TW201118134A - Curable resin composition and cured product thereof - Google Patents

Abstract

An objective of the invention is to provide a curable resin composition, providing a cured product excellent in optical properties such as the erosion resistance against the gas in the environment, resistance to heat coloring, or light extraction efficiency and so on. The curable resin composition of the invention takes polyorganosiloxane (A) and zinc salt and/or zinc complex (C) as the essential ingredients, wherein the polyorganosiloxane (A) satisfies the following criteria. The polyorganosiloxane (A) is an epoxy resin at least having glycidyl group and/or epoxy cyclohexyl in the molecule.

Description

201118134 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , A factory for optical semiconductor components such as products, which is a fat-based composition in terms of balance between performance and economy. Um "...called epoxy enamel for illusion wood, ..." is widely used for excellent balance of heat resistance, transparency, and mechanical properties. The epoxy propylene = fat composition represented by the "type epoxy resin". n% of the milk tree ',,, and the Ministry is pointed out that 'the short wavelength of the light-emitting wavelength of the LED product: the LED product that emits blue light is 48〇 fine), and the result is under the influence of short/long light. The sealing material is colored on the LED wafer, and finally the illuminance is reduced as an LED product. Therefore, 'Compared with the epoxy-propyl urethane epoxy resin composition having an aromatic ring, 3,4 -ί oxacyclohexylcarboxylic acid 3,4·epoxycyclohexyl ketone represents the ring epoxy resin Because it is excellent in transparency, it has been actively studied as (4) materials to be sealed (Patent Document No. 2, 2). λIn addition, in recent years, LED products have been promoted with high brightness due to illumination or τν backlights, and the LEDs are lit with a large amount of heat, so even the resin composition using the alicyclic epoxy resin is used. In the LED chip, coloring is also caused. Finally, the illuminance is lowered as an LED product, and there is a problem in terms of financial durability (Patent Document 3). Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 〇〇〇2〇〇〇_174347号 [Summary of the Invention] From the consideration of the durability of the above epoxy resin, it is being studied to introduce a nonoxyl alkane represented by a polyoxymethylene resin or a polyoxymethylene-modified epoxy resin. The resin of the skeleton (specifically, the skeleton having the Si_◦ bond) is used as a sealing material (the resin and the epoxy resin which are specifically known to be suspended from the skeleton are more stable to heat and light than the epoxy resin. In the case of a dense material applied to a LEd product, in terms of a μ L 々', especially on the LED chip, it is generally considered that the durability is superior to that of the epoxy resin. Compared with the epoxy tree, the moon scorpion of the oxygen house skeleton is inferior in gas permeability. Therefore, when the dimeric oxysulfide resin or the polyoxygen modified epoxy resin is used as the material of the LED (four), The color of the LED crystal moon does not become internal Deterioration of the building member's door of coloring... When the person will use it in the environment of the introduction, it will grow into a kind of 516 in the inner ring of life, and this compound will infiltrate the opportunity to use it. For example, The above-mentioned resin has the following problems: The 荨 荨 LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED Rate and f color or blackening, the most #τ + and silver plating) 6), to reduce the performance of the product as (4) (Patent Document 5, 201118134 In order to eliminate the gas permeability, # ^ ^ 4砀In Patent Document 5, a method in which a metal portion to which a rolling resistance protective agent is applied is coated with an inorganic material is used, but this method has a problem that the step is increased and the productivity is deteriorated. Previously, 完成 ^ completed without any technology, the purpose of which is to provide a curable resin composition which can provide a hardened material which satisfies the requirements of the electric material of the electric wind electric material, in particular, the optical semiconductor sealing material (4) + especially A curable resin composition capable of providing a cured product having excellent corrosion resistance to a gas or the like in the environment, heat-resistant coloring property, or light extraction efficiency, and excellent in hand and the like. The present inventors have considered the above. The present invention has been completed in the past, and the present invention has been completed. That is, the present invention relates to the following: (1) A curable resin composition which is organic polyfluorene (oxime), salt and/or zinc The compound (C) is an essential component 'wherein' the organopolyfluorene (Α) satisfies the following conditions, the organic polyoxo (Α): which has at least a glycidyl gr〇up and/or in its molecule The epoxy resin composition of the above-mentioned (1), wherein the zinc salt and/or the complex (C) is selected from the group consisting of phosphates and phosphoric acid. At least one of a group consisting of one or more acid salts and a zinc complex containing the above acid and the above zinc salt as a ligand; 201118134 (3) The curable resin according to the above item (1) a composition wherein the above zinc salt and/or the octyl complex (C) is selected from the group consisting of carbon numbers 1 to 3 One of a group consisting of a carboxylic acid salt of 0 and a zinc complex containing the above acid and the above zinc salt as a ligand; (4) Any one of the above items (1) to (3) The curable resin composition, which comprises a polybasic slow milk (B) having two or more carboxyl groups and having an aliphatic hydrocarbon group as a main skeleton; (5) a curable resin composition according to the above item (4), wherein the above plural The acid (7)) is a compound obtained by reacting a 2 to 6-functional polyol having a carbon number of 5 or more with a saturated aliphatic cyclic acid anhydride; (6) according to any one of the above items (1) to (5) (7) The curable resin composition according to any one of the above items (1) to (6), which contains a party-blocking amine-based light stabilizer and/or an anti-oxidant; (8) A cured product obtained by hardening a curable resin composition according to any one of the above items (1) to (7). The curable resin composition of the present invention is excellent in optical properties such as corrosion-resistant gas resistance, heat-resistant coloring property, and light extraction efficiency, and is therefore used as an illumination in the optical material.

It is extremely useful to use the adhesive material for the semiconductor (LED 4) used in the life jacket. [Embodiment] The curable resin composition of the present invention is described. The % oxygen resin composition of this month is an organic poly-and/or zinc complex (c) as an essential component. , 匕 s organopolylithium (A) is characterized in that it has at least a propyl group and/or a oxycyclohexyl group epoxy resin in its molecule, usually by having an oxypropyl group or The % oxygen-hexyl group of the three hospitals (8) Xian (10) (four) 丨 3 is obtained by the sol-gel reaction of the raw materials. Specifically, Japanese Laid-Open Patent Publication No. 2_2566(), Japanese Patent Laid-Open Publication No. 2004-346144, Japanese Patent Publication No. 2004/346, No. 72i5 No. 曰, 曰本特开 2006-8747 _Jian 99 (), Japanese Patent Laid-Open No. 2006-104248, Japanese Patent Publication No. Hei. No. 7/1359〇9, Japanese Patent Application No.-1, No. 2, Japanese Patent Publication No. 2_359933, W〇2 〇〇5/100445, and Japanese Laid-Open Patent Publication No. 2008-174640, etc., have a T-dimensional s 〇a having a quasi-expanded network structure of silsesquioxane type organic polymerization. Oxygen. The structure of the organic polyoxo oxygen is not particularly limited, but since the simple three-dimensional network structure of the oxirane compound is too hard, it is desirable to relax the hardness of the structure in the present invention, and it is particularly preferable to have a polyoxo oxygen in the i molecule. The bond segment and the block structure (bI〇Ck StrUCtUre) of the above-mentioned seso-oxygen structure obtained by a sol-gel reaction (hereinafter referred to as a block type siloxane compound (A1)). The Xinshi type oxime oxy-compound compound (A1) is not a compound having a repeating unit on a straight chain like the usual block copolymer 201118134, and has the following structure: a network structure having a dimensional expansion, sesquiterpene The oxyalkylene structure is a core, and the chain poly-stone phase segment is extended and bonded to the τ-double-cut oxy-fired structure. The structure imparts a balance between hardness and flexibility to the cured product of the curable resin composition of the present invention. Effective in meaning. The oxime-type oxoane compound (Α丨) can be, for example, a compound (4) represented by the formula (1) and a polyoxosulfuric acid (b) represented by the formula (2). For the production, the alkoxydecane compound (4) represented by the formula (3) can also be used as a raw material. a chain-type polyoxynene chain system of a block type oxoxane compound (4)), which is formed by polysulfuric acid (b), and a three-dimensional network sesquiterpoxide group is composed of alkoxy (4) (4) (and Each of the raw materials is described in detail below. The alkoxylated compound (4) is represented by the following formula (1): (1) XSi (〇R2): (X in the formula (1) Indicates that it has a propylene group and/or an epoxy group. A plurality of R2 represents a linear number of a carbon number, and an organic cyclic alkyl group of eight, which may be the same or different from each other. X in the general formula (1) is not particularly limited as long as it is an organic group having a hexyl group. For example, it can be listed; epoxy epoxyethyl group (coffee id. M), propylene oxide: ^Epoxypropoxy butyl group, etc. Epoxy propoxy carbon number 丨~彳:# soil, epoxy propylene epoxy cyclohexyl) ethyl, Bu (3 4_epoxy ^ U propyl ' 6-(3 , 4-hexyl)propyl '~epoxy 201118134 cycloheptyl)ethyl, /3-(3,4-epoxycyclohexyl)propyl, stone _(3,4-epoxycyclohexyl)butyl , without -(3,4-epoxycyclohexyl)pentyl, etc. having ethylene oxide Replaced by the sum of the carbon number of 5 ~ 8 carbon atoms, cycloalkyl of Shu ~ 5 alkyl group. Among these, a carbon number of 碳~3 alkyl group substituted with a glycidoxy group and a carbon number substituted with a cycloalkyl group having an epoxy group of 5 to 8 are preferably used. Alkyl group, for example,/5 _glycidoxyethyl, y-glycidoxypropyl, s-, 4-epoxycyclohexyl)ethyl, especially preferably 0-(3,4-ring Oxycyclohexyl)ethyl.

Here, when a combination of an alkoxydecane compound wherein X is a glycidyl group and an alkoxydecane compound wherein X is an epoxycyclohexyl group is preferred, it is preferably an alkoxy group in which X is an epoxycyclohexyl group. The money compound is used in an amount of 80% or more based on the total amount of the alkoxy compound (4). Λ Λ (1 艸 复 复 复 表示 表示 表示 L L L L L 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直Butyl, isobutyl, tertiary butyl =, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, etc. These & preferably are in terms of reaction conditions such as compatibility, reverseness and the like. Preferably, it is a methyl group. Oxygen: a specific example, which may be exemplified by: 々-epoxypropene fluorene; base stone jin...-glycidoxyethyl triethoxy oxalate == oxypropyl 2 oxy, Glycidoxypropyl-(34; Erguang (3'4-epoxycyclohexyl)ethyltrimethoxyxanthine, hydrazine (3,4-% hexyl)ethyltriethoxy money, etc. , especially, cyclohexyl) ethyltrimethoxylate. This can be used alone or in combination with two or more types, and has the following formula (2): Oxygenated oil: 201118134 Combined. Polylithic oxygen (b) The end of the structure represented by the chain polyglycol group has r3 HO-t—'S1-〇 k

(2) (In the formula (2), there are a plurality of carbon numbers "14 fang A represents a carbon number of 1 to 1 烧, and the thiol group of the square number, the number of 2 to 1 ,, may be the same as each other. M is also different. m represents the number of repeating units. In the formula (2), a plurality of groups, an aryl group having 6 to 14 carbon atoms, and 3 an alkane having an inverse number of 1 to 1 may be different. The alkenyl group may be the same as each other, and the octa group having a carbon number of 1 to 1 G may be a linear group having a carbon number of u, a branched or a cyclic group, and examples thereof include a methyl group, an ethyl group, and a n-propyl group. Base, isopropyl, n-butyl, isobutyl, secondary, tertiary butyl, n-decyl, isopentyl, decyl, n-hexyl, decanohexyl, pentyl, cyclohexyl, octyl 2, ethylhexyl fluorenyl, etc. Among 3, etc., in consideration of light resistance or durability, methyl, ethyl, n-propyl 'cyclohexyl group is preferred. Examples of the aryl group of 1-4, such as a phenyl group, a phenyl group, a tolyl group, a p-tolyl group, a dimethyl group, and the like. The group is a dilute group having a carbon number of 2 to 1 Å, and examples thereof include an ethyl bake group and a methyl group. Ethyl propyl propyl, butyl, pentane An alkenyl group such as a hexenyl group or the like is preferably a methyl group, a phenyl group, a 10 201118134 cyclohexyl group or a n-propyl group, and more preferably a methyl group or a phenyl group from the viewpoint of light resistance and heat resistance. The compound of the compound - repeating the number of early m is 3~200, preferably 3~1〇〇, and Wenjia is 3~50. If m is lower than 3, the hardened material becomes too hard and low elasticity掇# The modulus characteristic is lowered. If m is higher than 200, the mechanical properties of the cured product tend to deteriorate, so it is not preferable. The weight average molecular weight (4) of the polysulfuric acid (b) is preferably 〜1 8,000 (condensed) Gel permeation chromatography

