TW201245288A - Polycarboxylic acid resin and composition thereof - Google Patents

Abstract

A polycarboxylic acid composition containing a polycarboxylic acid resin having a siloxane structure of exceptional heat stability and an organic backbone imparting a cured product with exceptional strength. The polycarboxylic acid composition provides a resin composition that is useful for electrical and electronic materials, molding materials, casting materials, laminate materials, coatings, adhesives, resists, and a broad range of other applications; and, in particular, is extremely useful as a material where optical properties and properties of close adhesion to machinery are required; e.g., adhesives and sealing materials for optical semiconductors (LED products and the like). This polycarboxylic acid composition contains an epoxy resin and a polycarboxylic acid resin having a siloxane structure and an organic backbone.

Description

201245288 VI. Description of the Invention: [Technical Field] The present invention relates to a variety of materials for use in an optical semiconductor, and a polyacid resin suitable for use in electrical and electronic materials, and a polybasic composition thereof, particularly a carboxylic acid composition. 】 1==2: to obtain = followed by - mechanical specialties, so τ Μ electrical properties and other excellent hard materials ... agents, composite materials, molding materials, washing town '氡: kinds of coating materials, anti-surge agents, etc. Used in a wide range of fields. As the curing agent used in the oxygen (4), it is usually, for example, a compound, a few acid, an aged compound, a thiol compound or the like. : "In the case of the use of a transparent or heat-resistant one-month shape or a moderate service life for a hardened material, most of the use of various thin acid compounds or carboxylic anhydrides, especially liquid compositions In the above, the liquid m acid is usually used as the hardener m (d). The strong hydrogen bond between the molecules of the compound (m) not only causes crystallization & but also has poor compatibility with other resins, so the actual situation is to avoid its use. As a resin for sealing light j-conductors such as LEDs (Light Emitting Diodes), bisphenol type epoxy resin and alicyclic epoxy resin are used for direct application in terms of mechanical strength and adhesion. A liquid epoxy resin composition such as a resin (see Patent Document 1). In recent years, it has been gradually used in the field of high brightness required for automotive headlamps or lighting applications. As a result, the resin for sealing optical semiconductor elements is required to be particularly resistant to 201245288 uv. It is difficult to say that the bisphenol type epoxy resin or the fat type epoxy resin as described above is JL, and the temple has sufficient UV resistance and heat resistance, and sometimes it cannot be used for requirements. Highlight the Af Destinator m τ 7 in. Therefore, as a sealing material having a high resistance to enthalpy, heat, etc., a polychlorinated resin sealing material using an organic polysulfide-containing oxygen-containing oxygen-containing compound and an organic hydrogen-concentrating compound has been used. (Refer to Patent Document 2). However, the sealing material made of such a polysulfide resin is excellent in UV resistance and heat resistance, but has a problem that the adhesion to the substrate is low or the sealing surface is sticky. In order to solve the above problems, the use of a condensate of an epoxy group-containing compound and a liquid acid-salt liver promotes the development of a sealing material which is excellent in f UV properties and heat resistance and has good adhesion (see Patent Document 3). Patent Document 4). As a carboxylic acid anhydride used in such a use, hexahydrophthalic acid anhydride and methyl hexahydroortholine are used for reasons such as colorless and transparent, 2 liquid at room temperature, and easy handling. Phthalic anhydride, tetrahydrophthalic anhydride, : tetrahydrophthalic anhydride, 'degraded carboxylate such as alkane 2,3-dicarboxylic anhydride, methylnorbornane- 2,3-dicarboxylic anhydride Anhydride or a mixture of these. However, such acid-cracking needles are mostly low molecular weight compounds. Therefore, in the epoxy resin composition in which the tarenic anhydride is used as a curing agent, volatilization of phthalic anhydride during thermal curing becomes a problem. The volatilization of the carboxylic anhydride is not only caused by the hardening reaction, but also the problem of poor curing of the epoxy resin composition due to the absence of the necessary amount of the carboxylic anhydride (hardener), and the adverse effects on the human body due to its harmfulness. 'The pollution of the production line, and then the air pollution, has a greater impact on the environment. Therefore, for the low volatility, a liquid polyoxyl skeleton 201245288 $ acid compound was studied at room temperature. However, since the strength of the cured product which can be tolerated is not exhibited, there is a problem that cracks occur when used as a photo-semiconductor sealing material (see Patent Document 5). Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Document 5: International Publication No. 1/〇71168 [Invention] The object of the present invention is to provide a liquid at room temperature, which is less volatile at high temperatures, especially as a hardener for epoxy resins. When the volatility in the hardening step is small, a cured product (colorless and transparent), a cured product excellent in hardenability, and a polycarboxylic acid resin excellent in mechanical strength of the cured product can be provided. In view of the facts as described above, the inventors of the present invention found that by using "a polyoxo compound having a specific skeleton, a polyoxo compound having two or more hydroxyl groups in the molecule, and two molecules in the molecule" The above-mentioned problem can be solved by the above-mentioned problem that the above-mentioned problem is solved by the above-mentioned problem that the compound of the above-mentioned tarenic acid anhydride-based compound and, if necessary, a compound having an acid anhydride group in the molecule, is reacted as a hardener of an epoxy resin, thereby completing the present invention. . That is, the present invention relates to a polyvalent tick acid resin (4) which is obtained by modifying the two terminal sterols represented by the following formula (1) into a polyoxyxanic oil (a), and having a plurality of hydroxy groups in the early knives. The alcohol compound (e) and the intramolecular compound have two or more carboxylic acid anhydride groups (1) 201245288 (C) obtained by an addition reaction,

