TW201116555A - Polycarboxylic acid composition, process for preparation thereof, and curable resin compositions containing the polycarboxylic acid composition - Google Patents

Abstract

Provided is a polycarboxylic acid composition which ensures reduction in the volatilization of a curing agent in curing and which can provide cured products that exhibit excellent heat resistance, light resistance, resistance to corrosive gas permeation, tight adhesion, and toughness. The polycarboxylic acid composition is characterized by comprising both (J) a carboxylic acid compound obtained by addition reaction of (a) a silicone oil represented by general formula (1) with (b) a compound that contains at least one carboxylic anhydride group in the molecule and (K) a polycarboxylic acid compound obtained by addition reaction of (c) a saturated aliphatic polyhydric alcohol that has two or more alcoholic hydroxyl groups with (d) a compound that has at least one carboxylic anhydride group in the molecule. In general formula (1), R1 is an alkylene group that contains 1 to 10 carbon atoms in total and may be interrupted by an ether linkage; R2 is methyl or phenyl; and n represents the number of repeating units, with the weight-average molecular weight of the compound of general formula (1) being 500 to 5000.

Description

201116555 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to a polyvalent decanoic acid = product suitable for use in electrical and electronic materials and a method of manufacturing the same. Further, the present invention relates to a curable resin composition containing the above-mentioned cerium carboxylic acid composition as a curable component. [Prior Art] ^Manganic acid has high thermal stability, good electrical properties, and chemical resistance. In addition, it has been excellent in the production of a raw material for a polymer, and has been widely used as a raw material for polymer production in recent years. Further, polycarboxylic acids are also known as hardeners for epoxy resins. A curable resin composition containing an epoxy resin is used as a resin excellent in heat resistance in the fields of construction, earthenware, automobiles, airplanes, and the like. In recent years, especially in the field of semiconductor-related materials, "light, 溥, short, and small, such as mobile phones with cameras, ultra-thin LCD or electric τν, lightweight notebook computers, have become the key words. Electronic machines, therefore, have begun to require very high characteristics for packaging materials represented by epoxy resins.曰μ 卞,,,~π卬X to 躅目0 ', is accompanied by the recent high level of information 'for the smooth transmission and processing, the information' ^ in the previous electrical wiring for signal transmission, and to ensure effective use The technology of optical signals. In addition, it has been desired to develop a resin composition of a cured product having excellent transparency in the field of optical components such as an optical waveguide, a blue LED, and an optical semiconductor. The hardeners of epoxy resins generally used in the above-mentioned fields are exemplified by the compounds of the 2011-11555 acid group. In particular, the acid liver compound formed by the saturated hydrocarbon is excellent in the optical property, and therefore it is used more (for example, benefits: 1 and 2). The acid anhydrides are generally alicyclic acid needles such as methyl-tetrahydrophthalic anhydride, hexahydro-o-benz-anhydride, and phthalic anhydride, which are easy to use. t ' is mainly used for methyl hexahydrophthalic anhydride or decyl tetrahydrophthalic anhydride which is liquid at normal temperature. However, in the case of using the above alicyclic acid needle as a hardener, the present hardener has a higher vapor pressure, and a portion tends to evaporate when hardened. Therefore, the use of the alicyclic anhydride as an epoxy resin is used. When the hardener is thermally hardened by an open system, the alicyclic acid liver is volatilized in the atmosphere, pollutes the environment due to release of harmful substances in the atmosphere, and has an adverse effect on the human body. In addition, there are also pollution production lines, and the problem of poor curing of the epoxy resin composition due to the absence of a specific amount of acid anhydride (hardener) in the hardened material is not only a flaw, but its characteristics are also greatly affected by the hardening conditions. The change 'it is difficult to stably obtain a cured product having a target property. The effect of the above volatilization on the hardened material is remarkably exhibited in the case where the led, particularly the sealing SMD (Surfaee Μ〇 _ Deviee, surface mount member), is sealed by using a cured product using a prior acid anhydride as a hardener. Since the amount of resin used for sealing the LED is small, if a volatilization of phthalic anhydride occurs, j will cause a depression, and in severe cases, a line exposure will occur. Further, since cracking or peeling occurs during reflow soldering, or hardening is insufficient, there is a problem that the obtained cured product is hard to withstand long-term lighting. JP-A-2003-277473, JP-A-2003-277473, JP-A-2003-277333, JP-A-2003-277333, discloses a method of using a multi-component tannic acid as a curing agent for such a problem. However, the usual multi-hearted ^ ^ ^ is difficult to cure due to its hydrogen bonding, especially crystallization. It is very difficult to use in the form of a liquid composition. In order to solve such a problem, the inventors of the present invention conducted a discussion on the use of polyoxic acid as a hardener in the group, and in the case of the use of a polyfluorene-based carboxylic acid as a hardener. In the following, although it is possible to solve the problem of volatility, it is difficult to use as a seal in terms of adhesion and corrosion-resistant gas permeability. Hardened material such as materials. Further, the hardening obtained in the hardening of the epoxy resin of the organic oxy-oxygen type is liable to be brittle, and there is a problem in the toughness. An object of the present invention is to provide a polyvalent m acid composition and a method for producing the same. The polycarboxylic acid composition can provide volatilization of a curing agent during curing, thereby further improving heat resistance, light resistance, and corrosion resistance. Excellent hardened material such as adhesion and toughness. Further, an object of the present invention is to provide a curable resin composition containing the polyvalent m acid composition. The present inventors have actively conducted discussions on the above-mentioned actual conditions, and as a result, have completed the present invention. In other words, the present invention relates to: () a compound of the compound of the formula, comprising a slow acid compound (1) and a polycarboxylic acid compound (K), which is represented by the following formula (1) The poly-shixi Oxygen oil (4) is reacted with 6 (1) 201116555 compound (b) in the molecule with more than one slow acid needle base:

R2

IT—Ri - OH R2 (In the formula (1), Ri represents a stretching group having a total number of carbons of 1 to 10 via an ether bond, and R 2 represents a fluorenyl group or a benzoquinone; and η represents a repeating unit, a formula (丨) The weight average molecular weight of the compound is 500 to 5000). The polycarboxylic acid compound (K) has one or more saturated aliphatic polyols (c) having an alcoholic trans group having two or more functional groups. (2) A polycarboxylic acid composition according to the above item (1), wherein the above compounds (匕) and (d) are a cyclic saturated hydrocarbon as a parent skeleton. (3) The polycarboxylic acid composition according to the above item (1) or (2), wherein the above compounds (b) and (d) are selected from the group consisting of mercaptohexahydrophthalic anhydride and hexahydrophthalic acid. At least one acid anhydride in the group consisting of an acid anhydride, cyclohexane-1,2,4-tridecanoic acid-1,2-anhydride, and bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride; 4) The polycarboxylic acid composition according to the above item (3), wherein the above compounds (b) and (d) have methylhexahydrophthalic anhydride as an essential component; (5) if the items (1) to (4) Diversified a carboxylic acid composition, wherein the compound (c) is a polyol having a functional group number of 2 to 6, and the total carbon number in one molecule is 5 to 20; (6) a method for producing a polybasic citric acid composition, which is used for The polycarboxylic acid composition according to any one of the above items (1) to (5), which is characterized in that: a saturated aliphatic polyhydric alcohol containing a polyfluorene oxide (a) and an alcoholic hydroxyl group having two or more functional groups ( a mixture of c), a compound (b) and (d) having more than one carboxylic acid anhydride group in the molecule, and then simultaneously performing an addition reaction of the above polyoxo oil (a) with the above compound (b), and The addition reaction of the above compound (c) with the above compound (d); (7) A method for producing a polyvalent carboxylic acid composition for producing the polycarboxylic acid composition according to any one of the above items U) to (5) And characterized in that: step (A), step reaction is carried out successively in a single pot; step (A): the polyoxosulfuric acid (a) has more than one carboxylic anhydride group in the molecule Compound (b) addition reaction step, step (B extensively saturating the alcoholic hydroxyl group having 2 or more functional groups) a method for producing a polyhydric carboxylic acid composition according to the above item (6) or (7), wherein the aliphatic polyol (c) and the compound having more than one carboxylic acid anhydride group in the molecule (the ruthenium addition reaction step; (8) Wherein in the absence of a solvent, or in an organic solvent in an amount of 50% by weight or less based on the total amount of the reaction substrate in the raw material to be used, the above addition reaction is carried out at 4 Torr to 15 Torr; (9) A curable resin composition comprising the polycarboxylic acid composition of any one of the above items (1) to (5), and an epoxy resin; (10) The curable resin composition according to the above item (9), wherein the ring The oxygen resin is an alicyclic epoxy resin and/or an epoxy group-containing polyoxyl resin; (11) The curable resin composition according to the item (9), wherein the epoxy resin 8 201116555 contains an epoxy group. Polyoxyl resin. (12) A cured product obtained by hardening any of the beading-reforming resin compositions according to the above items (9) to (1). The polycarboxylic acid composition of the present invention can be used as a hardening of an epoxy resin. The agent 'especially the curable resin composition of the present invention' is generally used in a temperature region which is usually used for curing an epoxy resin, and has a low volatility of not only a polybasic acid component as a curing agent but also heat resistance, light resistance, and adhesion. It is also excellent in sulfur resistance, toughness, etc. The polyvalent carboxylic acid composition of the present invention can be used as a coating material, an adhesive, a molded article, a semiconductor, a resin for a sealing material of an optical semiconductor, and a solid crystal of an optical semiconductor (die b〇nding) Materials such as resin, polyimine resin, etc., or modifiers, plasticizers, lubricant raw materials, medical pesticide intermediates, raw materials for coating resins, and resins for colorants (t〇ner), especially Since it is excellent in the hardening ability of the enamel tree and the cured product obtained therefrom, it can be used as a curing agent for an epoxy resin for sealing an optical semiconductor typified by a high-intensity white LED or the like.The polycarboxylic acid composition of the invention is characterized by comprising a carboxylic acid compound () and a sulfonium compound (K) which is represented by the following formula () (a) an addition reaction with a compound (b) having one or more slow acid anhydride groups in the molecule:

9 201116555 (in the formula (r, r represents an alkylene group having a total carbon number of 1 to 10 via an ether bond, R 2 represents a nonyl group or a phenyl group; in addition, n represents a repeating unit, a compound represented by the formula (1) The weight average molecular weight is 500 to 5000); the polycarboxylic acid compound (K) is a saturated aliphatic polyol (c) having an alcoholic hydroxyl group having two or more functional groups and more than one carboxylic anhydride group in the molecule. The compound (d) is obtained by addition reaction. The polycarboxylic acid (J) and the polycarboxylic acid (K) in the production of the polycarboxylic acid composition of the present invention can be separately prepared and mixed according to the following, or each of them can be used. The raw material is reacted successively. The polyoxygenated oil (a) is represented by the above formula (1). In the above formula (1), specific examples of 1 include a methylene group, an ethyl group, a propyl group, and a butyl group. a pentyl group, a hexanyl group, a heptyl group, a hexyl group, and the like, and a soil having a total carbon number of 1 to 1 Å without an ether bond;