The range of Permeation Chromatography. (GPC) is entangled in the I 5 hai special. If the elastic modulus at low temperature is taken into consideration, the molecular weight is better at 300~10, _, and then, if considering The compatibility of the composition into the physicochemical, 刖 灶 &amp; λ λ is more preferably 3 (9) ~ 5, the best, especially better than 50 〇 3 '000. Heavy! When the average molecular weight is lower than the case, there is difficulty in that the characteristic of the chain (tetra) oxygen moiety of the characteristic segment occurs, and the characteristic of the intrusive type is impaired if it exceeds (8, 〇〇〇, it becomes severe). When the layer separation structure is used for an optical material, the permeability is deteriorated and it becomes difficult to use. In the present invention, as the molecular weight of the polyoxyxanic oil (b), Gpc can be used, and polystyrene can be measured under the following conditions. Calculate the weight average molecular weight (Mw). GPC various conditions Manufacturer: Shimadzu Corporation Pipe column: Protection column SHODEX GPC LF-G LF-804 (3 pieces) Flow rate: 1.0 ml/min. Column temperature: 4 〇t: Solvent: THF (tetrahydroanthracene D South) Detector: RI (differential refraction detector) 201118134 Polyoxygenated oil (b) The dynamic viscosity is preferably in the range of 1 〇 to 200 cSt, more preferably 30 to 90 cSt. When the temperature is lower than cSt, the viscosity of the block type oxalate compound (A1) becomes too low, which is not suitable as a photo-semiconductor sealant, and is higher than 200 cst. In the case of 'the presence of a block type siloxane compound (A 1), the viscosity increases, The preferred disadvantages of the polyoxygenated oil (b) include the following product names. For example, PRX-413 and BY16-873 manufactured by Toray Dow Corning Silicone Co., Ltd.; Shin-Etsu Chemical Co., Ltd. manufactures χ21-584ΐ, KF-9701; Momentive's XC96-723, TSR-160 'YR-33 70, YF-3 800, XF-3 905, YF-3057, YF-3 807' YF-3 802, YF-3 897, YF-3 804, XF-3905; DMS-S 1 manufactured by Gelest 2, DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS -S32, DMS-S33, DMS-S35, DMS-S42, DMS-S45, DMS-S5, PDS-0332, PDS-1615, PDS-9931, etc. Among the above, in terms of molecular weight and dynamic viscosity, Preferred are PRX-413, BY16-873, X-21-5841, KF-9701, XC96-723, YF-3800, YF-3804, DMS-S12, DMS-S14, DMS-S15, DMS-S21, PDS -1615. Among these, due to the flexibility of the polyoxygenated segment, it is particularly preferable to be X-2, 5841, XC96-723 'YF-3800, YF-3804, from the viewpoint of molecular weight. DMS-S14, PDS-1615. These polyoxygenated oils (b) may be used singly or in combination of two or more. This is followed by a detailed description of the alkoxydecane (c). The alkoxydecane (c) has a structure of the following formula (3). 12 201118134 R4(〇R5)3 (3) (R4 of formula (3) A represents a fluorenyl group or a phenyl group. There are a plurality of Rs which are not linear or branched, or branched or branched. The alkyl groups may be the same or different from each other. In the formula (3), a plurality of Rs are represented by a straight chain, a branched or a cyclic alkyl group having a carbon number of 1 to 1 Å, which may be the same as each other. different. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl and the like can be mentioned. The R5 is preferably an anthracenyl group or an ethyl group from the viewpoints of reaction conditions such as compatibility and reactivity. Preferred examples of the alkoxydecane (C) include methyltrimethoxydecane 'phenyltrimethoxydecane, methyltriethoxydecane, and phenyltriethoxydecane. Among the above, methyltrimethoxy decane and phenyltrimethoxy sulphate are preferred. In the present invention, in order to adjust the molecular group of the block type siloxane compound (A 丨), in order to improve the compatibility as a composition, and to adjust the heat resistance, light resistance, low moisture permeability, and lowness of the cured product, Gas permeability, etc., alkoxylate (c) can be used in combination with alkoxydecane (a). In the case of using a spent oxygen oxy-stone (4), it is preferred that the alkoxy sulfonium (4) and (C) are in a molar range, and the alkoxy decane (c) is in the range of 5 to 7 〇 mol%. Use, more preferably 5 to 50% by mole, and especially preferably 丨0 to 40% by mole. If it is more than 70 mol%, the crosslink density of the hardened material is lowered, and the mechanical strength is lowered, and the lower the mechanical strength, 13 201118134, is unsatisfactory. The reaction ratio of the field oxydecane (a), the polyoxyxane oil (b), and the alkoxy decane (c) is preferably 1 equivalent of the decyl alcohol group relative to the polyoxyxane oil (b), such that the alkoxylate The alkoxy group in the alkane (a) (and the alkoxydecane (c) used as needed) is from 1.5 to 200, preferably from 2 to 200, particularly preferably from 2 to 1, in terms of equivalent weight. The reaction is carried out between. When the equivalent value exceeds 200, the cured product using the block type siloxane compound (A1) becomes too hard, and the low elastic modulus characteristic of the target is lowered. Hereinafter, a preferred method for producing the block type oxoxane compound (A) is a method for producing a block type siloxane compound (A1), preferably as shown in the following (i) and (ii). Manufacturing step. Manufacturing step (i): carrying out the decyl alcohol terminal polyoxy olefin oil (b) and the alkoxy decane (a) having an alkoxy group (and the alkoxy decane (c) used as needed) The step of alcohol condensation is carried out by using the reaction production step (ii): adding a water to carry out the alkoxydecane (a) (and, if necessary, the step of hydrolytic condensation, the alkoxydecane (c) can be carried out in any order) The alkoxy groups are produced in the steps (i) and (ii), and the preferred production methods are as follows. Specifically, the following three production methods are described. <Manufacturing method 1> / The manufacturing method 1 is: Manufacturing step (1): First, borrowing The dealcoholization condensation reaction of agglomerated oxygen (8) having a sulphuric acid group at the end and alkoxy oxime (10) having an alkoxy group and an alkoxy decane (C) used according to 201118134 Alkoxydecane modification at the end of the polysulfate oil, thereby obtaining an alkoxy group Step of the decane-modified body (d). Production step (ii): followed by the alkoxy decane (a) (and alkoxy decane (c) used as needed) of the oxime compound having an alkoxy group And a step of producing a block type oxime by adding a step of hydrolytic condensation reaction between the alkoxy groups by adding water' to the alkoxy decane modified substance (d) of the polyoxyxylene oil obtained in the step (i). The alkane compound (A1). &lt;Production method 2&gt; The production method 2 is a production step (i is first performed by performing an alkoxy oxime (4) (and an alkoxy decane (c) if necessary) The step of obtaining an alkoxy group in the molecule by the hydrolysis-condensation reaction between the alkoxyses produced by the addition of water'. The manufacturing step (Π): then 'passing through the money (8) The reaction with the sesquiterpene oxygen to carry out the step of the dealcoholization condensation reaction of the alkoxy group remaining in the sesylene structure, the compound (Αυ. minus "read (4) oxygen burning &lt; manufacturing method 3 &gt; The manufacturing method 3 is: manufacturing step (1): first, by the end oil (b) and having a stanol group The dealcoholization condensation reaction of the alkane Iu decyl decane (a) (and the alkyl decane decane (4) used as needed), which is used for polyoxygenation, is modified by alkoxylation as an oily/sinking modified body. (d), then add water to the system in 15 201118134, and carry out the manufacturing step (ii) by one pin method (0ne_P〇t): the alkoxy decane (a) remaining in Say (and the alkoxy group used as needed) The hydrolysis and condensation reaction of the alkane (C)) and the alkoxy group of the alkoxydecane modified product (d) with each other 'manufacture of a block type oxoxane compound (A". In the present invention, the manufacturing step is shortened. From the viewpoint, it is preferred to use the above-described production method 3 in which the reaction is carried out one by one in a row. The manufacturing method 3 will be described more specifically below. In the case of the reaction in the one-pot method, if the production step is carried out in the reverse order of the above-mentioned production method 3, that is, after the production step (ii), the alkoxy group formed in the production step (ii) is doubled. The semi-oxane oxide oligomer is incompatible with the polyoxyxane oil (b), and no dealcoholization condensation polymerization is carried out in the subsequent production step (1), and the possibility of residual polyoxyxene oil is high. On the other hand, if the method of the production step (1)) is carried out in a one-pot method after the production step (1) as in the production method 3, the polyoxygenated oil (b) and the alkoxydecane (a) or alkoxydecane are used. (c) The compatibility is relatively high, so that the problem of being incompatible without reacting as described above can be avoided. Further, since a large amount of unreacted low molecular alkoxydecane is present with respect to the stanol group, it is also preferable from the viewpoint of reactivity. In the case of the one-pot method, first, in the production step (1), the polysiloxane oil (b) and the alkoxy decane (a) (and the alkoxy decane (c) used as needed) are removed. The alcohol is condensed, and the alkoxysilyl group is subjected to alkoxysilyl modification to obtain an alkoxydecane modified body (d). It is considered that since the production step (1) does not require the addition of water, the alkoxy group is not hydrolyzed and condensed with each other, and when a reaction is carried out using an alkoxy group of 3 equivalent or more with respect to the decyl alcohol group oxime equivalent, the alkoxy group is used. The decane modified body (d) exists as shown in the following formula (4) of 16 201118134.

(In the formula (4), R3 and m have the same meanings as described above, and a plurality of R6 each independently represent the above-mentioned enthalpy or the above-mentioned R4, and when it is bonded to the same 矽R, which is the above-described X, it means In the above rule 2, when r0 which is bonded to the same 矽 is the above-mentioned heart, I represents the above r 〇 7 in the production step (1), and the alkoxy group is less than 丨# with respect to the decyl alcohol group! The amount is reacted, and % is not promoted to the production step (ii) because the alkoxy group is not present at the end of the production step (1), and if the alkoxy group is reacted between 丨 and ^ equivalents, the oxygen is burned. Two of the secantane (3) (and the methoxy group #(4) used) are reacted with a methoxy alcohol group of (4) oxy oil (8), and are too polymerized at the end of the production step (1). Therefore, the alkoxy group is required to be reacted in an amount of 1.5 equivalent or more with respect to the decyl alcohol group oxime equivalent. From the viewpoint of reaction control, it is preferably 2 equivalents or more, more preferably 3 equivalents or more. After the completion of the production step (1), the water is directly added to carry out hydrolysis and condensation of the oxo groups. The second-stage reaction (manufacturing step (u)). The reaction of (1) to (10) shown below is produced in the manufacturing step (Π). (1) System &quot;Knocking of the burnt oxygen money U) (and used as needed The emulsion of the base of the milk-based crushed (c)) is condensed with each other. The anti-methane olefin is modified (d) with the alkoxylate (II). The oxygen-burning oxygen obtained in the step (i) is manufactured. (a) (and optionally alkoxydecane (c)) alkoxy groups are condensed with each other. (ΠΙ) a part of the alkoxydecane modified body (d) obtained in the step (i) and the alkoxy decane (and the alkoxy decane (c) used as needed) The alkoxy group of the condensate is condensed with each other. The above reaction is compounded in the production step (ii), and the formation of the sesquiterpene oxide segment and further contracting with the chain-like polyoxynene segment derived from the polyoxygenated oil are carried out. The production of the block type oxalate compound (Α1;) can also be carried out in the absence of a catalyst. However, if the catalyst is not used, the reaction proceeds slowly, and from the viewpoint of shortening the reaction time, it is preferably It is carried out in the presence of a catalyst. The catalyst which can be used can be used as long as it exhibits an acidity or a test compound. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; and organic acids such as formic acid, acetic acid, and ethylic acid. In the case of an 'inferiority catalyst, an alkali metal hydroxide such as sodium hydroxide 'potassium hydroxide, lithium hydroxide or barium hydroxide' sodium carbonate, potassium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate can be used. An inorganic base such as an alkali metal carbonate; an organic base such as ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine or tetramethylammonium hydroxide. In particular, it is preferable to use an inorganic base, and particularly preferably sodium hydroxide or potassium hydroxide. The total amount of the catalyst added is 〇.001 to 7.5 wt%, based on the total weight of the alkoxy decane (a) in the reaction system (and the alkoxy broth (c) used as needed). It is preferably 0 · 0 1 to 5 wt%. The catalyst addition method is directly added or used in a state of being dissolved in a soluble solvent 18 201118134 agent or the like. In the middle, it is preferred to add the catalyst in a state in which the catalyst is dissolved in an alcohol such as a yeast, a tea, a propanol or a butanol. In this case, as an aqueous solution using water or the like, there is a possibility that, as described above, the condensation of the one-way propionate (4) (and the use of the oxygen (four) calcination (4) as needed), thereby forming a double cut The oxygen-fired oligomer is incompatible with the polysulfuric acid (b) and is cloudy. The production of the block type monoxide compound (A1) can be carried out in the absence of a solvent or a solvent. Further, a solvent may be added in the middle of the production step. The solvent to be used is not particularly limited as long as it is a solvent for dissolving the alkoxydecane (a), the alkoxydecane (c), the polyoxyxanic acid (b), and the alkoxydecane modified product (d). . Such a solvent may, for example, be an aprotic polar solvent such as dimethyl decylamine, dimethylacetamide or tetrahydroanion; mercaptoethyl ketone, decyl isobutyl ketone, cyclopentane Ketones such as ketone; esters such as ethyl acetate, butyl acetate, ethyl lactate, isopropyl butyrate; alcohols such as methanol, ethanol, propanol and butanol; hexane, % hexane, Hydrocarbons such as toluene and xylene. In the present invention, from the viewpoint of reaction control, a reaction in an alcohol is preferred, and decyl alcohol and ethanol are more preferred. The amount of the solvent to be used is not particularly limited as long as it is in the range in which the reaction proceeds smoothly, and the alkoxydecane (a) (and the alkoxy furnace (c) used as needed) and the polyoxygenated oil (b) The total weight of the compound is 1 part by weight, and usually about 0 to 900 parts by weight is used. The reaction temperature is also dependent on the amount of the catalyst, but it is usually 20 to 16 (TC, preferably 40 to 140 T:, preferably 50 to 15 Torr. (:. Further, the reaction time is in each manufacturing step, respectively, usually It is 1 to 4 hours, preferably 5 to 3 hours. After the reaction, the catalyst is removed by quenching and/or washing as needed. 19 201118134 In the case of water washing, it is preferably used according to the use. A solvent which can be separated from water is added to the kind of the solvent. Preferably, (4), for example, a ketone member such as methyl ethyl ketone 'methyl isobutyl pentyl or cyclopentane ketone; ethyl acetate, butyl acetate, Ethyl lactate, styling, 7 s long isopropyl ester and other esters; hexane, cyclohexane, toluene, xylene and the like, etc. Although the reaction can be carried out by washing only with water, However, since the reaction is carried out under the conditions of acidic and test conditions, it is preferably quenched by a neutralization reaction; 隹~, ^ is transferred to a water-washing agent or after adsorbing the catalyst with an adsorbent, The adsorbent is removed by filtration. When neutralizing the reaction, as long as it exhibits acidity or Examples of the compound which can be used are acidic compounds such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as formic acid, acetic acid, and oxalic acid; and examples of compounds which exhibit an inspectability can be used. : metal hydroxide, such as sodium hydroxide, hydroxide dehydration, hydrazine hydroxide, barium hydroxide, metal carbonate, such as sodium carbonate, potassium hydrogencarbonate, potassium hydrogencarbonate; acid filling, Inorganic tests such as sodium dihydrogen dihydrogen phosphate disodium hydrogen phosphate, trisodium phosphate, polyphosphoric acid, sodium polyphosphate, etc.; 4, triethylamine, diethylenetriamine, n-amine An organic test such as aminoethanol, diethanolamine or tetramethylammonium oxide. Among them, 'X is easy to remove from the product... preferably inorganic or inorganic acid' and further preferably easier to PH The value is adjusted to a phosphate or the like in the vicinity of neutral. Adsorbent, synthetic adsorbent Activated clay is called J inactive clay, activated carbon, zeolite, inorganic-organic, ion-exchange resin, and the like, and specific examples thereof include the following products. For example, it can be cited: Dongshin Chemical Co., Ltd. Sexual viscosity 20 201118134 Soil SA35, SA Bu T, R-15, E, Nikkanite G-3 6, G-153, G-168; Galleon Earth, Mizuka Ace, etc. manufactured by Mizusawa Chemical Industry Co., Ltd. Activated carbon, for example, : CL-H, Yl〇s, Yi〇SF manufactured by Ajinomoto Fine-Techno Co., Ltd.; S, Y, FC, DP, SA1000, K, A, KA, M, CW130BR, CW130AR, GM1 30A, etc. manufactured by Futamura Chemical Co., Ltd. Examples of the zeolite include Molecular Sieve 3A, 4A, 5A, and 13X manufactured by Union Showa. For the synthetic adsorbent, for example, Kyoword 100, 200, 300, 4, 500, 600, 700, 1000, 2000 manufactured by Kyowa Chemical Co., Ltd.; manufactured by Rohm and Haas