(In the formula (1), I independently represents a carbon number! 〜1〇 of an alkylene group or a number of 1 to 1G of a sub-house group containing an ether bond, and R2 each independently represents a methyl group or a stupid group, and η is an average value A multi-dimensional acid-reducing resin (A) is represented by the following formula (1): a terminal methanol-modified polysulfuric acid (1), and two or more molecules in the molecule: The polyol compound (e), the compound (c) having two or more carboxylic anhydride groups in the molecule, and the compound (d) having one carboxylic anhydride group in the molecule are obtained by an addition reaction.

R2 / HO - Rj - Si + 〇 - a sub-alkyl group or a methyl group or (in the formula (1), R1 independently represents an alkylene group having an ether number of 1 to 10 carbon atoms 1 to 10, and R 2 respectively The independent stupid base 'n is represented by an average value of 1 to 100); the polycarboxylic acid resin (Α) of (1) or (2), wherein the intramolecular 201245288 has two or more transbasic polyol compounds (e) The terminal alcohol polyester compound (b); (4) The polycarboxylic acid resin (a) according to (3), wherein the terminal alcohol polyester compound (b) is represented by the formula (2),

(In the formula (2), R3 and R_4 each independently represent a carbon number of 1 to a calcining group 'm represents an average value of 1 to 1 〇〇); (5) a polycarboxylic acid such as (1) or (2) a resin (a) wherein the polyol compound (e) having two or more via groups in the molecule is a hydrocarbon polyol compound (Ο; a polybasic acid resin (A) according to any one of (1) to (5) The compound (1) having two or more carboxylic acid heganes in the sub-group is one or more selected from the group consisting of the following 彡(3) to (5), 201245288

The polycarboxylic acid resin (A) according to any one of (2) to (6), wherein the compound (d) having a carboxylic anhydride group in the molecule is selected from the group consisting of the formulae (6) to (10). More than one,

A polyvalent carboxylic acid composition comprising the polycarboxylic acid resin (A) according to any one of (1) to (7), and an epoxy resin (B); 201245288 (9) a hardened material 'system (8) The polycarboxylic acid composition is hardened; (10) A light-emitting diode having the cured product of (9). According to the present invention, the multi-repulsive resin having the structure of the poly-stone compound is liquid, so that the operation is relatively easy, and a cured product excellent in heat resistance, hardness, transparency, and light resistance can be obtained, and thus the multi-rebel of the present invention is contained. The polycarboxylic acid composition of the acid resin is useful in a wide range of applications such as electrical/electronic materials, molding materials, casting materials, laminate materials, coatings, (4) agents, resists, and the like, especially as a material having necessary optical properties. For example, it is extremely useful as an adhesive material or a sealing material for an optical semiconductor (such as an LED product). [Embodiment] The polycarboxylic acid resin (A) of the present invention is a resin obtained by modifying a two-terminal sterol to a poly-molecular oil (a) and having two or more thiol compounds in the molecule ( e), and a compound having two or more carboxylic anhydride groups in the molecule (Ο (and optionally a compound having a slow acid liver group in the molecule) (obtained by an addition reaction of Sichuan, having a polywei structure in the molecule) The polyoxane composed of Si 〇 bond is the main skeleton) " ^ Γ / Γ Fucheng's organic skeleton ' the same - there are two domains in the molecule (the silk of the present invention, the polycarboxylic acid resin can be made by a two-terminal methanol-modified polyoxo-oxygen oil (an alcoholic sulfhydryl group of a polyol compound (7) having two or more hydroxyl groups in the molecule and a compound having two or more carbonyl groups in the molecule (〇) (and optionally The carboxylic acid group having a carboxylic anhydride group-containing compound (d)) is subjected to an addition reaction, and an addition reaction is carried out by reacting a compound (c) having two or more 201245288 carboxylic anhydride groups in the molecule. Two-end methanol modified polyoxygenated oil (a) And/or a polyol compound having two or more hydroxyl groups in the molecule (e), and/or a two-terminal sterol-modified polyoxyl oil (a) and a polyol compound having two or more hydroxyl groups in the molecule (e) Polymerization to the same molecule>> The following two-terminal methanol-modified polyoxo oil (a) which is a raw material of the polycarboxylic acid resin (A), a polyol compound (e) having two or more hydroxyl groups in the molecule, and intramolecular The compound (c) having two or more carboxylic anhydride groups and the compound (d) having one carboxylic acid anhydride group in the molecule will be described. First, the two-terminal sterol-modified polyoxygenated oil (a) will be described. The methanol-modified polyanthracene oil (a) is a polyfluorene oxide compound having an alcoholic hydroxyl group at both terminals represented by the following formula (1).