_C3H6-〇.C2H4-, -C2H4-〇-C2h4_, _c H 4 ^3H6-〇-C3H6- and the like have a total carbon number of 1 to 1 o of the ether bond. Among the 忒4, it is easy to obtain from the market, and 5 is preferably propyl or _c3H6_〇_C2H4_. When the chain of Ri exceeds the total carbon number of 1 〇 厌 厌 厌 厌 厌 厌 厌 厌 厌 厌 厌 厌 厌 厌 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 聚 。 。 The preferred molecular weight range of the polysulfuric acid (4) is, the weight average molecular weight is more preferably 600 to 4 Å, and the Lashi & υυϋ 佳 is 000 to 2500. In addition, the most range is 600 ~ 1500. ;^ 分 i 的 的 ^ ^ In the case of less than 5 刀 in the knife, the intermolecular force of the obtained product becomes higher, 捽, .w τ viscosity is easy to rise, in addition to more than 5000 months /, and other The compatibility of the ingredients G ^ 々 谷 r 生 生 生 , , , , , , , , , , , , , , , , , , , , , , , , Such a methanol-modified polyoxo compound can be synthesized, for example, by the method described in JP-A-2007-508424. The compounds which can be obtained from the market include D〇wc〇rning 5562 (T〇ray D〇w 匚〇1^, called the company), X22-160-AS, KF-6001, KF-6002, KF-6003. (all manufactured by Min Yue Chemical Industry Co., Ltd.), XF42-B0970 (manufactured by Momentive Co., Ltd.), Silaplane FM-4411, FM-4421, FM-4425, and the like. The saturated aliphatic polyol having a bifunctional or higher alcoholic hydroxyl group may be a previously known alcohol, but in terms of the balance between heat resistance, light resistance, and toughness, it is particularly preferable that the number of functional groups is 2 to 6. The polyol, preferably the total carbon number in the i molecule is 5-20. Further, it is preferably a chain alkanediol having a branched structure, a diol having a cyclic structure, a triol, a tetraol, a hexaol or the like. The chain alkanediol having a branched structure is specifically: neopentyl glycol, 2-ethyl-2-butyl-l, 3-propanediol, 2,4-diethyl-hydrazine, 5_ Pentylene glycol and the like. The diol having a cyclic structure may, for example, be tricyclodecane diol, pentacyclopentene pentanediol, 1,4-cyclohexanediol or norbornanediol ( N〇rb〇rnanedi〇1), dihexylene glycol, spirogly C〇i, and the like. Examples of the triol include glycerin and trimethylolpropane. Examples of the tetraol include pentaerythritol, ditrihydroxyhydrinylpropane, and the like, and hexaol, and dipentaerythritol. . In terms of excellent optical properties, heat-resistant colorability, and light-resistant coloring property, 2,4-diethyl-1,5-pentanediol, tricyclodecanediol, and neopentyltetraol are preferably used. 201116555 is not limited to these specific examples in the present invention, and may be used in combination of two or more types. The compounds (b) and (d) having one or more carboxylic anhydride groups in the molecule (further, the compounds (b) and (d) may be the same or different), and preferably have one or two in the molecule. Carboxylic anhydride base. Specific examples include phthalic acid needles, trimellitic anhydride, pyromellitic dianhyddde, maleic anhydride, tetrahydrophthalic acid needle, and methyl group. Tetrahydrophthalic anhydride, methylic acid anhydride, nad1C anhydride, hexahydro-dodecanoic anhydride, methylhexahydrophthalic acid needle, butadiene tetracarboxylic anhydride, bicyclo[2] ,2, ! ]Gengyuan _2,3·dicarboxylic acid needle, methylbicyclo[2'2'1]g-burning 2,3·dicarboxylic acid Xuan, Huanjiyuan_1>2,4 tricarboxylic acid-on 2·needle, Cyclobutane tetracarboxylic acid dihydrate (caffeine (four) coffee (four) ... with a " dihydrate), butane tetracarboxylic dianhydride and the like. Among these, a compound having a saturated smoke structure is particularly preferable from the viewpoint of the 2,000-dimensional nature of the optical characteristics.胄 ' 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就 就Phthalic acid liver; hexane-1'2,4·tricarboxylic acid-1,2·anhydride'bicyclo[mmm: citric acid i cyclobutane tetradecanoic acid dihydrate, butane four from Doosan It is not limited to this purpose, but it can be used in one type or in combination of two or more types. : Ben: Mingzhong 1 is easy to operate: it is especially suitable for those with i-needle base, among which methyl hexamethylene phthalate, phthalic acid anhydride, cyclohexane oxime, 2, 4·三_义_, 2_Needle, Bicyclo [2 2 庚 Geng Shao 2,3-Dicarboxylic anhydride. Especially in terms of optical properties...[,,] pays for a while and is particularly good for methyl 12 201116555 hexahydro phthalic anhydride or cyclohexane-1,2,4-tricarboxylic acid - i, 2 _ needle . Addition of a polyoxygenated oil (a) to a compound (b) having a carboxylic anhydride group, or an addition reaction of a polyol (c) with a compound (d) having a carboxylic anhydride group, such as an alcohol and an acid anhydride The reaction is generally an addition reaction using an acid or a base as a catalyst. In the present invention, in terms of the ease of post-treatment and the adverse effect of removing the catalyst remaining in the product, it is particularly preferred to be non-catalytic. The next reaction. In addition, it is preferable to use one or more types of hardening accelerators or additives to be used in the curable resin composition to be described later, since it is not necessary to carry out subsequent purification. In the case of using a catalyst, for example, acidic compounds such as hydrochloric acid, sulfuric acid, sulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, nitric acid, trifluoroacetic acid, or tri-acetic acid, sodium hydroxide, and the like may be mentioned. Potassium hydroxide, calcium hydroxide, magnesium hydroxide 4 metal hydroxide, amine compound such as diethylamine, tripropylamine, tributylamine, pyridine, dinonylaminopyridine, hydrazine, 8-diazabicyclo[54 〇] eleven carbon-7-ene, imidazole, triazole, tetrazole and other heterocyclic compounds, tetradecyl hydroxide, tetraethyl hydroxide, tetrapropyl hydroxide, tetrabutyl oxynitrene , tridecylethyl hydroxide, trimethyl propyl oxynitride, trimethyl: hydroxyhydroxide, trimethyl hexahydro hydride, trioctyl decyl ammonium oxynitride, Japanese A quaternary ammonium salt such as ammonium sulfoxide, tetramethylammonium bromide, tetradecyl ammonium iodide, tetramethylammonium acetate, trioctylmethyl ethane sulfonium G ® under-cage, and the like. These catalysts may be used alone or in combination of two or more kinds in μ^t or more. Among these, triethylamine, pyridine, and dimethylaminopyridine are preferred.