Amberlyst 15JWET, 15DRY, 16WET, 31WET, A21, Amberlite IRA400JCI, IRA403BLCI, IRA404JCI; Dowex 66, HCR-S, HCR-W2, MAC-3, etc. manufactured by Dow Chemical Company. The adsorbent is added to the reaction liquid, and after the catalyst is adsorbed by stirring or heating, 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, the product can be purified by a conventional separation and purification method in addition to washing with water and filtration. Examples of the purification method include column chromatography, concentration under reduced pressure, distillation, and extraction. These purification methods are carried out separately or in combination of plural kinds. Preferably, after the quenching, the reaction solvent mixed with water is washed with water. The reaction using a solvent mixed with water as a reaction solvent is carried out by distillation or concentration under reduced pressure from the system, and then a solvent which can be separated from water is used to obtain a block type water-washing, 'concentration by decompression, etc. Removal of solvent, 21 201118134 oxirane compound (A1). The appearance of the ester-type oxygen-burning compound (A1) thus obtained is usually a liquid which is colorless and transparent and has fluidity at 25 °C. Further, the molecular weight thereof is preferably 8 Å to 2 Å, more preferably 1,000 to 10% by weight average molecular weight measured by GPC, and particularly preferably 1,5 〇〇 to 6 , the leader. When the weight is less than 8000 in the average knife, there is a decrease in heat resistance. When the temperature is higher than 20, the viscosity is increased, and workability is disadvantageous. Further, the molecular weight may be based on the alkoxydecane (a) (and the equivalent ratio of the alkoxylate (0) to the polyoxyxane (b) used, and the molecular weight of the polyoxyxane (b), The amount of water added during the reaction, the reaction time, and the reaction temperature are adjusted. The weight average molecular weight is a weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography) under the following conditions. GPC various conditions Manufacturer: Shimadzu Manufacturing Pipe column: Protection column SHODEX GPC LF-G LF-804 (3) Flow rate: 1. 〇ml/min.

Column temperature: 40 ° C Solvent: THF (tetrahydrofuran) Detector: RI (differential refractive index detector) Further, the epoxy equivalent of the block type siloxane compound (A1) (as described in JIS K-7236) The method is preferably 3 〜1,6 〇〇g/eq., more preferably 400 〜1, 〇〇〇g/eq·, especially preferably 45〇~9〇〇g/eq. By. When the epoxy equivalent is less than 300 g/eq., the hardened material becomes hard and the elastic modulus tends to be too high. When it is higher than the above, the mechanical properties of the hardened material deteriorate. The tendency is therefore not good. The viscosity of the block type oxalate compound (A1) (E-type viscometer, measured under 25) is preferably 50 to 20,000 mPa · s, more preferably 500 to 10, 〇〇〇mPa s , especially good for 8〇〇~5, 〇〇〇mpa·s. When the viscosity is lower than 5 〇 mPa · s, the viscosity is too low, which is not suitable for use as an optical semiconductor sealing material. When the viscosity is higher than 2 〇, 〇〇〇mPa · s, the viscosity is too high, and the operation is too high. Poor sex. The ratio of the sesquioxanes derived from sesquioxanes in the block type siloxane compound (A1) to the ruthenium atoms of 3 oxygens relative to the total ruthenium atoms is preferably 5 to 5 〇 mol%, more preferably 8 ~30% by mole, especially good for 1〇~2〇 Mo Er. If the ratio of the sesquioxanes derived from the argon helium to the three argon atoms to the total argon atoms is less than 5 mol%, then there is a characteristic of the chain condensed oxygen chain segment, and the hardened material becomes The tendency of softness is the result of surface stickiness or damage. On the other hand, if it is more than 50% by mole, the cured product becomes hard as a characteristic of the sesquisoidal bond segment, which is not preferable. The ratio of the presence of the Shixia atom can be determined by ih NMR, 29si NMR, elemental analysis or the like of the block type sand (4)). Ingredients The curable resin composition of the present invention contains a plurality of polyphenolic acids (8) as a preferred polybasic acid (bh is characterized as having a servant bauxite having at least two or more eucalyptus aliphatic hydrocarbon groups as the main skeleton and not only on the day of the month) ...:: In the Ming Dynasty, the so-called polybasic acid, the early-structured acid, and also includes a plurality of compounds having different or different substituents: acid composition, in the present invention, collectively referred to as plural ^竣23 201118134 Multi-repulsive acid W' is preferably a 2- to 6-functional slow acid, more preferably a compound obtained by reacting a polyol having a carbon number of 5 or more and 2 to 6 mesh energy with an acid anhydride, and then Che Yijia is The above-mentioned acid anhydride is a saturated aliphatic cyclic acid acid. The 2 to 6-functional polyol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, and examples thereof include ethylene glycol, propylene glycol, and U-propylene glycol. 'Alcohol 1,4 butanol, hydrazine, 5-pentanediol, hydrazine, 6 hexanediol, cyclohexane dimethanol, decanediol, tricyclic terpineol, decanediol and other diols Class; glycerin, three-armed-and-single-burning, three-story-a-birth, three-family, Dingyuan, 2• .a triols such as butanediol; tetraols such as pentaerythritol and tris(tetra)propanol; hexaols such as dipentaerythritol; etc. More preferred polyols are alcohols having a carbon number of 5 or more. Especially preferred is U•hexanediol: 1,4-cyclohexanedimethanol, cyclohexanedimethanol' &amp; cyclohexanedimethanol, 2G of diethyl pentanediol, 2·ethyl_2_ Base], % propylene glycol, neopentyl glycol, tricyclodecane dimethanol' decene diol, etc., more preferably 2_ethyl 2-butyl hydrazine, 3 propylene glycol 'neopentylene glycol, 2 , 4_diethylpentanediol, I oxime, hexane-methanol, dicyclodecane dimethanol, norbornene diol, etc., having a branched chain structure or a cyclic structure. Tetrahydrophthalic anhydride, methyl nadic anhydride, benzoic acid anhydride, hexahydrophthalic anhydride, mercapto hexahydrophthalic acid: formic anhydride, butadiene tetracarboxylic anhydride, hydrazine Ring [221] heptane-2,3-di-f-anhydride, methylbicyclo[221]heptane_23•dicarboxylic anhydride, cyclohexane-1,3,=tricarboxylic acid·3,4-anhydride, etc. Preferred are methylhexahydrophthalic acid = anhydride, cyclohexane-1,3,4·tricarboxylic acid·3,4-anhydride. 24 201118134 Addition reaction conditions, not specified, with -, can be used to make acid anhydride, polyol in the absence of catalyst, no reaction conditions of 40 ~ 15 (TC reaction and heating, after the reaction is completed directly: The method is not limited to the reaction conditions, but the polycarboxylic acid thus obtained is preferably a compound of the following formula:

(In the formula, there are a plurality of q representing at least one of U/N, methyl and slow bases of the nitrogen source X. P is derived from the above-mentioned multi-alumina-like I branched or cyclic aliphatic The base m is a polyphenol, and the number of the numerators is ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The curable resin composition of the present invention preferably has an acid anhydride. Specific examples of the acid anhydride include: phthalic anhydride, benzene, phthalic anhydride, pyrogallic anhydride, maleic anhydride, tetrahydrophthalic yttrium, stynyl tetradecanoic acid anhydride, Acidic liver, and "also anhydride", _ stearic acid needle, methyl hexahydrophthalic acid needle, Dingyuan tetracarboxylic anhydride, bicyclo [2·21 trace 2,3 dicarboxylic acid:, methyl Double-ring [2.2.U Gengzhuo.2,3. dicarboxylic acid oxime, cyclohexylmethyl k - 3,4-anhydride and other anhydrides. Yu Jia is a four-neighboring 曱-------------------------------------------------------------------------------------------------------------------------------------- Alkane 25 201118134 tetraphthalic anhydride, bicyclo "2 2 11 &amp; α 芰衣1二人1]heptane-2,3-diphthalic anhydride, methylbicyclo[2 2 l heptane-2'3·-phthalic anhydride And cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride. Further, in the above-mentioned acid liver, 'the following formula (6) is preferred.

