TW201120000A - Multivalent carboxylic acid composition, curable resin composition, cured article and method for producing multivalent carboxylic acid composition - Google Patents

Abstract

The present invention relates to a multivalent carboxylic acid composition containing a multivalent carboxylic acid represented by the following formula (1), an epoxy resin curing agent composition containing the same, a curable resin composition containing the curing agent composition and an epoxy resin, a cured article thereof, and a novel multivalent carboxylic acid. When the multivalent carboxylic acid and a composition containing the same are used as a curing agent for epoxy resin, evaporation of the curing agent during cure is little, and the obtained cured article has excellent optical properties and thermal durability. (in this formula, R respectively independently represents hydrogen atom, C1-C6 alkyl group or carboxyl group, P represents a divalent cross-linking group defined by the following (a) or (b), (a) A cross-linking group which is a chained-shape alkyl chain having a C6-C10 branched structure, the chained-shape alkyl chain having a C3-C12 straight chain as a main chain, and two to four side chains, and at least one of the side chains is C2-C10. (b) A divalent cross-linking group formed by removing two hydroxyl groups from at least one cross-linked polycyclic diol selected from tricyclodecane dimethanol or pentacyclopentadecane dimethanol, which may have a methyl group on a cyclic ring.

Description

201120000 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a hardenable epoxy resin which is particularly suitable for use in electrical and electronic materials, finely divided compositions, and hardeners containing the polyacid acid group. Composition. Further, the ruthenium phthalic acid composition may be used in addition to the field of multi-dimensional oxic acid, and may be used as a coating, an adhesive, a molded article, a semiconductor, a photo-semiconductor, a functional resin, or a photo-semiconductor die bQnd material. Raw materials such as resin materials, resins, etc., or modifiers, plasticizers, lubricant raw materials, = drug intermediates, raw materials for coating resins, or resins for toners (pre-technical), s, ° The polycarboxylic acid has excellent thermal stability, good electrical properties, excellent chemical resistance, and good reactivity when forming a condensate, and can be used as a coupling agent or a condensing agent. Therefore, polycarboxylic acids have been extremely prominent and widely used in recent years as raw materials for polymer production. Further, it is known that a polyvalent carboxylic acid can also be used as a hardener for an epoxy resin. (3) The curable resin composition having an epoxy resin is used in the fields of construction, civil engineering, automobiles, and airplanes as a resin excellent in heat resistance. In recent years, especially in the field of semiconductors, it is full of camera-equipped mobile phones, ultra-thin honey LCD or plasma TVs, lightweight notebook computers, etc., which have become the key to light, thin, short and small. Characteristic electronic machine. Extremely high properties are also required for the materials used in these semiconductor-related fields, particularly in the packaging materials represented by the ring tree. 5 322150 . VB- 201120000 Moreover, in recent years, the use of epoxy resin in the optoelectronic related jaw domain has attracted attention. In particular, with the recent high level of informationization, in order to smoothly transmit and process huge amounts of information, we have developed and utilized technologies that change the transmission of signals by electrical wiring and transmit information by optical signals. In the field of optical elements such as optical waveguides, blue LEDs, and optical semiconductors, the cured resin used therein is required to have a cured product excellent in transparency and durability. In general, the hardener of the epoxy resin used in such a field may, for example, be an acid anhydride-based compound. In particular, a cured product of an acid anhydride formed of a polyvalent carboxylic acid of a cyclic aliphatic hydrocarbon is used, and since it has excellent light resistance, the acid needle is often used. For example, an alicyclic acid anhydride such as mercaptotetrahydrofurfuric anhydride, hexahydrophthalic anhydride or tetrahydrophthalic anhydride is generally used. Among them, sulfhydryl hexahydrophthalic anhydride or methyltetrahydrophthalic anhydride which is liquid at normal temperature is mainly used because of ease of handling. However, when the above-mentioned alicyclic acid anhydride is used alone as a hardener, since the vapor pressure of the hardeners is high and partial evaporation occurs during hardening, there is no prescribed amount of carboxylic anhydride (hardener) in the cured product. Therefore, there is a problem that the epoxy resin composition is poorly cured, and the curing condition is changed by a large amount of 1 Hz, and there is a problem that it is difficult to obtain a cured product having a desired performance. Further, when the hardened material is mass-produced in an open system, the hardener is volatilized in the atmosphere and releases harmful substances to the atmosphere to cause environmental pollution, adverse effects on the human body, and contamination of the production line. In addition, when the LED is sealed, especially when the SMD (Surface Mount Device) is sealed, the use of the resin 322150 6 201120000 is small, and there is a lower (four) problem: the above hardening is poor. And the effect that the stability performance cannot be obtained is extremely remarkable, and the wiring is exposed due to the occurrence of the dent, and the occurrence of cracks and/or peeling during the solder reflow (s〇lder reH〇W) is caused. Or problems such as poor quality due to long-term lighting. Further, a polyvalent carboxylic acid similar to the polyvalent carboxylic acid of the present invention is known to be used as an emulsifier, for example, in Patent Documents 4 and 5. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2008-063333 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-063333 [Patent Document 3] Japanese Patent No. 2813028 (Patent Document 4) [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 3-26743. a novel polycarboxylic acid used for a hardening agent and a hardening agent, a epoxy resin composition containing the polycarboxylic acid or hardener composition (curable resin composition), and the epoxy resin composition (hardened resin composition) cured product. Thus, useful novel polycarboxylic acids and compositions containing the polycarboxylic acids are provided. In particular, the purpose is to provide a curable resin composition which is excellent in optical properties such as a heat retention property of a cured product, specifically, a transmittance retention ratio and an illuminance maintenance ratio in an LED. Therefore, it is 7 322150 201120000 carboxylic acid. And a polycarboxylic acid composition containing the polycarboxylic acid. [Means for Solving the Problems] The present inventors completed the present invention by focusing on the results of the review in view of the above facts. That is, the present invention relates to the inventors described below. A polycarboxylic acid composition containing a polyvalent carboxylic acid represented by the following formula (1),

Wherein R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a carboxyl group; and P represents a divalent crosslinking group as defined in the following (a) or (b): (a) is a carbon number 6 a cross-linking group of a chain alkyl chain of a branched structure of 20, wherein the chain alkyl chain has a linear main chain of 3 to 12 carbon atoms and 2 to 4 side chains, and at least the side chain 1 is a carbon number of 2 to 10, (b) is a crosslinked polycyclic second having at least one selected from the group consisting of tricyclodecanedioxane or pentadecanedioxanol having a mercapto group on the ring. A divalent cross-linking group in which two hydroxyl groups are removed from the alcohol, and when P is (b), R represents a group other than a hydrogen atom. 2. The polycarboxylic acid composition according to the above 1, wherein the divalent crosslinking group is a crosslinking group defined by (a), and the crosslinking group defined by (a) is the following formula (al) Any one of the two valence groups indicated, (al) = 8 322150 201120000

In the formula, the 氺 mark at the end of each group indicates the oxygen atom adjacent to the bond at the * mark. 3. The polycarboxylic acid composition according to the above 1 or 2, wherein the main chain in the crosslinking group (a) is a linear chain having a carbon number of 3 to 6, and at least two of the side chains are a carbon number of 2 to 4. Alkyl group. 4. The polycarboxylic acid composition according to any one of 1 to 3 above, wherein the crosslinking group defined by (a) is removed from 2,4-diethyl-1,5-pentanediol 2 A divalent group after a hydroxyl group. 5. The polycarboxylic acid composition according to the above 1, wherein the cross-linking group defined by the cross-linking group of (2) is (b), and the cross-linking group defined by (b) is the following formula (bl) Any of the two valence groups, formula (bl):

S 9 322150 201120000

In the formula, a plurality of R2 present in each structural formula each independently represent a hydrogen atom or a methyl group. 6. The polycarboxylic acid composition according to any one of the above 1 to 5, which is obtained from a polyvalent carboxylic acid wherein R2 is a hydrogen atom. 7. The polyhydric carboxylic acid composition according to any one of the above 1 to 6, which is a polyvalent carboxylic acid containing 50 mol% or more of the formula (1) wherein R is a mercapto group and/or a carboxyl group. The polycarboxylic acid composition according to any one of the above 1 to 7, wherein R of the formula (1) is a methyl group or a carboxyl group. 9. The polycarboxylic acid composition according to the above 8, wherein the group other than the hydrogen atom is a mercapto group. The polycarboxylic acid composition according to any one of the above 1 to 8, wherein the polycarboxylic acid composition contains at least one of the polycarboxylic acid represented by the formula (1) and a C4 which may be substituted by a methyl group. To C? ring di-, tri- or tetracarboxylic anhydride. 11. The polycarboxylic acid composition according to the above 10, wherein the C4 to C? ring di, tri or tetracarboxylic anhydride which may be substituted by a methyl group is a cyclohexane di or tricarboxylic anhydride which may be substituted with a mercapto group. A curing agent for an epoxy resin comprising a polyvalent carboxylic acid of the formula (1) or a polyvalent carboxylic acid composition according to the above 10 or 11. 13. The hardener composition for an epoxy resin according to the above 12, which is: 10 322150 201120000 The divalent crosslinked group represented by P of the formula (1) is a cross-linking group defined by (a) and is a U) The crosslinked group is defined as a polyvalent carboxylic acid having a valence group of the following (1), and an anthracene selected from the group consisting of the acid anhydrides of the following (2), and a polyvalent carboxylic acid composition. , (1) Divalent group: • A divalent group obtained by removing two hydroxyl groups from 2,4-diethyl-1,5-pentanediol; (2) Anhydride: mercapto hexahydrophthalic anhydride, and ring Hexane-1,2,4-tricarboxylic acid- 14. The epoxy resin hardening product according to the above 12, which is characterized in that: the divalent crosslinked group represented by P of the formula (1) is (8) (4) The cross-linking group and the cross-linking group defined by (b) are a group of a poly-methane acid of any of the divalent intermediates represented by the following formula (1) and an acid anhydride selected from the group (2) below. ;^ One less acid anhydride, the resulting polycarboxylic acid composition, (1) Formula (bl):

The plural or each of the structural formulas t exist independently to represent the gas (2) acid anhydride: methyl hexa _, and cyclohexene 322150 11 201120000 anhydride. A hardening resin composition comprising the polycarboxylic acid of the formula (1) as set forth in any one of the above-mentioned 丨 to 7 or the hardener composition according to any one of the above 12 to 14 , with epoxy resin. 16. The curable resin composition according to the above 15, wherein the epoxy resin is an alicyclic epoxy resin. The curable resin composition according to the above-mentioned item 16, wherein the hardener composition is the hardener composition described in the above item 13. 18. The curable resin composition according to the above-mentioned item 16, wherein the hardener composition is the hardener composition described in the above 14. 19. A cured product of the curable resin composition according to the above item 15. 20. The method for producing a polybasic acid represented by the above formula (1), wherein the diol of the following (a) or (b) is reacted with (c), wherein (a) a chain aliphatic diol having a branched structure of 6 to 20 carbon atoms, wherein the chain alkyl chain has a linear main chain of 3 to 12 carbon atoms and 2 to 4 side chains, and the side chain At least one of a carbon number of 2 to 1 Å, or (b) at least one selected from the group consisting of tricyclodecane decyl alcohol or penta pentadecane dimethanol having a fluorenyl group on the ring Cross-linked polycyclic diol; (c) at least one selected from the group consisting of hexahydrophthalic anhydride, decyl hexahydroauhydride, and cyclohexane-1,2,4-tricarboxylic anhydride The acid anhydride, if it is (b), is at least an acid anhydride containing any one of mercaptohexahydrophthalic anhydride or cyclohexane-1'2,4-tribasic acid anhydride. The method for producing a polyvalent carboxylic acid composition according to the above 20, wherein the diol of (a) or (b) and the acid anhydride of (c) are phase-sealed to an acid anhydride group of 1 equivalent of 322150 12 201120000 The base equivalent of the diol is 0.001 to 2 equivalents, and the reaction is carried out at a reaction temperature of 40 to 150 °C. 22. The method for producing a polyvalent carboxylic acid composition according to the above 21, wherein the acid anhydride of the (c) is a mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride. 23. The method for producing a polycarboxylic acid composition according to the above 21 or 22, wherein the diol is 2,4-diethyl-1,5-anthracene or 2-ethyl-2-butyl- 1,3-propanediol. 24. The method for producing a polycarboxylic acid composition according to the above 21, which comprises reacting 2,4-diethyl-1,5-pentanediol with a mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride. Made. 25. The method for producing a polycarboxylic acid composition according to the above 21, which is an unsubstituted tricyclodecane decyl alcohol or pentacyclopentadecane dimethanol, hexahydrophthalic anhydride, and methyl hexahydrophthalic anhydride. The mixture is reacted. 26. A polycarboxylic acid represented by the following formula (1), formula (1)

Wherein R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a carboxyl group; and P represents a divalent crosslinking group as defined in the following (a) or (b): (a) is a carbon number a crosslinked group of a chain alkyl chain having a branched structure of 6 to 20, and the chain alkyl chain has a linear main chain of 3 to 12 carbon atoms and 2 to 4 side chains, and the side chain At least one of which has a carbon number of 2 to 10, and (b) is at least one selected from the group consisting of tricyclodecanedioxane or pentacyclic es 13 322150 201120000 pentadecane didecyl alcohol having a methyl group in the ring. In the crosslinked polycyclic diol, a divalent crosslinking group is obtained by removing two hydroxyl groups, and when P is (b), R represents a group other than a hydrogen atom. 27. The polycarboxylic acid according to the above item 26, wherein P is a divalent crosslinking group defined by (a), and at least two of the side chains are a crosslinking group having 2 to 10 carbon atoms. 28. The polycarboxylic acid according to the above 27, wherein the two-valent crosslinking group defined by (a) is obtained by removing two hydroxyl groups from 2,4-diethyl-1,5-pentanediol. base. 29. The polycarboxylic acid according to the above item 26, wherein P is a divalent crosslinking group defined by (b). The polycarboxylic acid according to the above item 26, wherein R in the formula (1) is a methyl group or a carboxyl group. [Effect of the Invention] The polyvalent carboxylic acid or polyvalent carboxylic acid composition epoxy resin of the formula (1) of the present invention is excellent in curing ability and can be used as a curing agent for an epoxy resin. Further, the polyvalent carboxylic acid or the polycarboxylic acid composition in the epoxy resin is emulsified in a temperature range generally used for hardening an epoxy resin. As a result, the purpose of the operation is easy and the purpose of the cured product is stabilized. Specifically, an epoxy resin cured product having high transparency and excellent heat durability can be obtained. In particular, the heat durability of the optical characteristics such as the reflow resistance, the transmittance retention rate, and the illuminance maintenance ratio of the LED under long-term lighting can be cited. [Embodiment] The polyvalent carboxylic acid of the present invention is a polyvalent carboxylic acid represented by the following (1), and the polyvalent carboxylic acid of the present invention is characterized by comprising a polycarboxylic acid represented by the following formula (1): 14 322150 201120000 By,

Wherein R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a carboxyl group; and P represents a divalent crosslinking group as defined in the following (a) or (b): (a) is a carbon number 6 a cross-linking group of a chain alkyl chain of a branch structure of 20, wherein the chain-like alkyl chain has a linear main chain of 3 to 12 carbon atoms and 2 to 4 side chains, and the side chain At least one is a carbon number of 2 to 10, and (b) is a crosslinked polycyclic ring having at least one selected from tricyclodecanedioxane or pentadecanedioxanol having a methyl group in the ring. A divalent cross-linking group in which two hydroxyl groups are removed from the diol. More specifically, the polyvalent carboxylic acid of the present invention is a compound in which at least one R represented by the formula (1) is a methyl group or a carboxyl group, and particularly preferably a compound having two R groups as a mercapto group or a carboxyl group. The polycarboxylic acid composition of the present invention contains at least two or more compounds represented by the above formula (1), or a composition comprising at least one compound represented by the above formula (1) and an acid anhydride having a saturated structure. Among them, preferred anhydrides are c4 to anthracene di, tri or tetracarboxylic anhydrides which may be substituted by a methyl group, and more preferably a C4 to c7 ring di or a tricarboxylic acid anhydride which may be substituted with a mercapto group. In the above formula (1), the cross-linking group represented by P is a divalent cross-linking group defined by the above (a) or (b), and the details thereof will be specifically described below. The divalent cross-linking group defined by the above (a) is a divalent chain-like alkane obtained by removing a hydroxyl group from a divalent alcohol (diol) having a branched structure of 6 to 20 carbon atoms.