The amount of I catalyst used is not particularly limited. The total weight of the catalyst is 1 〇〇 by weight and is usually 0_001 to 5 parts by weight. 13 201116555 The reaction is preferably a solvent-free reaction, but an organic solvent can also be used. The amount of the organic solvent used is 〇.005 丨, preferably 0.005 to 0.7, more preferably 0.005 to 〇.5, based on the total amount of the reaction substrate, which is 5 总 in total. Weight% or less). In the case where the weight ratio exceeds 1, the progress of the reaction is extremely slow, which is not preferable. Specific examples of the organic solvent which can be used include an alkene such as hexane, cyclohexane or heptane, an aromatic hydrocarbon compound such as toluene, and methyl ethyl ketone and methyl isobutylene. A ketone such as a ketone, a cyclopentanone or a cyclohexanone; an ester compound such as an ethyl acetate, a butyl acetate or a methyl formate such as a di-butyl scale, a tetrahydroanion or a two-port. The reaction temperature is preferably from 40 to 200 t, particularly preferably from 40 to 150 °C. In particular, in the case where the reaction is carried out under the condition of no solvent, the volatilization of the acid anhydride is present, so that it is preferably a reaction of 10 ° C or less, more preferably a reaction of 40 to loot, particularly preferably 4 〇 8 (Reaction under rc. In addition, in the case of using a compound having a high crystallinity at room temperature, such as cyclohexane-1,2,4-tricarboxylic acid-oxime, 2•anhydride, etc., in order to crystallize sufficiently It is preferred to carry out the dissolution of '100 to 150. (The reaction is lower.) In addition, by using a volatile acid anhydride and an acid anhydride having a higher crystallinity, the temperature of the acid anhydride can be prevented from being volatilized by a stepwise increase in temperature. In order to obtain a reaction ratio of the compound (a) to (b), (c) and (d) in the reaction of the polycarboxylic acid (1) with the polycarboxylic acid (K), it is theoretically preferable that the reaction of the molar is 'but visible' It is described later, that is, as described later, in the case of the hardener composition of the present invention, if the acid anhydride used in combination is the same as the acid anhydride used herein, it may be carried out in excess (4) at the time of manufacture. The reaction is used to obtain a reaction between the polycarboxylic acid (J) and the polycarboxylic acid. 4 201116555 A mixture of an anhydride and a polycarboxylic acid composition of the present invention. The specific reaction ratio is compared with its functional group equivalent, and (4)) is set to i, in terms of its molar ratio, (4) (or (4)) Further, 〇_〜 more preferably ο.οκο' is further preferably 〇. In the above, a mixture of the polycarboxylic acid composition of the present invention and another acid anhydride is produced; wherein, the above ratio is 〇·〇1~0 7 It is preferably in the range of 0 0 丨 to 〇 4. The reaction time also depends on the reaction temperature, the amount of the catalyst, etc., and from the viewpoint of industrial production, a long-time reaction consumes a large amount of energy, which is not preferable. A too short reaction time means that the reaction is imminent, and it is not preferable in terms of safety. A preferred range is i - hour, preferably ^ 36 hours 'and more preferably 1 to 24 hours. Thereafter, in the case of using a catalyst, the catalyst is removed by decantation, washing with water, adsorption, or the like, and the solvent is distilled off to obtain the target polycarboxylic acid (1) or (K). In the reaction, the solvent is distilled off as needed. It can be obtained by direct extraction without solvent or catalyst, and the polybasic acid (1) or polycarboxylic acid (K) can be obtained. The best manufacturing method is 5' in the absence of catalyst and solvent. The reaction is carried out at 40 to 150 ° C, and the reaction is directly carried out after completion of the reaction. By mixing the polycarboxylic acid (J) and the polycarboxylic acid (κ) thus obtained, the target polycarboxylic acid composition can be obtained. In terms of weight ratio, (J) / (K) = 99.7 / 0.3 ~ 50 / 50' is more preferably 99.7 / 0.3 ~ 40 / 40. In the case of excessive amount of polybasic acid (]), the hardness of the cured product Corrosion gas permeability and problem with reflowability. When the polycarboxylic acid (K) is too much, it becomes difficult to cure and operate 15 201116555. What? ^, especially the ratio of (J) / (K) is preferably 99/1~80/2〇 'better horse 99/1 ~ss/ις # 篡财腐你 > . By mixing (K) at a weight ratio of 1 or more, it is possible to particularly improve the performance of the emulsion permeability. Further, by using a weight ratio of 80 or more, the light resistance is excellent, and peeling or cracking from the substrate is less likely to occur. : It is not easy to cause illuminance deterioration performance. In particular, by mixing (1) at a weight ratio of 85, the above characteristics can be balanced well. Further, in the present invention, the polycarboxylic acid (1) and the polycarboxylic acid (K) can be simultaneously produced. The specific method is as follows. (1) A compound (8) and (4) having one or more carboxylic acid groups in the molecule are added to a mixture of the polyoxo oil (a) and the polyol (c) to cause simultaneous reaction. (ϋ) The following steps (A) and (B) are reacted one by one in a single container. Step (A): a step (B) of reacting the polysulfuric acid (4) with a compound (b) having i oxadine groups on the oxime in the molecule (> (吏) having an alcoholicity of 2 or more functional groups The step of reacting the saturated aliphatic polyol (4) with the compound (4) having one or more (iv) needle groups in the molecule, that is, the method of the above (11) is after performing the step (A) (or performing the step (B)), The compound used in the step (B) (or the step (A)) is successively introduced, and the reaction and mixing are carried out in the reaction system. (iii) Compounds (b) and (d) having one or more carboxylic anhydride groups in the molecule. ) For the same case of 16 201116555, add the polysulfate (4) (or polyol (c)) fish molecule = compound with more than one (four) Xuanji (8) Bu (4)) (4) (or polysulfuric acid (4)), the reaction is carried out. The polycarboxylic acid composition of the present invention thus obtained is usually a colorless liquid to semi-solid material. The polybasic acid-inhibiting composition of the present invention is excellent in transparency, and can be used as a curing agent for a curable resin such as a ring-shaped resin, a coating material, an adhesive, a molded article, a resin for a sealing material for a semiconductor or an optical semiconductor, and a solid I for an optical semiconductor. Raw materials for materials such as resins, polyamides, polyimides, modifiers, plasticizers or raw materials, pharmaceutical and pesticide intermediates, raw materials for coating resins, resins for toners, especially for rings A hardener for oxyresin. In the case where the multicomponent of the present invention is used as a curing agent for an epoxy resin, the multi-reading acid composition of the present invention exhibits excellent hardening ability, and further, the cured product has excellent transparency, and thus is particularly It is extremely useful as a hardener for epoxy resins used in high UD Μ semiconductor sealing. In the case where the polyacid composition of the invention of the invention is used as a curing agent for a curable resin such as an epoxy resin, particularly a liquid composition, it is preferred to mix the poly-m-acid composition of the present invention with other acid anhydrides. The form of the hardener composition is used. The acid liver which can be used is preferably a compound (e) having one or more slow acid needle groups in the molecule, and particularly preferably an acid anhydride having no aromatic ring structure. The compound (e) having i or more citric acid needle groups in the molecule may specifically be: hexahydrophthalic acid needle, methyl hexahydrophthalic anhydride, butadiene tetracarboxylic acid 17 201116555 needle' Bicyclo[2,2,1] hydrazine dicarboxylic anhydride, methyl bicyclo [called] heptane _2, 3-dicarboxylic anhydride, cyclohexane-1,2,4-tricarboxylic acid decahydrous anhydride, and the like. In the case of being mixed with an acid anhydride and used as a hardener composition, the ratio of the polybasic acid composition of the present invention to the total weight of the above-mentioned other acid anhydride and the poly-reading acid composition of the present invention is Q 5 (5) Weight%, preferably 0.1 to 30 parts by weight. The effect of the fluidity of the composition, the heat resistance of the cured product, and the mechanical strength is exhibited by the use of "in this range". The following is a description of the hardenable resin composition of the present invention containing the multi-drug composition of the present invention. The curable resin composition of the present invention contains an epoxy resin as an essential component. The epoxy resin which can be used in the curable resin composition of the present invention may, for example, be a novolak type epoxy resin or a bisphenol A type epoxy resin. , biphenyl type epoxy resin, triphenylmethane type epoxy resin 'phenol aralkyl type epoxy resin, and the like. Specifically, 'bisphenol A, bisphenol S, thiodiphenyl, bisphenol, stilbene, 4,4,-biphenol, 2,2,-terphenyl, 3,3, ,5,5,_tetramethyl-[1,1·-biphenyl]-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, tri-(4-base group) ) A hospital, 1,1,2,2-tetrakis(4-pyridylphenyl), cholera, phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthalene, two Base benzene, dihydroxynaphthalene, etc.) with furfural, acetaldehyde, benzaldehyde, p-hydroxybenzoic acid, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone 'dicyclopentadiene, furfural, 4, 4'-bis(cyclomethylbiphenyl, 4,4,_bis(methoxymethylbiphenyl, 1,4-bis(methylmethyl)benzene, iota,4-bis(methoxymethyl)) a polycondensate of benzene or the like, a modified substance thereof, a dibasic bisphenol such as tetrabromobisphenol A, a glycidyl ether compound of Hesheng, which is known as 18 201116555, an alicyclic cyclic amine oxime epoxy resin, and a glycidol. Epoxy resin oxyresin (glycidyl group in the structure of chain, ring, ladder, or (4) structure A solid or liquid epoxy resin such as a mixed epoxy resin, but the second == especially in the case where the curable resin composition of the present invention is used for optical use, preferably an alicyclic ring An oxy-resin and/or an epoxy group-containing polyoxo resin, more preferably an sesquioxane-based epoxy resin. In the case of a ring-type epoxy resin, it is preferred to have an epoxy ring in the skeleton. The compound of the hexamethylene compound is more preferably an epoxy resin obtained by a reaction of a compound having a cyclohexene structure. The alicyclic epoxy resin may be exemplified by cyclohexanecarboxylic acid ( Esterification of cyclohexene carboxylic acid with alcohols or esterification of cyclohexene sterols with carboxylic acids (Tetrahedr〇nv〇1, 36p, (10) (1980), Tetrahedron Letter p. 4475 (1980), etc. The method described in the above, or the method described in the Japanese Patent Application Laid-Open No. 2003-170059, and the method described in JP-A No. 2-262871, and the cyclohexene acrylate. Transesterification reaction (described in JP-A-2006-052187, etc.) The epoxy resin obtained by the method of production is exemplified. The oxidized alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group: ethylene glycol, propylene glycol, 1,3-propylene glycol, hydrazine, and 2-butylene. Glycols such as diol, 1,4-butanol, 1,5-pentanediol, i,6-hexanediol, cyclohexanedimethanol, 19 201116555 glycerol, trishydroxylethane ethane trishydroxyl Mercaptopropane, decylbutane, tetraol, etc.. Acidic 'anti-butylene-deficient phthalic acid' meta-dicarboxylic acid, adipic acid' yield p ^ 夂 匕 匕 二甲 二甲 二甲- triols such as 1,4-butanediol, and other 'carboxylic acids, such as neopentyl alcohol, oxalic acid and cis-butene, but not limited to this acid, and the alicyclic epoxy other than the above The resin may, for example, be an acetal or a fluorene obtained by reacting an aldehyde-producing derivative with an acetal of an alcohol. The reaction method can be carried out by using a general acetalization reaction, for example, a method in which a solvent such as a stupid or xylene is used as a medium, and a method in which a dehydration reaction is carried out in the same manner (U.S. Patent No. 294 No.) is used. A method of reacting a salt after slowly dissolving a polyhydric alcohol, and slowly adding an acid (Japanese Patent Publication No. SHO 48-96590), a method of using water in a reaction medium (U.S. Patent No. 3092640), and an organic solvent for a reaction medium The method (Japanese Unexamined Patent Publication No. Hei 7-215979), a method using a solid acid catalyst (JP-A-2007-230992), and the like. A cyclic acetal structure is preferred in terms of structural stability. Specific examples of the epoxy resin such as β-Hei include erl_422i, UVR-6105, and ERL-4299 (all of which are trade names, all manufactured by D〇w Chemical Co., Ltd.), Celloxide 2021P 'Epolead GT4〇1, EHPE315〇, EHPE3150CE (all trade names, all manufactured by Daicel Chemical Industry Co., Ltd.) and a J-pentadiene diepoxide, etc., but not limited to these (Reference: General Epoxy Basics Ιρ76·85) .忒, etc. may be used singly or in combination of two or more. In the curable resin composition of the present invention, the polycarboxylic acid 20 201116555 composition (or hardener composition) of the present invention may be used in combination with other hardeners. In the case of use in combination, the proportion of the polyvalent carboxylic acid of the present invention in all the hardeners is preferably 20% by weight or more, particularly preferably 3% by weight or more. Other hardening agents which can be used together include an amine compound, an acid anhydride compound, a guanamine compound, a phenol compound, and a carboxylic acid compound. Specific examples of the hardener which can be used include diaminodiphenylnonane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, and Polyamide resin synthesized from cyanodiamine, linolenic acid dimer and ethylenediamine, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, methyltetrahydroortene benzene Dicarboxylic acid maleic anhydride, tetrahydrophthalic acid needle anhydride, methyl acid anhydride, ceric acid anhydride, hydrogen phthalic anhydride, mercapto hexahydrophthalic acid gf, Dingxuan tetracarboxylic anhydride ,bicyclo[m]heptane_2,3_一甲fee if methyl double ί [2,2,ι]heptane_2,3_diphthalic anhydride, cyclohexane-1,3,4-tricarboxylic acid -3,4-anhydride, bisphenol VIII, bisphenol 17, bisphenol 3, bismuth bisphenol, stilbene, 4,4,-biphenol, 2,2,-diphenol, 3,3,,5, 5|_Tetramethylhydrazine, _biphenyl]-4,4,-diol, hydroquinone, resorcinol, naphthalenediol, tris-(4-cysylphenyl) anthracene, 1, 1,2,2-tetrakis(4·p-phenylene)ethene, expectant (benzene, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, two Ketone, etc.) with formic acid, Ethylene, Benzyl, and p-Binyl: o-benzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, decanoic acid, 4, 4-bis(chloromethyl)]/·biphenyl, 4,4,_bis(p-oxyindenyl)_ι, 广苯苯,Μ,-bis(gasmethyl)benzene, anthracene, di(a) Polycondensate of oxymethyl)benzene and the like, and these modified substances, Sishuang double # A f _ _ bis, imi. The condensate t of the sitting, the three-dosing boron (tnflu〇r〇b〇rane)·amine complex, the hydrazine derivative %, the box thinner and the expectant class 21 201116555 is not limited to these. These may be used alone or in combination of two or more. In the curable resin composition of the present invention, the ratio of the total hardener to the epoxy resin is preferably from 0.5 to 1.5 equivalents per equivalent of the epoxy group of the epoxy resin (further, the anhydride group is considered to be monofunctional). It is especially good for 〇·5~ I. In the case where the equivalent amount of the epoxy group is less than 0.5 equivalent, or more than 1.5 equivalents, the hardening is not complete and the good hardened physical properties are not obtained. In the curable resin composition of the present invention, a hardening accelerator may be used in combination with the curing agent. Specific examples of the hardening accelerator which can be used include 2-mercaptoimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 2-phenyl-4-anthracene. Imidazole, 1-benzyl-2-phenylimidazole' 丨-benzyl-2-methylimidazole, 1-cyanoethyl-2-mercaptoimidazole, 1-cyanoethyl-2-phenylene Mizozol, 1-cyanoethyl-2-pyrene-pyranylpyrazine, 2,4-diamino-6 (2'-fluorenyl-sodium (1')) Ethyl-symmetric two-well, 2 4-Amino-6(2'--|--院基啼. Sit(Γ))Ethyl _ Symmetrical Sancha, 2,4-·-Amino-6(2'-ethyl_ 4_曱基σ米. Sit (1 ')) Ethyl-symmetric tri-α well, 2,4-diamino _6 (2'-methyl mer. Sit (1')) Ethyl-symmetric tri Well _ iso-cyanuric acid adduct, 2-methyl imiline isocyanate 2: 3 adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-3 , 5-dihydroxydecyl imidazole, 2-phenyl-4-hydroxyindolyl-5-methylimidazole, 1-cyanoethyl-2·phenyl-3,5-dicyanoethoxymethyl Various imidazoles of Mimi, and such imidazoles with phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyrophoric acid a salt of a polyvalent carboxylic acid such as naphthalenedicarboxylic acid, maleic acid or oxalic acid; a guanamine such as dicyandiamine; '丨,8-diazabicyclo (5.4.0) undecene-7, etc. Aza 22 201116555 (diaza) compound and salts of such tetraphenylborate, phenol novolac and the above polybasic carboxylic acid or phosphinic acid salt, tetrabutylammonium bromide, Cetyltrimethylammonium bromide, trioctylmethyl desertification and the like ammonium salt, triphenylphosphine, tris(tolylmethyl)phosphine, tetraphenylphosphonium bromide, tetrabenzamine a phosphine or an anthracene compound such as tetraphenylphosphonium tetraphenylborate, a metal compound such as a phenolic 'amine adduct' such as tin octylate such as 2,4,6-triaminomethylphenol, or the like, and such a hardening accelerator A microcapsule type hardening accelerator or the like which is made into a microcapsule. In the present invention, it is preferred to contain a zinc salt and/or a zinc complex. In the curable resin composition of the present invention, the zinc salt and/or the zinc complex function as a hardening accelerator for the epoxy resin and the curing agent. The salt and/or zinc complex is a salt and/or a complex of zinc ions as a central element, preferably having a carboxylic acid, a phosphate, or a phosphoric acid selected from the group consisting of a carbon number of 丨3 to 3 alkyl groups. At least one of the species acts as a relative ion and/or a ligand. Examples of the alkyl group having 1 to 30 carbon atoms include a mercapto group, an isopropyl group, a butyl group, a 2-ethylhexyl group, an octyl group, an isodecyl group, an isostearyl group, a decanyl group, a hexadecyl group, and the like. . In the present invention, a zinc carboxylate or a zinc phosphate is particularly preferred. Corrosion resistance gas permeability can be improved by using a carboxylic acid word or a zinc phosphate body. In the present invention, it is preferred that the compound contains an alkyl group having a chain knive structure or an alkyl group having a functional group such as an olefin, and it is preferably a hindrance of 3 to 3 G. For carbon number 5~2g. This is preferable in terms of compatibility, and when the number of the barriers is too large (the case where the carbon number exceeds 3 ()) or the structure having no branched structure or functional group, the compatibility with the resin is poor, which is not preferable. 23 201116555 Specifically, zinc acrylate or the like can be mentioned. 2-ethylhexanoic acid, zinc isostearate, eleven carbon Preferred phosphates in the present invention, bismuth is preferably phosphoric acid, phosphate (monoalkyl Sa, monoalkyl ester, trialkyl) The zinc and/or zinc complex of α, disc or a mixture thereof may also contain polyterpenes & Specifically, in the δ acid acid design, the molar ratio of the T # alkyl steroid, the dialkyl brew, and the trialkyl brew (the gas chromatogram) The purity of the method is η朁. Among them, the difference in sensitivity is required because of the need to perform the trimethylation, and the amount of the single-burning group (4) in the stage of performing the trimethyl group treatment is preferably Μ area% or more. Such a zinc phosphate salt of zinc phosphate and / 哎铉 f zinc complex can be made, for example, by phosphoric acid