(wherein 'Z represents at least one of a hydrogen atom, a methyl group and a carboxyl group) hexahydrophthalic anhydride, mercaptohexahydrophthalic anhydride, cyclohexane-1,3,4 - tricarboxylic acid _3,4-anhydride, wherein methyl group is preferably: ruthenium (tetra), cyclohexane-cut-tricarboxylic acid _3, ... when the curable resin composition of the present invention contains an acid anhydride, The amount of hydrazine used is determined by the ratio of the polybasic acid (B), preferably m. &8 &lt; W 1/(W1 + W2) (wherein W1 represents the blended parts by weight of the polycarboxylic acid (B), The blending weight fraction of the W2 anhydride is not - 夂丄 In the above, the range of W1/(W1 + W2) is more preferably 〇.〇5~〇65, and further preferably 〇.1〇~〇65' For 03~06. If it is less than 〇〇5, the tendency of the acid anhydride to volatilize during hardening tends to be strong, which is not preferable. If it exceeds 〇 65, it becomes difficult to operate as the viscosity. In the case where the acid anhydride is not contained (except for the case of a small county A - except for the residual of the Wenchuan.1), the shape of the polycarboxylic acid (B) is at a normal temperature and is in a state of two concave or sturdy shapes. 26 201118134 When the polycarboxylic acid (B) is used in combination with an acid anhydride, in terms of the ease of handling, in the manufacture of the polybasic acid (B), the excess acid liver A method of producing a mixture of a polyvalent carboxylic acid (B) and an acid anhydride is also preferred. The curable resin composition of the present invention contains a zinc salt and/or a zinc complex (4) as an essential component. Salt and/or zinc The complex compound (c) functions as a curing accelerator for an epoxy resin and a curing agent in the present invention. The zinc salt and/or the zinc complex (C) is a salt having zinc ions as a central element and The complex compound is not particularly limited, but preferably contains at least a ruthenium acid selected from the group consisting of a carboxylic acid having a carbon number of 1 to 30, a phosphate, and a phosphoric acid as a relative ion and/or coordination. Base. In the invention, the illusion is a zinc acid body or a phosphate vinegar body, especially in terms of compatibility. Preferably, the above alkyl group is methyl, isopropyl, butyl, 2-ethylhexyloctyl, isodecyl, isostearyl, decyl, cetyl, undecene. λ, etc. The zinc carboxylic acid body may be a group consisting of a zinc complex selected from the group consisting of a zinc salt of a carboxylic acid having 1 to 30 carbon atoms, a dilute acid having an anisotropic number of 30 and a zinc salt as a ligand. The carboxylic acid having a carbon number of 丨% or more is preferably an alkyl group having a chain branch structure or an alkyl group having a functional group such as an olefin, and more preferably a carbon number of 3. Those with a carbon number of ~30, especially those having a carbon number of 5 to 20. These are preferred in terms of compatibility, when the carbon number is too large (1⁄4 is more than 3 〇), or in a branched structure or In the case of a structure which does not have a structure such as a dilute: ^, etc., it is inferior in compatibility with a resin, and is therefore inferior. 27 201118134 Specifically, zinc 2-ethylhexanoate, zinc isostearate, undecene Zinc acid, etc. The ruthenium citrate can be selected from the group consisting of a zinc salt of a phosphate ester and a zinc complex containing cerium sulphate and the above-mentioned salt as a ligand. The phosphoric acid ester may also contain phosphoric acid ester-derived phosphoric acid as a relative ion and/or a ligand. In the present invention, a particularly preferred phosphate ester, preferably a phosphate ester (monoalkyl ester) The zinc salt and/or zinc complex of the compound, the monoalkyl ester, the trialkyl ester, or a mixture thereof, may also contain a plurality of phosphate esters. Specifically, it is preferably included in In the phosphate ester of phosphate ester, the molar ratio of monoalkyl ester, dialkyl ester, and dialkyl ester (replaced by gas chromatography), wherein dimethyl is required In the case where the trimethylsilyl group is used, the amount of the monoalkyl group is 50% by area or more in the stage of the alkylation treatment of trimethyl hydrazine. The zinc salt and/or the zinc complex can be obtained, for example, by reacting a phthalic acid ester with, for example, zinc carbonate, zinc hydroxide or the like (Patent Document EP699708). The phosphate ester is preferably 2-ethylhexylphosphoric acid, stearylphosphoric acid or the like. The details of the zinc salt and/or zinc complex of the acid vinegar, the ratio of the atom to the zinc atom (P/Zn) is preferably from 1.2 to 2.3, more preferably from 1.3 to 2.0. Yu Jia is 1.4 to 1 · 9. That is, in the form of Yu Jia, the acid ester (or acid-derived from the maleic acid ester) is 2.0 moles or less relative to the zinc ion i mole, preferably not having a simple ion structure but having A structure in which several molecules are related by an ionic bond (or a coordinate bond). Such a zinc salt and/or zinc mismatch 28 201118134 can be obtained, for example, by the method described in JP-A-2003-51495. As such a compound, a carboxylic acid substance of a commercial item can be exemplified by Zn_st,

Zn-St 602, Zn-St NZ, ZS-3, ZS-6, ZS-8, ZS-8, ZS-7, ZS-10, ZS-5, ZS-14, ZS-16 (曰东化成工业Manufacturing), XK-614 (manufactured by King Industry), 18% 〇ct〇pe Zri, 12% 〇ct〇pe

Zn, 8% 〇 ctope Zn (manufactured by H〇pe Pharmaceutical Co., Ltd.); phosphate ester and/or zinc phosphate body, exemplified by LBT-2000B (manufactured by SC Organic Chemicals) and xc_92〇6 (manufactured by King Industry). The ratio of the organopolyfluorene (A), the salt and/or the zinc complex (c) to the organopolyoxo (A)' salt and/or in the curable resin composition of the present invention. Or the zinc complex (c) is 〇〇1 to 8% by weight, more preferably 0.05 to 5% by weight, still more preferably 〇1 to 4% by weight, based on the weight ratio. Further, it is preferably 0.1 to 2% by weight. When the curable resin composition of the present invention is used for an optical material, particularly a photo-semiconductor encapsulant, a preferred component is preferably a hindered amine compound as a light stabilizer and a phosphorus-based compound as an antioxidant material. Compound. The towel of the present invention preferably contains a hindered amine compound, and contains a phosphorus compound. ^ The above amine compound, for example, tetrabutane tetracarboxylic acid tetrakis(1,2,2,6,6-pentamethyl-4-indanyl) vinegar, 1,2,3,4-butanetetracarboxylic acid tetra (2,2,6,6-tetramethyl-4_piperidinyl), 1,2,3,4-butanetetracarboxylic acid and 1'2'2'6'6-pentamethyl_4 _Break octopus and 3,9_bis(2•trans-n-dimethylethyl)-2,4,8,10.tetrazole snail [55] eleven-burning mixed vinegar, 癸二二Double 29 201118134 (2,2,6,6-tetradecyl-4-piperidinyl) ester, bis(1-undecyloxy-2,2,6,6·tetradecylpiperidine-4) -yl)ester, 2,2,6,6-tetradecyl-4-piperidyl methacrylate, bis(2,2,6,6-tetradecyl-4-piperidinyl) sebacate _, azelaic acid bis(1,2,2,6,6-pentamethyl-4-piperidinyl) vinegar, 4-phenylhydrazineoxy-2,2,6,6-tetradecylpiperidine , l-[2-[3-(3,5-di-tertiary butyl-4-hydroxyphenyl)propenyloxy]ethyl]-4-[3-(3,5-di-secondary Butyl-4-Phenylphenyl)propanol]-2,2,6,6-tetradecylpiperidine, 1,2,2,6,6-pentamethyl-4-indole (1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate), [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl] Bis-butylmalonate bis(1,2,2,6,6-pentamethyl-4-acridinyl)g, azelaic acid bis[2,2,6,6-tetradecyl-1 -(octyloxy)-4-piperidinyl]-, the reaction product of 1,1-dimethylethylhydroperoxide and octane, hydrazine, Ν', N", N&quot;'-tetra-[ 4,6-bis-[butyl-(N-methyl-2,2,6,6-tetradecyl oleyl 11-yl)amino]-two well-2-yl]-4 ,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-three wells-Ν,Ν'-bis(2,2,6,6-tetradecyl-4- Polycondensate of piperidinyl-1,6-hexanediamine and Ν-(2,2,6,6-tetradecyl-4-piperidyl)butylamine, poly[[6-(1,1, 3,3-tetradecylbutyl)amino-1,3,5-three well-2,4-diyl][(2,2,6,6-tetrafyl-4-piperidinyl) Amino]hexamethylene[(2,2,6,6-tetradecyl-4-piperidyl)imido]], dimethyl succinate and 4-hydroxy-2,2,6, Polymer of 6-tetramethyl-1-piperidineethanol ' 2,2,4,4-tetradecyl-20-( yS -lauryloxycarbonyl)ethyl-7-oxa-3,20-di Aza-bispiro[5.1.11.2] eicosane-21-one, /3-alanine small-(2,2,6,6-tetradecyl-4-0 melon.定定)-Twelve-six/fourteen-supplied, N-acetyl-3,t-dodecyl-1-(2,2,6,6-tetramethyl-4-acridinyl)pyrrolidine-2 ,5-diketone, 2,2,4,4-tetradecyl-7-oxa-3,20-diazaspiro[5.1.1 1.2]hexadecane-21-one, 2,2 , 4,4-tetradecyl 30 201118134 -21-oxa-3,20-diaza-%-[5.1.11.2]- twenty-one burnt _2〇_ dodecyl propionate/tetradecyl ester, Malonic acid [(4-decyloxyphenyl)-y-fyl]-bis(1,2,2,6 6 pentamethyl-4-0 melon) vinegar, 2,2,6,6- Higher fatty acid ester of tetradecyl-4-pyrrolidine, anthracene, Ν'-bis(2,2,6,6-tetramethyl-4-acridinyl)ι,3·benzamide A hindered amine compound or the like. As the amine compound of the above light-stable material, a commercially available product shown below can be used. For example, TINUVIN765, TINUVIN770DF, TINUVIN144, TINUVIN123, TINUVIN622LD, TINUVIN152, CHIMASSORB944 manufactured by Ciba Specialty Chemicals; LA-52, LA-57, LA-62, LA-63P, LA-77Y, LA-81 manufactured by Adeka, LA-82 'LA-87 and so on. In the curable resin composition of the present invention, the light stabilizer is used in an amount of 0.005 to 5% by weight, more preferably 0.01 to 4% by weight, or 0.1 to 2 parts by weight based on the weight of the organic polyoxo (A). weight%. The above-mentioned filling compound is not particularly limited, and examples thereof include 1,1,3 _ tris(2-mercapto-4-di-tridecyl sulphate-5-tributylphenyl) butadiene. , distearyl neopentyl alcohol diphosphite, bis(2,4-di-tert-butylphenyl)neopentitol diphosphite, bis(2,6-di-tertiary butyl -4-mercaptophenyl) pentaerythritol di sulphate, phenyl bis-A pentaerythritol di sulphate, dicyclohexyl neopentyl alcohol diphosphite, tris(diethyl Phenyl)phosphite, tris(di-isopropylphenyl)phosphite, tris(di-n-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl) Phosphite, tris(2,6-di-tertiary butylphenyl) phosphite, 'tris(2,6-di-tert-butylphenyl) phosphite, 2,2,-indenylene Γ ·£*

L 31 201118134 Bis(4,6-di-tertiary butylphenyl)(2,4-di-tertiary butylphenyl)phosphoric acid, 2,2'-methylene double (4,6 -di-tertiary butylphenyl)(2_tris-butyl-4-indenylphenyl) sub-filler '2,2'-arylene di(4-methyl-6-tridecyl) Phenyl)(2-tert-butyl-4-indolyl)phosphite, 2,2,-ethylenebis(4-mercapto-6-tributylphenyl) (2- Tert-butyl-4-mercaptophenyl) sub-allate, tetrakis(2,4-di-tert-butylphenyl)-4,4,-extended biphenylphosphonate (tetrakis (2) ,4-di-tert-butylphenyl)-4,4'-biphenylenediphospho nite), tetrakis(2,4-di-tert-butylphenyl)·4,3,-extended biphenylphosphonate, four (2,4-di-tertiary butylphenyl)-3,3'-extended biphenylphosphonate, tetrakis(2,6-di-tri-butylphenyl)-4,4'- Diphenyldiphosphinate, tetrakis(2,6-di-tributylphenyl)-4,3'-extended biphenylphosphonate, tetrakis(2,6-di-tridecyl) Phenyl)-3,3'-extended biphenylphosphonate, bis(2,4-di-tert-butylphenyl)-4-indolyl-phenylphosphonate, double (2 ,4-di-tertiary butylphenyl)_3_ -Phenylphosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphinate, bis(2,6-di-triphenyl) -4-phenyl-phenylphosphonite 'bis(2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphinate, tetrakis(2,4-di.3) Grade butyl-5-mercaptophenyl)-4,4'-extension of stannodiphosphonic acid vinegar, tributyl sulphate, 'trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophosphate Phenyl ester, triethyl phosphate, diphenylphosphonium phosphate, diphenyl mono-o-phenyl ester, tributoxyethyl phosphate dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate Wait. Commercially available products can also be used as the above scaly compound. For example, Adekastab PEP-4C manufactured by Adeka, Adekastab PEP-8' Adekastab PEP-24G' Adekastab PEP-36 ' 32 201118134

Adekastab HP-10 &gt; Adekastab 2112 &gt; Adekastab 260 &gt;