S 15 322150 201120000 The base chain has a structure in which a main chain having an alkyl chain interposed between two alcoholic hydroxyl groups of a glycol and an alkyl chain (referred to as a side chain) branched from the alkyl chain. The side chain may be branched from any carbon atom constituting the main chain, and includes, for example, a branch of a carbon atom (the carbon atom at the end of the main chain) to which the alcoholic hydroxyl group is bonded. As a crosslinking base having such a structure, a specific example of such a crosslinking group is shown in the following formula (al). Formula (al)

In the above formula, the * symbol is bonded to the oxygen atoms on both sides of P in the formula (1). The alkylene-crosslinking group defined by the above (a) is not particularly limited as long as it has an alkyl group (side chain) with respect to the main chain alkyl group (the side chain), and the carbon number of the main chain is The main chain of 3 or more is preferably one having at least one alkyl side chain, and particularly preferably having two or more alkyl side chains. Preferred examples thereof include a main chain having a linear chain of 3 to 12 carbon atoms and 2 to 4 side chains, and at least one of the side chains is a crosslinking group having 2 to 10 carbon atoms. 16 322150 201120000 At this time, it is more preferable that at least two of the side chains are crosslinked groups having a carbon number of 2 to 10. The crosslinking group defined in the above (b) is exemplified by a divalent group represented by the following formula (b1). Formula (bl):

In the formula, a plurality of R2 present in each structural formula each independently represent a hydrogen atom or a thiol group. Among these, it is preferred that R2 is a crosslinking group of a hydrogen atom. The polycarboxylic acid composition represented by the formula (1) of the present invention can be obtained by reacting a diol compound corresponding to P of the above formula (1) with a (^ to C6 alkyl group (preferably a thiol group). Or a carboxy-substituted hexahydrophthalic anhydride is obtained by an addition reaction. The polycarboxylic acid composition of the present invention can be obtained by the following method. In the present invention, a polycarboxylic acid represented by the above formula (1) is obtained. A method of mixing at least two kinds of polyvalent carboxylic acid compositions, wherein at least two of the polycarboxylic acids represented by the formula (1) obtained by the above method are mixed; or the above formula (1) When the polycarboxylic acid shown is synthesized, a mixture of at least two kinds of the above-described hexahydrophthalic anhydride or a mixture of two kinds of the above-mentioned diols is used, and then an addition reaction is carried out. In the present invention, A method of arranging at least one polyvalent carboxylic acid represented by the formula (1) and a polyvalent carboxylic acid composition of a C4 to C7 cyclodi, tri or tetracarboxylic anhydride 5 - 5⁄4 17 322 150 201120000 which may be substituted by a methyl group, The following method: (1) The single equation (1) obtained by the above method is shown. a polycarboxylic acid having one hydrazine, a method of mixing with a methyl group (: 4 to C7 ring two, a needle; or, β (2) a polycarboxylic acid represented by the above formula (1) When the synthesis is carried out, the hexahydrophthalic anhydride which can be used as a raw material by a methyl group or a carboxyl group is used in excess, and the polyhydric carboxylic acid represented by the formula (1) used as a raw material in the reaction liquid after the reaction is used. The acid and the above-mentioned phthalic anhydride are in a coexistence manner. The above-mentioned acid anhydride used in the synthesis of the polyvalent carboxylic acid represented by the formula (1) may, for example, have a cyclohexane structure and have a methyl group on the cyclohexane ring. Substituted or carboxy-substituted, or unsubstituted, and having more than one (more preferably one) in the molecule bonded to the poly-citric acid liver of the acid-based G-based group. Specifically, for example, 1 ' 2, 4_ already married * a slow acid ~ 1,2_ wild, 4 ~ • • methylcyclohexan-1, 2_ dicarboxylic anhydride or cyclohexane-1,2-dicarboxylic anhydride, etc. (1) When a single compound of a polybasic acid retardation is shown, any one of the above acid anhydrides can be used to carry out the reaction. The polybasic acid composition of the present invention is obtained. As described above, at least two of the carboxylic acids are used to carry out the reaction, or at least one of the carboxylic acids is used in an excess amount to react with the diol, preferably at the end of the reaction. Then, the type of the acid anhydride is contained in the reaction liquid. When the acid anhydride is used in at least two kinds, it may be any two, but in the present invention, the optical property is 'Ci to Ce alkyl (in the case of A Preferably, the base is preferably or carboxy substituted hexahydrophthalic anhydride, and the unsubstituted hexahydro styrene is preferably less than 50% by weight 'below 40% by weight or less, 35% by weight or less and 18 322150 201120000' Further, it is particularly preferably 30% by weight or less. In the following description, % is meant to be % by weight unless otherwise specified. When at least two kinds of acid anhydrides are used, the hexahydrophthalic anhydride substituted with a methyl group or/and a carboxyl group is preferably 65% or more in all the acid anhydrides, more preferably 85% or more, and particularly preferably 90% or more. The τ octanol of the above-mentioned starting materials used in the synthesis of the polycarboxylic acid represented by the formula (1) is exemplified as a diol having a hydroxyl group at the end of the crosslinking group p. Specifically, it is a diol having a chain alkyl chain having a branched structure of a total carbon number of 6 to 20 in the crosslinking group defined by (4). More specifically, having a hydroxyl group at both ends of the main chain having 3 to 12 carbon atoms, and having 2 to 4 side chains ' on the main chain and at least i of the side chains (preferably at least 2) ) is a glycol having 2 to 1 carbon atoms. Specific examples of the oxime system include a compound in which a hydroxyl group is bonded to a position of a * mark in the parent group described in the above formula (al). The diol used as a raw material is preferably a diol having at least two of the side chains and at least two of the side chains of a side chain having 2 to 4 carbon atoms. Among such skeletons, particularly preferred glycols include, for example, 2,4-diethyl-1,3-propanediol, 2-ethyl-2-butene propylene glycol, 2-ethylidene-3 hexanediol, and the like. In particular, 2'4 diethyl, 5_pentanediol is preferred. , - (1) + cross-linked polycyclic ring when the cross-linking group is defined by the above (6):

The transgenic line is composed of the tricyclic Wei structure and the five-material five-domain structure as the main bone (four), and the alcohol is expressed by the following formula (b2). J 322150 19 £· 201120000

In the formula, the plurality of R2 present independently represent a hydrogen atom or a methyl group. Specific examples thereof include tricyclodecane dimethanol, methyl tricyclodecane dimethyl alcohol, pentacyclopentadecanedonol, and the like. The reaction of the acid anhydride with the diol is generally an addition reaction using an acid or a base as a catalyst, but in the present invention, it is particularly preferred to carry out the reaction without a catalyst. When a catalyst is used, examples of the catalyst that can be used include acidic compounds such as hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, nitric acid, trifluoroacetic acid, and tri-glycolic acid; a metal hydroxide such as potassium hydroxide, hydrogen hydroxide or magnesium hydroxide; an amine compound such as triethylamine, tripropylamine or tributylamine; pyridine, diammonium pyridine, 1,8-diazabicyclo[5 4. 0] 杂环-carbon-7-ene, _° sitting, three-degree sitting, four-sigma sitting and other heterocyclic compounds; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, hydrogen hydroxide Butyl ammonium, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylhexadecyl ammonium hydroxide, trioctylmethylammonium hydroxide, a tetra-ammonium salt such as tetraammonium chloride, tetrabromide, mothium tetraammonium chloride, tetraammonium acetate, trioctyl ammonium thioglycolate or the like. These catalysts may be used alone or in combination of two or more. Among these, it is preferred to use triethylamine, pyridine or diamine. 20 322150 201120000 The amount of catalyst used is not limited, but it is preferably used in an amount of from 1 to 5 parts by weight based on 100 parts by weight of the total amount of the raw materials as needed. This reaction system is preferably a reaction in the absence of a solvent, but an organic solvent may also be used. The amount of organic ,, the phase reaction is determined by the total amount of the above acid anhydride and the above diol, the weight ratio of G to i, 〇. 005 to 〇. 7 is better, U05 to When 0.5 parts by weight (i.e., 50% by weight or more) is used in an amount exceeding 1 part by weight based on the weight of the reaction substrate i, the progress of the reaction becomes extremely slow and unsatisfactory. Examples of the organic solvent that can be used include (4) aromatics such as hexane, roast, and gypsum; aromatic hydrocarbon compounds such as toluene and xylene; and ethyl b-isobutyl ketone, cyclopentanone, cyclohexanone, and the like. Ketones; diethyl ether: ethers such as tetrahydrofuran and dioxane; ethyl acetate vinegar and other brewing compounds, etc. us 曰 曰 曰 巧 虚 虚 本 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 。 。 。 。 From the reaction time, the reaction temperature is set to 3 〇 to 1 〇 to a better voyage', especially 4Q to the boots. It is especially good for the 隹' no: under the agent, due to the evaporation of sour liver , in the 7 2: r should be better '(4). To the boots - to the second: Moe down = said: can be:: reaction ratio, theoretically should be in the above, in the present invention 4: If necessary, it is changed as follows: 'In particular, the acid anhydride used in the synthesis of the polycarboxylic acid of the formula (1) 21 322150 201120000 is the same as the acid anhydride formulated in the polycarboxylic acid composition. At the time of production, the reaction is carried out in excess of the above-mentioned acid anhydride with respect to the above-mentioned diol, and when the reaction of the acid anhydride and the diol is completed, the acid anhydride and the polycarboxylic acid of the above formula (1) can be used. a mixture (hardener composition). The feed ratio of the specific two at the time of the reaction is, based on the functional group equivalent, 1 equivalent of the anhydride group, to feed the diol to have a hydroxyl equivalent of 0. The ratio of 001 to 2 equivalents is preferably from 0.01 to 1.5 equivalents, and more preferably from 0.01 to 1.1 equivalents. When the hardener composition is produced as described above, the diol is The hydroxyl equivalent weight is generally used in the range of 0.01 to 0.7 equivalents, preferably from 0.01 to 0.5 equivalents. - The reaction time also varies depending on the reaction temperature, the amount of catalyst, etc., from the viewpoint of industrial production. Because long-term reaction will consume a lot of energy, and too short reaction time means that the reaction is impatient, which is not good from the safety surface. The preferred range is about 1 to 48 hours, from 1 to 36 hours is better, 1 to 24 hours is better, and 2 to 10 hours is especially good. After the completion of the reaction, when the catalyst is used, the catalyst is removed by neutralization, water washing, adsorption, or the like, and the desired polycarboxylic acid is obtained by distilling off the solvent, and in the reaction without a catalyst, If necessary, the solvent is distilled off, and when it is solvent-free or catalyst-free, it can be directly taken out as a product. The most suitable production method is to make the above-mentioned acid anhydride and the above-mentioned glycol at 40 to 150 ° C and without catalyst, The reaction is carried out under the condition of no solvent, and the reaction is directly taken out after the completion of the reaction. The polycarboxylic acid represented by the above formula (1) or the tree containing the plural 22 322150 201120000 colorless to pale yellow, I-hang When the cross-linking group p of the formula (1) is a stretching group as defined in (a), the tree exhibiting a colorless to pale yellow color has a cross-linking group P having a side chain as defined in (4). When the fluorene ring (1) is a 2-valent cross-linking group after the base, and even if it is (4): removing the warp-presenting liquid=reverse material, the reaction product (4), the cross-linking group p of the shape 1 (1) is (b) The polycarboxylic acid defined by cross-linking is a hydrogen atom which is visible during hardening: disubstituted : Not available on optical purposes. R is a methyl or sulfhydryl group: do not have such a color in the strict h' to improve its fresh characteristics. In the above, the person I of the cross-linking group defined by the above formula (1) (a) is Si. The compound of the base or the county, _ enhances the optical secret t is a hair loss: the preferred one of the two substances preferably contains R 熳 熳, or both of the formula (1), such as two or more Yuan_❹元_ == f. At least R is not a hydrogen atom of the formula (1), the (10) acid (7) is: the base is preferably) or the sulfhydryl group is a polybasic acid, and the L, the meta-soil is the total amount of the π ΧΓΠ ΧΓΠ ΧΓΠ 竣 竣The composition of more than % by mole is preferred. More preferably, the multi-ship composition of the hydrogen atom of the formula (1), the multi-thief 7 (), the mol% or more, the ', the 3's/the non-ears % or more. The residue is taken from a 90% polybasic acid. a polybasic acid of the formula (1) 23 S. 322150 201120000 H which is an oxygen atom, preferably a polybasic acid of the hydrogen group (more preferably R is a mercapto group or a carboxyl group), or The polybasic acid composition of the present invention containing the above-mentioned plural (4) is excellent in transparency, and can be used as a curing agent for a cycloolefin resin, a coating material, an adhesive, a molding, a semiconductor, a resin for a sealing material for an optical semiconductor, and an optical semiconductor. A raw material for a viscous material, a polyamic acid resin, a polyimide resin, or the like, a modifier, a plasticizer, a lubricant raw material, a pharmaceutical pesticide intermediate, a resin for a coating resin, and a resin for a toner. In particular, when the polyvalent carboxylic acid composition of the present invention is used as a curing agent for an epoxy resin, it has excellent curing properties and excellent transparency of the cured product. Therefore, the polycarboxylic acid composition of the present invention is extremely suitable as a curing agent for epoxy resins used for sealing high-brightness white LEDs and other optical semiconductors. Next, the multicomponent acid composition of the present invention containing the polybasic acid of the formula (1) and the phthalic anhydride will be described when it is used as a liquid hardener in the polyvalent carboxylic acid composition of the present invention. The preferred composition of the polycarboxylic acid composition comprises a multi-repulsive acid of the formula (丨) and a C4 to C7 ring di-, tri- or tetradecanoic acid substituted by a mercapto group, the ratio of which is 'relative to the formula ( 1) The polycarboxylic acid is 1 part by weight, and the ratio of the acid anhydride is 0.1 to 10 parts by weight, preferably 5 to 8 parts by weight, more preferably 1 to 8 parts by weight. When the polybasic acid-reducing composition contains the same acid as the acid anhydride used in the production of the polycarboxylic acid of the formula (1), as described above, in the case of producing the polybasic acid of the formula (1) The acid anhydride used as a raw material is obtained by using an excess amount of the acid used as a raw material, and the acid needle remaining after the reaction is in the range of 322150 24 201120000, which is produced by excess use, or as the present invention. The user of the multi-repulsive acid composition is a liquid, and the other manufacturing method of the multi-component composition can be obtained by using the above-mentioned multi-dimensions of the formula (1) and the above-mentioned keis-substituted two to & Two or four (four) (four) The above ratio is uniformly dissolved and mixed to obtain. = yuan (four) (four) financial materials (1) ^ reading acid can be (^ or more than two kinds of multiple species. The multi-nucleus of formula (1) is a multi-component of β As described above, R is methyl or silk and 'in the total amount of the formula (1), the total amount of the phase = the base in the formula (1) or the multicomponent 夂 3 1 of the filament is 50 moles. More than % is better, more preferably 65 mol% or more. r 5 2 can be methyl substituted ^ to ^7 ring two, three or four reduction needles, such as two to four (two to three are preferred) on the Xiqiao, the multiple retardation = anhydride 'has no special obstacles. Specifically, for example Hexazone needle, : hexahydrophthalic anhydride, Ding Xuan read _, double ring [2, 2, 丨] heptane _2, 3_ phthalic anhydride _ f bis-[2, 2, 3_ bis-acid Liver, cyclohexanone, 2,4-tricarboxylic acid-1,2-anhydride, etc. It is preferred to be substituted by methyl or carboxyl group = hexanol hexahydro anhydride (six gas which can be substituted by methyl or secret) Examples of the citrate liver/such as: hexahydro (tetra)if, methylhexaic anhydride or % hexane-1,2,4-tricarboxylic acid-1,2-anhydride, etc. In the acid composition, the proportion of the polycarboxylic acid of the formula (1) is preferably from 2 to 80% by weight, based on the total weight of the above acid anhydride and the polycarboxylic acid, of from 30 to 75% by weight. Next, the hardener for epoxy resin of the present invention will be described. 25 322150 «9 201120000 The hardener for epoxy resin of the present invention contains a polybasic acid of the formula (1) or contains a hardening of the polycarboxylic acid and an acid anhydride. The preferred polybasic acid of formula (1) can be exemplified as R as a wind atom. A multi-repulsive acid, preferably a polycarboxylic acid in which r is a methyl group or a carboxyl group, especially all polybasic acid acids in which R is a methyl group or a carboxyl group. The polycarboxylic acid of the formula (1) is used as an epoxy resin. The hardening agent, particularly when used as a liquid hardener, is preferably a mixed liquid anhydride as a liquid polyvalent carboxylic acid composition of the present invention. The liquid composition can be applied to the epoxy of the present invention. A resin composition for a resin. A liquid acid anhydride which can be used is preferably an acid anhydride having a saturated ring structure without an aromatic ring in the structure. Specifically, it can be enumerated in each of the above-described multi-component compositions of the present invention. Acid needles. Also, the proportion of blending is also better than the range indicated in the same place. Therefore, the polyvalent carboxylic acid composition of the present invention containing the polyvalent carboxylic acid of the formula (1) and the acid anhydride can be directly used as the hardener composition for the epoxy resin of the present invention, and may also contain the following Hardened catalysts, additives, inorganic fillers, etc. described. > The following is a description of the curable resin composition of the present invention containing the polyvalent carboxylic acid of the formula (1) or the hardening agent for epoxide of the present invention. The curable resin composition of the present invention contains a reactive epoxy resin. Epoxy resin used in the curable resin composition of the present invention: phenolic epoxy resin, bisphenol A epoxy resin, biphenyl epoxide, diphenylmethane epoxy Resin, phenol aralkyl type epoxy resin, and the like. 322150 26 201120000 Specifically, for example, double enzyme A, double expectation s, thiophene, 4, 4'-bisphenol, 2, 2,-bis, 3, phenolphthalein, base]-", -二^对笨二^'^/Tetramethylhydrazine-biphenylphenyl) 曱, 1,1,2,2-tetra (4 'Caidiol' three (4~ replaced, Cai , burning base to take (Lao, Xuanji, etc.) and formaldehyde, acetaldehyde, benzamidine, monohydroxynaphthalene, p-aminophenylide, ortho-base =, ortho-phenyl (tetra), 4, 4 , a condensation polymer of bis (gas methyl (4) decadiene, sulfonium thiophene, 1, fluorene, biphenyl, 1'4-di " bis(nonyl fluorenyl) _ and the modification of these ), Ben, ^4, bis(methoxymethyl)benzene, etc., and glycidol derived from alcohols: two f: double glacial glycerin amine epoxy resin, glycidol brewing system; = t shrink (silsesquiQxane) $μ钱_, sesquiterate or continuation of at least 2 records, read tree 曰 (in a mixed structure of key, ring, ladder, ===' • with liquid Ring: 环氧树脂g dihexane structure epoxy resin) and other solid or shaped oxy-trees, but not limited to these. The curable resin composition of the invention is used in an optical resin epoxy resin, a wax ring type epoxy resin or/and an epoxy group-containing stone oxyphyllin (preferably, a sesquiterpene oxide structure) Epoxy resin is preferred, especially in combination with both. _ Especially in the case of an alicyclic epoxy resin, a compound having an epoxycyclohexane structure on the skeleton is preferred, and a cyclohexene structure is used. The epoxy resin obtained by the oxidation reaction of the compound is particularly preferred. The alicyclic epoxy resins may, for example, be esterified with cyclohexene carboxylic acid and ti. 322150 27 201120000 alcohol or cyclohexene oxime. Esterification of an alcohol with a carboxylic acid (Tetrahedron vol. 36 ρ. 2409 (1980) 'Tetrahedron Letter P. 4475 (1980), etc.) or a cyclohexene aldehyde (Tischenko reaction) Japanese Patent Publication No. 2003-170059, the method described in JP-A-2004-262871, and the like, and a transesterification reaction of a cyclohexene phthalate (Japanese Patent Publication No. 2〇〇6_〇52187) The compound produced by the method described in the above is oxidized or the like. The compound having an alcoholic trans group is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, 13-propylene glycol, hydrazine, 2-butanediol, hydrazine, dibutylene glycol, and 1,5-pentanediol. a triol such as i,6-decanediol, cyclohexanedialol glycerol, trimethylethaneethane, trimethylolpropane, trimethylolbutanyl, 2-dimethylmethyl-butanediol; Pentaerythritol, etc. Examples of the carboxylic acid include, for example, dioxane phthalic acid, isophthalic acid, hexanyl acid, and anti-butyl, and are not limited thereto. &, Yijiyuan-ship, etc., but the shrinkage of the ruthenium derivative and the alcohol body by the phlegm of the ruthenium has been revealed, for example, in the anti-aging secret anti-riding can be manufactured, a total of dehydration, - While doing the solvent of the heart, the second and the second, and the like, the solvent is dissolved in the concentrated salt (the method of the reaction of the United States Patent No. 2945_ (the Japanese side, slowly adding the aldehyde, a medium) The method of using water in the medium (Izumi No. 48'9__); in the reaction medium, the timing of the solvent is controlled by the No. 3g9264g; in the counter-report; the use of the solid acid catalyst is the Japanese special Kaiping 7_21 _ No. in the public (Japan Special Open 2007-230992, public 322150 28 201120000 report) and so on. From the viewpoint of structural stability, a cyclic acetal structure is preferred. The alicyclic poly-membered olefin such as vinyl cyclohexene or limonene, dicyclopentadiene, tricyclopentene, decyl dicyclopentadiene, dicyclohexene or octadiene may be oxidized. Things and so on. Specific examples of such epoxy resins include ERL-4221 and ERL 4299 (all of which are trade names, all manufactured by d〇w Chemical Co., Ltd.), EPOLEAD GT401, EHPE3150, and EHPE3150CE (all of which are trade names, all of which are Daicel chemical). It is not limited to these (manufactured by Industrial Co., Ltd.) and dicyclopentadiene diepoxide, etc. (Reference: Basic Principles of Epoxy Resin, page I p76-85). These may be used alone or in combination of two or more. Preferred alicyclic epoxy resins are epoxycyclohexyl groups which may have a methyl group, for example, -C00-CH2-, -C00-(a C2 to C8 divalent saturated aliphatic group)-COO-, -Clh -COO-(2-valent saturated aliphatic group of C3 to Cs)-C00- or -CHz-COO-CC3 to Cs 2-valent saturated aliphatic group)-C00-CH2-is cross-linking bonded 2-functional ring Oxygen resin is preferred. The epoxy group-containing linoleic ketone resin is an epoxy resin having a sesquiterpene oxide structure. The epoxy resin having a sesquiterpene oxide structure is preferably an organopolyoxane having an epoxycyclohexane structure. More preferably, the epoxy group-containing fluorenone resin having a weight average molecular weight of 1,000 or more and 20,000 or less (preferably 1000 or more, 1 Å or less) is more preferably an epoxy ring. An organic polyoxane of hexane structure. In the present invention, a compound obtained by a sol-gel reaction (So 1 - Ge 1 React i on) which is used in a raw material of an alkoxy oxime having an epoxycyclohexyl group. 29 322150 201120000, for example, Japanese Patent Laid-Open No. 2004-2566-9, Japanese Patent Laid-Open No. 2004-346144, International Publication No. 2/4/7215, and JP-A-2006-8747. International Publication No. 2〇〇6/〇〇399〇, . Japanese Patent Publication No. 2006-104248, International Publication No. 2/7359/9, Japanese Patent Laid-Open Publication No. 2004-10849, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. A sesquiterpene-type organopolyoxane having a network structure distributed in a three-dimensional space as described in JP-A-2008-174640. The sesquioxane structure is not particularly limited. However, since the simple three-dimensional space mesh structure is hard to burn, it is expected to have a structure that can alleviate hardness. In the present invention, in particular, the above-mentioned cleavage oxygen-forming block structure obtained by reacting a linaloketone moiety in one molecule with a sol-gel reaction is preferred. The production method and structure of the compound are as described in International Publication No. 2010/026714. In the curable resin composition of the present invention, the polycarboxylic acid (or the chemical composition) of the formula (i) may be used in combination with other hardeners. When used in combination, the ratio of the sulfocarboxylic acid of the formula (1) to the total amount of the hardener is preferably 20% by weight or more, more preferably 30% by weight or more. The curing agent to be used in the polyvalent carboxylic acid of the formula (1) may, for example, be an amine compound, an acid anhydride compound having an unsaturated ring structure, a guanamine compound, a phenol compound or a carboxylic acid compound. Specific examples of the hardener which can be used include diaminodiphenyl, diethylenetriamine, triethylenetetramine, diaminediphenyl, isophorol, diamine, dicyandiamide, and Linoleic acid 322150 201120000 2-mer and polyethylenediamine synthesized polyamine resin, citric acid liver, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrofurfuric acid if, sulfhydryl Nadic Methyl Anhydride, Nadi Acetic Anhydride, Hexahydrophthalic Anhydride, Mercapto Hexahydrophthalic Anhydride, Butane Tetracarboxylic Anhydride, • Bicyclo[2'2'1]heptane 3-Dicarboxyl Anhydride, methylbicyclo[2,2,1]heptane-2' 3-dicarboxylic anhydride, cyclohexane_丨, 3,4_tricarboxylic acid _3, 4-anhydride, bisphenol a, bisphenol F, bisphenol S, bisphenol, stilbene, 4, 4,-bisphenol, 2, 2,-bisphenol, 3, 3', 5' 5' _tetradecyl-[1,1,_ Biphenyl]_4, 4'-diol, hydroquinone, resorcinol, naphthalenediol, tris(4-hydroxyphenyl)decane, anthracene, anthracene, 2,2-14 (4-hydroxyl Phenyl) ethane, phenols (phenols, alkyl-substituted phenols, naphthols, alkyl-substituted naphthols, dihydroxy stupids, dihydroxynaphthalenes, etc.) Aldehyde, acetaldehyde, benzaldehyde, p-terenyl group, o-benzophenone, p-acetophenone, o-phenylphenidate, dicyclopentadiene, furfural, 4,4, - bis(gas methyl)-1,1,-biphenyl,-4,4-bis(methoxymethyl)-1,1,-biphenyl, 1,4,-bis(chloromethyl)benzene a polycondensate of 1,4 ''-mono(methoxymethyl)benzene and the like, and a halogenated bisphenol such as tetras/bisphenol A; imidazole, boron trifluoride _#胍彳4 The condensate of the genus and the hydrazine is not limited to these, and it may be used alone or in combination of two or more. In the curable resin composition of the present invention, a hardener and an epoxy resin