(In the formula (1), R each independently represents an alkylene group having 1 to 10 carbon atoms or an alkylene group having an ether bond having 1 to 10 carbon atoms, and R2 each independently represents a mercapto group or a phenyl group, and η is an average value. In the formula (1), specific examples of R include a methylene group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. a straight-chain alkylene group having a carbon number of 1 to 10, such as an alkylene group having a carbon number of 1 to 10, such as an isopropyl group, an isobutyl group or an isoamyl group, and an alkylene group having a carbon number of 1 to 10; Base, 201245288 propoxyethyl, propoxypropyl, ethoxypropyl, etc. may be represented by the following formula (11) - r5 - Ο - r5 - (Π) (in the above formula (11), Rs are independent An alkylene group having a carbon number of 1 to 5 and an alkylene group having an ether bond of 1 to 1 carbon atoms. Among them, preferred are propoxyethyl and ethoxypropyl. The specific example of Rz represents a mercapto group or a phenyl group, which may be the same or different. However, in order to make the polyvalent carboxylic acid resin (A) liquid at room temperature, it is more desirable than phenyl. base. In the formula (1), η is an average value, preferably 2 to 8 Å, more preferably 5 to 30. The both-terminal sterol-modified polyoxyxane oil (a) represented by the formula (1) may, for example, be a polyoxo-based compound # having an alcoholic group at both terminals. Specific examples thereof include x_22_16〇AS, KF_, (9)2, and KF_3 (both manufactured by Shin-Etsu Chemical Co., Ltd.) as a two-terminal sterol-modified polyoxygenated oil; ΒΥ16-2()1, Βγι Bu (9) 4, 8 difficult 7 (both TORAY. D0WC0RNING Co., Ltd.); Muscle 2 — B0970, XF42 — C3294 (all · 0inentive Performance

Materials Japan Co., Ltd. manufactures 箄 ) ) Temples are available from the market. These two kinds of ends may be used in combination with one or two or more kinds of alcoholic bases. Among these, it is better to go to the X-22-16〇AS kf6〇〇b 201245288 KF6002, ΒΥ16~· 201 or XF42-B0970. It is a human, and a polyol compound (e) having two or more radicals in the molecule is explained. Examples of the polyol compound (e) having two or more hydroxyl groups in the molecule include a terminal alcohol polyester compound (b), a hydrocarbon polyol compound (f), and a terminal alcohol polycarbonate compound. The terminal alcohol polyester compound (b)' is not particularly limited, and examples thereof include a polyester compound having a hydroxyl group at the terminal represented by the following formula (2).

(In the formula (2), I and I each independently represent an alkylene group having a carbon number of ι to 1 ', and m is represented by an average value of ι 〜1 〇〇). In the formula (2), as a specific example of & Listed: a straight-chain alkylene group having a carbon number i to 10, such as an ethyl group, a propyl group, a butyl group, a pentyl group, a decyl group, a heptyl group, a decyl group, and an exo isopropyl group. a branched alkylene group, a cyclopentane dimethylene group, a cyclohexane group, a propyl group, an isobutyl group, an isoamyl group, a neopentyl group, a diethylamyl group, and the like. An alkylene group having a cyclic structure such as a methylene group. Among them, a branched alkylene group having a carbon number or an alkylene group having a cyclic structure is preferred, and from the viewpoint of heat-resistant transparency of the cured product, ethyl butyl propyl group and exo- butyl butyl group are particularly preferred. Base: neopentyl, diethyl pentyl, cyclohexane dimethylene. δ 12 201245288 In the formula (2), as a specific example of I, carbon numbers such as an exoethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptane group, and an octyl group are exemplified. a linear alkylene group having a carbon number of isopropyl group, ethyl butyl propyl group, isobutyl group, isoamyl group, neopentyl group, diethyl pentyl group, etc. An alkylene group having a cyclic structure such as an alkylene group, a cyclopentane dimethylene group or a cyclohexane dimethylene group. Among them, a direct bond of a carbon number of 1 to 1 Å is preferred. From the viewpoint of adhesion between the cured product and the substrate, it is preferably a propyl group, a butyl group, a pentyl group or a hexyl group. In the formula (2), m is 1 to 1 Torr, preferably 2 to 4 Å, more preferably 3 to 3 0. The weight average molecular weight (Mw) of the terminal alcohol polyester compound (b) is preferably from 500 to 20,000, more preferably from 500 to 5,000, still more preferably from 500 to 3,000. When the weight average molecular weight is 5 Å or more, the hardness of the cured product of the polyvalent carboxylic acid composition is not excessively increased, and there is no concern that cracks occur in the heat cycle test or the like. Further, when the weight average molecular weight is 20,000 or less, it is preferable that there is no concern that the cured product is too thick. In the present invention, the weight average molecular weight is a weight average molecular weight (Mw) calculated by polystyrene conversion based on a value measured under the following conditions using GPC (Gel Perme® Chromatography). Various conditions of GPC Manufacturer: Shimadzu Manufacturing Column: Protection column SHODEX GPC LF- G LF- 804 (3) Flow rate: 1.0 ml / min.