The ester is reacted with, for example, zinc carbonate or HM lanthanum zinc oxide 4 to obtain the article EP699708. The details of the scallic acid® zinc salt and/or zinc complex are filled with atoms and zinc atoms (4) (P/Znm is preferably h2~2.3, more preferably 13~2〇. Tetra is " It is called 9. In the form of the best, it is preferably the following: relative to the zinc ion 1 mol, the linonic acid (10) (or derived from the phosphoric acid g) is below the Ηmole' is not a simple ionic structure a structure having several molecules linked by an ionic bond (or a coordinate bond). Such a zinc salt and/or a zinc complex can be obtained, for example, by the method described in Japanese Patent Publication No. 3_5 1495. Such a compound, commercially available zinc carboxylate, may be exemplified by Zn-St, Zn-St 6 〇 2, Zn-StNZ, zs_3, zs_6, ZS8, ZS8, zs_7, zsi〇, ZS 5 ZS 14, zs. -16 (manufactured by Mindong Chemical Industry Co., Ltd.), XK614 (manufactured by King Hulusuies Co., Ltd.), 18% 〇ct〇pe &, i2% 〇ct〇pe &, 24 201116555 8% 〇ct〇Pe Zn(Hc)pe (manufactured by Chemical Co., Ltd.), citric acid sulphate and/or zinc sulphate can be exemplified by LBT-2000B (manufactured by SC Organic Chemical Co., Ltd.) and XC-9206 (manufactured by King Industries Co., Ltd.). For example, which of the curing accelerators is appropriately selected depending on the properties required for the transparent resin composition obtained by transparency, curing rate, working conditions and the like. The hardening accelerator is usually used in an amount of 0.001 15 parts by weight, more preferably 1 to 5 parts by weight, more preferably in the range of 01 3 parts by weight, based on the weight part of the epoxy resin. In the present reaction, the curing may be carried out without using a curing accelerator, and in view of the problem of coloring during curing, it is preferred to add a curing accelerator. In particular, it is preferred to use a zinc salt and/or a zinc complex compound for the purpose of preventing coloring and corrosion-resistant gas characteristics. In the curable resin composition of the present invention, a can-containing chemical compound may be contained as a flame retardancy imparting component. The phosphorus-containing compound may be either a reactive type or an additive type. Specific examples of the scaly compound include tridecyl phosphate, triethyl phosphate, triterpene phosphate, trixylenyl phosphate, and diphenyl phosphate. ), cresyl-2,6-dixylenyl phosphate, 1,3-phenylene bis(diphenylene) vinegar, 1,4-phenylene bis(di(diphenylene) disc acid g), 4,4'-biphenyl (di(dimethylphenyl) wall acid ester) (4,4'-biphenyl (dixylenyl) Phosphate, etc.; 9,10-dihydro-9-oxa-ίο-phosphaphenanthrene 10-oxide, 1, Phosphonium (2,5-di-phenyl)-1 sulphur 9-oxa-1〇-disc phenanthrene 〇 氡 氡 等 ; ; ; ; ; ; ; ; ; ; ; 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂Hydrogen reaction obtained 25 201116555 phosphorus-containing epoxy compound, red phosphorus, etc.; preferably phosphate, phosphine or scaly % oxygen compound 'excellently 1,3_phenylene bis(di(xylene) Base) dish 酉文酉曰) 1,4-phenylene bis(di(dimethylphenyl) citrate) , 4, 4, biphenyl (bis(diphenyl) phosphate vinegar) or phosphorus-containing epoxy compound. The content of the phosphorus-containing compound is preferably a dish containing compound / all epoxy resin = 〇 1 ~ 〇 6 (When the weight ratio is less than 卜1, the flame retardancy is insufficient. When it exceeds 〇6, it has an adverse effect on the hygroscopicity and dielectric properties of the cured product. - Further, the curable resin composition of the present invention The oxidizing agent may be added as needed, and examples of the antioxidant which may be used include a phenol-based, sulfur-based, and phosphorus-based anti-oxidant. The antioxidant may be used singly or in combination of two or more. The amount of use is usually 〇〇〇8 to 1 part by weight, preferably 〇(1) to 〇·5 parts by weight, based on 100 parts by weight of the knives in the curable resin composition of the present invention. A phenolic antioxidant, a sulfur-based antioxidant, an antioxidant, etc. Specific examples of the phenolic antioxidant include: 2,6---t-butyl-p-cresol, butylated hydroxybenzoic acid Ether, 2,6-di-t-butyl-p-ethylbenzene, stearyl group, 5•di-tert-butyl-4-hydroxyphenyl) 驮@驮, isooctyl·3·(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4_1 bis-(n-octylthio)_6_(4_hydroxy·3,5_2 _T-butyl aniline earth), 3'5·two wells, 2,4·bis[(octylthio)methyl]-o-cresol and other monophenols; 2'-methylene double ( 4-methyl-6-t-butyl benzoate), 2,2,-methylenebis(4-ethyl-6.t-butylphenol), 4,4,-thio-bis(3_曱-6-tert-butyl benzene di 4,4 -butylene bis(3-mercapto-6-tert-butylphenol) 'triethylene glycol bis 3_(3 · tert-butylmethyl 4-hydroxybenzene Propionate], 1,6·hexanediol double 26 201116555 [3-(3,5-di-t-butyl-4-ylhydroxyphenyl)propionate], N,N'-hexa Methyl bis(3,5·di-t-butyl-4-hydroxy-phenylpropanamide), 2,2-sulfanyl-diethylidene bis[3-(3,5-di-t-butyl) _4_hydroxyphenyl)propionate], 3,5-di-t-butyl-4-transbenzylphosphonic acid _ diethyl ester, 3,9_bis[丨卜二曱基_2_ {Million-(3·t-butyl-4-hydroxy-5-nonylphenylpropenyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, Bis(3,5-di-t-butyl-4-4-hydroxybenzylsulfonate ethyl) Bisphenols; 1, hydrazine, 3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butyl, 1,3,5-trimethyl 2,4,6_three (3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis[methylene-3-(3,5,2-di-t-butyl-4,-hydroxyphenyl)propane Ester] bismuth, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butanoic acid]diol, tris(3,5-di-t-butyl _4·hydroxybenzyl)-iso-isocyanate, U3,5·3 (3',5'-di-t-butyl-4·-hydroxybenzyl)-symmetric Sanchajing-2,4 , 6-(1Η, 3Η, 5Η) high molecular phenols such as triketone and tocopherol. Specific examples of the sulfur-based antioxidants include dilauryl _3,3, thiodipropionate vinegar, dimyristyl _3,3| thiodipropionate, distearyl _3,3 , _ thiodipropionate S is intended. Specific examples of the phosphorus-based antioxidant include ruthenium, osmium, and 3 - tris(2_fluorenyl-4-iso-dodecyl)-perylenelate--5-t-butylphenyl-butane (l,l,3-tris(2-methyl-4-ditridecylph〇Sphito-5-t-butylphenyl)b utane), distearyl pentaerythritol diphosphite, double (2, heart two _ Tributylphenyl) pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-indolylphenyl)neopentitol diphosphite, phenylbisphenol A new Pentaerythritol diphosphite, dicyclohexyl neopentyl alcohol diphosphite, tris(diethylphenyl) phosphite, tris(di-isopropylphenyl) phosphite, phosphite (di-n-butylphenyl) 27 201116555 Xiqiaoya Phosphorus S夂2 (2,4.1 -t-butylphenyl) vinegar, sub-disc tris (2,6-di-third butyl S), yakisan (2,6·di-t-butylphenyl)a, 2,2,_methylenebis(4,6·di-t-butylphenyl) (2 , 4·di-t-butylphenyl) phosphite sorbate, 2,2,-methylenebis(4,6-di-t-butylphenyl) (2th butyl-4-methyl) Stupid base) acid filled vinegar, 2,2'. methylene bis(4) methyl Third butyl group) (2 di-butyl _4_ fluorenyl base) phthalic acid vinegar '2,2, _ethylene bis(4.methyl-6-tert-butylphenyl) (2 _T-butyl-4-ylphenyl) phosphite sorbate, tetrakis(2,4-di-t-butylphenyl)·4,4,·biphenyldiphosphinate (tetrakis) 254-di-tert-butylphenyl)-4,4'-biphenylenephosphoni te), tetrakis(2,4-di,t-butylphenyl)_4,3ι·extended phenyldiphosphinate, tetra(2) , 4-di-t-butylphenyl)·3,3,_biphenylphosphonic acid, tetrakis(2,6-di-t-butylphenyl)_4,4'-extension Phenyl diphosphinate, tetrakis(2,6-di-t-butylphenyl)-4,3'-extended stannyl diphosphinate, tetrakis(2,6-di-third Phenyl)-3,3'-extended biphenyl diphosphinate, bis(2,4-di-t-butylphenyl)-4-phenyl-phenylphosphinic acid vinegar, double (2 ,4-di-t-butylphenyl)-3-phenyl-phenylphosphinate, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphinic acid Ester, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphinate, bis(2,6-di-t-butylphenyl)-3-phenyl -benzene Phosphonate, tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4,4·-phenylene diphosphinate, tributyl phosphate, trimethyl phosphate , triterpene phosphate, triphenyl phosphate, triphenyl phosphate, triethyl phosphate, cresyl diphenyl phosphate, diphenyl monoorthoxyl phosphate, tributyl citrate Oxyethyl ester, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like. 28 201116555 A commercially available product can also be used as the above phosphorus compound. For example, 'Adeka manufacturer, can be mentioned: Adekastab PEP-4C,

Adekastab PEP-8, Adekastab PEP-24G, Adekastab PEP-36, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, Adekastab TPP. In the present invention, the phosphorus compound is used in an amount of 5 to 5 wt%, more preferably 1 to 4 wt%, particularly preferably 0 to 1 wt%, based on the weight of the epoxy resin. 2% by weight. These antioxidants may be used alone or in combination of two or more. Particularly preferred in the present invention are phosphorus-based antioxidants. Further, a light stabilizer may be added to the curable resin composition of the present invention as needed. The light stabilizer is particularly preferably a hindered amine compound, and preferably contains a phosphorus compound as needed. The above amine compound may, for example, be 1,2,3 4-butanetetracarboxylic acid tetrakis(1,2,2,6,6-pentainyl-4-piperidinyl) vinegar, 1,2, M-butyl Burning tetrakis(4,2,6,6-tetradecyl-4-piperidinyl) vinegar, hydrazine, 2,3,4·butane tetradecanoic acid and 1,2,2,6,6- Pentamethyl-4_piperidinol and 3,9-bis(2hydroxy-indole, oxime-dimethylethyl)-2,4,8,1〇_tetraoxaspiro[5·5]11 Mixed admixture of alkane, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, carbonic acid double (丨_十一院氧美-2,2,6 , 6_Tetramethylpiperidin-4-yl)S, 2,2,6,6-tetramethyl-4 piperidinyl methacrylate, azelaic acid bis (2,2,6,6_ Tetramethyl-4-ylpiperidinyl ester, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) vinegar, 4-phenylhydrazineoxy-2,2 , 6 6 tetramethylpiperidine, 1-[2_[3_(3,5-di-t-butyl-4-hydroxyphenyl)propenyloxy] 29 201116555 ethyl]-4-[3-( 3,5-di-t-butyl-4-ylhydroxyphenyl)propanyloxy]-2,2,6,6-tetradecylpiperidine, pentamethyl-4-methylpiperidyl acrylate , {[3,5-bis(1,1-dimethylethyl)_4-hydroxyphenyl]methyl}butylmalonic acid bis(1,2, 2,6,6-pentamethyl-4-piperidinyl)g, bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidinyl) sebacate Hydrogen peroxide 1, the reaction product of 丨-dimethylethyl and octane, N, N,, N", N",-tetra-(4,6-bis-(butyl-(N-methyl) -2,2,6,6-tetramethylpiperidin-4-yl)amino)-trimethyl-2-yl)-4,7-diazadecane-1,10-diamine, two Butylamine·1,3,5-three wells-N,N,-bis(2,2,6,6-tetramethyl-4-pyridinyl-1,6-tetramethylenediamine and n-( 2,2,6,6-tetradecyl-4-piperidinyl) butylamine polycondensate 'poly[[6-(1,1,3,3-tetradecylbutyl)amino-1,3 ,5-Tricotin-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imido]hexamethylene[[2,2,6,6 -tetradecyl-4-piperidinyl)imido]], dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1 piperidinol polymer, 2 ,2,4,4-tetradecyl-2〇-(^-lauroyloxycarbonyl)ethyl-7-oxa-3,20-diazaspiro[5·1.1 1.2]hexadecane- 21-keto, cold-alanine, N,-(2,2,6,6-tetradecyl-4-piperidyl)dodecaate/tetradecyl 'N-acetamido-3-dodecane ^-(2,2,6,6-tetramethyl-4-piperidinyl)pyridinyl Pyridin-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3,20-diazaspiro[5,1,1 1,2]-eicosane -21-keto, 2,2,4,4-tetramethyl-21-oxa-3,20-diazabicyclo-[5,1,11,2]- twenty-one -20-prop Acid dodecyl ester / tetradecyl ester, malonic acid, [(4-methoxyphenyl)-methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidinyl ) Stuffed, 2,2,6,6-tetramethyl-4-piperidin. Higher fatty acid ester of alcohol, l'3-benzenedicarboxamide 'N,N'-bis(2,2,6,6-tetramethyl-4-. A hindered amine compound or the like. 30 201116555 The amine compound of the above-mentioned light-stable material can be commercially available as follows. For example, Ciba Specialty Chemicals Co., Ltd. can be made by TINUVIN765, TINUVIN770DF, TINUVIN144, TINUVIN123, TINUVIN622LD, TINUVIN152, CHIMASSORB944, Adeka. LA-52, LA-57, LA-62, LA-63P, LA-77Y, LA-81, LA-82, LA-87, etc. are mentioned. In the present invention, the light stabilizer is used in an amount of from 0. 0.05 to 5% by weight, more preferably from 0.01 to 4% by weight, particularly preferably from 0.1 to 2% by weight, based on the weight of the epoxy resin. . When the amount is less than 0.005% by weight, the effect is insufficient, and when it exceeds 5% by weight, the effect on the heat-resistant coloring property is exhibited, which is not preferable. Further, in the curable resin composition of the present invention, a binder resin may be blended as needed. Examples of the binder resin include a butyral resin, a condensed resin, an acrylic resin, an epoxy-nylon resin, an NBR-phenol resin, an epoxy-NBR resin, a polyamine resin, and a polyfluorene resin. The blending amount of the imide resin and the polyfluorene binder resin is lower than that of the oxygen resin, but is not limited thereto. In the range of the flame retardancy and the heat resistance of the non-destructive hardened material, it is usually used in an amount of 5 to 5 parts by weight, more preferably 0.05 to 20 parts by weight, based on 100 parts by weight of the resin component. Add inorganic fill as needed