It is better than the epoxy group of the all-% oxygen resin to be 0. 5 to U, and the D 1 g of the tannic acid to the i-functional acid liver) is 5 to 1: 2 ^. With respect to the epoxy group equivalent, if it is less than $ eq or exceeds 1.5 liters, it is not sufficiently hardened to have a good hardening property. 31 322150 201120000 The curable resin composition of the present invention may be used together with a curing agent in combination with a curing agent. Specific examples of the hardening accelerator which can be used are exemplified by 2-indolyl sigma, 2-phenyl imidium, eleven alkyl carbazole, 2-heptacyl imidazole, 2-phenyl-4 - mercapto imidazole, benzylidene-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl~2methylimidazole, i-cyanoethyl-2-phenylimidazole, Cyano 9ethyl~2~undecylimidazole, 2,4-diamino-6(2'-nonylimidazolium (1,)) ethyl s-triazine, 2,4 diamine- 6 ( 2,-undecyl imidazole (1,)) ethyl s-triazine, 2,4-diamino -6 (2,-ethyl, 4-methylimidazolium (1,)) ethyl s-triazine 2,4-diamino- 6 (2,-methylimidazolium (1,)) ethyl s-triazine. Isocyanuric acid adduct, 2 · methylimidazole isocyanuric acid 2 : 3 plus Product, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3, 5-dimethylolimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, cyanide Various imidazoles of ethylethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and the imidazoles and citric acid, meta-citric acid, citric acid, phthalic acid, Pyromellitic acid, naphthalene dicarboxylic acid, maleic acid, oxalic acid, etc. a salt of a carboxylic acid, a guanamine such as dicyandiamide; a diazepine compound such as 1,8-dibicyclobicycle (5.4.0) undecen-7; and a salt of such a tetraphenylborate or a novolac. a salt of the above polycarboxylic acid or phosphonic acid; tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctyldecylammonium bromide, cetyltrimethylammonium hydroxide a quaternary ammonium salt (equivalent to (^ to Cm alkylammonium salt); triphenylphosphine, tris(indolyl)phosphine, tetraphenylphosphonium bromide, tetraphenyl quaternary Phosphonic acid or squama compound such as acid salt; 2, 4, 6-triamino sulfhydryl group; amine adduct; metal compound such as tin octylate; and microhardening of the hardening accelerator The type of the hardening accelerator, etc., which is used in the above-mentioned hard 32 322150 201120000 chemical accelerator, for example, the characteristics required for the transparent resin composition obtained by the transparency, the curing speed, and the working conditions are appropriately selected. Preferred examples of the invention include, for example, a scaly compound (better than a quaternary scale salt) or a quaternary salt. A hardening accelerator relative to the epoxy resin 10 When it is 0 parts by weight, it is generally used in the range of 001 001 to 15 parts by weight, preferably 5 to 5 parts by weight, more preferably 0.05 to 1 part by weight. The spheroidal compound which is a component which imparts flame retardancy is contained in the resin composition, and the male compound may be a reactive type. The specific examples of the phosphorus-containing compound may, for example, be trimethyl phosphate or phosphoric acid. Ethyl ester triammonium phosphate, tris(phenylenediphenyl) phosphate, phenylphenyl diphenyl ester, phenyl phenyl ester-2,6-bis(phenylenedicarboxy) ester, 1' 3- Phenyl bis(bis(phenylenediyl)phosphate), hydrazine, 4_phenylphenylbis(bis(phenyldimethyl)phosphate), 4,4'-biphenyl (bis(phenyldimethyl) Phosphate), etc.; 9,10-dihydro-9-oxa-10-phosphaphenium oxide, 10(2,5-phenylene)-10H-9-oxa-10 - a phosphine such as a phenanthrene 10 -oxide; a phosphorus-containing epoxy compound obtained by reacting an epoxy resin with an activated hydrogen of the above phosphine, a red phosphorus, etc., but a phosphate ester or a phosphine Or a phosphorus-containing epoxy compound is preferred, especially丨, 3_phenylphenylbis(bis(phenyldimethyl) phthalate), 1,4-phenylphenylbis(bis(phenyldimethyl)phosphate), 4, 4,-biphenyl (two (Benzyl) phosphate, 4,4,-butylene bis(3-methyl-6-t-butylphenyl-di-tridecyl yanoate) or an epoxy containing The compound is particularly good. The content of the phosphorus-containing compound is preferably from 0.1 to 0.6 (weight ratio). 〇. 1 or less, the flame retardancy is not sufficient,

