the first embodiment and the comparison, it is understood that the curable resin composition of the present invention is excellent in illuminance retention. Comparative Examples 5 and 6 The organopolysiloxane compound (Α_ι) obtained by Synthesis Examples 1 and 2, 57 201207043 (A-2) was used as the epoxy resin, and (τ_丨) and (τ·2) were used as the hardening. a zinc salt (zinc complex) ("), ((ii))) as an organometallic complex, a quaternary scale salt (manufactured by Sakamoto Chemical Industry, hIShICOLIN PX4MP, hereinafter referred to as C-3) ϋ υ υ 光 υ 光 光 光 光 光 光 光 光 光 光 光 光 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为(Corrosion gas permeability test) The obtained curable resin composition was filled in a syringe and cast by a precision discharge device, and the surface of the wafer having an outer diameter of 5 mm square was 465 Å. The molded molded article was placed in a heating furnace, hardened at t20 t for 1 hour, and hardened at 50° C. for 3 hours to form a led package. Place the LED package in the abundance gas under the condition In the middle of the observation/sealing, the color change of the silver-plated lead frame part is shown in the following table. The results are shown in the following table. The test conditions: the sulfuric acid 2G% aqueous solution (when the sulfur component reacts with silver, it turns black). Knife contact method: the container of the aqueous ammonium sulfide solution and the above-mentioned coffee package are simultaneously present in the wide-mouth glass bottle, covered with a lid of the wide-mouth glass bottle, and the vulcanized ammonium sulfide gas is brought into contact with the led package under the condition of density= Corrosion determination: Observe the time when the lead frame inside the LED package turns black (so-called blackening), and judge that the longer the discoloration time is, the more excellent the corrosion resistance gas is. 58 201207043 The observation system is taken out and confirmed after ίο hours, evaluation The person who has no discoloration is referred to as 〇, and the person who is blackened is referred to as X. Table 4] Example 1 Example of real k 2 Comparative Example 5 Comparative Example 6 Composition of organopolyoxane A-1 100 100 A-2 100 100 Hardening Composition T-1 24 •24 T-2 24 24 Organometallic and/or organometallic complex C-1 0.5 C-2 0.3 (J-3 0.5 0 3 Light stabilizer D-1 0.25 0.25 0.25 0.25 Hardening inhibitor E-1 0.25 0.25 X 丨 化The ___ 丨〇 hardening resin composition was excellent in gas resistance according to Examples 1 to 2 and Comparative Example. Comparative Examples 7 and 8 The organopolysiloxane compound (A_1 ) obtained by Synthesis Example 2 was used. (A-2) As an epoxy resin, use (1)), as a curing agent, as a light stabilizer, use it as an antioxidant, or as a blending ratio (parts by weight) in Table 5, 2 The W-phase composition of the present invention or comparative use (light durability transmittance test) was obtained by defoaming for eight hours. Use the obtained curable resin composition to form a long-lasting scale. Test 59 201207043 On the mold for the test, 'Make the cast molded product at 12 °C °C x 1 , and then pre-harden the strip at 15 〇〇 CX fly I q left ^ y 'down stone... harden under 3 hours of conditions to obtain test sputum. The obtained cured product was evaluated for "permanentness = over-rate test" under the conditions described below (the results are shown in Table 5 below). Company: Conditional testing machine: SuperUVTester (Iwasaki Electric Co., Ltd. Limited test conditions: 60 mw/cm2 · nm ' 2〇〇hr Test piece size: thickness 0.8 mm Parity condition: Measurement of the transmission of 400 nm by spectrophotometer Rate. The rate of change is shown. [Table 5] Composition Stones h Organic Polyoxane Example 1 Example 2 Comparative Example 7 A-1 100 100 •— Hardener Composition A-2 100 100 Μ Sickle 24 94 24 Organometallic salt and / or organometallic complex Cl 0.5 0.5 24 C-2 0.3 0.3 No stabilizer Dl 0.25 0.25 Hardening inhibitor El 0.25 0.25 Physical properties 4 (8) nm initial transmittance according to 91.7 91.5 91.8 91.7 I. 90.3 90.9 86.5 85.4 It is understood that the curable resin composition of the present invention is excellent in light-resistant coloring property according to Examples 1 to 2 and Comparative Examples 7 to 8. The present invention has been described in detail with reference to specific examples, but it is understood by those skilled in the art without departing from the invention. In the case of the spirit and scope, various changes and amendments can be made. In addition, the application is based on the application for the application of the 2012 2012 patent application (Japanese Patent Application No. 2010-133745). In addition, all references cited are incorporated herein as a whole. [Simple description of the diagram] Benefits &lt; * »&gt; [Description of main component symbols] Benefit 61 201207043 Instruction Manual (This manual format, smooth, &amp; ' .^ 斤 May do not change anyway, please do not fill in the ※ mark)! //9 n /y 〇L ( Π C〇SL S}/〇〇(2006.01) Co^KS/oJz (2006.01) c °SK %^Γ(2 0?6.01) C〇SK HoiL^y^c, (2010.01) ※Application number: ※Application date: /Μ / ※Listing class I, Invention name: (Chinese / English) Sclerosing Resin composition and hardened material thereof II. Abstract of the Chinese invention: Ο

L. The object of the present invention is to provide a new type of hardenable tree-like structure which provides excellent light-resistant coloring property, heat-resistant coloring property, and corrosion-resistant gas barrier property. The curable resin composition of the present invention comprises Organic polyoxane (VIII), polybasic acid (8), organometallic salt and/or organometallic complex (), and light stabilizer (9), wherein the organic poly 11 oxidant (Α) and poly 70 carboxylic acid (Β), light stabilizer (D) satisfies the following conditions: , organic polyoxane (A): is at least in the molecule and has 瑷 &amp; 琢4俨p A 虱 propyl and / or latex hexyl organic Polyoxane polybasic acid (B): a compound having at least two fluorenyl groups and having a main skeleton Λ月9 aliphatic hydrocarbon group as a light stabilizer (Ε): a compound represented by the structural formula (1) 〇| — o—x 2 (1) , English abstract

Claims (1)

201207043 aryl, alkoxy)). 2. The sclerosing resin composition according to claim 1, which comprises a compound of the formula (2) wherein γ is a carbon number. Structural formula (1) owing to alkoxy group of 1 to 20 3. The composition of the curable resin as in the scope of the patent application No. ^, #., 1 or 2 is cut into 'the organic metal salt and /10', or Zinc complex. Or the organometallic complex (C) is a zinc salt and/or 4. The sclerosing tree moonprint composition of any one of the claims to the third aspect of the invention, wherein the structural formula (曰4 1 X2 is The structural formula (2), and the structural formula (2) is 〇 〇 : : : 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 酸酐 酸酐 酸酐 酸酐 酸酐 酸酐 酸酐 酸酐 酸酐6. The sclerosing tree is a composition of any one of the first to fifth aspects of the patent application, wherein the polycarboxylic acid 醅f β, ...α 兀殁驮 兀殁驮 (Β) is hunted by a carbon number of 5 The above 2~ό Β叱 Β叱 多元 与 与 与 与 与 * * * * * * 化合物 化合物 化合物 化合物 化合物 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. 7. The sclerosing tree composition of any one of the items of Item 6 contains an antioxidant. 8. - A hardened material which is a curable resin composition of the above-mentioned items in the scope of claims i to 7 Hardened. 63 201207043