-/%, a sputum, a carbonized stone, a tantalum nitride, and a hardening resin composition of the present invention, a charge. Inorganic filling, alumina, 31 201116555 nitriding, oxidizing, sapphire, talc, spinel, dioxane, talc, etc. or spheroidized beads, etc., but It is not limited to these. These may be used alone or in combination of two or more. The content of the inorganic filler is such that it accounts for 5% to 95% by weight of the curable resin composition of the present invention. Further, in the curable resin composition of the present invention, a mold release agent such as a wonderful coupling agent, stearic acid, palmitic acid, zinc stearate or calcium stearate may be added, a surfactant, a dye, a pigment, and an ultraviolet absorption. Various preparation agents such as agents, and various thermosetting resins. When the curable resin composition of the present invention is used for an optical semiconductor encapsulant, a phosphor may be added as needed. The phosphor is, for example, a person who absorbs a portion of the blue light emitted from the blue LED element and emits a wavelength-converted yellow light to thereby form white light. After the crab light body is dispersed in the curable resin composition in advance, the sealing of the photo-semiconductor phosphor is not particularly limited, and a conventionally known glare may be used, and for example, an aluminate of a rare earth element or thiogallate may be exemplified. Salt (thi〇gallate), the original 矽酉文盐荨. More specifically, YAG (YttHUm-AlUminUm-Garnet, 钇- ing garnet) phosphor TAG (Terbium Aluminum Garnet) glory, bismuth silicate phosphor A phosphor such as a thiogallate phosphor or a sulfide phosphor can be exemplified by YAl〇3 : Ce, Y3Al5〇12 : Ce, Y4Ah〇9 : Ce, Y2O2S · Eu ' Sr5 (P〇4) 3Cl : Eu, (SrEu) Q . a1203 and so on. The particle diameter of the phosphor can be a particle diameter known in the art, and the average particle diameter is 1 to 25 Å #m, particularly preferably 2 to 50. In the case of using the phosphor, the amount of addition is relative to 100 parts by weight of the resin component is 1 to 8 parts by weight, preferably 5 to 60 parts by weight compared to 32 201116555. When the curable resin composition of the present invention is used for an optical material, particularly a photo-semiconductor encapsulant, in order to prevent sedimentation T from being hardened when various phosphors are hardened, a fine powder of nitric oxide (referred to as Aer〇sn or Aeros〇i) is a representative of the shake II only to give such a cerium oxide micropowder, for example,

Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil 0X50, Aerosil TT600, Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R812, Aerosil R812S, Aerosil R805, RY200, RX2〇〇 (Japan Aerosil Company manufacturing) and so on. The curable resin composition of the present invention is obtained by uniformly mixing the components. The curable resin composition of the present invention can be easily formed into a cured product by the same method as previously known. For example, the following method can be used: an epoxy resin and a curing agent, and if necessary, a hardening accelerator, a compound containing a filler, a binder resin, an inorganic filler, and a compounding agent, if necessary, an extruder, a kneader, a drum, etc. After sufficiently mixing until uniform, a curable resin composition is obtained, and in the case of a liquid, the curable resin composition is poured or cast, impregnated into the substrate, and poured into The mold is cast and molded, and is hardened by heating, and in the case of a solid, it is molded by melting, casting, or a molding machine, and is hardened by heating. The curing temperature and time are between 8 〇 and 2 〇 (rc is carried out for 2 to 10 hours. The hardening method can also be cured at a high temperature for one time, but it is preferred to gradually increase the temperature to carry out the hardening reaction. Specifically, at 8 〇~丨5 The initial hardening is carried out between the crucibles, and the step of hardening and hardening is carried out between l〇〇°C and 200t. 201116555 Grass is preferably divided into 2~8 stages, more preferably 2~4 stages. The curable resin composition of the present invention is dissolved in methyl benzene, mono-toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide-mercaptoacetamide, fluorenyl-hydrazinopyrrolidone In a solvent such as a curable shame composition varnish, it is impregnated into a glass fiber, such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and dried by heating. The ingot is subjected to hot press forming to thereby form a cured product of the curable resin composition of the present invention. The solvent at this time is usually used in a mixture of the curable resin composition of the present invention and the solvent, and usually accounts for 1 to 7 Torr. %, preferably in an amount of 15 to 70% by weight. In the state of the liquid composition, a hardened epoxy resin containing carbon fibers can be obtained by RTM (Resin Transfer M〇ldmg). Alternatively, the curable resin composition of the present invention can be used as a film type. The modifier of the composition can be used to enhance the flexibility in the B_stage, etc. The method for obtaining such a film-type resin composition is as follows: First, the curability of the present invention The resin composition is made into the curable resin composition varnish as described above, and is applied onto a release film, and the solvent is removed by heating, and then the process is carried out, and the sheet-like adhesive can be used. A film-type sealing composition is obtained. The sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like. 1 Next, a case where the curable resin composition of the present invention is used as a sealing material or a solid crystal material of an optical semiconductor A detailed description will be given of the case where the curable resin composition of the present invention is used as a sealing material or a solid crystal material for a high-intensity white LED optical semiconductor, by including 34 201116555 The multi-read acid hardener (hardener composition) of the invention is sufficiently mixed with an epoxy resin, an additional hardening accelerator, a coupling material, an antioxidant, a light stabilizer, and the like to prepare a curable resin composition. The method comprises the steps of: using a kneading machine, a second-stage grinding machine, a universal mixer, a # star mixer, a homogenizer, a homogeneous phase dispersing machine, and a bead mill, which are mixed under normal temperature or heating, and the obtained curable resin composition is obtained. It can be used for sealing materials, or both solid crystal materials and sealing materials. High-brightness white LED optical semiconductor components are generally made of an adhesive (a solid crystal material is deposited on a substrate such as sapphire, spinel, Sic, Si, Zn, etc.). The semiconductor wafers of GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AIN, InGaN, etc. are formed on a lead frame or a heat release plate or a package. There is also a form in which a gold wire or the like is connected in order to flow a current. The semiconductor wafer is sealed with a sealing material such as an epoxy resin. The sealing material is used to protect the semiconductor wafer from heat or moisture damage and the function of the lens. The curable resin composition of the present invention can be used as the sealing material or the solid crystal material. In terms of the step, it is preferred to use the curable resin composition of the present invention for both the die bonding material and the sealing material. A method of adhering a semiconductor wafer to a substrate using the curable resin composition of the present invention includes a method of applying a curable resin or composition of the present invention to a substrate by a dispenser, pouring, or screen printing. After that, the semiconductor wafer is placed on the curable resin composition and heat-hardened. By this method, the semiconductor wafer can be attached to the substrate. For heating, hot air circulation, infrared, high frequency, etc. can be used. 35 201116555 The heating condition is preferably, for example, about 8 〇 to 23 〇 1 for 1 minute to 24 hours. In order to reduce the internal stress generated during heat hardening, for example, it can be pre-hardened at 80 to 120 C for 30 minutes to 5 hours, and then 12 〇 to 18 〇 < 5 (:, 3 0 minutes to 1 〇 hours) Thereafter, the sealing material is formed by inserting a sealing material into a mold frame into which a substrate having a semiconductor wafer is fixed as described above, and then performing heat-hardening molding to form an injection method; The sealing material is injected in advance, and the semiconductor wafer fixed on the substrate is immersed therein, and after being heat-hardened, the compression molding method is released from the mold. The injection method includes a dispenser, transfer molding, injection molding, and the like. A hot air circulation type, an infrared ray, a high frequency or the like can be used. The heating condition is preferably, for example, 80 to 23 (TC heating for 1 minute to 24 hours or so. To reduce the internal stress generated during heat curing, for example, it can be made at (9) 120C. After pre-hardening for 30 minutes to 5 hours, it is post-hardened under the conditions of 12 Torr to 1 Torr C for 30 minutes to 1 Torr. Further, the use of the curable resin composition of the present invention is not only It can be applied to the general use of a thermosetting resin such as an epoxy resin for the above-mentioned use, and specific examples thereof include an adhesive, a coating material, a coating agent, a molding material (including a sheet, a film 'FRP, etc.), and insulation. Materials (including printed circuit boards, wire coatings, etc.), sealing materials, sealing materials, anaerobic resin compositions for substrates, or other resins such as acrylic acid vinegar resins used as a hardener for resists. Additives, etc. Examples of the following agents include civil engineering, construction, automotive, general-purpose, medical adhesives, and adhesives for electronic materials. 36 201116555: Substituents for sub-materials, Examples include a multilayer interlayer adhesive such as a build-up substrate, a semiconductor adhesive such as a die bond or a primer, a bga reinforcing primer, an anisotropic conductive film (acf), and anisotropy (ACP). The encapsulant for encapsulation, etc. The poor-encapsulation material includes a perfusion, impregnation, and transfer 1C or LSI type used in a capacitor, a transistor, a diode, a light-emitting diode, a 1C, an LSI, or the like. (1P 〇n Board, plate crystal Insulation seal used in sheet package), B 卬〇n FUm, film flip chip, TAB (TaPe Automated two-tape automatic bonding), etc. (4) Type 2 Γ V used primer, QFP, BGA and CSP 1c The present invention, which is obtained by curing the curable resin composition of the present invention, is used for various purposes represented by optical component materials. In the following, a material for use in the use of the visible light, the infrared ray, the ultraviolet ray, the X ray, and the ray is used, and more specifically, a sealing material for LEDs such as a type k and an SMD type, and the like. In the field of liquid-day display, liquid crystal display device for liquid helium, such as a wide-angle plate, a light guide plate, a cymbal sheet, a polarizing plate, and a film for viewing angles, an adhesive, a polarizing element protective film, and the like Peripheral materials. In addition, the display is subject to sealing materials such as 々 々 i i i i i i i i 电 电 电 电 电 电 电 电 电 电 电 电 电 电 i i i i i i i i i i i i i i i i i i i i i i The mold material in the coffee display device, the sealing material of the coffee, the protective glass substitute material of the front plate glass, the adhesive, and the substrate material, the light guide plate, the breeze plate and the deflecting plate in the electro-destructive liquid crystal (PALC) II 37 201116555 , phase difference plate, viewing angle correction film, adhesive, polarizing element protective film, and organic EL (electro-electrical it) 'display π H in the front plate glass protective film, front plate glass substitute material, follow-up agent, another field Various film substrates in the emission display (FED), and a protective film of the front plate glass instead of the material and the adhesive. In the field of optical recording, 'VD (Video Disc), CD/CD-ROM, CD-R/RW, DVD R/DVD-RAM, MO/MD 'PD (phase change disc), optical disc substrate material for optical cards, The disc player reads a lens, a protective film, a sealing material, an adhesive, and the like. In the field of optical equipment, it is a lens material for a static camera, a viewfinder 稜鏡 'target 稜鏡, a viewfinder cover (finder e. guess), and a light-receiving sensor unit. In addition, the camera lens and viewfinder of the camera. ^ Outside, the projection lens of the projection TV 'protective film, sealing material, adhesive, etc. The material for the lens of the light sensing machine, the sealing material, the adhesive, the film, and the like. In the field of (4), it is a fiber material around a light switch in an optical communication system, a lens, a waveguide, a sealing material for a member, an adhesive, and the like. Optical fiber material around the optical connector, ferrule rubber, (4) (four), adhesive, and the like. In the passive parts of the light and the parts of the photoelectric circuit, it is a lens 'waveguide, a sealing material for LEDs, a material of ccd (4), an adhesive, and the like. _ Body circuit (0EIC) surrounding substrate material, fiber material, component sealing material, adhesive, etc. In the field of optical fiber, it is used for industrial applications such as lighting/light guides for decorative displays, such as 'drying/identifying types', and for connecting optical fibers for communication infrastructure and digital devices in the home. Among the materials surrounding the semiconductor integrated circuit, Ma LSI 'Super LSI material uses a resist material for micro-etching technology. In the field of automobiles/transport machines, 38 201116555 Automotive lamp reflectors, off parts, headlights, (four) points, insect coating, open drive engine, brake f, ★, electric milk parts, various internal and external parts, / phase , car rust-proof steel plate, interior; te nnf · panel), interior trim panel (lnterior broken glass substitute. Two ==,: material hose, car lamp, structural material (10) Coating. Yu Jianju... Peripheral components, harnesses for protection/bundling, traits, 'interior/processing materials, lampshades, sheets, glass interlayers, glass instead of 〇, °σ, solar cell peripheral materials For agricultural use, it is a film for covering greenhouses. .^ , y Μ . „ , as a lower-generation light/electronic function, there are organic EL element peripheral materials, organic light-refracting elements, and optical amplifying elements as = conversion devices. , optical computing element, substrate material around the organic solar cell, fiber material, sealing material of the element, adhesive, etc. [Embodiment] Next, the present invention will be more specifically described by way of examples, hereinafter, Without special explanation Further, the present invention is not limited to the examples. Further, in the examples, the measurement of the gel permeation color (hereinafter referred to as "GPC") was carried out under the following conditions. :Shodex SYSTEM-21 column (kf_8〇3l, KF 8〇2 5 (x 2 roots), KF-802) linked solution: tetrahydrofuran, flow rate 1 ml/min column temperature: 40 ° C ' additionally detected as Ri (Refiective index) Calibration curve: Standard polystyrene synthesis example manufactured by Shodex 1 39 201116555 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, the two ends of the methanol were modified while applying a nitrogen purge. Polyxylene X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd., in formula (1), R, C3H6_0_C2H4_, R2 = CH3, weight average molecular weight of about 1000) 500 00 parts, HTMAn (1, 2, 4-ring Hexane tridecanoic acid_ι,2-anhydride, manufactured by Mitsubishi Gas Chemicals Co., Ltd.) 99 parts, MH-700 (mixture of hexahydrophthalic acid needle and 4-mercaptohexaphthalic anhydride) , manufactured by Nippon Chemical and Chemical Co., Ltd.) 84 parts, 50 parts of toluene added to the reaction volume After 2 hours of reaction at 9 ° C, the temperature was raised to 13 CTC, and GPC was measured 3 hours later, and the peak of the acid anhydride disappeared. Thereafter, the reaction was further carried out for 2 hours. After the reaction was completed, the solvent was removed under reduced pressure. 681 parts of a carboxylic acid compound (J1) of a colorless to pale yellow liquid was obtained. Synthesis Example 2 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring apparatus, a nitrogen purge was performed while one side of the tricyclic decanediol 98 parts 'HTMAn ( l,2,4-cyclohexane tridecanoic acid-1,2-anhydride, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 99 parts, MH-700 (hexahydrophthalic anhydride and 4·decyl hexahydrohexahydrogen) A mixture of phthalic anhydride (manufactured by Shin Nippon Chemical Co., Ltd.) 84 parts of 'toluene 1 aliquot was added to the reaction vessel, and the reaction was carried out at 6 CTC for 1 hour at 1 Torr. (: The reaction was carried out for 2 hours. After the completion of the reaction, the solvent was removed under reduced pressure to obtain 280 parts of a carboxylic acid compound (K-1) as a colorless solid resin. Example 1 was provided with a stirrer, a reflux cooling tube, and a stirring device. In the flask, the surface was subjected to nitrogen purge, and 68.3 parts of the carboxylic acid compound (j-1) was added thereto, and the mixture was stirred at 1〇〇40 201116555 C, and then a carboxylic acid compound (Κ-1) was added in an amount of 28.1 parts. When the mixture was mixed in this state, it was made compatible, whereby the polycarboxylic acid composition (MA-1) of the present invention was obtained as a colorless transparent liquid. Example 2 'Comparative Example 1 Example 2 Example of use 丨The polycarboxylic acid composition (MA-1) of the present invention obtained in the present invention is used as a hardener, and in Comparative Example i, hexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride are used. The mixture was manufactured by Shin-Nippon Chemical Co., Ltd., hereinafter referred to as H1) as a hardener, and both Example 2 and Comparative Example 1 used 3,4-epoxycyclohexyldecyl_3,4-epoxycyclohexylformate (d Rw Chemical Company's UVR_61〇5, hereinafter referred to as epoxy resin ^)) as epoxy resin, using cetyl Sulfhydryl ammonium hydroxide (25% sterol solution manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as C1) is used as a hardening accelerator, and is formulated according to the blending ratio (parts by weight) shown in the following table. The foam was defoamed for a minute to obtain a curable resin composition of the present invention. Using the obtained curable resin composition, the LED sealing test was carried out according to the following. The results are summarized in the table. Further, the hardening conditions were 15 〇χ 3 hours after pre-hardening at 120 ° C x 1 hour. (LED sealing test), the curable resin composition obtained in the examples and the comparative examples was subjected to vacuum defoaming for 20 minutes, filled in a syringe, and cast into an LED using a precision discharge device, and the LED system was mounted thereon. Surface-mounting type of light-emitting element with illuminating wavelength of 465 jaws (SMD type, outer diameter 5 mm square surface-package type led package, inner diameter 4·4 _, outer wall height 125 varnished ribs. Thereafter 'hardened by regulation It was hardened under conditions to obtain a test [ED. 41 201116555 Evaluation item Volatile: Visually evaluate the presence or absence of depression on the surface of the cured product after sealing. In the table, 〇: no depression was found △: a small amount of depression was found, x: found A large number of depressions (wired exposed). [Table 1]