S 33 322150 201120000, when you are on the 〇·6 ’, fear of hardening good influence. The insulating property is not affected by the curable resin composition of the present invention. The antioxidant which can be used is exemplified by adding an antimony antioxidant, a phosphorus-based antioxidant, or the like as needed. Antioxidant 2 anti-gasifier and sulfur are used in combination of two or more. The relative reducing agent may be used alone or in combination with 100 parts by weight of the resin component, and (10) of the curable composition of H, preferably 〇.01 to 0.5 by weight: by means of a suspension to ° ° to an antioxidant Specific examples of antioxidants such as phenolic antioxidants, antioxidants, and the like may be exemplified by, for example, a third butyl group, a butyl group, and a specific example of an antioxidant. Phytophthora (4), 2: Ding 6-: Ethylphenol, stearyl 5- 铉 Α Α , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,曰,, octyl-3-(3,5-di-t-butyl+periphenyl)propionic acid, 2,4-bis(n-octylthio)_6~(4-hydroxy-3, Bu-di-tert-butylaniline) 1'3,5-# 2,4 bis[(octylthio)methyl]--------- 2,2'-methylene double (4 曱Base_6_t-butylphenol), 2,2, _indenyl bis(4-ethyl-6-tert-butylphenol), 4,4, _ thiobis (3-indolyl-6_) Second butyl phenol), 4,4-butylene bis(3-methyl-6_t-butylphenol), diethylene glycol-bis[3-(3-t-butyl-5-methyl) -4-hydroxyphenyl)propionate], 1,6-hexyl Alcohol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], hydrazine, Ν'-hexamethylene bis (3, 5-di-t-butyl) -4-hydroxy-hydrogen cinnamylamine), 2, 2-thio-diethylidene bis[3-(3,5-di-t-butyl-4-ylphenyl)propionic acid vinegar] ,3,5-di-t-butyl-4-transbenzylphosphonate-diethyl ester, 3,9-bis[1,1-dimethyl- 2-{cold-(3-third Butyl-4-34 322150 201120000 mercapto-5-methylphenyl)propoxycarbonyl}ethyl]-2, 4, 8, 10-tetraoxaspiro[5, 5] eleven, double ( 3,5-di-t-butyl-4-hydroxybenzylsulfonate ethyl ester) Mom and other bisphenols; 1,1,3-tris(2-methyl-4-hydroxy-5-t-butyl Phenyl) Dingyuan, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-alkylbenzyl)benzene, tetra-(methylene _3_(3',5,_di-t-butyl-4-[,hydroxyphenyl)propionate) methane, bis[3,3,_bis-(4,_hydroxy-3, _ third Basic base) butyrate] glyceride, tris-(3,5-di-t-butyl-4-alkylbenzyl)-isocyanurate, 1,3,5-tris(3,,5, -di-t-butyl-4,-hydroxybenzyl)-S-triazine-2, 4, 6-(1Η,3H,5H High molecular weight such as triketone and tocopherol. Specific examples of the sulfur-based antioxidants include, for example, dilauryl _3, 3, thio-propyl hydrazine, hydrazinyl-3,3-thiodipropionate, distearyl-3 , 3'-thiodipropionate and the like. Specific examples of the hydrazine emulsifier include, for example, triphenyl phosphite, isodecyl phosphite, diisodecyl phenyl phosphite, tris(nonylphenyl) phosphite, Diisodecyl pentaerythritol phosphite, tris(2,4_bis"_t-butylphenyl)phosphite, cyclic neopentyltetraylbis(octadecyl) sulphite环环新魏四基二(2,4_二_三基基基基)兀土土破酸醋,环新钱四基二(2, 4-二-三丁+methyl=二[ 2-tert-butyl-" base + 丨2-(octadecyl-ethyl) ketone] phosphite citrate and other phosphites; 9,1 〇-dihydro-1 (tetra) phenanthrene-10 _oxide, 1 (K3,5-di-t-butyl+hydroxyl; earth)-9,10-dihydrogen+oxaluene dish phenanthrene oxide ruthenium oxy-, 10-dihydro-9 Oxaphosphorus oxide such as oxa-phosphorus oxide 322150 35 201120000 Oxide, etc. These antioxidants may be used singly or in combination of two or more. In particular, phosphorus is used in the present invention. Preferably, the antioxidant is preferred. In the curable resin composition of the present invention, A light stabilizer is added as needed. The light stabilizer is preferably a hindered amine light stabilizer, and particularly a Hinder: A Hindered Amine Light Stabilizer. HALS is not particularly limited. Representative examples include dibutylamine·1,3,5-triazine·Ν, Ν,-bis(2,2,6,6-tetramethyl- 4 piperidinium-1,6- Polycondensate of hexamethylenediamine and ^(2,2,6,6-tetradecyl-4-pyridinyl)butanamine, dimethylhydroxyethyl succinate)_4_hydroxy^-2, 2 , 6, 6-tetramethylpiperidine polycondensate, poly 3,3_tetradecylamino)-1,3,5-triazine-2,4-diyl}{(2, 2, 6 , 6-tetramethyl-4(piperidinyl)imido}hexamethylene {(2, 2, 6, 6-tetradecyl-4-piperidinyl)imido}], double (1 , 2, 2, 6, 6-pentamethyl-4-piperidinyl)[[3, 5-bis(1 ι-dimethylethyl)-4-hydroxyphenyl]methyl]butylpropane Acid ester, bis(2, && 6-tetradecyl-4-piperidyl) sebacate (li), bis 2, 2, 6 pentamethyl-4-piperidinyl) Acid ester, bis(1-octyloxy-2, 2, 6, 6-tetradecyl-4-piperidyl) sebacate, 2-(3,5-di-t-butyl- 4_hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,6,6-pentamethyl-4-piperidyl), etc., HALS can be used alone or in combination 2 More than one species. In the curable resin composition of the present invention, a binder resin may be blended as necessary. Examples of the binder resin include butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR phenol resin, 322150 36 201120000 epoxy-NBR resin, and polyamine resin. Polyimine-based resin, fluorene-based resin, etc., but is not limited thereto. The blending amount of the binder resin is preferably in the range of flame retardancy and heat resistance of the non-destructive and hardened material, and is generally used in an amount of 0.05 to 50 parts by weight based on 100 parts by weight of the tree ride. It is preferably up to 20 parts by weight. In the curable resin composition of the present invention, an inorganic filler may be added as necessary. Examples of the inorganic filler include, for example, crystalline cerium oxide, smelting cerium, aluminum oxide, strontium, calcium silicate, calcium carbonate, cerium carbide, cerium nitride, boron nitride, cerium oxide, magnesium sapphire, and blocks. Powders such as talc, spinel, dioxane, talc, or the like, or such spheroidized beads, are not limited thereto. 2 or the like may be used alone or in combination of two or more. The inorganic filler may be used in the curable resin composition of the present invention in an amount of from 〇 to 95% by weight. Further, a mold release agent such as a decane coupling agent, stearic acid, palmitic acid, zinc stearate or calcium stearate may be added to the curable resin composition of the present invention; zinc carbonate (2-ethylhexanoic acid) , zinc stearate, zinc betelate, nutmeg) or zinc compounds such as zinc phosphate (octyl phosphate, zinc stearyl phosphate, etc.), surfactants, dyes, pigments, ultraviolet rays Various preparation agents such as an absorbent, and various thermosetting resins. Preferred examples of the curable resin composition include the following resin compositions. (1) - The composition 'includes ·················································· The functional group equivalent of the material contains a hardening resin composition of 〇 5 to 1.5 equivalents. The resin composition may further contain 322150 37 201120000 ΙΓ 100 parts by weight of oxygen resin, up to 15 parts by weight. Generally, it is preferable to contain the hardening accelerator. The curable resin composition described in the above two is in which the ring-ring resin is burned (by weight gamma flat) and has an epoxy group. The organic polyorganic polylithic eclipse has a sub-quantity of 1000 to 2 〇, and an epoxy decane of about 〇〇0 is preferred, preferably about 1000 to 1 ).) The curable resin composition according to (1) or (ii), wherein the substance is an alicyclic epoxidation having an epoxycyclohexanthene structure ===== armor: "There" '-(10)--, -C() (wr /, a sulfhydryl-based cyclohexyl group, such as a 2-valent saturated aliphatic group of -CH2-C〇n-rr 3 C8)-C00- , (C3 to c of the two-valent saturated aliphatic group) - C (X) _ or _CH2-C00 ~ uterine epoxy resin. CH2- and other parental bond _ 2 (V) as above G) to ( Iv) Any one of the hardening resin compositions of the formula (1), which is a multi-component composition, which is described in any one of the above-mentioned items (1) to (iv). The agent of the curable resin composition 1 contains a sizing agent of the formula (1) or a curing agent of the cerium acid composition of the above-mentioned η. The hardening resin composition of the above (1) to (a) is defined. The hardening resin composition according to any one of the above-mentioned (a), wherein the hardener composition is the above-mentioned 13 The curable resin composition according to any one of the above aspects (1) to (viii), wherein the curing agent contains a polycarboxylic acid of the formula (1) or contains The curable resin composition according to any one of the above-mentioned (i) to (ix), wherein the hardening accelerator is scaly (a) a hardening resin composition as described in any one of the above (i) to (ix), wherein R of the formula (1) When a curable resin composition of the present invention is used in a photo-semiconductor blocking agent, a phosphor may be added as needed. The fluorescent system emits blue light by a blue LED element, for example, by absorbing portions. And emitting a wavelength-converted yellow light, that is, having a function of forming white light. The phosphor is previously divided into a curable resin composition, and then the photo-semiconductor is sealed. The phosphor is not particularly limited, and a conventionally known phosphor can be used, and examples thereof include a rare earth element acid salt, a thiogallate salt, and a oxetane salt. More specifically, examples thereof include a phosphor such as a YAG phosphor, a tag phosphor, a strontium silicate phosphor, a thiogallate phosphor, or a sulfide phosphor. : YAl〇3: Ce, Y3Al5〇12: Ce, Y4Al2〇9: Ce, Y2〇2S: Eu, Sr5(P〇4)3ci: Eu, (SrEu)O.Al2〇3, and the like. The particle size of the phosphor is a conventional particle size used in the art, and the average particle diameter is preferably from 1 to 250 / zm, more preferably from 2 to 50 am. When the phosphors are used, the amount thereof is from 1 to 80 parts by weight, preferably from 1 to 80 parts by weight, more preferably from 5 to 60 parts by weight, based on 1 part by weight to the total of the resin component. The curable resin composition of the present invention can be obtained by uniformly mixing the components. The curable resin composition of the present invention can be easily produced into the cured product in the same manner as conventionally known. For example, an epoxy resin and a hardener of the present invention, and a hardening accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent which are required for use, and an extruder, a kneader, and a roll are used as needed. When the curable resin composition is in a liquid state, it is sufficiently mixed and homogenized, and the composition is poured into a model by potting, casting, impregnating the substrate, and curable resin. The method of casting, heating and hardening; if it is solid, it is formed by casting after melting, or by using a transfer machine or the like, and then hardening by heating. The hardening temperature and time are between 80 and 20 (TC is carried out for 2 to 1 hour. Although the hardening method can be cured once at a high temperature, it is preferred to gradually increase the temperature to carry out the hardening reaction. Specifically, at 80 to 15 (The initial hardening is carried out between rc, and then post-hardening is carried out between 100 C and 20 (TC. The hardening stage is preferably carried out by dividing into 2 to 8 stages, preferably 2 to 4 stages. The hardening of the present invention. The resin composition is dissolved in toluene, xylene,