Adekastab 522A ' Adekastab 1178 ^ Adekastab 15〇〇 ,

Adekastab C ^ Adekastab 135A ^ Adekastab 3〇l〇 &gt; Adekastab TPP. The curable resin composition of the present invention is used in an amount of 〇 to 5% by weight, more preferably 0.01 to 4% by weight, based on the weight of the organic polyoxo (A)'s compound. 1~2 weight 〇/〇. The curable resin composition of the present invention contains an organic polyfluorene oxide (A) as an epoxy resin, a zinc salt as a curing accelerator, and/or a rhythm compound (c) as essential components, and further contains a curing agent. The polycarboxylic acid (B) and an acid anhydride, a hindered amine light stabilizer as an additive, and a phosphorus-containing antioxidant are preferred components, and these may be used in combination with other epoxy resins, hardeners, and agents. In the epoxy resin component, the ratio of the organic polyfluorene (A) to the other epoxy resin and the organic polyoxo (4) in the total epoxy resin is preferably 6% or more, more preferably 7 〇% by weight or more. ... Other epoxy resins which can be used together with the organic polyfluorene (A) include phenol 2 lacquer epoxy resin, (IV) A type epoxy resin, and biphenyl type epoxy resin. A base methane type epoxy resin, a phenol aralkyl type epoxy resin, or the like. Specifically:: bisphenol bismuth, bisphenol S, thiodiphenol, g bisphenol, diphenol, 4:4, = this, 2,2'-biphenyl, 3,3, '5, 5, tetradecyl _π, Guanglian 44, · _ alcohol, pair of stupid age, resorcinol, 葶-pan, -M a non-phenol, di-(4-3⁄4-ylphenyl) methane, Four (4-transbasic) B&amp;, categorical (benzene, substituted by the burnt base, and Cai Pan's substituted by naphthoquinone, dipyridylbenzene, dipyridyl, etc.) 33 201118134 A road, acetic acid, serotonin, p-hydroxybenzaldehyde, o-hydroxybenzene = ethyl ketone, ortho-formis, dicyclopentadiene, hydrazine... bis (chloromethyl)-1,1 Condensation of '-biphenyl, 4,4··bis' (formylmercaptobiphenyl, 1,4-bis(chloro:yl)bendi, 1,4-bis(methoxymethyl)benzene, etc. And the modified substances on both sides are double-awaited, etc., and the double enzymes are derived from alcohol-derived epoxy alicyclic epoxy resin, epoxy propylamine epoxy resin, epoxy bismuth epoxy resin, etc. The solid or liquid epoxy resin is not limited to a knot or the like. These may be used singly or in combination of two or more kinds. In particular, the curable resin of the present invention The adult system is mainly used for optical purposes. When used for optical applications, it is preferably used in combination with an alicyclic type of latex resin. In the case of an alicyclic epoxy resin, the temple is preferably a skeleton. A compound having an epoxycyclohexane structure, particularly preferably an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure. The epoxy resins are exemplified by the following reaction. Emulsification of compounds, etc.: acetalization of cyclohexenecarboxylic acid with alcohols or esterification of cyclohexene methanol with carboxylic acids (Tetrahedr〇n ν〇1. 36 ρ 24〇9 (1980), Tetrahedr〇 n Letter ρ 75 (ΐ 98〇), etc., or a cyclohexenal quaternary reaction (Tishchenk〇reacti〇n) (Japanese Unexamined Patent Publication No. 2003- PCT No. And the transesterification reaction of the cyclohexene acrylate (the method described in JP-A No. 2-6-〇5 21 87, etc.). The alcohol is as long as it is alcoholic. The compound of the hydroxyl group is not particularly limited, and examples thereof include ethylene glycol. Propylene glycol, hydrazine, 3-propylene glycol, hydrazine, 2-butanediol, 14-butanediol, 1,4-pentanediol '1> hexamethylene glycol, cyclohexanedimethanol, 34 201118134 diethyl pentyl Glycol, 2-ethylamide, 7 butyl, G|-2-butyl-1,3-propanediol, neopentyl glycol, three-yellow yam*, A-®, suisu-two Guchu-36 Containing #ε Τ 布 布 醇 专 专 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; Famous Ρ — - hydroxy hydrazine propanol and other four alcohols. Further, examples of the carboxylic acid include oxalic acid, cis-butane-&amp;r; _ beryllone, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and if hexane. Diterpenic acid, etc., but is not limited thereto. Further, examples of the other epoxy resin include an epoxy resin obtained by epoxidizing an acetal compound obtained by reacting a cyclohexenal derivative with an acetal of an alcohol by an oxidation reaction. s Hai and other epoxy resin and @ 也丨曰 (eight body examples, can be cited: ERL-4221, UVR-6105, ERL-4299 (All-Chief Helmet also σ 々, (Wang Weishi αο名, both by Dow Chemical w Celloxide 202lP, Epolead GT401, EHPE3150, EHPEWOCE (all of which are trade names, all manufactured by 丨Chemical Industries) and dicyclopentane diepoxide, but not limited to materials (Reference: General Epoxy Resin base I p76_85). These may be used singly or in combination of two or more. The curing agent in the present invention is not limited, and the η 夕 战 knife is not particularly limited, and it is preferable to use a carboxylic acid compound (Β). Separately #司1 is used in combination with an acid anhydride, and may be used in combination with other hardeners. In the case of octagonal &amp; combined, the total weight of the polycarboxylic acid compound (Β) and the anhydride is in 蜱4. The proportion of the sclerosing agent is preferably 3% by weight or more, and more preferably 40% by weight or more. The hardener which can be used in combination can be listed as a compound, an acid anhydride, and an anhydride. a compound, an amine compound, a ruthenium compound, a carboxylic acid Compounds, etc. Specific examples of hardeners that can be used, amines or polyamine compounds (II 35 201118134 Aminodiphenylnonane, diethylenetriamine, triethylenetetramine, diamine Reaction of an acid anhydride with a polyoxyl alcohol by a base of a sulfone, an isophorone diamine, a dicyandiamide, a polyamine resin synthesized from a dilinoleic acid dimer and an ethylenediamine (o-phthalic anhydride, trimellitic anhydride, pyrogallic anhydride, maleic anhydride 'tetrahydrophthalic anhydride, mercapto tetrahydrophthalic anhydride, mercapto-resistant acid anhydride, ground resistance Anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane tetraphthalic anhydride, bicyclo[2.2.1]heptane·2,3-diphthalic anhydride, methylbicyclo[2.2.1 Acid heptane-2,3-diphthalic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-needle and the like, and methanol-modified polyoxo-alcohol Reactant, etc.), polyphenols (bisphenol A, bisphenol F, bisphenol S, bisphenol phenol quinolol, 4,4'-biphenol, 2,2,-biphenol, 3,3, 5,5,-tetramethyl _[1,1,-linked stupid]-4,4,-diol, p-benzoquinone, between Di-, naphthalene, tris-(4-pyridylphenyl)anthracene 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenols (phenol, substituted by substituting Phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with formic acid, ethylene, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-tetrabromobisphenol A, etc. Halogenated bisphenols, condensates of terpenes and phenols),

Hydroxy acetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4, bis (gas f-)-1,1,-biphenyl, 4,4,_bis (methoxy Polycondensates such as bisphenyl, 1,4,-bis(gasmethyl)benzene, bis(methoxymethyl)benzene, and the like, and the modified or hydrazine derivatives may also be used.