Column temperature: 40 °C 201245288 Solvent: THF (tetrahydrofuran, tetrahydrofuran) Detector: RI (differential refractive index detector) The terminal alcohol polyester compound represented by formula (2) (b) Examples thereof include polyester polyols having an alcoholic hydroxyl group at the terminal. Specific examples thereof include KYOWAPOL 1000PA, KYOWAPOL 2000PA, KYOWAPOL 3000PA, and KYOWAPOL 2000BA (all manufactured by Xiehe Yeast Chemical Co., Ltd.) as a polyester polyol; Adeka New Ace Y9-10, Adeka New Ace YT-101 (all manufactured by ADEKA Co., Ltd.); PLACCEL 220EB, PLACCEL 220EC (all manufactured by Daicel Chemical Industry Co., Ltd.); Polylite OD - X - 286, Polylite OD-X-102, Polylite OD-X-355, Polylite OD —X - 2330, Polylite OD - X — 240, Polylite OD - X - 668, Polylite OD-X-2554, Polylite OD — X - 2108, Polylite OD -X - 23 76, Polylite OD - X - 2044, Polylite OD - X- 68 8, Polylite OD - X - 2068 ' Polylite OD - X - 2547, Polylite OD -X - 2420, Polylite OD - X-2523, Polylite OD-X-2555 (all manufactured by DIC Corporation); HS2H-201AP, HS2H-351A, HS2H-451A, HS2H-851A, HS2N-221A, HS2N-521A, HS2H-220S, HS2N-220S, HS2N-226P, HS2B-222A, HOKOKUOL HT-110, HOKOKUOL HT-210, HOKOKUOL HT- 12, HOKOKUOL HT - 250, HOKOKUOL HT — 310, HOKOKUOL HT — 4 0M (all manufactured by Fengguo Oil Co., Ltd.), etc., are available from the market. These polyester polyols can be used in one type or in combination of two or more types. Among these, K.YOWAPOL 1000ΡΑ, Adeka New Ace Y9-10, HS2N — 221 A are preferable. Next, the hydrocarbon polyol compound (f) will be described. The hydrocarbon polyol compound (f) is a hydrocarbon compound having two or more hydroxyl groups in the molecule, and examples thereof include ethylene glycol, propylene glycol, propanediol, butanediol, dimethyl alcohol, and pentane. Glycol, neopentyl glycol, hexanediol, dimercapto butanediol, heptanediol, dimethyl pentanediol, diethyl propylene glycol, octanediol, dimethyl hexanediol, diethyl butyl Glycol, decanediol, dimercaptoheptanediol, diethyl pentanediol, decanediol, dinonyl octyl alcohol, monoethyl hexane diol, ethyl butyl propylene glycol, 3- fluorenyl _ ι,5 a chain hydrocarbon polyol compound such as pentanediol, diglycerin or dipentaerythritol, or cyclopentanediol, cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, A cyclic hydrocarbon polyol compound such as a bicyclononanediol, a tricyclodecane dioxitol, a norbornanediol, or a decyl alcohol. These hydrocarbon polyol compounds (f) may be used alone or in combination of two or more. Among these, from the viewpoint of the strength of the cured product and the transparency of the cured product, propylene glycol (Propylene giyc®), decanediol, and diethyl glutarate tricyclodecane decyl alcohol are preferable. Next, the terminal alcohol polycarbonate compound will be described. The term "detailed alcohol polycarbonate compound" is not particularly limited, and examples thereof include a compound of the following formula f0t_I, which has a via-based polycarbonate. 15 201245288