The sclerosing tree which can be used as the sclerosing tree of the present invention is the solvent of the curable resin of the present invention 322150 40 201120000. The mixture of the composition and the solvent is generally used in an amount of 10 to 70% by weight, and 15 to 70% by weight. The amount of % is better. Further, the liquid composition can be directly obtained by RTM to obtain an epoxy resin cured product containing carbon fibers. Further, the curable resin composition of the present invention can also be used as a modifier for a film-type composition. Specifically, it can be used in the case where flexibility or the like is improved in the B-stage. In such a thin resin composition, the curable resin composition A of the present invention can be applied as a curable resin composition varnish to a release film, and after removing the solvent by heating, a B-stage can be obtained. As a sheet-like adhesive. The sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like. Next, the epoxy resin composition of the present invention will be described in detail when it is used as a sealing material or a die-bonding material for a photo-semiconductor. When the epoxy resin composition of the present invention is used as a sealing material or a die-bonding material of a photo-semiconductor such as high-brightness white LED, a curing agent (hardener composition) containing a polyvalent carboxylic acid of the formula (J), The epoxy resin composition is sufficiently mixed with a cerium additive such as a curing accelerator other than an epoxy resin, a coupling agent, an antioxidant, or a light stabilizer to be used as a sealing material, or as both a die-bonding material and a sealing material. . The mixing method is carried out by using a kneader, a triaxial roll, a multi-functional agitating machine, a planetary mixer, a homogenizer, a homogenizer, a bead mill, or the like at normal temperature or under heating. Optical semiconductors such as high-brightness white LEDs are generally GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN, etc. laminated on substrates such as sapphire, spinel, SiC, Si, and ZnO. The semiconductor wafer is bonded to the lead frame, heat sink or package with an adhesive (adhesive material) to 41 322150 201120000. There is also a type in which a metal wire or the like is connected by a current. The semiconductor wafer is sealed with a dense alloy such as an oxygen resin in order to prevent heat or moisture and to achieve the function of the lens function. The epoxy resin composition of the present invention can be used as the material or the die bonding material. In the step, the curable resin composition of the present invention is conveniently used on both the die-bonding material and the sealing material. The semiconductor wafer is coated with the curable resin composition of the present invention and then applied to the substrate. The epoxy resin composition of the present invention is coated by a dispenser, infusion, screen printing, and the semiconductor wafer is placed thereon. The heat curing can be performed to make the semiconductor wafer follow. The heating system can use a method such as hot air circulation type, infrared ray, or high frequency. The heating conditions are, for example, 80 to 230X: preferably 1 minute to 24 hours. For the purpose of reducing the internal stress generated during heat hardening, it can be pre-hardened at 8 〇 to 120 ° C for 30 minutes to 5 hours, and then 12 〇 to 丨 8 〇 7 and 30 minutes to 1 〇 hour. It hardens afterwards. The molding method of the sealing material can be formed by heating and hardening the sealing material in the frame inserted into the substrate of the semiconductor wafer as described above, and then forming the sealing material by pre-applying the model on the model. A semiconductor wafer that is fixed to the substrate is immersed therein, and is subjected to a compression molding method such as mold release by force η. Examples of the injection method include dispensing, tanker molding, and injection molding (injecti〇n m〇iding). For heating, a method such as hot air circulation type, infrared ray, and high frequency can be used. The heating conditions are, for example, 80 to 23 Torr. (:, about 1 minute to 24 hours is preferred. For the purpose of reducing the internal stress generated during heat hardening, 322150 42 201120000 can be pre-hardened for 30 minutes to 5 hours at 80 to 120 ° C, 盅,,, 丹The post-hardening of the curable resin composition of the present invention can be used for the general use of the thermosetting resin such as Epoxy resin, etc., from 12 to 180 ° C for 30 minutes to 10 hours. Specifically, it can be used as a sealing agent, a coating material, a coating agent, a molding material (sheet, film, PRP, etc.), an insulating material (including a printed substrate, a wire coating, etc.), a sealing material, a sealing material, and a substrate. The cyanate resin composition, the acrylate resin used as a curing agent for the nose, the sputum, and the like, the additives to other resins, etc. The following agents are used for civil engineering, construction, automotive, general affairs. Examples of the adhesive for medical use include an adhesive for an electronic material. Examples of the adhesive for an electronic material include an interlayer adhesive of a multilayer substrate such as a build-up substrate; Agent, bottom An adhesive for semiconductors such as a filler (such as underfiii); an underfill for BGA reinforcement, an anisotropic conductive film (ACF. Anisotropic Conductive Film), and an adhesive for encapsulation such as an anisotropic conductive paste (ACP). Examples of the sealing material include perfusion, impregnation, and transfer molding sealing for capacitors, transistors, diodes, light-emitting diodes, 1C, LSI, etc.; so-called perfusion for IC, LSI COB, COF, TAB, etc. Sealing, bottom filling for flip chip, etc., sealing of ic package such as QFP, BGA, CSP, etc. at the time of mounting (including underfill for reinforcement), etc. The present invention is obtained by hardening a curable resin composition of the present invention. The cured product can be used in various applications mainly including optical component materials, and the optical material generally means a material used for the purpose of passing visible light, infrared rays, ultraviolet rays, xenon rays, laser light, etc. through the material. 322150 43 201120000 In addition to the LED sealing materials such as the lamp type and the in i SMD type, the film for the left eye, the corner correction film, the adhesive, the pseudo liquid crystal, etc. (4) The first color film protects the 5 vine film and displays the surrounding materials. It is the color PDP (display (4)) sealing material expected for the next generation of the half-face display,: reflection 2, light correction film, shell material, front glass Protective film, front glass 1 substitute material, adhesive; or led nuclear plastic material used in LED display device, LED sealing material, front glass protective film, front glass substitute material, adhesive; or The substrate material, the light guide plate, the cymbal sheet, the deflecting plate, the phase difference plate, the viewing angle correction film, the adhesive agent, the polarizing plate protective film in the liquid crystal (ΡΑΙΧ) display, or the organic EL (electric field illuminating) display device The protective film of the front glass; the substitute material of the front glass, the adhesive; or various film substrates in the field emission display (FED), the protective film of the front glass, the substitute material of the front glass, and the adhesive. In the field of optical recording, it is VD (image disk;), cd/CD-ROM, CD-R/RW, DVD-R/DVD-RAM, M0/MD, PD (phase-change optical disc), magnetic for optical cards. Disc substrate material, reading lens, protective film, sealing material, adhesive, and the like. In the field of optical machines, there are materials for lenses for still cameras, finder mirrors, mirrors, viewfinder masks, and photoreceptors. There are also camera lenses and viewfinders. There are also projection mirrors for projection TVs, protective films, sealing materials, and adhesives. There are also lens materials, sealing materials, adhesives, films, and the like for photosensitive machines. In the field of optical components, there are optical materials in the optical communication system, fiber optic materials, frog mirrors, waveguides, sealing materials for components, and adhesives. Fiber optic materials, metal hoops, sealing materials, and 322150 201120000 coatings. The light passive element and the optical circuit element are a lens, a waveguide, a sealing material for an LED, a sealing material for a CCD, an adhesive, and the like. Substrate material, fiber material, and sealing material for components around the optoelectronic integrated circuit (0EIC) • Subsequent agents. In the field of optical fibers, there are lighting/light guides for decorative displays, sensors for display applications, display/labeling, etc., or communication bases for telecommunication infrastructure and digital connection machines for digital devices in the home. Among the materials surrounding the semiconductor integrated circuit, there are resist materials for microetching for LSI and super LSI materials. In the field of automobiles/transport machines, there are automotive reflectors, bearing retainers, gear parts, corrosion layers, switching parts, headlights, engine parts, electronic parts, various interior and exterior parts, drive engines, brake tanks, and automobiles. Use anti-recording steel plate, inner side plate, interior material, protection/end harness, fuel pipe, lamp, glass substitute. There is also a laminated glass for railway vehicles. It can also be a fine agent for the structural material of the aircraft, an engine peripheral member, a wire harness for protection/end, and a barrier layer. In the construction field, there are interior/processing materials, electrical masks, sheets, and glass interlayer films: glass substitutes, and solar cell peripheral materials. Agricultural users have membranes for greenhouse covering. As the next generation of light/electronic functional organic materials, there are organic L-component peripheral materials, organic light-refracting elements, optical-amplifying elements, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, and components. The sealing material is an adhesive or the like. Examples of the sealant include perfusion, impregnation, transfer molding and sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, etc.; ic, LSI-based COB, CQF, TAB, etc. Sealing; Cladding and other bottoms# Filling, BGA, CSP and other 1C packages are sealed at the time of installation (including strong 322150 45 201120000 for bottom filling). The other use of the optical material is a general use of the curable resin composition A or the curable resin composition B, and examples thereof include an adhesive, a coating material, a coating material, a molding material (including a sheet, a film 'FRp, etc.), Insulation materials (including printed boards, wire coatings, etc.), sealants, additives to other resins, etc. The adhesive agent may be an adhesive for electronic materials, in addition to an adhesive for civil engineering, construction, automotive, general use, and medical use. Examples of the adhesive for the electronic material in the above-mentioned materials include an interlayer adhesive for a multilayer substrate such as a build-up substrate; a semiconductor adhesive for a die bond or an underfill; and a BGA-reinforced underfill agent for an anisotropic conductive film. (ACF), an adhesive for encapsulation such as an anisotropic conductive paste (ACP). [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the following $ is not particularly limited, that is, parts by weight. Further, the invention is not limited to the embodiment. Further, in the present invention, the measurement of gel chromatography (hereinafter referred to as "Gpc") is as follows. The column is Shodex SYSTEM-21 (KF-803L, KF-802. 5U2), KF-802), the eluent is tetrahydrofuran, the flow is 1 mL/min, and the column temperature is 4 (rc, The detection system was carried out under RI (reflectance), and the standard curve was a standard polystyrene produced by Shodex. The functional group equivalent was calculated from the ratio determined by GPC, and the carboxylic acid and the acid anhydride were respectively obtained as one equivalent. Example 1 (Polycarboxylic acid composition A1) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, toluene ι 322150 46 201120000 parts were added while nitrogen purge was performed. 2'4-diethyl 5-pentanediol (manufactured by Kyowa Fermentation Chemicals (8); Condensed Glycol PD9) 80 parts, a mixture of methyl hexahydro sulphate and a hexahydrate acid needle (New Japan Physicochemical Co., Ltd.) ;Rikacid MH700 ratio: 7:3, the following is called acid needle H1) 168 parts, at 1 〇〇. (: 4 hours of heating and mixing. At this point, the point where the material disappears (1 area% or less) After the end of the reaction, the reaction should be completed. After the reaction is completed, the residual solvent is introduced using a rotary evaporator. In addition, 246 parts of the polycarboxylic acid composition (A1) of the present invention were obtained. The obtained colorless solid resin had a polycarboxylic acid content of 97% by area via GPC, and a functional group equivalent of a carboxyl group and an acid anhydride (hereinafter referred to as The functional group equivalent is 245 g/eq·. Further, although the shape is solid, it has a slight fluidity and is slowly deformed at room temperature to have a shape close to a semi-solid shape. Example 2 (hardener composition B1) Relative to 25 parts of the polycarboxylic acid composition (A1) obtained in Example 1 was uniformly dissolved by adding 75 parts of an acid anhydride (Η1) to obtain a hardener composition (Β1) of the present invention. The viscosity at 50 ° C was 450 mPa. .s (£-type viscometer). Example 3 (hardener composition B2) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, while blowing nitrogen gas, 2, 4_diethyl 5 was added. _Pentanediol (Concord Fermentation Chemicals Co., Ltd.; Concord Glycol PD9) 2 parts, sour liver (hi) i〇〇 part 'heated and stirred at 60 ° C for 4 hours. Confirm 2, 4- 2 via gpc Ethyl-1,5-pentanediol is 1% by area or less. A polycarboxylate containing the present invention is obtained. The hardener composition (B2) of the acid composition is 12 parts by weight. The obtained reaction product is a colorless liquid resin. The ratio of the combination of GPC is: 52% by area of decanoic acid (μ), fluorenyl hexahydrophthalic anhydride The total amount with hexahydrophthalic anhydride is 48 area 47 322150 201120000%, and the functional group equivalent is 197 g/eq. The viscosity at 50 ° C is 1340 niPa.s (19700 mPa.s at 25 ° C; E-type viscosity) instrument). Examples 4 and 5 (curable resin composition) The curing agent was obtained by using the curing agent compositions B1 and B2 of the present invention obtained in Examples 2 and 3, respectively, and using 3, 4-epoxycyclohexyl group as the epoxy resin. Methyl-3,4-epoxycyclohexylcarboxylate (manufactured by Dow Chemical Co., Ltd.; UVR-6105 hereinafter referred to as epoxy resin (EP-1)), and hardening accelerator are cetyltrimethyl hydroxide The ammonium amide (manufactured by Tokyo Chemical Industry Co., Ltd.; 25% sterol solution, hereinafter referred to as C1) was prepared by blending ratio (parts by weight) shown in Table 1 below, and after defoaming for 20 minutes, the present invention was obtained. A curable resin composition. Comparative Example 1 (Compacting Curable Resin Composition) In the above Examples 4 and 5, except that the curing agent was changed to the acid anhydride (H1), the same steps as in Examples 4 and 5 were carried out, and the comparative hardening property was obtained. Resin composition. Using the obtained curable resin composition, a volatilization test and an LED test were carried out at the points indicated below, and the results are shown in Table 1. Further, the curing conditions were 15 °C for 5 hours after preliminary hardening at 120 ° C for 2 hours. Volatilization test: The curable resin compositions obtained in Examples 4 and 5 and Comparative Example 1 were vacuum-deaerated for 20 minutes, and then slowly injected. The heat-resistant adhesive tape is used as a dam on a glass substrate to be molded into a size of 30 mm x 20 mm x 1 mm. After the weight of the resin of the mold is correctly measured, the mold is hardened under the above conditions. 0 48 322150 201120000 The weight of the material was measured to confirm the decrease in weight at the time of hardening. Further, either of the curing examples 4 and 5 and the comparative example were carried out in the same oven. LED test: Examples 4, 5 and Comparative Example i Each of the obtained curable resin compositions was subjected to vacuum defoaming for 2 G minutes, and then individually filled in a graduated cylinder. The above-mentioned one was injected and molded into a surface package each having a light-emitting element having an emission wavelength of 46 glasses, using a precision discharge device. Type (10) type 3m_) LED. Then, the evaluation was carried out under the above-mentioned hardening conditions to obtain an evaluation item and evaluation criteria: (a) Volatileness: The surface of the cured product after sealing was visually observed for irregularities and evaluated. The evaluation criteria in the table are as follows. 〇: I can't see a hole. △: I saw some micro-pits. X: I see most of the holes (with lines exposed). (b) Reflow test: The obtained test was absorbed by a led at 30 ° C, 7 ° C for 72 hours, and then confirmed by a high-temperature observation device (SMT Scope SK, 5 〇〇〇; manufactured by Sanyo Seiko Co., Ltd.). The presence or absence of cracking in the LED under the following reflow conditions. The test was carried out at n=3 and evaluated by (〇κ number)/(test number). At the same time, the above (0K number) does not show the number of passes produced by the crack. The condition means that the temperature is raised to 150 at 25 ° C at 2 ° C / sec. (:, then maintained at 150 ° C for 2 minutes, then heated to 260 ° C at 2 ΐ / sec and maintained for 10 seconds, then cooled to room temperature at 1.30 / sec. 322150 49 201120000 Table 1 B1 ~ B2 TTi - 4 Example 5 Comparative Example 1 Unit hardener composition 18.7 - Parts by weight 19.9 parts by weight of hardener HI EP1 '_ 16.8 parts by weight of epoxy resin 13.0 13.0 13.0 parts by weight of hardening accelerator Cl 0. 05 0. 05 0. 05 Parts by weight -- Volatilization test (volatilization) 4.6 5.8 13.0% by weight (a) LE1D test (匕) Em 〇 X X 3/3 ------1 3/3 1/3 Examples 4, 5 and In Comparative Example J, when the amount of volatilization of the curable resin composition of the present invention is 彡, no problem such as exposure of the wire is caused even in the case of sealing (four), and the occurrence of turtles is not observed even during reflow. From the above results, it is understood that when the curing agent composition of the present invention containing the multi-frequency acid composition of the present invention and the acid needle is used as a curing agent, volatility resistance and excellent resistance to cracking can be obtained. The curable resin composition of the cured product. Example 6 (hardener composition β3) In the flask of the mixing machine, reflux condenser and stirring device, :==' Add 2'4-based diol (made by Co., Ltd.), 12 parts, and anhydride (ηι) ) 73 soil, ', 4 ring has been tempered acid _1, 2-anhydride (Η-ΤΜΑη Mitsubishi Gas Chemical Manufacturing 'hereinafter referred to as Η 2) 15 parts, at 6 (TC for 4 hours heating and stirring. Confirmed by 2GPC 2 '4. Diethyl-1,5-pentanediol is 1% by area or less and then 322150 50 201120000 100 parts of the hardener composition (B3) of the present invention containing the polycarboxylic acid of the formula (1) and an acid anhydride are obtained. The obtained colorless liquid resin had a functional group equivalent of 183 g/eq. The viscosity at 50 ° C was 1010 mPa·s. Example 7 (hardener composition B4) was equipped with a stirrer, a reflux condenser, and a stirring device. In the flask, • 2, 4-diethyl 4,5-pentanediol (manufactured by Kyowa Fermentation Chemicals Co., Ltd.; Condensed Glycol PD9) was added to the flask while the nitrogen purge was performed. Hexanedicarboxylic anhydride (manufactured by Nippon Chemical and Chemical Co., Ltd.; Rikacid ΜΗ H3), at 60 ° (: 4 hours heating and stirring. via 6? It is confirmed that 2,4-diethyl-1,5-pentanediol is 1% by area or less. 120 parts of the hardener composition (B4) containing the polycarboxylic acid of the formula (1) and an acid anhydride is obtained. The functional group equivalent is 2 〇ig/eq. 5 (The viscosity in TC is 1100 mPa.s (25t: medium is 16200mPa.s; E-type viscometer). Example 7a From the hardener composition (B4) 50 parts 'The use of a rotary evaporator to remove excess methyl hexahydrophthalic anhydride from 1 Torr to 150 ° C (from the point where the fluorenyl hexahydrophthalic anhydride no longer flows out) In the case where the acid anhydride was sufficiently removed by heating under reduced pressure for a few minutes, 25 parts of the polycarboxylic acid composition (B4a) of the present invention was taken out. The shape is a colorless semi-solid to solid resin. The viscous viscosity of the resin is 0. 08Pa.s. The softening point of the resin is 5.8 °C. Example 8 (hardener composition B5) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 2, 4-diethyl-1,5-pentanediol was added while purging with nitrogen. 51 322150 s- 201120000 and fermentation chemistry (stock); 12 parts of copolydiol diol PD9), 73 parts of acid anhydride (H3), 15 parts of acid anhydride (H2), heated and stirred at 60 ° C for 4 hours. It was confirmed by GPC that 2,4-diethyl-1,5-pentanediol was 1 area% or less. A hardener composition (B5) containing the polybasic acid of the formula (1) and an acid anhydride was obtained in a portion. The result is a colorless liquid resin. The functional group equivalent weight was 186 g/eq. The viscosity at 50 °C is 1050 mPa*s. Example 9 (hardener composition B6) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 2,4-diethyl-1,5-pentanediol was added while performing nitrogen purge. Fermentation chemistry (manufacturing); 20 parts of copolydiol diol PD9), 100 parts of cyclohexanone dihydroxanthate' was heated and stirred at 60 ° C for 4 hours. It was confirmed by gpc that 2,4-diethyl-1,5-pentanediol was 1 area% or less. 120 parts of a hardener composition (B6) containing the polyvalent carboxylic acid of the formula (1) and an acid anhydride was obtained. The functional group equivalent was 188 g/eq. The viscosity at 50 ° C is 1200 mPa.s (E-type viscometer). Synthesis Example 1 (Comparative Hardener Composition B7) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 1,4-cyclohexanedimethanol was added while purging with nitrogen gas. Manufactured; SKY-CDM) 20 parts, an acid anhydride (Hl) 1 part, heated at 6 ° C for 4 hours; mixed. 120 parts of a hardener composition (B7) containing a plurality of polyphenolic acid and acid liver for comparative use were obtained. The functional group equivalent was 171 g/eq. The point in 25ΐ is 18900mPa.s (E-type viscometer). Synthesis Example 2 (Comparative Hardener Composition β8) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, while purging with nitrogen, 2 parts of neopentyl glycol and an acid anhydride (ηι) were added. 52 322150 201120000 parts, heated and stirred at 60 ° C for 4 hours. A 12 part portion of the hardener composition (B8) containing the polycarboxylic acid and the acid anhydride used in the comparative example was obtained. The functional group equivalent was 197 g/eq. The viscosity at 25 ° C is 238 〇〇 mPa.s (E-type viscometer). Synthesis Example 3 (Comparative Hardener Composition B9) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, ruthenium, 6-hexanediol, and an acid anhydride (hi) were added while purging with nitrogen. 100 parts 'heated and stirred at 60 ° C for 4 hours. The hardener composition (B9) containing the polycarboxylic acid and the acid anhydride used in the comparative example was obtained in 12 parts. The functional group weight was 197 g/eq. The viscosity at 25 ° C was 15600 mPa·s (E-type viscometer). Synthesis Example 4 (Epoxy Resin EP-2) 106 parts of stone-(3,4-epoxycyclohexyl)ethyltrioxoxalate was introduced into a reaction vessel, and the weight average molecular weight n〇〇 was measured by GPC. Value) 234 parts of sterol-terminated methyl phenyl fluorenone oil (sterol equivalent 850; calculated using 1/2 of the weight average molecular weight measured by GPC) and 18 parts of 0.5% KOH (KOH) methanol solution The bath temperature was set to 75 Ϊ: and the temperature was raised. After warming up, it was allowed to react under reflux for 8 hours. Next, after adding 305 parts of methanol, 86. 4 parts of a decyl alcohol solution (concentration: 5% by weight) of distilled water was added dropwise thereto over 60 minutes, and the mixture was reacted at 75 ° C for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with a 5% aqueous solution of sodium dihydrogen phosphate, and then methanol was recovered at 80 ° C for about 90%. 380 parts of decyl isobutyl ketone was added and washed with water for 3 times with 200 parts of water. Next, by dissolving the organic phase under reduced pressure at 100X: using a rotary evaporator, it was obtained that 300 parts of epoxy resin (EP_2) having a helium-ane structure was obtained. The obtained compound had an epoxy equivalent of 729 g/eq, a weight average molecular weight of 2,200, and an appearance of no 322150 53 201120000 color transparent. Synthesis Example 5 (Organic Compound D-1 of Epoxy Group) In a flask equipped with a scrambler, a reflux condenser, a scrambler, and a Dean Stark, a nitrogen purge was performed while adding a 1,4-ring. Dimethyl hexanedicarboxylate (manufactured by Iwaswas Co., Ltd.; DMCD_p) U{) 'Injury. 314 parts of cyclohexene-4-nonanol, tetrabutyloxytitanium 〇. 7 parts, one side of 12 〇C1 hour, 150 °C1], hour, 17 (TC1 hour, 190 °C 12 hours to remove the reaction In the gas chromatography (GC), after confirming that the raw material peak was 1 area% or less, it was cooled to 50 Torr. After the end of the portion, 347 parts of benzene was added to make it uniform, and then, the heart was 80 parts of a 10% by weight aqueous sodium hydroxide solution was washed three times, and then washed again with 100 parts/time of water to make the wastewater neutral. Under the heating and decompression by a rotary evaporator, toluene and no 3_cyclohexylmethyl hydrazine was reacted, and 24 parts of a compound (D1) having a bis (3-cyclohexylmethyl)H,4-cyclohexyl dicarboxylic acid as a main component in a liquid state was obtained. 6 (Epoxy resin EP-3) In a flask equipped with a stirrer, a reflux condenser and a stirring device, the yoke was purged with nitrogen while adding π parts of water, ι2 - strontium tungstate phosphate. , trioctyl acetic acid recorded in a 50% xylene solution 2.7 wounds, 180 parts of toluene and the compound (d_i) i obtained in Synthesis Example 5 were injured. The solution was heated to 6 (TC, while stirring vigorously, one small