Ring 36 201118134 The oxygen group is 1 equivalent, and the hardener component is 0.7 to 1.2 equivalents, particularly a ratio of 1 to 1 equivalent, and a curing agent is used. - 〇 · 75 相对 环 环 75 环 环 环 环 环 环 环 环 环 环 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞 虞In the curable resin composition of the present invention, the zinc salt and/or the zinc complex (C) as an essential component directly exhibits a function as a curing catalyst, so that a curing catalyst may not be added, but And use other hardening catalysts. Examples of the hardening accelerator which can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and hydrazine-benzyl Benzyl-2-phenylimidazole, fluorenyl-pyrrolyl-2-mercaptoimidazole, hydrazine-cyanoethyl-2-indolyl imidazole, 1-cyanoethyl-2-phenylimidazole, fluorenyl-cyanoethyl Base 2_undecyl imidazole, 2,4-diamino-6 (2'-methylimidazolium (1,)) ethyl _ three wells, 2,4-diamine _6 (2, eleven Imidazole (1')) ethyl-all three wells, 2,4-diamino _6 (2, _ethyl _4 曱 咪 咪 咪 (Γ)) ethyl - three wells, 2, 4 -diamino-6 (2,-nonyl imidazole (1')) ethyl-distillary iso-cyanuric acid adduct, 2-methylimidazole isocyanuric acid 2:3 addition , 2-phenylimidazolium isocyanurate adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxyindolyl-5-mercaptoimidazole, 1- Various imidazoles of cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole; and these imidazoles and o-dibenzoic acid, isophthalic acid, p-dicarboxylic acid,丨, 2,4_ benzenetricarboxylic acid, pyromic acid, naphthalenedicarboxylic acid, cis-butyl succinic acid a salt of a polycarboxylic acid such as oxalic acid; a guanamine such as dicyandiamide; a ruthenium compound such as ruthenium, 8-di-bicyclo-bicyclo(5.4.0) undecen-7, and the above-mentioned tetraphenylboronic acid a salt of a phenolic novolac varnish or the like; a salt of the above-mentioned multi-repulsive or phosphinic acid (phosphinic 37 201118134 acid), tetrabutylammonium bromide, cetyltrimethylammonium bromide, three An ammonium salt such as a methyl group-developing ammonium; a phosphine or a scaly compound such as triphenyl lin, tris(toluene) lin, tetraphenyl brominated sulphate or tetraphenyl quaternary tetraphenyl borate; 2, 4 , a 6-triaminomethyl phenyl group, a metal compound, a metal compound such as tin octylate, etc.; and a hardening accelerator which is a microcapsule type hardening accelerator of a microcapsule. The use of these hardening-promoting shots is appropriately selected depending on the properties required for the obtained transparent resin composition, for example, transparency, curing speed, working conditions and the like. The hardening accelerator is usually used in an amount of from 0.001 to 15 parts by weight based on the parts by mass of the epoxy resin component ι. The curable resin composition of the present invention may be added with various additives and auxiliary materials listed below. The curable resin composition of the present invention may further contain a phosphorus-containing compound as a flame retardancy imparting component. The phosphorus-containing compound may be of a reactive type or may be an additive type. Specific examples of the scaly compound include: tridecyl sulphate triethyl sulphate tricresyl phosphate, tris(xylylene) phosphate, phenyl phenyl phosphate, and bismuth phosphite-2. 6-di(diphenyl) ester, anthracene, 3_phenylene bis(mono(phenyl)phosphonate), 1,4-extended bis(diphenylene phosphate), 4, 4, _ Lian (phosphonium di(xyl) phosphate) and other phosphates; 9,1 〇 _ dihydro _9 _ oxa 〇 〇 磷 磷 phenanthrene-10-oxide, 10 (2,5- Phosphines such as dihydroxyphenyl)_1〇Η_9·oxa-1〇-phosphaphenanthrene-10-oxide; phosphorus-containing epoxy obtained by reacting an epoxy resin with active hydrogen of the above-mentioned phosphines The compound, red phosphorus or the like is preferably a phosphoric acid @-type, a wall-type or an epoxide-containing compound, and particularly preferably a 1,3 _phenylene bis(xylylene) vinegar, 1,4- Phenyl bis (disc bis(diphenyl benzene) cool) ' 4,4% sputum (acid di(dimethyl) gB) or dish epoxy compound. The content of the compound containing lanthanum 38 201118134 is preferably phosphorus-containing compound / epoxy resin = ι ι ~ denier ratio). When it is less than (M, the flame retardancy is insufficient, and if it exceeds 〇6, H = the hygroscopic property of the cured product and the dielectric properties are adversely affected. Further, the curable resin composition of the present invention is optionally required. It is also possible to push in the binder resin. Examples of the binder resin include butyral resin, acetal: fat, acrylic resin, epoxy-nylon resin, and 峨 纷 resin: % milk-dirty system The resin, the polyamide resin, the polyimide resin, the silicone resin, and the like are not limited thereto. The binder resin preferably has a flame retardancy and heat resistance without impairing the cured product. The range is preferably from 5 to 50 parts by weight, preferably from 5 to 2 parts by weight, based on 1 part by weight of the resin component and the hardener component. The curable resin composition of the present invention is regarded as a component. Additives are required. Inorganic fillers include, for example, crystal dioxotomy, smelting of sulphur dioxide, emulsification of yttrium, yoghurt, carbon _, carbon carbide, nitriding, boron nitride, Powder of zirconia, forsterite, talc, &amp; spar, titanium dioxide, talc, etc. The inorganic fillers may be used alone or in combination of two or more kinds. The contents of the inorganic fillers are used in the present invention. The amount of the curable resin composition is from 0 to 95% by weight. Further, in the curability (IV) of the present invention, the Shi Xi Xuan coupling agent, stearic acid, palmitic acid, and stearin may be added to the group::::: : various kinds of admixtures such as a release agent such as a fatty acid, a pigment, and the like, and various thermosetting secrets. The use of the curable resin composition of the present invention for an optical material is an optical semiconductor sealing agent. Inorganic filling used; &lt;r- 39 201118134 The particle size of the material, by using a nano-level filling material, can make up the mechanical strength without hindering transparency. From the viewpoint of transparency, as a nano level The standard is preferably a filler having an average particle diameter of 5 Å or less, and more preferably an average particle diameter of 200 ηη or less. The curable resin composition of the present invention is used for an optical material glazing semiconductor sealing agent. In case, add fluorescent light as needed The phosphor has the following effects: for example, absorbing a portion of the blue light emitted by the blue LED element and emitting wavelength-converted yellow light, thereby forming white light. Dispersing the phosphor in advance in the curable resin composition In the meantime, the photo-semiconductor is sealed. The phosphor is not particularly limited, and a conventionally known phosphor can be used, and examples thereof include a rare earth element salt, a rock salt, a protopanalate, and the like. The term "YAG phosphor, tag phosphor, protopium salt phosphor, thiogallate phosphor, sulfide phosphor, etc." can be exemplified as: YA1〇3 : Ce, γ3Α15〇ΐ2 :, ΜΑ : Ce &gt; Y202S . Eu ^ Sr5(P〇4) 3ci : Eu ^ (SrEu)O · A1203 # = ^ The particle size of the phosphor can be used in the art. The particle size, the average particle diameter, preferably 1 to 25 G heart 'is especially 2 to Μ (four). In the case of using the above-mentioned phosphors, the amount thereof is preferably from 1 to 80 parts by weight, based on the organic component of the organic polysiloxane (4), of from 1 to 80 parts by weight, preferably from 5 to 60 parts by weight. ;: The hardening resin composition of this month is used for optical materials, especially optical semiconductor encapsulants, 1· Kui; ^ Moon shape, based on prevention of hardening of various phosphors; especially::, can be added With cerium oxide micropowder (also known as octagonal (10)... Μ Μ , , , , , , , . . . . . . . A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A 3 80, Aerosil 0X50, Aerosil TT600, Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R812 'Aerosil R812S, Aerosil R805, RY200, RX200 (manufactured by Japan Aerosil Co., Ltd.), etc. The curable resin composition of the present invention may contain a phenol system The phenol compound is not particularly limited, and examples thereof include 2,6-di-tertiarybutyl-4-mercaptophenol, n-octadecyl-3-(3,5-di-tridyl). Butyl-4-hydroxyphenyl)propionate, tetrakis[methylene-3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate]methane, 2,4- Di-tertiary butyl-6-nonylphenol, 1,6-hexanediol-bis-[3-(3,5-di-tri-tert-butyl-4-phenylphenyl)propionic acid g] , three (3,5-di-tertiary butyl -4-hydroxybenzyl)-isocyanate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tri-butyl-4-yl) Stupid, pentaerythritol-tetrakis[3-(3,5-di-tri-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis-[2-[3-(3- Tert-butyl-4-hydroxy-5-fluorenyl)-propenyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5] Mono-, triethylene glycol-bis[3-(3-tert-butyl-5-indolyl-4-hydroxyphenyl)propionate], 2,2'-butylene bis(4,6-di - Tert-butylphenol), 4,4, butylene bis(3-indolyl-6-tertiary butylphenol), 2,2'-indenylene bis(4-mercapto-6-tertiary Phenol), 2,2·-methylenebis(4-ethyl-6-tributyl), 2-secondylbutyl-6-(3-tertiary butyl-2-yl)- 5-fluorenyl cyclyl)_4_methylphenol acrylate, 2-[1-(2-hydroxy-3,5-di-triamylphenyl)ethyl]-4,6-di-tri-pentane Phenyl acrylate, 4,4'-thiobis(3-indolyl-6-tertiary butyl phenol), 4,4,-butylene bis(3-methyl-6-tertiary butylphenol ), 2-tert-butyl-4-nonylphenol, 2,4-di-tertiary butylphenol, 2,4-di-three 201118134 Amyl phenol, 4,4'-thiobis(3-mercapto-6-tertiary butyl phenol), 4,4·-butylene bis(3-methyl-6-tertiary butyl phenol), Bis-[3,3-bis-(4.-hydroxy-3'.tris-butylphenyl)-butyric acid]-diol ester, 2,4-di-tertiary butylphenol, 2,4- Di-second fluorenyl benzene, 2-[1-(2-propionyl-3,5-di-nonyl-nonylphenyl)ethyl]-4,6-di-triamylphenyl acrylate Ester, bis-[3,3-bis-(4'-hydroxy-3'.tris-butylphenyl)-butyric acid]-glycol ester, and the like. Commercially available products can also be used as the phenolic compound. For example, 歹1J: IRGANOX1010, IRGANOX1035, RGANOX1076, IRGANOX1 135, IRGANOX245, IRGANOX259, IRGANOX295, IRGANOX3114, IRGANOX1098, IRGANOX1520L manufactured by Ciba Specialty Chemicals; Adekastab AO-20, Adekastab AO-30, Adekastab AO-40 manufactured by Adeka, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-90, Adekastab AO-330; Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, manufactured by Sumitomo Chemical Industries, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, etc. In addition to this, commercially available additive materials can be used as the anti-staining agent for the resin. For example, TINUVIN328, TINUVIN234, TINUVIN326, TINUVIN120, TINUVIN477, TINUVIN479, CHIMASSORB2020FDL, CHIMASSORB119FL manufactured by Ciba Specialty Chemicals, and the like can be cited. In the case where the phenolic compound is added, the amount of the phenolic compound to be added is not particularly limited, and may be added in an amount of 0.005 to 5 · 0 42 201118134% by weight in the curable resin composition of the present invention. The curable resin composition of the present invention can be obtained by uniformly mixing the components. Further, the curable resin composition of the present invention can be easily produced into a cured product by the same method as previously known. The curable resin composition of the present invention may be, for example, an extruder, a kneader, a roll or a planetary mixer, if necessary, and the epoxy resin component and the hardener component and the salt and/or the complex (c) are sufficient. Mix until it is uniform. When the obtained curable resin composition is in the form of a liquid, it is potted or cast, or impregnated into the substrate, and the caster is poured into the mold into the curable resin composition for casting. It is hardened by heating to form a cured product. On the other hand, when the curable resin composition is solid, it may be cast after melting, or molded by a transfer molding machine or the like, and further cured by heating, whereby the compound can be produced. Furthermore, other hardening accelerators, amine compounds, phosphorus-containing compounds, phenol compounds, binder resins, inorganic fillers, and the like, which are optional components, may be added and mixed in the above mixing step, and the curing temperature and time are ~ 2〇〇°C, 2~1〇 hours. The hardening method may be a secondary hardening at a high temperature, but it is preferred to carry out a hardening reaction by gradually increasing the temperature. Specifically, the initial hardening is performed between the ribs ~1 Μ c, and the hardening is performed at 10 (rc~20 (r. rc). The h segment is more preferably divided into 2 to 8 stages for temperature rise, and more preferably 2 ~ stage. ' 〜 Further, the curable resin composition of the present invention is dissolved in toluene, a book, propionate, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide 43 201118134 A curable eucalyptus varnish is prepared in a solvent such as acetamide or N-methylpyrrolidone, and is impregnated with glass fiber, carbon fiber, polyester fiber, polyamide fiber, oxidized fiber, paper. The substrate _ is heated and dried, and the obtained pre- 7 body is subjected to hot press forming, whereby the hardened resin composition of the present invention can be obtained. The solvent at this time is the hardenability of the present invention: the fat composition 4 Do not mix with the solvent, the 系 often makes 10~70 weights, preferably 15~70% by weight. Also, RTM (Resin Trans such as MGMding' resin transfer molding), directly The state of the liquid composition obtains an epoxy resin hardened material containing carbon fibers. The curable resin composition is used as a film-type dense composition. The method for obtaining such a film-type sealing composition is exemplified by first curing the curable (four) composition of the present invention. This is applied to a release film, and the solvent is removed by heating to carry out a B-stage process, whereby a film-type sealing composition as a sheet-like adhesive can be obtained. A multilayer film sealing material for an interlayer insulating layer or an optical semiconductor in a multilayer substrate or the like. Next, a case where the epoxy resin composition of the present invention is used as a sealing material of a photo-semiconductor or a dlebQnd material will be described in detail. The use of the curable resin composition of the present invention as a sealing material or a die-bonding material for a high-brightness white (10) body is achieved by a ring: a tree, a hardener, a coupling agent, an antioxidant, and a light. A curable resin composition is prepared by blending an additive such as a stabilizer, and a mixing method is used as long as a kneader, a three-roller, a universal mixer, a planetary mixer, a homomixer, a homogenizer, a bead mill, or the like is used. It can be mixed at room temperature or under heating. 44 201118134 The crystal material and the obtained curable resin composition can be used for both sealing materials and adhesive sealing materials. - Same as 7C white LED, etc. jjL road ship -ja + The conductor element is usually formed by laminating a semiconductor wafer such as sapphire, spinel, Sic, si, zn0, etc. on a lead frame or a heat sink or a package using an adhesive (adhesive material). °In order to flow current 'there is also a type of wire connecting a gold wire. Aspects are semiconductor wafers, sealed with a sealing material such as epoxy resin. The sealing material is used to protect the semiconductor wafer from heat or moisture. And it is used for the function of the lens. The curable resin composition of the present month can be used as the sealing material or the die-bonding material H, and t' is suitable for the use of the curable resin composition of the present invention for the die-bonding material and Both of the sealing materials. A method of adhering a semiconductor wafer to a substrate using the curable resin composition of the present month, and applying the curable resin composition of the present invention to the substrate by dispenser, filling or screen printing, A method in which a semiconductor wafer is mounted on the curable resin composition and heat-hardened. The semiconductor wafer can be attached to the substrate by the 3H method. Hot air circulation type, infrared ray, high frequency, etc. can be used for heating. The heating conditions are, for example, preferably from 80 to 230 ° C and from 1 minute to 24 hours. . In order to reduce the internal stress generated during heat hardening, for example, it can be pre-hardened at 8 〇 to 12 ° C for 30 minutes to 5 hours, after 12 〇 18 〇 t 〇 〇 t t t 〜 〜 〜 〜 〜 〜 After the hardening. The sealing material can be formed by using:

45 201118134 An injection method in which a sealing material is injected into a mold of a substrate of a semiconductor wafer, and then formed by heat curing; a sealing material is preliminarily injected onto the mold to impregnate the semiconductor wafer fixed on the substrate, and after heat curing 'Compression forming method for demolding from the mold. Examples of the injection method include a dispenser, transfer molding, and injection molding. For heating, a hot air circulation type, an infrared ray, a high frequency, or the like can be used. The heating condition is, for example, preferably 80 to 23 (rc '1 minute to 24 hours or so.) To reduce the internal stress generated during heat curing, for example, it can be pre-hardened at 8 Torr to 120 ° C for 30 minutes to 5 hours. 12 〇 18 〇 匚 匚 μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ Examples thereof include an adhesive, a coating material, a coating agent, a film of a molding method, an FRP film, an insulating material (including a printed circuit board 'wire coating, etc.), a sealing material, and a sealing material; A magical lift &amp; sealant, a cyanate resin for a substrate, or an additive such as an acrylic acid vinegar resin as an anti-surname hardener, an additive such as a resin, or the like. Examples of the subsequent agent include an adhesive for civil engineering, construction, automotive, general affairs, and medical use, and an adhesive for the use of electronic materials for the use of electronic materials. ^ Among them, the adhesive for electronic materials, for example, layered substrate (four) substrate) and other layers of the multilayer substrate indirect f; m Chuu · ... Zeng μ W sticky sundraft, underfill (under 1), etc. + conductor Adhesive; _ bottom filler (called anisotropic conductive paste (ACP) and other adhesives for installation. Sealant's can be cited: capacitors, transistors, diodes, illuminating two 46 201118134

Packing, impregnation, transfer molding and sealing for polar body, IC, LSI, etc.; filling and sealing for COB, COF, TAB, etc. of IC and LSI; flip-chip filling; QFP, BGA, CSP, etc. The same as the use of the bottom filler). F-package-sealing seal (including the hardened material obtained in the present invention can be used for various purposes in optical zero. The so-called optical material is usually used to make visible light, infrared rays, ultraviolet rays, X-rays, lasers, etc. Through the material in the material: two more specifically - in addition to the lamp type, (10) type and other coffee sealing materials can be: the following: in the field of liquid crystal display substrate materials, guide plates, sheet materials, deflection A liquid crystal display device such as a liquid crystal film such as a plate, a retardation film, a viewing angle correction film, an adhesive, or a polarizer (P〇larizer) protective film. X, a color PDP that is expected as a next-generation flat panel display (PlaSma) Display, anti-reflective coating, optical correction film, outer casing material, protective film for front glass, front glass replacement material, adhesive; and (4) mold materials used in LED display devices, LED Sealing material, protective film on front glass field, front glass replacement material, adhesive; and electric forging address liquid crystal (piasma (4) (10)