(In the formula (12), R0 represents an alkylene group having a carbon number of 1 to 〇, and p represents an average value of 1 to 100. In the formula (12), specific examples of R6 include a methylene group and a stretching group. Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and the like, a linear alkylene group having a carbon number of from 1 to 10, an extended isopropyl group, an ethyl butyl propyl group, a branched alkylene group having a carbon number of from 1 to 10, such as isobutyl, isoamyl, neopentyl, diethylhexyl, cyclopentane dimethylene, cyclohexane dimethylene An alkylene group having a cyclic structure. Among them, the viscosity of the terminal alcohol polycarbonate compound is not too high, and from the viewpoint of workability, a linear chain of 4 to 7 carbon atoms such as a butyl group, a pentyl group, a hexyl group, and a heptyl group is preferred. alkyl. The plurality of Res present in the formula (12) may be the same or different. In the formula (12), p is 1 to 1 Torr in terms of an average value, preferably 2 to 4 Å, more preferably 3 to 30 Å. The weight average molecular weight (Mw) of the terminal alcohol polycarbonate compound is preferably from _~2_〇', more preferably to the side, and more preferably to 〜3. ^When the weight average molecular weight is more than or equal to the above, the hardening hardness of the multi-dimensional acid-reducing composition is not excessively high, and there is no concern that cracks occur in the heat cycle test or the like, which is preferable. X, if the weight average molecular weight is 2 〇〇〇〇 or less, then 201245288 produces a hardened 'dry x mad. In the Yu et al., the weight average molecular system indicates the value (Mw) determined by polystyrene conversion based on the value measured by GPC (gel permeation chromatography) in a quantity. Sub-quantity GPC various conditions Manufacturer: Shimadzu Manufacturing Co., Ltd. Pipe column: Protection column SHODEXGPCLF-GLF~8()4 Flow rate: 1.0 m 1 / m i η.