While adding 70 parts by weight of 70 parts by weight of an aqueous solution containing hydrogen peroxide, it was stirred at 60 ° C for 13 hours. The progress of the reaction in the gas chromatography was confirmed, and the peak of the raw material was 1 area%. 54 322150 201120000 Receiver, after neutralizing with 1% by weight sodium hydroxide aqueous solution, add deduction "Deputy Wei Caichun 25 (four) line 3Q classification after the secret. The organic layer separated into 2 layers was taken out. Here, 20 parts of activated carbon (Ajinomoto Fine Chemicals; manufactured by CP); and turbid soil (20 parts of Bengel® manufactured by 屻un Co., Ltd.) were mixed at room temperature. After the lapse of the filtration, the obtained mash was washed three times with water, and the toluene was removed from the organic layer to obtain a normal temperature olefinic epoxy resin (EP-3M 19 parts. The epoxy equivalent of the obtained epoxy resin was 217 g). /eq. The viscosity in 25 C is 9200 mPa.s (E-type viscometer). Synthesis Example 7 (diolefin compound d_2 of epoxy resin) Refer to PCT/JP2_/m432, equipped with a mixer, reflux condensation In the flask of the stirring device and the stirring device, 150 parts of water, 55.1 parts of 3-cyclohexene formaldehyde, 62 parts of ditrimethylolpropane, and 7.3 parts of concentrated hydrochloric acid were added to the flask while purging with nitrogen. (TC was reacted for 1 hour. After the completion of the reaction, 1 part of water and 3 parts of 3% aqueous sodium hydroxide solution were added to the reaction liquid, and then the reaction liquid was neutralized with sodium hydrogen phosphate. The butanone fraction was washed three times with 100 parts of water, and then the solvent was distilled off to obtain 10 parts of a dipotassium compound (D-2). Example 8 (Epoxy Resin EP-4) Refer to PCT/JP2009/067432 'In a flask equipped with a stirrer, a reflux condenser, and a stirring device, while purging nitrogen gas, adding 15 parts of water, 12-pyridinium phosphate. 47 parts, 39 parts of dibasinium bismuth hydride, 1.4 parts of a 50% xylene solution of ammonium dioctyl ammonium acetate, 9 parts of a hydrazine, and 54 parts of a compound (D-2) obtained in Synthesis Example 7. The solution was heated to 6 (rc, while violently disturbing) while adding 35 parts by weight of 35 parts by weight of 322150 55 201120000 aqueous solution containing peroxidic gas for 35 hours, and stirring directly at 6 (rc for 13 hours. Confirmed by gas chromatography) When the reaction was carried out, the peak of the raw material was less than or equal to the area of 丨. Next, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 12 parts of a 2% by weight aqueous sodium thiosulfate solution was added, and the mixture was stirred for 3 minutes, and then allowed to stand. 2 layers of organic layer, add 10 parts of activated carbon (made by Ajinomoto Fine Chemicals Co., Ltd., CP1), montmorillonite QQJNIMINE INDUSTRIES (manufactured by Kunming), 10 parts, stirred at room temperature for 3 hours. Filtration. The obtained filtrate was washed 3 times with 100 parts of water and passed through The organic layer was distilled off toluene to obtain 49 parts of epoxy resin (EP-4) at room temperature. The epoxy equivalent of the obtained epoxy resin was 262 g/eq·. The viscosity in 25 t was 230,000 mPa·s (E plastic Viscosity meter. Example 10 (curable resin composition) Epoxy resin was obtained by using the epoxy resin (EP2) obtained in Synthesis Example 4, and a curing agent using the hardener composition (B2) obtained in Example 3, and hardening promotion. The agent uses a quaternary scale salt (manufactured by Nippon Chemical Industry Co., Ltd.; Hishicolin® 41 hereinafter referred to as 匚2), and the additive system uses bis(2,2,6,6-tetramethyl-4-pyridinyl) ) sebacate (manufactured by Nippon Ciba (stock); TINUVIN 770DF hereinafter referred to as L1) and phosphorus compound using 4,4'-butylidene bis(3-indolyl-6-t-butanyl-di- Tridecyl phosphate (manufactured by Adeka; Adekastab 260 hereinafter referred to as M1), formulated in a blending ratio (parts by weight) shown in Table 2 below, and defoamed for 20 minutes to obtain a curable resin of the present invention. Composition. The obtained curable resin composition was subjected to a pot life (p〇t-iife) test in the following method. The results are shown in Table 2 below. 〇56 322150 201120000 The obtained curable resin composition is slowly injected into the test piece and molded in a mold. The casting is hardened by the condition of i50〇Cxl hours after preliminary hardening at 120 ° C for 3 hours. Various hardened materials for the test were obtained. The following heat durability transmittance test and LED lighting test were evaluated for the obtained cured product in accordance with the conditions described below. The results are shown in Table 2 below. Application period The viscosity of the resulting curable resin composition at room temperature was changed, and it was measured after 3 hours and 6 hours. Then, the viscosity was raised (advanced viscosity / initial viscosity χ 1 〇〇) (%). Thermal long-term penetration rate test Confidence test conditions: 96 hours in a l5〇〇c oven Test piece size: thickness lmm Evaluation conditions: The transmittance of 400 nm was measured by a spectrophotometer. And calculate its change value. In the LED lighting test, the obtained curable resin composition was filled in a graduated cylinder and injected and molded into a surface mount type LED package (having an inner diameter of 4.4 mm, which was provided with a center light-emitting wave 465 ηηη < The outer wall returns 1.25mm). The pound was placed in a heating furnace and subjected to 12 (TC '1 hour, and then hardened at 15 (rc, 3 hours) to prepare a lED package. After the LED was sealed, the LED was turned on after the following conditions were measured. Illumination, the results are not shown in Table 2. Lighting detailed conditions Light-emitting wavelength: 465nm 57 322150 201120000 The predetermined current is 30mA) Drive mode: constant current mode, 6QmA (light-emitting element drive environment: 85. (:, 85% Drive time: 200 hours) 4 hours evaluation: Illumination maintenance rate after lighting comparison Example 2, 3, 4 or 3 = Γ " 'In addition to changing the hardener to the synthesis example h === or ~, with solid each curing resin The composition was subjected to the same test. The results are shown in the following Table 2. The cured resin composition for comparison with the above-mentioned results was subjected to the same hardening as in Example 10, and the resulting hardening was carried out. For the following, the following /, thermal durability penetration test, LED lighting test, according to the following description, line 5 " U. And the results are recorded in Table 2. 58 322150 201120000 Table 2 Item Embodiment 10 Comparative Example 2 Comparative Example 3 Comparative Example 4 Resin Polyoxane EP-2 10.0 10.0 10.0 10.0 B2 2.8 Hardener Hardener Composition B7 2.8 Composition B8 2.8 B9 2.8 Hardening_Accelerator Grade IV Scale Salt C2 0.01 0.01 0.01 0.01 Additive Light stabilizer L1 0.03 0.03 0.03 0. 03 Phosphorus compound Ml 0.03 0. 03 1 0.03 0.03 Curable resin composition Applicable viscosity increase rate (3 hours) % 120 121 129 122 Viscosity increase rate (6 hours) % 155 190 202 172 Thermal durability penetration test Transmittance (400nm) % 91.4% 91.5% 92. 0% 91.0% Hardenability retention (400nm) _ Illuminance maintenance rate (after 200 hours) % .88.7% 87. 3% 87.9% 88. 6% LED lighting Test % 105% 71% 102% 105% Illumination retention rate (after 400 hours) % 99% - - _ - 52% 393⁄4 From the above results, it is understood that the curable resin composition of the present invention has a low viscosity increase rate and has The longer the probation period, and the cured product using the multi-material of the present invention is superior in illuminance maintenance ratio and excellent in optical characteristics as an LED compared to the use of other skeletons (IV). Examples 11 and 12 ( Curable resin composition) For the epoxy resin, the epoxy resin (Ep-3, EP-4) obtained in Synthesis Examples 6 and 8 + and the curing agent were used. The hardener composition (B4) obtained in Example 7 and the hardening accelerator were used. Grade scale salt (manufactured by Japan Chemical Industry Co., Ltd.; Hishicolir T* PX4MP hereinafter referred to as (2), additive system used "bis(2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate ( Japanese Ciba (share) f; Measured below the shoulder called L1) and phosphorus compound used 59 S. 322150 201120000 4'4' - Butylene bis (3-methyl-6_T-butylene) Manufactured by SIXADEKA., Adekastab 260 is hereinafter referred to as Ml), and is blended in the proportions (parts by weight) shown in Table 3 below, and after 2 minutes of defoaming, the hardening of the present invention is obtained. Resin composition. The obtained curable resin composition was slowly poured into a test piece mold, and the cast product was cured under the conditions of 15 C « 3 hours of preliminary hardening at 120 C x 3 hours to obtain various hardened materials for the test. For the obtained cured product, the following LED lighting test was evaluated under the conditions described below. The results are shown in Table 3 below. In the LED lighting test, the hardened resin composition was filled in a graduated cylinder and a surface mount type (10) package (outer diameter) having an outer diameter of 5 mm cube mounted on a wafer having a central light-emitting wave of 465 nm was molded by a precision device. "Li, outer wall 4 h 25mD 〇 ° put the sputum into the heating furnace, and then 12 吖, i J and then 150C, 3 hours of hardening treatment to form a led package. After packaging the LED, the following conditions make (4) The illuminance was measured after lighting, and the results are shown in Table 3. Detailed lighting conditions of the lighting: 465 nm 60 mA (the predetermined current of the illuminating element is 3 mA) Driving mode: constant current mode Driving environment: 85 ° C, 85% Driving time: 200 Hour evaluation: illuminance after 丨200丨 322150 60 201120000 Table 3 Item Example 11 Example 12 Composition Epoxy EP-3 21. 7 EP-4 26. 2 Hardener Hardener Composition B4 17. 1 17. 1 Hardening accelerator quaternary salt C2 0. 02 0. 02 Additive light stabilizer L1 0. 04 0.04 Phosphorus compound Ml 0. 03 0. 03 tED lighting test illuminance maintenance rate (after 200 hours) % 102 % 102% Examples 13, 14, 15 (sclerosing tree Composition) J ethoxylate resin is an epoxy resin (EP-i, ep-3), and a hardener is used as a hardener composition (B2, B4, B6) obtained in the respective examples, and a hardening accelerator is used ( C2) was prepared by blending in a proportion (parts by weight) shown in the following Table 4, and defoaming was carried out for 20 minutes to obtain a curable resin composition of the present invention. The curable resin composition was slowly injected into the test piece. The molded product was hardened by molding in a mold for 1 hour at 110 CX for 3 hours, and various hardened materials for the test were obtained. For the obtained cured product, the following LED lighting test was carried out according to the conditions described below. The evaluation was carried out, and the results are shown in the following Table 4. In the LED lighting test, the obtained curable resin composition was filled in a measuring cylinder and a precision discharge device was used; the master was molded on a wafer equipped with a central luminescent wave (10). The surface of the 5 cubic cube is sealed with a type of LED package (inner diameter 4·-, outer wall height 1.25 mm). The cast compound is placed in a heating furnace at 120 ° C, 1

S 61 322150 201120000 hours, and then 15 (TC '3 hours hardening treatment, made lED package. After the LED was sealed, the LED was lit and the illuminance was measured under the following conditions. The results are shown in Table 4. Conditional emission wavelength: 465nm Driving mode. Constant current mode, 60mA (lighting element predetermined current is 30mA) Driving environment: 85ΐ, 85% Driving time: 2〇〇hour evaluation: Illumination maintenance rate after lighting for 200 hours Table 4 – ___ Project Example Example 14 Example 15 Cyclone Compensation EP-1 ~ ΎΓ~~ 6.0 6.0 ---- EP-3 4.0 4.0 4.0 Composition Hardener B2 11.6 Hardener Composition B4 1.8 A Hard B5 11.0 —-- Four-stage scale salt C2 0.01 0.01 0.01 LED lighting test — Illuminance maintenance rate (after 200 hours) % 72% 78% 70% Example 16, Π, ι8 (curable resin composition) Epoxy resin The epoxy resin (EP-; l, ΕΡ-3) and the hardener are the hardener compositions (Β3, Β5) obtained in the examples of the acid (H1, Η2), and the hardening accelerator (C2) is used, and the following The blending ratio (parts by weight) shown in Table 5 is adjusted to '20 After the defoaming of the bell, the curable resin composition of the present invention was obtained. The obtained curable resin composition was slowly injected into the test piece and molded in a model 62 322150 201120000, and after preliminary hardening at 110 Cx for 3 hours (Γ(:χ1) The cast product was hardened to obtain various cured products for the test under the conditions of the hour. The obtained LED lighting test was evaluated according to the conditions described below for the obtained cured product, and the results are shown in Table 5 below. In the lighting test, the obtained curable resin composition was filled in a measuring cylinder and injected and molded into a special 5 mm cubic surface-mount type LED package (having an inner diameter of 4 4 coffee) equipped with a central light-emitting wave (10) wafer using a precision discharge device. The outer wall is 1.25mm south. The orthodontic material is placed in a heating furnace, and is subjected to hardening treatment for 12 hours and hours, and then hardened at 150C for 3 hours to form a package. After the LED is packaged, the LED is made under the following conditions. The illuminance was measured after lighting, and the results are shown in Table 4. Lighting conditions: Illumination wavelength: 465 nm 6 〇 mA (predetermined current of the illuminating element is 3 mA) Driving method: constant current mode, driving environment: 85 ° C, 8 5% driving time: 200 hours. and illuminance maintenance rate after hours. Comparative Examples 5 and 6 (comparative use of 魏 纟 成 成 成 ) ) 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述, do the same thing, get the hard = fat composition for comparison. Further, in the same manner as in the above Examples 15, 16 and 17, the obtained four cured products were tested. The results are shown in Table 5 below. POINT 322150 63 201120000 Table 5 Item Comparative Example 5 Example 16 Example | Comparative Example 17 η Epoxy Resin EP-1 6.0 6.0 6.0 10.0

Example 18 TO EP-3 4.0 4.0 4.0 Composition Hardener anhydride hardener composition H1 H2 B3 6.9 8.2 13.3 2.0 10. Hardening accelerator B5 Strict 镌 salt exposure retention rate (200, ED lighting test - ~ L After the hour) % 10.8 0.01 82% 0.01 94% 102% 0.01 12.9 ΌΓ 83% 93% Example bl (polycarboxylic acid composition Abl) was carried out in a flask equipped with a mixer, a reflux condenser and a stirring device. Nitrogen purged, while adding 10 parts of hydrazine, tricyclodecane dimethanol (manufactured by 0XEA, TCD-AlcholDM) 98 parts, a mixture of decyl hexahydrophthalic anhydride and hexahydrophthalic anhydride (7: 3) (New Japan Physical and Chemical) (manufacturing) (Rikacid MH700, hereinafter referred to as anhydride H1) 168 parts, carried out in 8th generation for 15 minutes, l〇 (TC was heated for 4 hours. It was confirmed as raw material by Gpc (area% or less. After the reaction was terminated, The residual solvent was further removed by using a rotary evaporator to obtain a multicomponent composition (10) of the present invention; a mixture of the structural formula of the following formula (3) was applied. The obtained colorless solid resin had a softening point of 74 C. Further, the melt viscosity is 0.22 Pa.S in the 15th generation. The purity according to GPC is 99 area%. Further, the functional group equivalent weight of 266- ·. 32215064 201 120 000