Substrate material, light guide plate, prism sheet, deflecting plate, phase difference plate, viewing angle correction film, adhesive, polarizer protective film in Uqiud Crysta PALC) display; and organic EL (Electr〇 Luminescence) display A protective film for a face glass, a front glass substitute material, an adhesive; and various film substrates in a field emission display (Field Emissi® 11 Display, FED), a protective film for the front glass, a front glass replacement material, and an adhesive. In the field of optical recording, it is VD (Vide〇Disc, video CD), 47 201118134 CD/CD-ROM, CD-R/Rw, DVD-R/DVD-RAM, MO/MD, PD (PhSae-Change Disc, Phase change optical disc), optical card (the disc substrate material for 〇pticai, pickup_up lens, protective film, sealing material, adhesive, etc.) In the field of optical equipment, it is a still camera. The material for the lens, the viewfinder, the target, the viewfinder [the light sensor unit. Also, the camera lens of the video camera, the framing stomach. In addition, the projection of the projection TV (four) head '(four) film '(four) material' A material for a lens of a light sensing device, a sealing material, an adhesive, a film, etc. In the field of optical parts, a fiber material, a lens, a waveguide, a sealing material for a component, and an adhesive for an optical switch in an optical communication system. Etc. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. In the passive parts of the light, in the circuit parts, it is a lens, a waveguide, a material of the LED (4), a sealing material of the CCD, a follower, etc. Photoelectrons Integrated circuit (〇EIC) Substrate material 'fibrous material, sealing material for components, adhesive, etc. In the field of optical fiber, it is used for lighting/light guides for decorative displays, sensors for industrial use, display/logging, etc.; An optical fiber used for connection between digital devices in facilities and homes. It is used as a resist material for microlithography for LSI and ultra-lsi materials in the peripheral materials of semiconductor integrated circuits. 'For automotive reflectors, bearing retainers, gear parts' corrosion resistant coatings, switch parts, headlights, engine parts, motor parts, various internal and external products, drive engines, brake oil tanks, automotive rust-proof steel, In-car electric disc (lnten〇r P followed by 1), interior materials, harness for protection/bundling, fuel soft, auto lamp, glass substitute β χ 'for the complex layer of railway vehicles 48 201118134 for the second aircraft Resilience members for structural materials, wiring harness for protection/twisting, corrosion-resistant coating w, engine peripheral packaging/processing materials, electrical cover~: in the construction field, for inner Tt ¥ 虱盍 料 、 、 、 、 太Battery peripheral material ^ Intermediate film, broken sputum substitute, for lower-generation use, for greenhouse coating film. For the branch, organic (four) shooting element% of peripheral materials, organic solar cell peripheral heart (four) enlargement 7 &quot; , sealing materials for optical transportation, adhesives, etc. Other uses of board materials, fiber materials, and materials for component optics, for general use, for example, can be exemplified by the use of a hardening resin to form a shape boat. An adhesive, a coating, a coating agent, a handle sheet, a film, an FRP, etc., an insulating material (including a printed circuit, a wire coating, etc.), a sealant, and an additive added to a special one. EXAMPLES Hereinafter, the present invention will be described in more detail by way of Synthesis Examples and Examples. Furthermore, the present invention is not limited to the above-described synthesis examples and examples. Further, in the following synthesis examples and examples, "parts" means parts by weight, and "%" means reset 〇/〇. Further, each physical property value in the examples was measured by the following method. (1) Molecular weight: The weight average molecular weight was calculated by a gel permeation chromatography (Gpc) method under the following conditions. GPC various conditions Manufacturer: Shimadzu Manufacturing Bureau column: protection column SHODEX GPC LF-G LF-804 (3) Flow rate · 1·〇rni/min 49 201118134 Column temperature: 40 °C Solvent: THF (four Hydrogen furan 0) Detector: RI (differential refractive index detector) (2) Epoxy equivalent: Measured by the method described in isJis K-7236. (3) Viscosity. The measurement was carried out at h ° C using an e-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd. Synthesis Example 1 Manufacturing step (1): (1) 3,4-epoxycyclohexyl)ethyltrimethoxyxanthene, weight average molecular 4 17 〇〇 (calcical value) 234 parts of Weiyou oil (calculated as the equivalent of the weight average molecular weight measured by Gpc), 18 parts of the methanol solution of 〇·5% potassium hydroxide (KOH) (KOH part Α η λο &amp;, the number of turns is 0·09 parts), placed in a reaction vessel, and the bath temperature was set to 75 ° C. The temperature was raised to 0 liters, the field was opened, and the dish was refluxed for 8 hours. Production step (ii): adding decyl alcohol 3 After 5 parts of drunken water, 86.4 parts of a methanol solution of 5 % by weight of distilled water was added dropwise thereto over 6 minutes, and reacted at 75 Torr for 8 hours under reflux with 4 π. After completion of the reaction, the mixture was neutralized with 5% phosphoric acid-gas, aqueous sodium sulphate solution, and then distilled under methanol at 8 ° C. Add fluorenyl isobutyl ketone (MIBKP 80 h, repeat water washing 3 times. Then, under π decompression, i 〇〇 C, there is a solvent removed) to obtain a reactive functional group (A-1) 3^. The obtained compound has an epoxy equivalent of 718 g/eq, and the M average molecular weight is 2200'. The appearance is colorless and transparent. q·Weight Synthesis Example 2

In a flask equipped with a mixer, a refluxing AL condenser, and a stirring device, a nitrogen purge was applied to the surface, and in the flask __ &lt; 1 &lt; k bottle, 20 parts of dicyclodecane dimethanol was added to the surface of the flask. Six 50 201118134 Hydrogen phthalic anhydride (manufactured by Shinji Ryo Chemical Co., Ltd., Rikacid μη, hereinafter referred to as anhydride (Η-1)) 100 parts 'reacted at 40 ° C for 3 hours, at 70 ° C Heating and stirring for 1 hour (confirmation of disappearance of tricyclodecane decyl alcohol by GPC (1 area% or less)), thereby obtaining a hardener composition containing a plurality of polyphenolic acid (B-1) and an acid needle (η-1) (T-1) 1 20 copies. The obtained hardener composition 丨) was a colorless liquid resin, and the purity obtained by GPC was 53.% area acid anhydride (H-1) was 45 area%. Further, the functional group equivalent was 201 g/eq. The viscosity at '25C is 18900 mPa · s (E-type viscometer).

Synthesis Example 3 In a flask equipped with a stirrer, a reflux condenser, and a stirring device, while nitrogen gas was purged, 20 parts of 2,4-diethylpentanediol and 2 parts of acid oxime (Η-1) were added thereto. After reacting at 4 ° C for 3 hours, the mixture was heated and heated at 70 ° C for 1 hour (the disappearance of 2,4-diethylpentanediol (1 area% or less) was confirmed by GPC". The hardener composition (T-2) of the carboxylic acid (B-2) and the acid anhydride (H-1) was 120 parts. The obtained hardener composition (T-2) is a colorless liquid resin 'purity obtained by GPC, the polycarboxylic acid (B-2; the following formula 8) is 5 Å area%, and the acid anhydride (H-1) is 50 area. %. Further, the functional group equivalent is 2〇1 g/eq_. Also, 25. (The viscosity below is 16200 mPa · S (E-type viscometer). 51 201118134

Synthesis Example 4 Manufacturing step (i): Α μ Λ ^ Μ point - (3,4-epoxycyclohexyl)ethyltrimethoxy 矽 2 2 2 6 parts, heavy 詈 泊 分 j j β 卞 卞 summer 505 parts of 1700 (GPC measured value) of decyl alcohol end methylphenyl polyoxyl oil (the amount of broken alcohol is 85 〇, #出为为为为重量的重量的均均均均均的半半) 〇5. 40 parts of the potassium oxide (κ〇Η) methanol solution (KOH portion, 份, part, 〇 2 parts) was placed in a reaction vessel, and the bath temperature β was again increased to 75 C ' to raise the temperature. After the temperature was raised, the reaction was carried out under reflux for 8 hours. Production step (ii): After adding 51 parts of methanol, 5 parts by weight of methanol (4) (10 parts) was added dropwise thereto over 6 minutes, and the mixture was reacted under reflux for 8 hours under reflux. After the completion of the reaction, the mixture was neutralized with a 5% aqueous solution of sodium dihydrogen phosphate and then recovered at 8 〇 c. 7 〇 4 parts of 曱-isobutyl hydrazine (mibk) was added, and washing was repeated 3 times. Then, the solvent was removed from the organic phase under reduced pressure at &lt;t&gt;, whereby 697 parts of an organic polyfluorene oxide (?-2) having a reactive functional group was obtained. The obtained compound had an epoxy equivalent of 598 - and a weight average molecular weight of 2,370 Å. The appearance was colorless and transparent. Synthesis Example 5 In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 12 parts of tricyclodecane dimethanol and 18 parts of 2,4-diethyl-1,5-pentanediol were added while performing nitrogen purge. 'Methylhexahydrophthalic anhydride (manufactured by Shinji Ryo Chemical Co., Ltd., equivalent to Rikacid MH anhydride (H_1)) 155 parts, hydrazine, 3,4-cyclohexanetricarboxylic acid _3,4-anhydride ( Manufactured by Mitsubishi Gas Chemical Co., Ltd., Η_ΤΜΑη', the following 52 201118134 is called anhydride (H-2)) 15 parts 'reacted at 40 ° C for 3 hours, at 70. (: heating was carried out for 1 hour (by GPC, the disappearance of the raw material alcohol (% by area or less) was confirmed), whereby hardening of the polycarboxylic acid (8_丨) (3_2) and the acid anhydride (H_i) (H_2) was obtained. The composition of the agent (T-3) was 200 parts. The obtained hardener composition (τ·3) was a colorless liquid resin, and the purity obtained by GPC, the polycarboxylic acid (Β_丨, β_2) was 52 area%, and the acid anhydride ( 11_丨, Η_2) is 48% by area. Further, the functional group is 9〇g/eq. Further, the viscosity at 25C is i5500mPa.s (E-type viscometer). Synthesis Example 6

Manufacturing step (i): 44 parts of 々_(3,4-epoxycyclohexyl)ethyltrimethoxydecane, weight average molecular weight 17 〇〇 (Gpc measured value) of decyl alcohol terminal methyl phenyl poly secoxide 153 parts of oil (money alcohol equivalent (four), #1 is an alcohol solution using a weight average molecular weight measured by GPC, 11.2 parts (the KOH fraction is 75 ° C, the temperature is raised. Half), 0.5% potassium hydroxide (KOH) 曱〇, 份 56 parts) placed in the reaction vessel, will. After the temperature was raised, the reaction was carried out under reflux for 8 hours. "Step (il): After adding 157 parts of methanol, 19 parts of 5 methanol solution was added dropwise over 60 minutes, and under reflux, after the reaction was heard, the reaction was completed. The sodium dihydrogen phosphate aqueous solution was neutralized, and then recovered by distillation of the dibutyl alcohol. The methyl isobutyl ketone (MIBK) 1 was added and washed twice with water, and then under reduced pressure, (10). The solvent is removed, thereby obtaining an organic polyfluorene oxide having an identifiable g-energy group, and the epoxy equivalent of the compound is set to 2100, and the appearance is colorless and transparent. 53 201118134 Example 1, 2 ' 3. 4. Comparative Example 1 '2, 3 The organic oxime compound (Α-1) obtained as a synthetic example of the epoxy resin, and the hardener composition obtained in Synthesis Examples 2 and 3 as a curing agent (τ- υ, (τ-2) (the ratio of organopolyoxygen (Α) to hardener composition (丁_丨), (τ·2) is 1:1 in terms of functional group equivalents), as a salt and/or 2-ethylhexyl phosphate of zinc complex (phosphoric acid: monoester: diester: triester 3 5 : 68.2 : 26.5 : 1_8 ' The basic treatment, so the sensitivity is different, not the correct weight ratio. Hereinafter referred to as the salt complex and / or zinc complex (C-1) zinc complex (disc: zinc = 1 _7: }, using ICp It is determined by light emission spectroscopy and is produced according to JIS K0166) propylene glycol solution (manufactured according to 曰本特表 2003-51495, hereinafter referred to as a four-stage scale salt as a hardening accelerator (manufactured by Sakamoto Chemical Industry, Hishic〇) Hn PX 4 Μ P 'hereinafter referred to as catalyst (I _ 1)) 'As an additive, bis(2,2,6,6-tetradecyl_4_piperidinyl) sebacate (manufactured by ciba Japan, TINUVIN770DF, hereinafter referred to as (L-1)), and 4,4,_butylidene bis(3-methyl-6-tris-butylphenyl-di-tridecylphosphoric acid) as a phosphorus compound (ADEKA manufactured 'Adekastab 260, hereinafter referred to as (M-1)), and blended with the blending ratio (parts by weight) shown in Table 1 below for '20 minutes of defoaming' to obtain the present invention or comparative use thereof. A curable resin composition. The obtained curable resin composition was slowly cast in a test piece mold, and the cast material was pre-hardened at 12 〇t x 3 hours. The hardened material for various tests was obtained under the conditions of l50 ° Cxi, and the obtained cured product was evaluated for the following hardness and thermal durability transmittance test under the conditions described below. And shown in Table 1 below. 54 201118134