_________ - Example 2 Comparative Example 1 Unit hardener composition MA-1 32.1 parts by weight B2 parts by weight hardener H1 16.8 parts by weight __mai oxygen resin EP1 13.0 13.0 parts by weight hardening accelerator C1 0.05 0.05 parts by weight led test (Volatilization) 〇X When Comparative Example 2 and Comparative Example 比较 are compared, the amount of volatilization of the curable resin composition of the present invention is small, and even when the LED is sealed, there is no problem that the line is exposed. Further, it can be seen that it is also possible to reduce the tendency of cracks during reflow soldering. From the above results, it is understood that the polyvalent carboxylic acid of the present invention and the hardener composition containing the polycarboxylic acid can provide a curable resin composition effective for volatility. Synthesis Example 4 59 parts of 2-(3,4-epoxycyclohexyl)ethyltrimethoxy oxane, and a poly(diphenyl)diphenyl group having a calcined alcohol group of: S 1700 (GPC dec. 1 · 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 Then, after adding 135 parts of methanol, it takes 6 minutes to add 5〇% X distilled water methanol solution 25.9 f minutes to further reflux at 75. The reaction is 8 42 201116555 hours. After the reaction, 5 weights After neutralizing the aqueous solution of sodium hydrogen phosphate disodium, the distillation of decyl alcohol was carried out at 80 ° C. Thereafter, 70 parts of methyl ibuprofen _ (MIBK) was added for washing, and then washed three times with water. The solvent was removed under reduced pressure at 100 ° C to obtain 162 parts of an epoxy resin (EP2). The obtained compound had an epoxy equivalent of 707 g/eq., and a weight average molecular weight of 2680'. The appearance was colorless and transparent. Example 3 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, a nitrogen purge was performed on the surface, and a methanol-modified polyoxane was added at both ends. 22-160 people 8 (manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts,] ^ 曱 曱, hydrogen hydrogen o-dicarboxylic anhydride, 曰 曰 理 理 168 168 168 168 168 168 168 168 168 168 168 168 168 168 After that, Kyowadiol PD9 (2,4-diethyl-1,5-pentanediol, manufactured by Kyowa Essence Chemical Co., Ltd.) was added in an amount of 8 parts, ΗΤΜΑη(1,2,4_^hexane tridecanoic acid_丨, 2 - Anhydride, manufactured by Mitsubishi Gas Chemical Co., Ltd., 198 parts, reacted at 7 ° C for 1 hour, and reacted at 1 30 ° C for 5 hours, thereby obtaining a polycarboxylic acid composition (MA-2) of the present invention. The obtained polycarboxylic acid composition is a colorless and transparent liquid (close to a semi-solid, but has fluidity at room temperature). (Although it cannot be correctly calculated, it is derived from the end of the sterol-modified polyoxyl The carboxylic acid (J) is about 7% by weight, and the polycarboxylic acid (Κ) derived from 2,4-diethyl 15 pentane diol is about 30% by weight. Example 4 Preparing a mixer, a reflux cooling tube, In the flask of the mixing device, one is flushed with nitrogen, and the two ends are added with sterol modified polyfluorene 43 201116555 X22-160AS (Shin-Etsu Chemical Industry Co., Ltd. Manufactured parts, y-methylcyclohexane succinic acid needle 'manufactured by New Japan Physicochemical Co., Ltd.) 168 parts, PD9 (2,4-diethyl), 5-pentylene glycol, manufactured by Kyowa Essence Chemical Co., Ltd., HTMAn (1,2,4-cyclohexane tricarboxylic acid·1&gt;2, manufactured by Mitsubishi Gas Chemical Co., Ltd.) m parts, reacted at 7 (rc for 2 hours, after 5 hours at 13 〇t, 'cooled to After that, 33.6 parts of mh (methylhexahydrophthalic anhydride, manufactured by Nippon Chemical Co., Ltd.) was added to make it completely compatible, whereby the polycarboxylic acid composition (MA_3) of the present invention was obtained. The obtained multi-repulsive composition is a colorless and transparent liquid. (Although it cannot be calculated correctly, the polycarboxylic acid (J) derived from the two-terminal sterol-modified polyfluorene oxide contains about 7% by weight, derived from 2,4-diethyl-1,5-pentanediol. The polycarboxylic acid (κ) is about 27% by weight and the acid anhydride is about 3% by weight. Examples 5 and 6, Comparative Examples 2 and 3 Examples 5 and 6 respectively use the plural of the present invention obtained in Examples 3 and 4. The carboxylic acid composition (ΜΑ-2, ΜΑ·3) was used as a curing agent, and in Comparative Examples 2 and 3, the carboxylic acid (j_丨) and the acid anhydride (Η丨) produced in Synthesis Example 1 were used as the curing agent, respectively. 6 and Comparative Examples 2 and 3, the epoxy resin (EP2) obtained in Synthesis Example 4 was used as the epoxy resin, and hexadecyltrimethylammonium hydroxide (25% methanol manufactured by Tokyo Chemical Industry Co., Ltd.) was used. The solution, hereinafter referred to as C 1), as a curing accelerator, was prepared according to the blending ratio (parts by weight) shown in Table 2 below, and defoamed for 20 minutes to obtain a curable resin composition of the present invention or comparative use. Using the obtained curable resin composition, various tests were carried out in accordance with the procedures shown below. The result areas are shown in Table 2. 44 201116555 (1) Depression test: The curable resin composition obtained in Examples 5 and 6 and Comparative Examples 2 and 3 was subjected to vacuum defoaming for 20 minutes, and then filled into a syringe, and a precision ejection device was used to open the opening. It was cast in a planar manner into a surface mount type LED in which a light-emitting element having an emission wavelength of 465 nm was mounted. After pre-hardening at 120 ° C for x 3 hours, it was hardened at 150 ° C for 1 hour to seal the surface-sealed LED. The depression of the surface of the resin accompanying the volatilization of the hardener after such sealing was visually evaluated. In the table, 〇: no depression was found, △: a small amount of depression was found 'X: a large number of depressions were found (line exposure) (2) Reflow soldering test: Composition of the curable resin obtained in Examples 5 and 6, Comparative Examples 2 and 3. After the vacuum was defoamed for 20 minutes, it was filled in a syringe, and was molded into a surface mount type [ED] having a light-emitting element having an emission wavelength of 465 nm by using a precision discharge device. After pre-hardening at 1 2 ° C for 3 hours, it was hardened at 1 5 〇 X for 1 hour to seal the surface-mount LED. After the obtained test LEE) was used for 3 (TC 70% x 72 Hr moisture absorption, a high temperature observation apparatus (SMT Scope SK-5000, manufactured by Sanyo Seiko Co., Ltd.) was used, and the following reflow conditions were visually observed. The test used cracks generated on L·ED. The test was performed with η = 3 and evaluated by (〇κ number) / (test number). The condition was raised from 2 ° C / sec to 1 ° at 25 ° C. 5: (:, then held at 1 50 C for 2 minutes, and then raised to 260 at 2 ° C / sec. (3, after maintaining the temperature for 1 〇, cool to room temperature at 1 _ 3 ° C / sec. 3) Financial gas permeability test (corrosion gas permeability test): 45 201116555 The curable resin composition obtained in Examples 5 and 6, Comparative Examples 2 and 3 was subjected to vacuum defoaming for 20 minutes, and then filled into a syringe. Using a precision ejector, it was washed into a chip packaged with a center emission wavelength of 465 nm and an outer diameter of 5 mm square-surface package type LED package (inner diameter 4_4 mm, outer wall height 1·25 mm). Into the heating furnace, at 12 〇t: hardening treatment for 1 hour, and then ISOT hardening treatment for 3 hours, to form an LED package The LED package was placed in a corrosive gas under the following conditions, and the color change of the silver-plated lead frame portion inside the seal was observed. <Measurement conditions> Corrosion gas: Ammonium sulfide 20% by weight aqueous solution (sulfur component reacted with silver) When the time is changed to black), the contact side &amp; is in the wide-mouth glass bottle, and the above-mentioned LED package is mixed and placed in a state in which the lid of the wide-mouthed glass bottle is closed and sealed. Volatile vulcanized gas. Contact with led package. Determination of rot silver: (referred to as blackening) the better the time permeability. [Table 2] Observe that the lead frame inside the LED package turns black. Long, judged to be a corrosion-resistant gas