Example b2 (hardener composition Bb1) With respect to 25 parts of the polycarboxylic acid composition (Abl: a mixture of the structural formula of the formula (3)) obtained in Example bl, 75 parts of an acid anhydride (jji) was added to uniformly dissolve it. The hardener composition (Bbi) of the present invention was obtained. Example b3 (hardener composition Bb2) In a flask equipped with a scrambler, a reflux condenser, and a scrambler, nitrogen gas was purged, and tricyclic terbene dinonol was added thereto, and an acid anhydride (Hl) was added. 100 parts, heated and stirred at 50 ° C for 4 hours. It was confirmed by GPC that tricyclodecanedioxanol was 1 area% or less. 120 parts of a hardener composition (Bb2) containing the polycarboxylic acid composition of the present invention was obtained. The obtained colorless liquid resin has a structure of a polyvalent carboxylic acid composition (Ab2; a mixture of the structural formula of the formula (3)) of 43% by area, methyl hexahydrophthalic anhydride and hexahydrophthalic anhydride depending on the purity of GPC. The total amount is 57 area%. Further, the functional group equivalent was 199 g/eq. Examples b4 and b5 (curable resin composition) and Comparative Example bl (comparative curable resin composition) The curing agent was obtained by using the hardener compositions (Bbl) and (Bb2) of the present invention obtained in Examples b2 and b3. And the anhydride (H) of the comparative example; the epoxy resin system uses 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl carboxylate (Dow Chemical Co., Ltd.; UVR-6105 or less) It is called epoxy resin (EP-1)); the hardening accelerator is made of hexadecyl trimethylammonium hydroxide (East 65 322150 201120000 Jinghuacheng Industry Co., Ltd.; 25% sterol solution, hereinafter referred to as ci 'The blending ratio (parts by weight) shown in the following Table 1 was adjusted, and after defoaming for 20 minutes, the curable resin composition of the present invention or comparatively obtained was obtained. The obtained curable resin composition was subjected to a volatilization test and an LED sealing test at the points indicated below, and the results are shown in Table bl. Further, the curing conditions were 15 ° after the preliminary hardening at 120 ° C for 2 hours (rcx 5 hours. Volatilization test: The curable resin composition obtained in the examples and the comparative examples was subjected to vacuum defoaming for 20 minutes, and then slowly poured into a heat-resistant tape. The shape of the glass substrate of the barrier (dam) is 30ππππ20ππιχ1 mm. The weight of the resin of the mold is accurately measured, and the mold is hardened under the above conditions. The weight of the cured product thus obtained is measured. The weight loss at the time of hardening was confirmed. (The curing of the examples and the comparative examples was similarly cured in the same oven.) Led test: The curable resin composition obtained in the examples and the comparative examples was subjected to vacuum defoaming for 20 minutes. After that, it is filled in a graduated cylinder, and the above-described one is injected and molded into a surface mount type (SMD type 3 mn^) LED having a light-emitting element having an emission wavelength of 465 nm, and then hardened under the predetermined hardening conditions. , Test LEDs were obtained. Evaluation items: (W Volatile: Visually observe whether there is unevenness on the surface of the cured product after sealing and evaluate it The evaluation criteria in the table are as follows: 〇: No pits are visible. 322150 66 201120000 △: Look at some micro-pits. X: See most holes (with exposed lines). (b) Reflow test : The obtained test LED was absorbed at 30 ° C and 70% x 72 hours, and then a high-temperature observation apparatus (SMT Scope SK-5000; manufactured by Sanyo Seiko Co., Ltd.) was used to confirm whether or not the LED under the following reflow conditions were present. Cracking occurred. The test was carried out at n=3 and evaluated by (0K number) / (test number). Condition means heating from 25 ° C to 2 ° C / sec to 150 ° C, then at 150 ° C After maintaining for 2 minutes, the temperature was raised to 260 ° C at 2 ° C / sec and maintained for 10 seconds, and then cooled to room temperature at 1.3 ° C / sec. Table bl: Example b4 Example b5 than the example bl unit Hardener composition Bbl 18.7 parts by weight Bb2 19.9 parts by weight hardener HI 16.8 parts by weight epoxy resin EP-1 13.0 13.0 13.0 parts by weight hardening accelerator Cl 0.05 0.05 0.05 parts by weight volatilization test (volatilizing amount) 4.6 5.8 13.0% by weight LED 5 Formula·13⁄4 (a) 〇〇X (b) 3/3 3/3 1/3 When comparing Examples b4 and b5 with Comparative Example b 1 The curable resin composition of the present invention has a small amount of volatilization, and does not cause problems such as exposure of the steel wire even when the LED is sealed. Further, cracks can be reduced during reflowing. From the above results, it is understood that the present invention The polyvalent carboxylic acid composition and the hardener composition containing the polyvalent carboxylic acid composition can provide an effective curable resin composition for reflow-resistant cracking. 67 322150 201120000 Example b6 (hardener composition Bb3) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, while blowing nitrogen gas, 20 parts of tricyclodecanedioxan, decyl hexahydrogen was added. 100% of phthalic anhydride (manufactured by Nippon Chemical and Chemical Co., Ltd.; Rikacid MH, hereinafter referred to as anhydride H3), 4 (after 3 hours of TC reaction, 7 (TC was heated for 1 hour). Confirmation of the three-ring broth by GPC The alcohol is 1% by area or less. 120 parts of the hardener composition (Bb3) containing the polycarboxylic acid composition of the present invention is obtained. The obtained colorless liquid resin is a polycarboxylic acid composition (Ab2; The formula (4)) is 49% by area, and the mercapto hexahydroabietic acid Sf is 51% by area. Further, the functional group equivalent is 2〇1 g/eq. Formula (4):

From the hardener composition (Bb3) 50 parts, an excess of mercapto hexahydrophthalic anhydride was removed by using a rotary evaporator at 10,000 Torr to 150 °C. This removal system was allowed to flow into the nitrogen gas for 4 minutes from the point where the methylhexahydrophthalic anhydride no longer flowed out, and the acid anhydride was sufficiently removed under heating and reduced pressure. As a result, 25 parts of the polycarboxylic acid (Bb3a) of the formula (1) of the present invention was taken out. The shape is a colorless semi-solid to solid resin. The softening point of the obtained resin (based on JIS K-7234) was 77 〇 ° C ', and the melt viscosity at 150 ° C was Pa 24 Pa·s. Example b7 (hardener composition Bb4) 322150 68 201120000 In a flask equipped with a stirrer, a reflux condenser, and a stirring device, while blowing nitrogen gas, 15 parts of tricycloanthracene dimethanol and methyl hexahydroquinone were added. Anhydride (manufactured by Nippon Chemical and Chemical Co., Ltd.; Rikacid MH, hereinafter referred to as anhydride 113) 70 parts, cyclohexane-1,2,4-tricarboxylic acid-1,2-xuan (manufactured by Mitsubishi Gas Chemical Co., Ltd.; H - TMAn) 15 parts, reacted at 40 ° C for 3 hours and then heated and stirred at 7 ° C for 1 hour. It was confirmed by GPC that tricyclodecanedioxanol was i area% or less. 100 parts of a hardener composition (Bb4) containing the polycarboxylic acid composition of the present invention was obtained. The obtained colorless liquid resin, according to the purity of GPC, the multi-repulsive acid composition (Ab3; the following formula (5)) is 37 area%, cyclohexene-1,2,4-tris-acid-1,2 The anhydride was 11 area%, and the mercapto hexahydroabietic acid liver was 52 area%. Further, the functional group equivalent was 171 g/eq. Equation (5):

Example b8 (hardener composition Bb5) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 50 parts of the hardened sword product (Bb3) obtained in Example 6 was added while purging with nitrogen. 5 parts of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.; H-TMAn-S), and mixed at 2 ° C for 2 hours. The hardener composition (Bb5) of the present invention is obtained. The resulting composition was a colorless liquid composition. 69 322150 201120000 Example b9 (hardener composition Bb6) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, while blowing nitrogen gas, 20 parts of pentacyclopentadecanedimethanol and an acid anhydride (H3) were added. 100 parts, reacted at 40 ° C for 3 hours, and then heated and stirred at 70 ° C for 1 hour. It was confirmed by GPC that pentacyclopentadecanedonol was 1 area% or less. A hardener composition (Bb6) 110 # containing the polycarboxylic acid composition of the present invention was obtained. The obtained liquid composition was a colorless liquid, and the polycarboxylic acid composition (Ab4; the following formula (6)) was 40% by area and the methylhexahydrophthalic anhydride was 60% by area based on the purity of GPC. Further, the functional group equivalent was 201 g/eq. Equation (6):

Example bl0 (hardener composition Bb7) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 10 parts of tricyclodecanedioxan and 100 parts of an acid anhydride (Hl) were added while purging with nitrogen. The mixture was heated and stirred at 50 ° C for 3 hours (it was confirmed by GPC that tricyclodecane dimethanol was 1 area% or less). 10 parts of a hardener composition (Bb7) containing the polycarboxylic acid composition of the present invention was obtained. The obtained colorless liquid resin had a polycarboxylic acid composition (Abl; the following formula (3)) of 27% by area and decyl hexahydrophthalic anhydride of 73% by area based on the purity of GPC. Also, the functional group 70 322150 201120000 equivalent is 185 g/eq. Synthesis Example bl (Comparative Hardener Composition Bb8) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, while blowing nitrogen gas, 20 parts of bicyclodoxime dimethanol and hexahydrophthalic anhydride were added (new Made by Japan Physicochemical Co., Ltd., Rikacid ΗΗ) 1 ,, 5 〇.加热 It was confirmed by GPC that the tricyclodecanedioxanol was 1 area% or less by heating and stirring for 3 hours. 120 parts of a hardener composition (Bb8) containing a comparative polycarboxylic acid composition was obtained. The obtained hardener cylinder was a colorless liquid composition. According to the purity of GPC, the polycarboxylic acid composition (A5; the following formula 7) was 48 area%, and the methylhexahydro acid needle was 52 area%. Further, the functional group equivalent was 200 g/eq. Equation (7):

Synthesis Example b2 (Comparative Hardener Composition Bb9) In a flask equipped with a stirrer, a reflux condenser, and a mixing device, 1 part of ethylene glycol and an acid anhydride (Ηΐ) were added while purging with nitrogen. The mixture was reacted at 40 ° C for 3 hours and then heated at 70 ° C for 1 hour. It was confirmed by GPC to be 1 area% or less of the raw material. 10 parts of a hardener composition (Bb9) containing a comparative polycarboxylic acid composition was obtained. The obtained hardener composition is a colorless liquid composition, and the polycarboxylic acid composition (Ab6; the following formula (8)) is 25 area%, methylhexahydrophthalic anhydride and hexahydrophthalic anhydride according to the purity of GPC. The total amount is 75 area%. Further, the functional group equivalent is 322150 201120000 185g/eq. Equation (8):

Synthesis Example b3 (Comparative Hardener Composition Bbl〇) Nitrogen purge was carried out in a flask equipped with a stirrer, a reflux condenser, and a stirring device, and cyclohexane dimethanol = part and anhydride (Hl) 100 parts were added. 4 (TC was reacted for 3 hours and then at 7 Torr. Heating and stirring was carried out for a working hour. It was confirmed by GPC that the area of the raw material was i% or less = a hardener composition containing a comparative polycarboxylic acid composition was obtained ( Bbl0) 120 parts of the obtained hardener composition is a colorless liquid composition, according to the purity of GPC, the polycarboxylic acid composition (Ab7; the following formula 8) is 53 area%, mercapto hexahydrophthalic anhydride and hexahydrogen The total amount of phthalic anhydride is 47 area%, and the 's energy base equivalent is 2 〇〇g/eq.. (9):

Synthesis Example b4 (Comparative Hardener Composition Bb11) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 20 parts of 1,6-hexanediol and an acid anhydride (H1) were added while yoke was purged with nitrogen. 72 322150 201120000 100 parts '40 ° c for 3 hours of reaction and then 1 hr of heating for 1 hour. It was confirmed by GPC to be 1 area% or less of the raw material. 120 parts of a hardener composition (Bbl 1) containing a comparative polycarboxylic acid composition was obtained. The obtained color is a colorless liquid resin. According to the purity of GPC, the polycarboxylic acid composition (Ab8; the following formula 10) is 65 area%, and the total amount of the mercapto hexahydro sulphur acid needle and the hexahydrophthalic anhydride is 35 area%. . Further, the functional group equivalent was 200 g/eq. Equation (10):

Synthesis Example b5 (epoxy synthetic raw material dilute hydrocarbon) In a flask equipped with a stirrer, a reflux condenser, a stirring device, and a Dean-Stark tube, 1,4-% hexane was added while purging with nitrogen gas. 172 parts of acid, 448 parts of 3-cyclohexene-1-methanol, 600 parts of toluene, and 4 parts of toluenesulfonic acid were adjusted to reduce the degree of pressure in the system to remove water generated by refluxing at 45 Torr. The reaction was carried out for 12 hours. After the completion of the reaction, the reaction solution was washed three times with 120 parts by weight of a sodium hydroxide aqueous solution, and then washed with water 7 times/time to make the wastewater neutral, and then heated under reduced pressure by a rotary evaporator. From the distillation of toluene and unreacted 3-cyclohexene-1-methanol, 343 parts of a diene compound which is liquid at normal temperature can be obtained. Synthesis Example b6 (epoxy resin EP-b2) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 322150 73 201120000 was purged with nitrogen, and 15 parts of water and 12-tungstophosphoric acid were added. , disodium hydrogen phosphate 〇. 78 parts, acetic acid ditallow alkyl dimethyl ammonium 2. 7 parts (manufactured by Lion Akzo; 50% by weight hexane solution, Arquad 2HT acetate), 180 parts of toluene and synthesis The 118 parts of the diolefin compound obtained in Example b5 was re-stirred to prepare a liquid in an emulsion state. The solution was warmed to 50 ° C, and while vigorously mixing, 70 parts of a 35 wt% aqueous solution containing hydrogen peroxide was added over 1 hour, and the mixture was stirred at 50 ° C for 13 hours. After confirming the progress of the reaction in the gas chromatography, the peak of the raw material has disappeared. Subsequently, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 25 parts of a 20% by weight aqueous sodium thiosulfate solution was added thereto, and the mixture was allowed to stand for 30 minutes, followed by standing. The organic layer separated into two layers was taken out. Here, Wako gel (C-30 〇) 1 〇 part of activated carbon (manufactured by N0RIT; CAPSUPER) 20 parts, bentonite (Bengel SH manufactured by H〇jun Co., Ltd.) 20 was added. The mixture was stirred at room temperature for 1 hour and then transferred. The filtrate obtained was washed with water three times with 10 parts of water, and toluene was removed by the obtained organic retort. 119 parts of an epoxy resin (EP-b2) containing a compound of the following formula (U) as a liquid at room temperature was obtained. The epoxy equivalent of the obtained epoxy resin was 217 g/eq. Equation (11):

Examples b11 and bl2 (curable resin composition) and Comparative Example b2 (comparative curable resin composition) The curing agent was obtained by using the hardener group 322150 74 201120000 (Bb2) of the present invention obtained in Examples 3 and 6. (Bb3)' and the hardener composition (Bb8) for comparison obtained in Synthesis Example bl; epoxy resin (Ep_1) for epoxy resin; and hardening accelerator (C1), which are shown in Table 2 below. The blending ratio (parts by weight) was blended, and after defoaming for 20 minutes, a curable resin composition of the present invention or comparatively obtained was obtained. The LED lighting test examples b11, bl2 and the curable resin composition obtained in Comparative Example 2 were subjected to vacuum defoaming for 20 minutes, filled in a graduated cylinder, and molded and molded on a light emitting wavelength of 465 nm using a precision discharge device. The surface mount type LED of the device (SMD type 5ππηφ; predetermined current is 30 mA). Then, it was hardened under predetermined hardening conditions to obtain an LED for lighting test. The lighting test is performed at a current of twice the predetermined current of 30 mA. The detailed conditions are as follows. In the measurement item, the illuminance before and after lighting for 2 hours was measured using an integrating sphere, and the maintenance ratio of the illuminance of the test LED was calculated. The results are not in Table 2. Detailed lighting conditions Light-emitting wavelength: Center light-emitting wavelength, 465nm Drive mode: Constant current mode, 6〇mA (light-emitting element predetermined current is 3〇mA) Three simultaneous lighting in series Drive environment: 85. (:, 85% damp heat machine lighting evaluation: before and after lighting 200 hours, after the illumination and its illuminance maintenance rate, and the color of the wafer * (* If visual evaluation, lighting test is deterioration, then color on the wafer Thus, there is a tendency for the illuminance to decrease sharply.) 75 322150 201120000 Table b2