(Hardness) The Shore A was measured in accordance with JIS K 7215 "Test Method for Hardness of Plastic Durometer". (Thermal durability penetration test) Heat resistance test conditions: % hour in the i 50 oven. Test piece size: thickness 1 mm Evaluation conditions: The transmittance of 4 〇〇mm was measured by a spectrophotometer, and the rate of change was calculated ( Retention rate). (LED lighting test) Further, the curable resin composition obtained in the examples and the comparative examples was subjected to vacuum defoaming for 20 minutes, and then filled in a syringe, and cast using a precision discharge device. A surface mount type LED having a light emitting element having an emission wavelength of 465 nm. Thereafter, it was cured under specific hardening conditions (2 hours at TC (2 hours at TC, then 3 hours at i50 °C) to obtain an LED for lighting test. The lighting test was performed with a predetermined current. That is, the lighting test under 60 mA (fixed current drive 'specified current 30 mA) was measured, and the initial illuminance was measured. 55 201118134 [Table i] Item Example 1 Example 2 Comparative Example 1 Composition of epoxy resin organopolyoxyl A- 1 10.0 10.0 10.0 Hardener hardener composition T-1 2.8 2.8 2.8 T-2 Hardening accelerator zinc salt (complex) C-1 0.01 0.03 Grade IV salt 1-1 0.01 Additive light stabilizer L-1 0.03 0.03 0.03 Phosphorus compound M-1 0.03 0.03 0.03 Hardened physical hardness test Xiao A 97 97 98 Thermal durability penetration test retention (400 nm) % 98.3% 98.6% 97.7% LED spot test initial illumination mW 9577 9597 8183 Item Example 3 Comparative Example 2 Composition Epoxy Resin Organic Polyoxo A-1 10.0 10.0 Hardener Hardener Composition T-1 T-2 2.8 2.8 Hardening Accelerator Zinc Salt (Zinc Complex) C-1 0.03 Quaternary Phosphate 1-1 0.03 Additive Light Stabilizer L-1 Phosphorous compound M-1 Hardening physical hardness test Xiao A 90 90 Thermal durability penetration test retention (400 nm) % 95.1% 82.1% LED spot test initial illuminance mW 7737 4993 Item Example 4 Comparative Example 3 Composition Epoxy Resin Organic Polyoxygen A-1 10.0 10.0 Hardener Hardener Composition T-1 T-2 2.8 2.8 Hardening Accelerator Zinc Salt (Zinc Complex) C-1 0.01 Grade IV Salt 1-1 0.01 Additive Light stabilizer L-1 0.05 0.05 Phosphorus compound M-1 0.05 0.05 Hardened physical hardness test Xiao A 93 92 Thermal durability penetration test retention (400 nm) % 97.5% 95.3% LED dot test initial illumination mW 9037 9030 56 201118134 Examples 5, 6 and Comparative Example 4 The organic polyphosphate compound (A-2) obtained in Synthesis Example 2 as an epoxy resin and the hardened rubber 2 obtained as a curing agent were used. Composition (T-1) (the ratio of organopolyoxane (A) to hardener composition (τ_ι) is 1:0.8 in functional US equivalent), zinc salt as a hardening accelerator, and/or dysfunctional (C-1), catalyst (1), additive 丨). The blending ratio (parts by weight) shown in the following Table 2 was blended, and defoaming was carried out for 2 minutes to obtain a curable resin composition of the present invention or comparatively. The obtained curable resin composition was slowly cast into a test piece. The molded product was hardened under conditions of (9) hours after pre-hardening of TCx for 3 hours, and hardened materials for various tests were obtained. The test of the following heat resistance test, hardness, and penetration test was carried out under the article # and the rail under the article described below. The results are shown in Table 2 below. (Fuel and heat characteristics test) Measurement conditions DMA-2980 Dynamic Viscoelasticity Measurement. Τ Λ . + β I Job · lA_lnstruments Manufacturing Measurement Temperature Range: · 3 〇.〇~2 8 〇t Heating rate: 2°C/min mm (thickness about 800 test piece size) : Use to cut into 5 mmx50 // m). Analysis conditions

Tg: The peak point of Tan_5 under DMA measurement is taken as ^30. (: Elastic modulus: elastic modulus at 敎3〇t.

57 201118134 (hardness test)

Xiao's A was measured according to JIS K 7215 "Testing method for hardness of plastic durometer". 0 (Permeability test) Test piece size: Thickness 1 mm Evaluation conditions: The transmittance of 4 〇〇 ηιη was measured by a spectrophotometer. Further, the obtained curable resin composition was filled in a syringe, and the surface mount type LED package having an outer diameter of 5 mm square, which was mounted on a wafer having a central light-emitting wave of 465 nm, was molded by a precision discharge device. (inner diameter 4 mm, outer wall height 丨 25 mm). The cast was placed in a heating furnace at 12 Torr. (: The hardening treatment was performed for 1 hour, and further hardening treatment was performed at 15 ° C for 3 hours to prepare an [ED package. The LED package was placed in a corrosive gas under the following conditions, and the seal was observed. The color change of the lead frame of the internal silver chain (corrosion gas permeability test). The results are shown together in Table 2. (Corrosion gas permeability test) Determination of the condition of the gas: ammonium sulfide 20% aqueous solution ( When the sulfur component reacts with silver, it turns black. Contact method: In a wide-mouth glass bottle, the container of the ammonium sulfide aqueous solution and the upper LED package are mixed and covered with a wide-mouth glass crucible in a sealed state. The volatilized ammonium sulfide gas is brought into contact with/exposed to the Led package. Judgment of the corrosion: Observing the blackening of the lead frame inside the LED package (referred to as 58 201118134 blackening) 'The longer the discoloration time, the corrosion-resistant gas is judged The more excellent the observation system was taken out after 丨 hours, 2 hours, 3 hours, and 4 hours later, the evaluation was regarded as 〇 without color change, and the color of brown to brown was regarded as X, and those who were completely blackened were regarded as XX. [Table 2] Composition | Hardening properties

J is a hardened material (LED lighting test) which is excellent in heat-resistant coloring property (heat-resistant transmittance test) of the present invention and which is excellent in heat resistance (LED lighting test), and optical examples 5, 6, and comparative examples. 4 It is understood that the hard twitch of the present invention provides a hardened material excellent in gas permeability (the gas permeable gas is to be used as a semiconductor wafer which is weak to the external environment or [in the field of heart-drying characteristics. 59 201118134 Example) 7-1 2. Comparative Examples 5 to 9 The organic polyoxosiloxane (Al) '(A-2) ' (A-3) obtained as a synthetic example of an epoxy resin, 4, 6 was used as a hardener. The ratio of the hardener composition (T_丨), (T_2) (organic polyfluorene oxide (a) to the hardener composition (T-丨) or (T_2) obtained in Synthesis Examples 2 and 3 is equivalent to the functional group. Calculated as 丨·· 〇8), the anhydride (Η-1) (the ratio of organopolyfluorene (Α) to anhydride (Η-1) is 1: 〇.8 in terms of functional group equivalent), as zinc salt and / Or zinc complex compound of zinc 2-ethylhexanoate (c_2), zinc undecylenate (C-3), zinc 2-ethylhexanoate (containing imidazole compound, magic %)

Manufactured by Industry, χκ_614, hereinafter referred to as (c_4)), a quaternary scale salt as a hardening accelerator (manufactured by Nippon Chemical Industry, Hishic 〇Hn ρχ·4Ετ, hereinafter referred to as catalyst (1-2)), an imidazole compound ( Manufactured by Shikoku Kasei, 2Ε4ΜΖ, hereinafter referred to as catalyst (1-3)), as an additive, bis(2,2,6,6-tetramethylpiperidyl) sebacate (manufactured by Ciba japan, TINUVIN77〇DF In the following, it is called "^)), and the blending ratio (parts by weight) shown in the following table is carried out, and the "Shaw/Pack" in the inside is obtained to obtain the curable resin composition of the present invention or comparatively. The curable resin composition to be poured is slowly cast into the test piece mold

In the case of i 1 (r χ 3 hr pre-hardening, hardening under 14 〇 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得The test (the same as the above) except for the test method and the like, except that after 2 hours, 3 hours, 3 hours, and 10 hours after the observation, the results are shown in Table 3 below. , 4 in. 201118134 [Table 3]

Item Example 7 Example 8 Example 9 Comparative Example 5 Comparative Example 6 Comparative Example 7 Composition Epoxy Resin Organic Polyoxo A-1 7.1 7.1 7.1 7.1 7.1 7.1 Organic Polyoxo A-2 Organic Polyoxo A-3 Hardener hardener composition T-1 1.6 1.6 Hardener, composition T-2 1.6 1.6 1.6 1.6 Anhydride H-1 Zinc salt (zinc complex) C-2 0.07 C-3 0.07 C-4 0.07 Hardening accelerator Grade 4 salt 1-2 0.07 Imidazole compound 1-3 0.07 Additive light stabilizer L-1 0.01 0.01 0.01 0.01 0.01 0.01 Hardening ^Do not corrosive gas penetration test exposure time 1 h 〇〇〇〇〇〇2h 〇〇 〇〇〇〇3h 〇〇〇〇〇〇6h 〇〇〇XXX lOh 〇〇〇XX XX XX

[Table 4]

Item Example 10 Example 11 Example 12 Comparative Example 8 Comparative Example 9 Composition Epoxy Resin Organic Polyoxo A-1 Organic Polyoxo A-2 6.0 6.0 6.0 6.0 Organic Polyoxo A-3 10.2 Hardener Hardener Composition T-1 1.6 1.6 1.6 Hardener Composition T-2 Anhydride H-1 1.3 1.3 Zinc Salt (Zinc Complex) C-2 0.06 C-3 0.06 0.06 C-4 Hardening Accelerator Grade IV Scale Salt 1- 2 0.06 0.06 mic. Sitting compound 1-3 additive light stabilizer L-1 hardening physical corrosion gas permeability test exposure time 1 h 〇〇〇〇〇2h 〇〇〇〇X 3h 〇〇〇〇X 6h 〇〇〇X XX lOh 〇〇 X XX XX 61 201118134 Example 1 3, 14 A synthetic polysiloxane compound (Α_3) obtained as a curing agent, a hardener composition obtained in Synthesis Example 5 as a curing agent (Τ- 3) (Comparative ratio of organopolyfluorene (Α) to hardener composition (τ_3) 舍番i dry M s忐基田t is 1: 〇.8), zinc salt and / or zinc complex (C- 1), (c_2), an additive, a hindered amine compound (manufactured by Adeka, LA_8丨, referred to as (L·2)), a phosphorus compound (manufactured by Adeka, Adeka 260, hereinafter referred to as (L_3)), The blending ratio (parts by weight) shown in the following Table 5 was blended, and defoaming was performed for several minutes to obtain a curable resin composition of the present invention. (the sulphur gas gas permeability test) The known curable resin composition is slowly cast into the test piece mold. 'The cast material is made at 12 (rCxl hour pre-hardening, 15 〇 it ^ It is hardened under the conditions of 3 j to obtain various hardened materials for the test. The gasification test of the gasification of the obtained compound is carried out (the test method and the like are the same as above). The results are shown together in Table 5 below. /. (LED dot test) The obtained curable resin composition was filled in a syringe, and cast into a surface mount type LED (SMD) equipped with a light-emitting element having an emission wavelength of 465 using a fine squirting device. Type, 5 _φ, specified current 2 〇 mA). Thereafter, it is hardened under specific hardening conditions (i 2 〇 under it for 2 hours and further at 15 ° C for 3 hours), thereby obtaining a lighting test. Led. The lighting test is performed on a lighting test that greatly exceeds the current of 2 mAi at 23 mA. The detailed conditions are shown below. The measurement items are measured by using an integrating sphere to measure the illuminance before and after lighting for 40 hours. Illumination for test (4) 62 2011 18134 Cao retention rate. The results are shown in Table 5. Point 1^ Detailed conditions Luminescence wavelength: Center emission wavelength, 465 nm Drive mode: Constant current mode, 230 mA (20 mA specified current of the illuminating element) Three driving environments: 25 ° C, lighting evaluation in a 65% damp heat machine: The illuminance after 20 hours and 40 hours and the illuminance retention rate were measured. [Table 5] Item Example 13 Example 14 Epoxy resin organic polymerization Neodymium A-3 10.2 10.2 Hardener Hardener Composition T-3 1.5 1.5 Zinc Salt (Zinc Complex) C-1 0.05 C-2 0.03 Additive Light Stabilizer L-2 0.02 0.02 Obstruction Compound L-3 0.02 0.02 Main 1 # t fp| iw Corrosion gas penetration test exposure time 10h 〇〇 lighting test (230 mA) illuminance (# W) / illuminance retention rate (%) 0 h (ref) 9900 9900 20 h 9950 10100 100% 102% 40 h 8400 10200 85% 103% The present invention has been described in detail with reference to the specific embodiments thereof, and it is understood that various changes and modifications can be made without departing from the spirit and scope of the invention. The application is based on November 30, 2009. Please refer to this patent application (Japanese Patent Application No. 2009-271469), the entire disclosure of which is incorporated herein by reference. Explanation of symbols] Μ # »»&gt; 64

Claims (1)

201118134 VII. Patent application scope: 1. A kind of hardening resin composition, which is composed of organic polyoxygen (A), zinc salt and/or zinc complex (c), among which, organic polyfluorene Oxygen (A) satisfies the following conditions: Organic polyfluorene (A): ";" An epoxy resin having a glycidyl group and/or an epoxycyclohexyl group in the knife. 2. The curable resin composition of claim 1, wherein the salt and/or the zinc complex (c) is one selected from the group consisting of lactic acid and phytic acid. At least one of the group consisting of a zinc salt and a zinc complex containing the acid and the zinc salt as a ligand.曰3. The curable resin composition of claim i, wherein the zinc salt and/or the zinc complex (c) is selected from the group consisting of a zinc salt of a carboxylic acid having a carbon number of 1 to a tannic acid with a And at least one of the group consisting of a zinc complex as a zinc complex of a ligand. 4. The curable resin composition according to any one of claims 1 to 3, which contains a polyvalent carboxylic acid (B) having two or more carboxyl groups and having an aliphatic hydrocarbon group as a main skeleton. 5. A curable resin composition as claimed in claim 4, wherein. The 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. 6. The curable resin composition according to any one of claims 1 to 5, which contains an acid anhydride. 7. The curable resin group 65 201118134 according to any one of claims 6 to 6, which contains a hindered amine light stabilizer and/or a phosphorus-containing antioxidant. A hardened material obtained by hardening a curable resin composition according to any one of claims 1 to 7. Eight, schema · (none) 66