46 201116555 As a result of the results shown in Table 2, the epoxy resin composition of the present invention can provide a cured product which is excellent in reflow resistance and has excellent corrosion resistance and gas permeability. Examples 7 to 13 and Synthesis Examples 6 and 7 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, a two-terminal sterol modified polyfluorene was added according to the mixing amount described in Table 3 below while performing nitrogen purge. Oxygen compound (one selected from SI-1 and SI-2), saturated aliphatic polyol (one selected from AL-1 and AL-2), and acid anhydride (selected from HI, H2, H3) At least one of them is allowed to react at 70 ° C for 5 hours and at 90 ° C for 3 hours, thereby obtaining a polycarboxylic acid composition (MA-4 to MA10) and a carboxylic acid resin (J- as a colorless transparent liquid. 2. J-3). In addition, SI-1: FM-441 manufactured by Chisso, SI-2: X22-160AS manufactured by Shin-Etsu Chemical Co., Ltd., AL-1: Kyowadiol PD-9, AL-2 manufactured by Kyowa Chemical Co., Ltd. : TCDAlchol-DM manufactured by OXEA, H1: Rikacid MH-700 manufactured by Nippon Chemical and Chemical Co., Ltd., H2: Rikacid manufactured by Nippon Chemical and Chemical Co., Ltd., H3: Ν-ΤΜΑη manufactured by Mitsubishi Gas Chemical Co., Ltd. [Table 3] Composition product SM SI-2 AL-1 AL-2 H1 H2 H3 polycarboxylic acid polycarboxylic acid (J) / (K) Shape Example 7 435 10 168 MA-4 95/5 Colorless liquid example 8 475 20 168 MA-5 90/10 Colourless liquid Example 9 335 26 168 MA-6 85/15 Colorless liquid Example 10 390 22 168 MA-7 90/10 Colorless liquid Example 11 300 39 168 MA -8 80/20 colorless liquid Example 12 300 39 164 MA-9 80/20 colorless to pale yellow liquid Example 13 450 10 160 20 MA-10 86/14 colorless liquid synthesis example 6 500 168 J-2 100/0 colorless liquid synthesis example 7 500 168 J-3 100/0 colorless liquid* In the table, C〇/(K) represents the weight/source of the polycarboxylic acid derived from the methanol-modified polyoxo compound at both ends. The weight of the polycarboxylic acid of the self-saturating aliphatic polyol. 47 201116555 Synthesis Example 8 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, a nitrogen purge was applied to the surface, and 100 parts of sour liver (H2) and a saturated aliphatic polyol (AL-1) were added thereto at 50°. C was stirred for 3 hours, and stirred at 70 ° C for 30 minutes, thereby obtaining a mixture of a colorless transparent carboxylic acid compound and an acid anhydride of 12 parts. The ratio of the obtained carboxylic acid to anhydride was determined by gel permeation chromatography to be about 52:48. Example 1 4, 1 5 A mixture of a colorless transparent carboxylic acid compound and an acid anhydride obtained in Synthesis Example 8 (Example 丨 4) and 2 parts (Example 15) were added to the plural obtained in the synthesis example. The carboxylic acid compound (J 2 ) was dissolved in 1 part and uniformly dissolved. Thereby, colorless polycarboxylic acid compositions MA-1 1 and ΜΑ-1 2 were obtained, respectively. Synthesis Example 9 39.4 parts of wan-(3,4-epoxycyclohexyl)ethyltrimethoxy oxime and a decyl alcohol terminal decyl phenyl polyfluorene oxide 1 37 having a weight average molecular weight of 1 900 (GPC measurement) The fraction (the stanol equivalent of 950, which was calculated to be one-half of the weight average molecular weight measured by GPC) and the 〇5% potassium hydroxide (K〇H) methanol solution were added to the reaction vessel, and the bath temperature was set to 75. (: and heat up. After luring, let it react under reflux for 1 hr. As a manufacturing step (ii), after adding 1 4 〇 曱 曱 , , , t 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 The decyl alcohol solution was 7.3 injured and allowed to react at reflux for 8 hours at 75 ° C. After the completion of the reaction, about 9% phosphorus-I-hydrogen sodium aqueous solution was used, and then about 9 〇% of methanol was distilled off at 8 〇〇c. Then, 2 parts of decyl isobutyl ketone (MIBK) was added and washed three times with water. The organic phase obtained in 48 201116555 was removed under reduced pressure at 1 Torr to obtain a ring-containing cyclohexyl group. 152 parts of organic polyoxane (EP-3). The obtained compound (EP/3) has an epoxy equivalent of 1040 g/ecl., a weight average molecular weight of 2290, and a colorless transparent liquid resin. 1 375 375 parts of 10,000-(3'4-epoxycyclohexyl)ethyltrimethoxy decane and a weight average knife of 9 〇〇 (GPC measured value) of decyl alcohol terminal sulfhydryl 475 parts (95 〇 of ethanol equivalent, calculated as -half of the weight average molecular weight measured by Gpc), 0.5% potassium hydroxide (K〇H) methanol solution was added to the residue The temperature of the bath was set to 75 t and the temperature was raised. After the temperature was raised, the reaction was carried out under reflux for 8 hours. After adding 65 parts of methanol, 144 parts of a 5 % by weight distilled sterol solution was added dropwise over 60 minutes. The reaction was carried out at 75 C for 8 hours under reflux. After the reaction was completed, the mixture was neutralized with a 5% aqueous solution of sodium dihydrogen phosphate, and about 9% by weight of decyl alcohol was recovered at 80 t. The methyl isobutyl ketone (MIBK) was then added. 750 parts were washed three times with water. The obtained organic phase was depressurized at 1 Torr. The solvent was removed to obtain 647 parts of an organic polyoxo-oxygen (ΕΡ·4) containing an epoxycyclohexyl group. The obtained compound (Ερ·4) had an epoxy equivalent of 541 g/eq., a weight average molecular weight of 21 Å, and a colorless liquid resin: Example 1 6 to 19, Comparative Example 4 Examples 16 to 19 used the poly-acid composition (MA_4, MA-5, MA_6, MA-1〇) of the present invention as a curing agent, and Comparative Example 4 used a poly-reactive acid resin (J-3) as a curing agent, and Examples 16 to 19 and Comparative Example 4, the epoxy resin (EP_4) obtained in Synthesis Example 10 was used as the epoxy resin, and octanoic acid 49 201116555 (PC) was used. I8% Oc tope manufactured by hemical, hereinafter referred to as C2) as a hardening accelerator, using a light stabilizer (LA-8 1, manufactured by ADEKA, called AD-U, an antioxidant (made by ADEKA) ^deka 260, the additive AD_2)), blended according to the blending ratio (parts by weight) shown in the following Table 4, and defoamed for 20 minutes to obtain the curable resin composition of the present invention and the curable orange fat composition for comparison. . Using the obtained curable resin composition, the test was carried out according to the procedure shown below. The results are collectively shown in Table 4. Further, the hardening conditions were 12 unless otherwise specified (15 times after TCx 2 hours of pre-hardening (rcx 5 hours. (1) Tensile test based on JIS κ 6911-like mouth thickness 0·9±0.05 mm sectional area 4 5 ± 〇2 _2 speed 5 mm/min, distance between clamps 丨5 mm (2) Thermal durability transmittance test, 30 mm x 2 mmmm height i mm, slowly obtained the curable resin composition Light tungsten to heat-resistant tape is used to form a barrier ((4) on the glass substrate. After the material is pre-hardened for 12Qtx for 3 hours, M is hardened and hardened to obtain a transmittance of 1 mm. The test is performed using δ Xuan et al. , by the apricot acne 4 ^ 丨 - ^ 楮田刀光度计 measured in a 150 ° C oven placed 72 hr before and after the macro; 丨 + rate (measured wavelength = 400 nm), Calculate the rate of change. /, ^ Price: If the transmittance is less than 5%, it is set to 〇, 5% or more and less than 10/❶ is set to △, and 10% or more is set to "201116555 [Table 4] Example 16 Example 17 Example 18 Example 19 Comparative Example 4 Composition of the polycarboxylic acid composition MA-4 9.2 MA-5 8.3 MA-6 7.8 MA-10 7.0 Polycarboxylic acid resin J-3 9.9 Epoxy resin EP-4 10 10 10 10 10 Catalyst C-2 0.04 0.04 0.04 0.04 0.04 Additive AD-1 0.02 0.02 0.02 0.02 0.02 AD-2 0.02 0.02 0.02 0.02 0.02 Hardened physical property Maximum point test Elongation % 38.4 49.6 65.1 39.4 20 Thermal durability transmittance test % 96.1 95.9 95.5 95.1 95.6 Evaluation Example 20 to 22, Comparative Example 5 Example 20~ 22 using the polycarboxylic acid composition (Ma_7, MA-8, MA-9) of the present invention as a curing agent, and Comparative Example 5 using a polyvalent carboxylic acid resin (j_3) as a curing agent, and Examples 20 to 22 and Comparative Example 5 were used. The % oxygen resin (EP-3, EP-4) known in Synthesis Example 9 and 1〇 is used as an epoxy resin, and a curing accelerator (C2) and an additive (α^, AD_2) are used, as shown in Table 5 below. The blending ratio (parts by weight) is blended, and defoaming is carried out for 2 minutes to obtain a curable resin composition of the present invention and a curable resin composition for comparison. The curable resin composition obtained is used as follows. The essentials of the test will be pure Bu addition, curing conditions for the hardening 12〇 ι5 hour pre Cx2 (Γςχ5 hours. (1) Peel test based on &lt;^8 ft 6911 Support: Use copper II rough surface, sample width: 1 Gmm, glass speed 51 201116555 Degree: 3 mm/min (2) Tensile test based on JIS K6911 Sample thickness 0·9 ± 0·05 mm sectional area 4·5±0·2 mm2 speed 5 mm/min, distance between clamps 15 mm [Table 5]