Column temperature: 40 ° C Solvent: THF (tetrahydrofuran) Detector: RI (differential refractive index detector) One or more kinds of polyol compounds (e) η having two or more hydroxyl groups in the molecule are used in combination of two or more kinds. The amount of the polyol compound (e) having two or more hydroxyl groups in the molecule is not particularly limited 'relative to the two-terminal methanol-modified polycondensation tongue θ eight (a) 1 〇〇 1 injury, preferably 0.5 〜 200 parts by weight, more preferably 5 to 5 Å, *: 5% by weight, still more preferably 10 to 30 parts by weight. If it is 55 parts by weight, the mechanical strength of the cured product is further improved. Therefore, if it is 2 parts by weight of r, the heat-resistant transparency of the cured product is further improved, or the obtained multi-dimensional resin resin is obtained. The viscosity of (A) becomes more suitable and therefore preferred. Further, a compound (e) having two or more carboxylic anhydride groups in the molecule will be described. The compound (c) having two or more carboxylic anhydride groups in the molecule may, for example, be 1,2,3,4-butanetetracarboxylic dianhydride, cyclobutanetetracarboxylic acid 269, 201245288 anhydride, 1,2,3, 4 cyclopentane tetracarboxylic acid dianhydride, i, 2,4,5-cyclohexane tetracarboxylic dianhydride, pyrogallic anhydride, 5-(2,5-dioxotetrahydrofuranyl)- 3~methyl-3-ring Hexene-1,2-diacetic anhydride, 4_(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-L2-dicarboxylic anhydride, and the like. Further, when the number of the carboxylic anhydride groups in the same molecule of the compound (c) is two, the viscosity of the polyvalent carboxylic acid resin (A) is not excessively increased, so that it is preferable from the viewpoint of viscosity control. The compound (C) having two or more carboxylic acid anhydride groups in the molecule may be used alone or in combination of two or more. In particular, it is preferable that the cured product obtained by curing the polyvalent carboxylic acid resin (A) and the polyvalent carboxylic acid composition of the epoxy resin (B) described below is excellent in heat resistance (heat-resistant transparency, etc.). '3,4 Dingyuan tetracarboxylic acid-hepatic, 1,2,4,5-cyclohexanin tetracarboxylic acid di-hepatic, 4-(2,5-dioxotetrahydrofuranyl-3-yl)- 1,2,3, 4-tetrahydronaphthalene-U-diphthalic anhydride, particularly preferably 1,2,3,4-butane tetracarboxylic dianhydride. Next, a compound (d) having a carboxylic anhydride group in the molecule will be described. The compound (d) having a carboxylic anhydride group in the molecule may, for example, be succinic anhydride, mercapto succinic anhydride, ethyl succinic anhydride, 2,3-butane dicarboxylic anhydride, 2,4-pentane dicarboxylic anhydride, 3,5_heptane dicarboxylic acid field and other saturated aliphatic carboxylic acid wild, cis-butyl diacid needle, 12-yard succinic acid field and other unsaturated aliphatic phthalic anhydride, hexahydrophthalic anhydride, methyl Hexahydrophthalic anhydride, D-cyclohexanedicarboxylic acid Xuan, lowering the hospital - 2,3-dicarboxylic acid, methyl-reduced _ 2,3-dicarboxylic acid wild, naic acid (nadicacid) Methyl-resistant acid liver, bicyclo[2,2,2]octane-2'3-dicarboxylic anhydride' ...~cyclohexane tri-indoline _ 201245288 base four: o-saturated aliphatic carboxylic anhydride, tetrahydrogen Phthalic anhydride, phthalic anhydride, ceric anhydride, methyl methicillin, 4,5-diindole-4-cyclo _2,3-diene- 1,2-dicarboxylic anhydride, Bicyclo[2.2.2]-5-octene's cyclic unsaturated unsaturated aliphatic phthalic anhydride such as formic acid, phthalic acid: sulphuric acid, phthalic acid, benzenetricarboxylic anhydride, etc. Wait. The compound (d) having a few acid anhydride groups in it can be used in one type or in two parts. In particular, it is preferred that the hardened material containing the polybasic acid-reducing resin (A) and the poly-m-acid composition of the first (B) is cured to have excellent transparency (resistance: transparency, etc.), preferably hexahydrogen. Dimethylhexahydrophthalic acid phthalate, tetrahydrophthalic anhydride, norbornane-2,3-dicarboxylic acid, methylnorzidine-2,3-dicarboxylic acid liver,... ― Cyclohexane tricarboxylic acid is called '2-anhydride. Here, more preferred are methylhexahydrophthalic anhydride and 1,2,4-cyclohexanetricarboxylic acid-dicarboxylic anhydride. #幻圭 is a compound having a carboxylic acid anhydride group in the molecule of methylhexahydroorthophenone. The amount of the compound (4) is particularly limited, and is relative to the compound having two acid-hepatic groups in the molecule (c) It is preferably 5 to 1,500 parts by weight, more preferably 5 parts by weight, and still more preferably 100 to 8 parts by weight. When it is 5 parts by weight or more, it is possible to suppress excessive polymerization of the polyvalent carboxylic acid resin (A), and it is preferable that the adhesiveness is not excessively increased, and workability is further improved. The mechanical strength of the cured product becomes good, so it is preferable. A wide range: a balance between the viscosity of the carboxylic acid resin (A) and the mechanical strength of the cured product: In particular, it is preferably 150 to 700 parts by weight. 19 201245288 As for the two-terminal f-alcohol-modified polywei oil (a), a polyol compound having two or more radicals in the molecule (e), a compound having two acid-based needle groups (C) in the molecule, and intramolecular The compound (d) having a carboxylic anhydride group is used in an amount of a total alcoholicity relative to the two-terminal methanol-modified polysulfuric acid (a) and the polyol compound (e) having two or more (d) in the molecule. The base (i), the compound (c) having two or more acid groups in the molecule, and the compound (d) having a (tetra) anhydride group in the molecule are preferably 〇5 to 2. 〇 equivalent, more Good is 0.8~1> 5 equivalents. When the amount of the cerium is 5 equivalents or more, the mechanical strength of the cured product becomes good. Therefore, if it is 2 eq. or less, the (4) Sf group does not remain much, and the stability of the material becomes good, which is preferable. The polybasic acid-reducing resin (A) of the present invention can be produced by adding the above-mentioned two-terminal methanol-modified polyoxoic acid (a), a polyolized content having two or more hydroxyl groups in the molecule (〇, two in the molecule) The compound (1) of the above acid group is reacted and reacted, and the age # or It is preferably added to further add the compound (d) having a carboxylic acid anhydride group in the molecule. Here, the addition of the component (d) suppresses an excessive increase in the molecular weight f of the plural resin (A), and therefore is preferable from the viewpoint of reaction control. In this case, the above respective compounds may be simultaneously mixed and added to cause a reaction, and each of the above compounds may be added in the order of 4 to cause a reaction. The production of the polybasic acid resin (A) of the present invention can be carried out in a solvent or in the absence of a solvent. The solvent is a compound having two or more phthalic anhydride groups, which are not modified with the two-end methanol, or a polyhydric alcohol compound having two or more radicals in the molecule. Intramolecular 201245288 A solvent having a reaction of the acid-containing needle group (4) can be used without particular limitation. The solvent which can be used is, for example, dimethylamine, m(tetra), dimethyl A gauge, tetrahydroanthracene, acetonitrile aprotic polar solvent such as methyl ethylamine, cyclopentanone, methyl isobutyl steel, such as toluene, xylene aromatic hydrocarbons, etc. Among them, aromatic hydrocarbons or ketones are preferred. These solvents may be used alone or in combination of two or more. The use of t in the case of using a solvent is based on the modification of both ends of the methanol. Oil "), a compound having two or more radicals in the molecule (1), a compound having two or more carboxylic acid hepato groups in the molecule (c), and a compound having a reductive hepatic group in the molecule (4) It is preferably 〇5 to 30 〇 by weight. Here, from the viewpoint of ease of manufacture, it is preferably produced without a solvent. The polybasic carboxylic acid resin (A) of the present invention can be produced without a catalyst, and a catalyst can be used to produce 4 a catalyst. The catalysts that can be used include H sulfuric acid, methyl acid, and trigas. Acidic compounds such as acid, p-toluene acid, nitric acid, trifluoroacetic acid, tri-acetic acid, metal hydroxides such as sodium argon oxide, potassium hydroxide, magnesium hydroxide, triethylamine, tripropylamine, An amine compound such as tributylamine, ... dimethylamino group. Than bite, 1, = diazabicyclo [5.4.0] ten _ — 7 — lean " m. Sitting, sitting three times, four. Wait for the heterocyclic compound 'tetramethylammonium hydroxide, tetraethylammonium hydroxide, hydrogen hydroxide, tetrapropylammonium, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, hydrogen emulsified dimercaptopropyl Kesui, trimethylbutyl sulphate, trimethyl succinate 21 201245288 hexadecanoyl, trioctylmethyl hydride, gasified tetramethyl, desertified tetramethylammonium, iodide Tetramethylammonium, tetramethylammonium acetate, tetraoctylmethyl sulphate and other four (10) salts, tetrabasic acid tetrazide, positive (tetra) tetramethyl glucosyl-like phthalic acid, zinc octoate, zinc octoate Metal soaps such as manganese octoate, calcium octoate, sodium octanoate and potassium octoate. When the catalyst is used, it may be used in a mixture of two or more types. The amount of use in the case of using a catalyst is based on a methanol-modified poly(oxygenated oil) at both ends (a), a polyol compound having two or more radicals in the molecule (e), and two or more carboxy groups in the molecule. The acid anhydride group-containing compound (c) and the compound (d) having one carboxylic acid anhydride group in the molecule are each in an amount of 1 part by weight, preferably 0.05 to 1 part by weight. The method of adding the catalyst is directly added or used in a state of being dissolved in a soluble solvent or the like. In this case, when an alcoholic solvent such as methanol or ethanol or water is used, 'the compound (c) having two or more carboxylic acid anhydride groups in the unreacted molecule or the compound (ci) having one carboxylic anhydride group in the molecule is reacted. It is better to avoid use. In the present invention, in the hardened material of the obtained polycarboxylic acid composition, the glutinous acid can be preferably used as a touch. The medium preferably reacts without a catalyst in terms of reducing the color of the obtained multi-repulsive composition. Among them, in order to obtain transparency and excellent sulphide, it is preferable to use calcium stearate and zinc carboxylate (zinc-ethylhexanoate, zinc stearate, zinc laurate, myristic acid). Zinc) or zincate (octyl zincate, stearyl)