Example b11 Example bl2 Specific Example b2 Epoxy Resin ~ EM 6.6 6.6 6. 6 Composition Hardener Bb2 10.0 Bb3 10.1 Bb8 10.0 Hardening Catalyst ~Cl ~~ 0.03 0.03 0. 03 Initial Illumination (mW) 8210 8280 7940 LED Illumination after 200 hours of lighting test (min 6280 6670 5710 illuminance maintenance rate (%) 76 81 72 The color 〇〇X of the wafer is confirmed by the above results, in which only R in the above formula (1) is a hydrogen atom The comparative illuminant composition (Bb8) composed of the polycarboxylic acid composition formed by the compound has a poor illuminance maintenance ratio, and is formed from a compound in which R is introduced into the thiol group with respect to the coloration of the wafer. The curable resin composition of the present invention which is composed of the polyvalent decanoic acid composition is excellent in illuminance after the initial illuminance and the lighting test, and has less coloration on the wafer, and can provide a cured product which is resistant to deterioration, and can be manufactured and applied. Ll for industrial use. Examples M3, bl4, bl5, bl6, bl7, comparative examples b3, b4, b5 Hardeners The hardener compositions of the present invention obtained in Examples 6, 7, 8, 9, and 10 were used. (Bb3), (Bb4), (B B5), (Bb6), (Bb7), and hardener compositions obtained in Synthesis Examples b2, b3, and b4 (9), (BblO), (Bbll); epoxy resin (Ep-u) , the sulphur oxide resin (EP-b2) obtained in the synthesis example b6; and a compounding ratio (parts by weight) shown in the following Table 3 using a hardening accelerator (manufactured by Nippon Synthetic Chemical Co., Ltd., HISHI COL IN PX4MP) After defoaming for 20 minutes, a curable resin composition of the invention or comparative use of 322150 76 201120000 was obtained. (Heat resistance test) The hardenability and resin compositions obtained in Examples bl3 to bl7 and Comparative Examples b3 to b5 were carried out. After vacuum defoaming for 20 minutes, it is slowly injected into a glass substrate with a heat-resistant enamel band as a dam. The mold becomes 3 brilliant x2 〇mmx height 1 s. '12' Cx3 hours of preliminary hardening i5 〇 °cxl The casting was hardened to obtain a test piece for a transmittance of 1 mm in thickness. The test piece was used to measure the transmittance before and after 96 hours in an oven placed at 15 ° C by a spectrophotometer (measuring wavelength: 4 〇〇nm), the retention rate of the penetration rate was calculated. The results are shown in Table 3. B3 EXAMPLES Comparative Examples Examples Comparative Example bl3 bl4 bl5 bl6 h3 b4 bl7 b5 Composition Epoxy Resin EP-1 6.6 6.6 6.6 6.6 6.6 6.6 EP-b2 10.9 10.9 Hardener Bb3 10.1 Bb4 8.6 Bb5 9.2 Bb6 10.1 Bb7 9.9 Bb9 9.3 BblO 10.0 Bbll 10.0 Hardening catalyst C2 0. 03 0.03 0.03 0. 03 0.03 0. 03 0.05 0. 05 Thermal endurance test (retention rate retention (%)) 74.6 80.1 80.0 75.0 54.6 47.7 64.0 17.8 From the above results, Since the curable resin composition containing the polyvalent carboxylic acid composition of the present invention has heat deterioration resistance and high maintenance ratio, it can be suitably used for optical applications. In a flask equipped with a stirrer, a reflux condenser and a stirring device, ' 322150 201120000 - while purging with nitrogen, add UP ring hexazone to the anhydride (Η — 菱 菱 菱 化学 化学 ;); Methyl hexanitroic acid needle (manufactured by Nippon Chemical and Chemical Co., Ltd.; Rikacid MH H3M03.2 wound, mercaptoethyl _ 349·9 parts, - while stirring, the temperature is raised to 4 rc, and the pre-addition is added at 30 minutes. Warm to 7 〇. 294·4 parts of tricyclodecanedioxanol, simmered for 30 minutes at 40 C, and then mixed for 4 hours with sputum. The resulting reaction solution was applied to a rotary evaporator at Vision 5 (rc The solvent was removed to obtain 816 parts of the polycarboxylic acid composition (X) of the present invention, and the shape was a colorless solid resin, and the functional group equivalent was 272 g/eq. The softening point of the obtained resin (based on JIS K-7234) was 99.8 °C 'The melt viscosity at 150 ° C is 〇92 pa.s. Melt viscosity measurement in the cone-plate method at 150 ° C. Machine: Cone-plate (ICI) high temperature viscometer (Manufactured by RESEARCH EQUIPMENT (LONDON) LTD.) Cone type: 3 (measurement range 〇 to 2.00 pa.s) The measurement was carried out. Example b From the hardener composition (Bb4) 50 parts, using a rotary evaporator, an excess of methyl hexahydrophthalic anhydride was removed at 1 to 150 ° C (from methyl hexahydrophthalic anhydride not At the time of re-flowing, when the nitrogen gas was directly infiltrated under heating and depressurization for 40 minutes, the acid anhydride was sufficiently removed, and 24 parts of the polycarboxylic acid composition (x2) of the present invention was taken out. The shape was a colorless solid resin. The softening point of the obtained resin (based on JIS K-7234) was 72.4 78 322150 201120000 C, and the melt viscosity at 150 C was 0. ·s. Example c In a flask equipped with a stirrer, a reflux condenser, and a stirring device ' ' While purging with nitrogen, add 1,3, 4-cyclohexanetricarboxylic acid-3,4- anhydride (H-TMAn Mitsubishi Gas Chemical Co., Ltd.; H2) 162 parts, methyl hexahydrogen 787 parts of phthalic anhydride (manufactured by Nippon Chemical and Chemical Co., Ltd.; Rikacid ΜΗ H3), 400 parts of mercaptoethyl ketone, and the temperature was raised to 40 ° C while stirring, and the tricyclic oxime preheated to 70 ° C was added in 30 minutes. 540 parts of alkane dimethanol, stirred at 40 ° C for 30 minutes, and then stirred at 703⁄4 for 4 hours. The reaction liquid was removed by a rotary evaporator at 100 to 150 ° C to obtain 1489 parts of the polycarboxylic acid composition (x3) of the present invention. The shape was a colorless solid resin, and the functional group equivalent was 271 g/eq. The softening point (according to JIS K-7234) is 80.6 ° C, and the melt viscosity at 150 ° C is 〇 43 Pa.s.

Synthesis Example A In a flask equipped with a stirrer, a reflux condenser, and a stirring apparatus, 110 parts of cyclohexenylnonylcyclohexene carboxylate, 140 parts of toluene, and 12-tungsole acid were added while purging with nitrogen. 1 part, 1 part of sodium citrate, 5 parts of disodium hydrogen citrate, 5 parts of trioctyl ammonium acetate 50% diphenylbenzene solution 1. 5 parts, the solution was heated to 45. (:, adding 110 parts by weight of a 35 wt% aqueous solution containing hydrogen peroxide in 20 minutes, and then maintaining it at 45 ± 5. (: and stirring for 1 hour). Next, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 2 parts by weight / 25 parts of aqueous sodium thiosulfate solution, stirred for 3 minutes, and then allowed to stand. Take S' 79 322150 201120000 and separate into two layers of organic layer, where activated carbon is added (Ajinomoto Fine Chemicals) Manufactured; CP2) 5 parts, montmorillonite (10) NIMINE industries (manufactured by NIMINE industries); 5 parts of Kunipia), stirred at room temperature for 3 hours and then filtered. The resulting solution was washed with water 100 times for 3 times, and organically obtained. In order to remove the toluene, 111 parts of the epoxy resin (EP5) containing 3,4-epoxycyclohexyldecyl _3,4-epoxycyclohexyl sulphuric acid vinegar as the main component was obtained. When $ is 130g/eq.. 25. (: viscosity is 211mpa.s (E-type viscometer). Examples a, b, c, d, e, f, g, h, i, j, k, l Epoxy resin (EP2), epoxy resin (Ep5); hardener used hardener composition (Bb3, Bb4, Bb5, χΐ, χ3), anhydride (Η3) '·The hardening accelerator is a four-grade scale salt (C2); the additive is (L1) (M1), a light stabilizer (made by ADEKA; LA-62 is hereinafter referred to as L2); and the phosphorus compound is a trialkyl phosphite. (made by ADEKA; Adekastab 3010 hereinafter referred to as M2), sulphur-based phosphorus: yttrium zinc (manufactured by King Industries Co., Ltd.; XC-9206 hereinafter referred to as M3), which is formulated by the blending ratio (parts by weight) shown in Table A below. After 20 minutes of defoaming, the curable resin composition of the present invention or the comparative product was obtained. The obtained curable resin composition was subjected to the following test. The results are shown in Table A below. (Reflow soldering. LED lighting Test) The curable resin composition obtained in the examples and the comparative example 1 was filled in a graduated cylinder, and this was injected and molded into a surface mount type LED having an outer diameter of 5 mm cube on which a wafer having a central light emission wave of 465 nm was mounted using a precision discharge device. The package (inner diameter 4. 4mm, outer wall height 1.25mm). The casting 80 322150 201120000 was placed in a heating furnace, 12Gt, 1 hour, and then hard-passed in 15th and 3th hours to form an LED package. For the gain ΕΙ) will be before and after reflow The measurement is easily performed using a calender element. (Under the light-shielding, the LED is made to emit light at a current of a predetermined current of 30 mA, and the light is received by the light-receiving element, and the current value flowing therein is used as a scale of illuminance.) The illuminance of the LED immediately after sealing and after the reflow test was measured, and the difference was confirmed. The results are shown in Table A. In addition, the reflow test uses a high-temperature observation device to simulate reflow soldering. The apparatus and conditions are as follows. Device: High temperature observation device (SMT Scope SK-5000; manufactured by Sanyo Seiko Co., Ltd.) Temperature conditions: from 25 ° C to 2 ° C / sec to 150 ° C, then at 150 ° C for 2 minutes, then The temperature was raised to 260 ° C at 2 ° C / sec and maintained at 1 3 3 after 1 。. (: / sec cool to room temperature. 81 322150 201120000 [Table A]

From the above results, it is understood that the hardener composition having the polybasic acid-inhibiting composition of the present invention can maintain illuminance at a high maintenance rate even when exposed to a high temperature at the time of reflow, and has high optical characteristics. [Industrial Applicability] The polyvalent carboxylic acid composition of the present invention is excellent in curing ability of an epoxy resin and can be suitably used as a curing agent for an epoxy resin. Moreover, the polybasic acid-inhibiting composition of the epoxy resin is blended, and the volatilization in the temperature domain generally used for hardening the epoxy resin is extremely small, and the purpose of the cured product can be stably achieved, such as high transparency and heat retention. (for example, resistance to reflow, hand illuminance retention rate in 322150 82 201120000 period lighting, maintenance rate of light transmittance, etc.), so it is extremely useful for LED sealing. [Simple description of the diagram] • Benefits [Description of main component symbols] None s· 83 322150

Claims (1)

201120000 VII. Patent application scope: 1. A polycarboxylic acid composition containing a polycarboxylic acid represented by the following formula (1), HO Wherein R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a carboxyl group; and P represents a divalent crosslinking group as defined in the following (a) or (b): (a) is a carbon number 6 a linkage of a chain alkyl chain to a branch of 2〇, and the chain alkyl chain has a linear main chain of 3 to 12 carbon atoms and 2 to 4 side chains, and the side chain At least the carbon number is 2 to 10, ?) can have a methyl group on the ring from the day of the day (four) ring of fifteen burnt methanol, at least the cross-linked polycyclic V8, Yiyi-I^ Cloud de-crosslinking cross-linking, but when p is (6), "representing hydrogen source i, if applying for special materials, reading the sputum, its application 2 f shell cross-linking system is defined by (a) eight exchange flat joints, And any one of the two valence groups represented by the following formula (al) defined by (a), my formula (al): 322150 84 201120000 In the formula, the * mark at the end of each group indicates the oxygen atom adjacent to the bond at the wood mark. 3. The polycarboxylic acid composition according to claim 1, wherein the main chain in the cross-linking group of (a) is a linear chain having 3 to 6 carbon atoms, and at least 2 of the side chains are carbon atoms. 2 to 4 alkyl groups. 4. The polycarboxylic acid composition according to claim 2, wherein the crosslinking group defined by (a) is removed from 2, 4-diethyl-1, 5-pentanediol. A divalent group after a hydroxyl group. 5. The polycarboxylic acid composition according to claim 1, wherein the cross-linking group of the divalent cross-linking group (b) is defined, and the cross-linking group defined by (b) is as follows Any one of the divalent groups represented by the formula (bl), and the formula (bl): 85 322150 201120000 wherein, a plurality of R2 present in each structural formula independently represent a hydrogen atom or a sulfhydryl group. 6. The polycarboxylic acid composition as described in claim 5, which is composed of a polycarboxylic acid wherein R2 is a hydrogen atom. 7. The polycarboxylic acid composition as described in claim 5, wherein the polycarboxylic acid having a methyl group and/or a carboxyl group in which R of the formula (1) is 5 mol% or more is contained. 8. The polybasic acid-reducing composition as described in claim 1, wherein R is a methyl group or a carboxyl group. 9. The polycarboxylic acid composition according to claim 8 of the patent application, wherein The group other than the hydrogen atom is a methyl group. The polycarboxylic acid composition according to claim 1, wherein the oxime acid composition comprises at least the polybasic acid represented by the formula (1). A polycarboxylic acid composition as described in claim 10, wherein the methyl group is substituted by a methyl group, and the C4 to C? ring is substituted with a methyl group. C? ring two, three or four slow acid anhydride, methyl substituted cyclohexane di or tricarboxylic anhydride. 12 · a kind of hardener for epoxy resin, containing the formula 1 (1) And a polycarboxylic acid composition as described in claim 1 of the invention. 13) A hardener for an epoxy resin according to the scope of claim 2, wherein: 1) The divalent cross-linking group represented by P is a cross-linking group defined by (a) and the cross-linking group defined by (a) is a valence group of the following (1) Element S6 322150 201120000 A carboxylic acid, an acid anhydride of at least one selected from the group consisting of the acid anhydrides of the following (2), a polycarboxylic acid composition, (1) a valence group: from 2, 4- Diethyl-1,5-pentanediol is a divalent group after removing two hydroxyl groups; (2) Anhydride: methylhexahydrophthalic anhydride, and cyclohexane-1,2,4-tris-acid-1, A sclerosing agent for an epoxy resin according to claim 12, wherein the divalent crosslinking group represented by P of the formula (1) is crosslinked by the definition of (b) The cross-linking group defined by the formula (b) is a polyvalent carboxylic acid of any one of the divalent groups represented by the following formula (1) (b), and an acid anhydride selected from the following (2) At least one acid anhydride in the group, the polycarboxylic acid composition formed, (1) Formula (bl): Wherein a plurality of R2 present in each structural formula independently represent a hydrogen atom or a hydrazine group; (2) an acid anhydride: 87 322150 201120000 methyl hexahydrophthalic anhydride, and cyclohexane-1,2,4-tricarboxylic acid -1,2- Anhydride. 15·=The type of the curable resin composition is a sulphuric acid resin composition as described in the U.S. Patent Application No. U. 16. The curable resin composition according to claim 15, wherein the epoxy resin is an epoxy ring epoxy resin. 17. The curable resin composition according to claim 16, wherein the hardener composition is a hardener composition for an epoxy resin according to claim 13 of the patent application. 18. The curable resin composition according to claim 16, wherein the hardener composition is a hardener composition for an epoxy resin according to claim 14. A cured product obtained by hardening a curable resin composition according to claim 15 of the patent application. 20. The method for producing a multi-repulsive acid represented by the formula (1) described in the first application of the patent application, wherein the following (a) or (1)) > ' (a) is a chain aliphatic diol having a branched structure of 6 to 20 carbon atoms, and the chain alkyl chain has a primary bond of 2 to 12 carbon atoms and 2 to 4 side chains, and At least one of the side chains is a hospital base having a % of 2 to 10, or (8) is a cross-linking of at least one selected from the group consisting of tricyclic fluorene dimethanol or pentacyclopentadecane dimethanol having a methyl group on the ring. The poly-polyol monool (c) is at least one selected from the group consisting of hexahydrotetrahydroanhydride, methylhexahydroindole (10), and 322150 88 201120000 cyclohexane-1,2,4-tricarboxylic anhydride. One type of acid anhydride, if it is (b), is an acid anhydride containing at least one of methylhexahydrophthalic anhydride or cyclohexane-1,2,4-tricarboxylic anhydride. 21. The method for producing a polycarboxylic acid composition according to claim 20, wherein the diol of (a) or (b) and the anhydride of (c) are one equivalent of 1 equivalent to the acid anhydride group. The hydroxyl equivalent of the primary alcohol is in a ratio of 0.001 to 2 equivalents, and is reacted at a reaction temperature of 40 to 150 °C. The method for producing a polycarboxylic acid composition according to claim 21, wherein the acid anhydride of (c) is a mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride. 23. The process for producing a polycarboxylic acid composition according to claim 21, wherein the diol is 2,4-diethyl-1,5-pentanediol or 2-ethyl-2- Butyl-1, 3-propanediol. 24. The method for producing a polycarboxylic acid composition according to claim 21, which comprises 2,4-diethyl-1,5-pentanediol, hexahydrophthalic anhydride and mercaptohexahydrogen A mixture of phthalic anhydride is reacted. 25. The method for producing a polycarboxylic acid composition according to claim 21, which is an unsubstituted tricyclodecane decyl alcohol or pentacyclopentadecane dimethanol, and a hexahydro ugly acid liver and A mixture of methyl hexahydro sulphate needles is reacted. 26. A polycarboxylic acid represented by the following formula (1), formula (1) 89 322150 201120000 Η R ^ R each independently represents a hydrogen atom, a calcining group or a mercapto group having 1 to 6 carbon atoms, and P represents a divalent cross-linking group defined by the following (4) or (8): a group F having a branch structure of & 6 to 2G a chain-like chain of a chain-like chain, and the chain-like alkyl chain has a main chain of 3 to 12 carbon atoms and 2 1 4 side chains, and at least one of the side chains has a carbon number of 2 To (1), after removing two hydroxyl groups from at least one crosslinked polycyclic diol selected from the group consisting of tricyclic casket dimethanol or pentane dimethanol, having a methyl group on the ring A divalent cross-linking group, wherein when p is (b), R represents a group other than a hydrogen atom. The polycarboxylic acid according to claim 26, wherein p is a divalent crosslinking group defined by (a), and at least two of the side chains are a crosslinking group having a carbon number of 2 to 10. 28. The polycarboxylic acid according to claim 27, wherein the divalent crosslinking group defined by (a) is removed from 2,4-diethyl-1,5-pentanediol by two The alkyl group after the hydroxyl group. 29. The polycarboxylic acid of claim 26, wherein p is a divalent crosslinking group as defined in (b). The polycarboxylic acid according to claim 26, wherein R in the formula (1) is a methyl group or a carboxyl group. 90 322150 201120000 IV. Designated representative map: There is no schema in this case (1) The representative representative figure in this case is: (). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: HQ (1) 4 322150