Example 20 Example 21 Example 22 Comparative Example 5 Composition of a polycarboxylic acid composition MA-7 6.3 MA-8 • 5.5 MA-9 5.4 Polycarboxylic acid resin J-3 7.2 Epoxy resin EP-3 6.0 6.0 6.0 6.0 EP -4 4.0 4.0 4.0 4.0 Catalyst C-2 0.04 0.04 0.04 0.04 Additive AD-1 The total peeling test of the hardened physical peeling test N 1.34 1.83 1.32 ND tensile test maximum point elongation % 32.8 49.1 23.5 ND *ND hardened material is more brittle 'not a level that can be evaluated. From the above results, it is understood that the curable resin composition of the present invention is excellent in adhesion, toughness, and heat resistance durability. Examples 23, 24, and Comparative Example 6 Examples 23 and 24 used the polyvalent oleic acid composition (MA_1^, ΜΑ-12) of the present invention as a curing agent, and Comparative Example 6 used a polyvalent carboxylic acid resin as a curing agent, and Examples 23, 24 and Comparative Example 6 using the epoxy resin (EP-4) obtained in the synthesis example 作为 as an epoxy resin, using a hardening accelerator (C2), an additive (AD-1, AD-2), according to the following The blending ratio (parts by weight) shown in Table 6 was blended, and defoaming was carried out for 20 minutes to obtain a curable resin composition of the present invention and a curable resin composition for comparison. 52 201116555 Using the obtained curable resin composition, the test was carried out according to the procedure shown below, and the results are summarized in Table 6. Further, the hardening conditions were 1 50 ° C x 5 hours after pre-hardening of 12 〇 ° C x 2 hours. (1) Tensile test based on JIS K 691 1 Sample thickness 0.9±0·05 mm Sectional area 4.5±0.2 mm2 Speed 5 mm/min, distance between clamps 15 mm (2) LED lighting test for examples and comparative examples The obtained curable resin composition was vacuum-defoamed for 2 minutes, and then filled into a syringe, and a precision discharge device was used to wash the surface-sealed LED ((()) with a light-emitting element having an emission wavelength of 465 nm. In the case of 5 mm), the LED for lighting test was obtained by hardening it under predetermined hardening conditions. The lighting test was an ignition test, and a lighting test of 7 10 mA, which is 7 times the predetermined current, was performed. The conditions are shown below. The measurement item 'measures the illuminance before and after lighting for 20 hours using the integrating sphere, and calculates the illuminance retention rate of the test LED. Lighting detailed conditions illuminating wavelength: 465 nm Driving method: constant current mode, 2 mA (The light-emitting element specifies a current of 30 mA)

Driving environment: 25 ° C, 65% RH (3) Gas permeation resistance test (corrosion gas permeability test): An LED package made of the obtained curable resin composition is placed on a corrosive gas under the following conditions In the middle, observe the color change of the silver-plated lead frame portion inside the seal. 53 201116555 &lt;Measurement conditions&gt; Corrosion gas: 20% aqueous solution of sulfurized money (black color when sulfur component reacts with silver) Contact method··In the wide-mouth glass bottle, the volume of the vulcanized money aqueous solution and the above (4) The package body is mixed and placed in a state of being closed with a lid of a wide-mouthed glass bottle to make the vulcanized ammonium sulfide gas and the led, and the rot is judged: the lead frame of the LED seal is observed to be black every 1 hour. In the case of blackening, the longer the discoloration time is, the more excellent the gas resistance is judged to be. [Table 6] Composition of multiple carboxy ruthenium composition MA-11 MA-12 Example 23 7.8 Example 24 7 A Comparative Example 6 Polycarboxylic acid This ring gas tree Moon Si grease J-2 / ♦ 〇 9 9 Purpose EP*4 10.0 10.0 10 0 Touch C-2 0.1 0.1 0 1 Additive AD-1 0.02 0.02 0.02 AD-2 0.02 0.02 ΤΓτη~~ Hardening physical property tensile test Maximum point elongation % 36.9 38.7 U.U2 ~22Τ~~ Lighting test Illuminance retention rate % 101 103 103^ Corrosion gas permeability test retention time time &gt; 2 hours&gt; 2 - Example 25 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, nitrogen gas was flushed while adding both ends Methanol modified polyoxonium oxide (SI-2) 365 parts, pentaerythritol (hereinafter referred to as saturated aliphatic polyol AL-3) 9 parts, and anhydride (H2) 168 parts, which reacted at 90 ° C After 2 hours, the reaction was carried out at 110 ° C for 3 hours. Thus, 542 parts of a multi-component composition (MA-U) was obtained as a colorless transparent liquid. (weight of polycarboxylic acid derived from si-2 (J) / source 54 201116555 Weight of polycarboxylic acid of scale from AL_3 (Κ) = 90/10) Example 2 6. Comparative Example 7 Example 26 using the present invention The polycarboxylic acid composition (μα_13) was used as a curing agent, Comparative Example 7 used a polyvalent carboxylic acid resin (J-3) as a curing agent, and Example 26 and Comparative Example 7 used the epoxy obtained in Synthesis Examples 9 and 10. The resin (ΕΡ-3, ΕΡ-4) is blended as an epoxy resin using a curing accelerator (C2) and an additive (AD_b AD-2) according to the blending ratio (parts by weight) shown in Table 7 below. The defoaming was carried out for 20 minutes to obtain a curable resin composition of the present invention and a comparative curable resin composition. Using the obtained curable resin composition, the test was carried out in accordance with the procedure shown below, and the results are summarized in Table 7. Further, the hardening conditions were 15 〇乞 μ hours after pre-hardening of 12 〇 C x 2 hours. (1) The peeling test is based on a 118-foot 6911 support: copper foil rough surface, sample width: 1 〇 mm, peeling speed: 3 mm/min (2) Tensile test based on JIS κ 6911 sample thickness 〇.9±0. 〇5 mm sectional area 4.5±0.2 mm2 speed 5 mm/min, distance between clamps 15 mm (3) LED lighting test The hardening resin composition obtained in the examples and the comparative examples was subjected to vacuum defoaming after 2 Torr. It was filled in a syringe, and was cast into a surface-mount type LED (cl) 5mrn) equipped with a light-emitting element having an emission wavelength of 465 11〇1 using a precision discharge device. Thereafter, the LED for lighting test was obtained by hardening it under predetermined curing conditions. The lighting test is specified for the accelerated test. 55 201116555 7 times the current, that is, the lighting test of 2 10 mA. Detailed conditions are shown below. Measurement item 'The illuminance before and after lighting for 40 hours was measured using an integrating sphere, and the illuminance retention rate of the test LED was calculated. Lighting detailed conditions Illumination wavelength: 465 nm Drive method: Constant current mode, 210 mA (light-emitting component specified current is 30 mA)

Driving environment: 25 ° C, 65% RH (4) Gas permeation resistance test (corrosion gas permeability test): An LED package made of the obtained curable resin composition is placed on a corrosive gas under the following conditions In the middle, observe the color change of the lead frame portion of the silver inside the seal. &lt;Measurement conditions&gt; Corrosion gas: 20% aqueous solution of ammonium sulfide (black color when sulfur component reacts with silver) Contact method: 'In the wide-mouthed glass bottle', the capacity of the aqueous solution of ammonium sulfide is mixed with the above-mentioned LED package 'The vulcanized ammonium sulfide gas is brought into contact with the LED package while the lid of the wide-mouthed glass bottle is closed. Corrosion determination: The time inside the LED package was observed every black hour (the time when the wood was only black (referred to as blackening), and the longer the color change time, the more excellent the corrosion resistance gas was judged. 56 201116555 [Table 7] Composition of hardened physical polycarboxylic acid composition polycarboxylic acid ^~~ Epoxy resin catalyst additive peel test tensile test peel strength ΜΑ-13 J-2 ΕΡ-3 ΕΡ-4 C-2 AD- AD-2 Example 26 9.8 6.0 4.0 0.1 0.008 0.008 Comparative Example 8.7 6.0 4.0 0.1 0.008 0.008 Lighting test Corrosion gas permeability test Maximum point elongation 聿 retention time

N % time Hardened material is brittle and not able to judge 2.0

ND 33.1

ND 105 &gt; 2 hours and 104. From the above results, the epoxy resin composition of the present invention can provide a cured product which is excellent not only in heat resistance and light resistance but also in excellent adhesion and toughness, and is excellent in corrosion resistance. . 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. </ RTI> This application is based on a patent application filed on Oct. 6, 2009 (Japanese Patent Application No. 2009-232113), which is incorporated herein by reference. Further, all references cited herein are incorporated as a whole. [Simple description of the diagram] Μ. ***\ [Description of main component symbols] &amp; 57

Claims (1)

201116555 VII. Patent application scope: 1. A polycarboxylic acid composition characterized by containing a plurality of acid compounds (j) and a polycarboxylic acid compound (κ), the carboxylic acid compound (J) being The polyoxo-oxygen oil (a) represented by the formula (1) is reacted with a compound (b) having one or more carboxylic acid anhydride groups in the molecule to obtain an addition reaction: f/ R2 \ R2 ho - r, a formazin Rl_0H (7) rA ^ The weight average molecular weight of the compound shown is 5 〇〇 5 5 〇〇〇); the polycarboxylic acid compound (K) is obtained by using a saturated aliphatic polyol (4) having an alcoholic hydroxyl group having 2 or more functional groups. # i or more of the carboxylic anhydride group compound (d) addition reaction derived. 2. The multi-read acid composition of claim 1, wherein the compounds (b) and (d) are anhydrides having a cyclic saturated hydrocarbon as a parent skeleton. The heptane of the heptane-2,3-dicarboxylic anhydride + &amp; Compounds (b) and (d) are composed of methylhexahydrophthalic acid monomethyl hexahydrophthalic anhydride, hexa-tricarboxylic acid-1,2-anhydride and bicyclo[2,2,1] polycarboxylic acid. And wherein the dicarboxylic anhydride is an essential component. 58 201116555 Patent No. 2 to 4 of the patent application scope of the multi-repulsive acid composition of the eighth, the compound (C) is a polyol having a functional group of 2 to 6, and the total carbon number in the ruthenium molecule is 5 to 20 . The invention relates to a method for producing a ternary carboxylic acid composition, which is used for producing the yttrium carboxylic acid composition of the first to fifth items of the patent application scope; characterized in that: the compound contains the polyoxic acid (4) and has 2 a mixture of a functional aliphatic alcohol-based saturated aliphatic polyol (4), a compound (8) and (4)' having a (iv) if group in the molecule, and then simultaneously carrying out the polyoxosulfuric acid (4) and the compound (b) An addition reaction and an addition reaction of the compound (4) with the compound (4). 7. A method for producing a multi-component composition, which is a method for manufacturing a patent range 1 to 5 H Φ cup a ji 夂 & &&;;;;;;;;;;;;;;;;;;;;;;;;;;;; Step (4), step (Β) reaction; Step (Α): a step of adding a polyfluorene oxide oil (4) to a compound (b) having i or more carboxylic acid anhydride groups in the molecule, and step (B): having 2 The polyol (c) has a step of reacting with the molecule. a compound having a functional or higher alcoholic transradical group, a saturated aliphatic one or more citric acid needle base compound (4), a carboxylic acid composition, which is produced in an organic solvent relative to the original solvent used, as in the patent application scope. The method of the sixth or seventh method of 'where' is in the absence of a solvent, or the total amount of the reaction substrate in the feed is 50% by weight. /〇 The addition reaction was carried out at 40 to 150 °C. 59 201116555 9 · A kind of hardening resin group 多元 5 items from one to the other _ 2 contains the patent application range 1 to residue k, ‘and products and epoxy resin. == The curable resin composition of the ninth patent range, the oxygen (tetra) alicyclic epoxy resin and/or the epoxy group-containing polylith, I: II? The sclerosing tree riding composition of the ninth aspect of the patent, wherein the oxy-resin is an epoxy group-containing polyoxyl resin. A cured product obtained by hardening a curable resin composition according to any one of claims 9 to &quot; Eight, schema: (none) 60