22 201245288 zinc phosphate, etc., etc. Zinc compound β The reaction temperature in the production of the polycarboxylic acid resin (A) of the present invention is also dependent on the amount of the catalyst and the solvent used, but is usually 20 to 16 (TC, preferably 50 〜 150 ° C ' is particularly preferably 60 to i45 〇 c. Further, the total reaction time is usually 1 to 20 hours 'preferably 3 to 丨 8 hours. The reaction can also be carried out in 2 stages or more 'for example, at 20 to l 〇 After reacting for 1 to 8 hours at 〇t, the reaction is carried out at 1 Torr to 16 ° C for 1 to 12 hours, etc. In this case, especially the compound (d) having a carboxylic anhydride group in the molecule is mostly volatile. The higher, in the case of using such a compound, it is previously 20 to 100. (: After the next reaction, it is reacted at 1 to 160 ° C, thereby suppressing volatilization. Thereby, not only harmful substances can be suppressed Diffusion in the atmosphere' and a multi-dimensional acid-reducing resin (A) according to the design. In the case of manufacturing with a catalyst, the catalyst can be removed by quenching and/or washing as needed, but it can also be left Residual and used as a hardening accelerator for the polycarboxylic acid composition. When the shape, the type of animal husbandry and more bite the good solvent to be used in accordance with the addition of a solvent can be separated from the water.

Preferred solvents are, for example, methyl ethyl ketone, decyl iso J 丞 丞 butyl hydrazine, ketone of cyclopentanone; ethyl acrylate, butyl acetate, ethyl lactate, p kan 3 a « 〇j Swen vinegar and other vinegar; such as hexane, cyclohexane, methyl, xylene hydrocarbons.除去 Remove by solvent or the like in the reaction or washing. In the case of the crucible shape, the liquid of the present invention obtained by the decompression concentration in this manner is liquid in the form of a fluidity. The carboxylic acid resin (A) is usually further used, and its molecular weight is preferably from 800 to 80,000, more preferably from 1,000 to 10,000', and still more preferably from 1,500 to 8,000, based on the weight average molecular weight determined by GPC 23 201245288. Good for 3000~8000. If the weight average molecular weight is 800 or more, it is 25. (The liquidity is improved and the compatibility with the epoxy resin is also improved, so it is preferable. The weight average molecular weight is determined by GPC (gel permeation chromatography) under the following conditions. Molecular weight (Mw). Various conditions of GPC Manufacturer: Shimadzu Pipeline: Protection column SHODEX GPC LF- G LF- 804 (3) Flow rate: 1.0 m 1 / mi η. Column temperature: 40. (: Use Solvent: THF (tetrahydrofuran) Detector: RI (differential refractive index detector)

The acid value of the polyvalent carboxylic acid resin (A) of the present invention (measured by the method of 3 in JIS K 250 1) is preferably 35 to 2 〇〇 mg K 〇 η / g, more preferably 50 to 180 mgK〇H/g, particularly preferably 60 to 150 mgKOH/g. When the acid value is 35 mgK〇H/g or more, the mechanical properties of the cured product are improved, and therefore, if it is 150 mgK〇H/g or less, the cured product does not become excessively hard, and the elastic modulus becomes moderate. Therefore, it is better. Further, the functional group equivalent of the polycarboxylic acid resin (A) of the present invention is preferably 280 to 16 〇〇g/eq, more preferably 35 Å to 50,000 g/eq, and particularly preferably 400 to 950 g/eq °. The viscosity of the polycarboxylic acid resin (A) (E-type viscometer, measured at 25 C) is preferably 5 〇 8 8 mPa.s, more preferably ~

S 24 201245288 lOO’OOOmPa.s, especially good for 8〇〇~3〇〇〇〇mPa.s. When the viscosity is lower than 5 〇 mPa.s, there is a case where the viscosity is too low and it is not suitable for use in the use of the optical semiconductor sealing material. When the viscosity exceeds 800,000 mPa.s, the viscosity is too high and the workability is poor. In order to obtain the storage stability of the polycarboxylic acid resin (A) of the present invention, the low-viscosity, the mechanical strength and heat resistance of the cured product of the polycarboxylic acid composition containing the polycarboxylic acid resin of the present invention (heat resistance) A preferred embodiment of the present invention, which is excellent in the balance of curability and light resistance, and which is excellent in the balance of curability and light resistance, is (i) a polycarboxylic acid resin (A) obtained by the following method. The amount of the polyol compound (e) having two or more hydroxyl groups is 5 to 50 parts by weight based on the weight of the two-terminal methanol-modified polyoxosiloxane (a), and has a carboxylic anhydride in the molecule. The compound (d) is used in an amount of 50 to 1000 parts by weight based on the weight of the compound (c) having two or more carboxylic anhydride groups in the molecule, and is modified with respect to the methanol at the both ends (a). a compound (c) having two or more carboxylic acid anhydride groups in the molecule and a compound having one carboxylic acid anhydride group in the molecule, together with a total alcoholic hydroxy oxime equivalent of the polyol compound (e) having two or more hydroxyl groups in the molecule ( d) the total carboxylic anhydride group is set to 〇·8~ι·5 equivalent reaction. Further, a more preferred embodiment is: (Η) by using a polyol compound (e) having two or more hydroxyl groups in the molecule in an amount of 1 part by weight relative to the two-terminal methanol-modified polyoxygenated oil (a) a multi-repulsive resin (A) which is obtained by (1) a (1) or a compound (d) having a carboxylic acid-based group in the molecule The amount of use of the compound (c) having two or more carboxylic acid anhydride groups in the molecule is set to 1 〇〇 to 8 〇〇 25 201245288 parts by weight, and is obtained in a wide range; The polycarboxylic acid resin (A) contained in the middle. Further, a preferred embodiment is: (iv) setting the amount of the polyol compound (e) having more than one merion in the molecule to 10 parts by weight based on the weight of the two alcohols. 3. parts by weight, = compound (d) having a (four) wild group in the molecule, relative to the compound having two or more carboxylic anhydride groups in the molecule (c) 100 100 to 800 heavy r r r Α "η 77 〇Jt ^ The polycarboxylic acid resin (A) which is obtained by a more serious injury (more preferably 400 to 700 parts by weight). Hereinafter, the polyvalent carboxylic acid composition of the present invention will be described. The composition is an essential component of the polybasic acid resin (A) and the epoxy resin (b) of the present invention. Examples of the epoxy resin (B) include an epoxy resin which is a glycidyl compound of an aged compound. Epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, heterocyclic epoxy resin, glycidol vinegar epoxy resin, glycidylamine epoxy resin, which are various (4) varnish resins Resin Μ吏halogenated phenolic glycidylated ring a resin: a condensate of a compound having an epoxy group and a cerium compound other than the compound, a copolymer of a polymerizable unsaturated compound having an epoxy group, and a polymerizable unsaturated compound other than the epoxy resin. The epoxy tree oxime of the glycidyl ether compound can be exemplified by 2-[4-(2'3__epoxypropoxy)phenyl b-2-[[4][U-double [4-(2,3) -Phenyl)phenyl]ethyl]phenyl]propanone, double expectant a, double F, (iv) S, 4,4'-linked pheno, tetramethyl bismuth, diterpene bis, A, IV Methyl biguanide F, dimethyl dip F, tetramethyl double s, dimethyl

S 26 201245288 Phenol) m-phenyltriphenyl-s-bis, S, tetradecyl-4,4,-linked, dimethyl-4,4,-linked, 1- (4-yl-based) -2— [4-(1,Bus-(4-diphenyl)ethyl)phenyl]propane, 2,2'-methylene-bis(4-fluorenyl-6-tertiary butyl Phenol), 4,4, monobutylene-bis(3_fluorenyl-6-tert-butylphenylhydroxyphenyldecane, resorcinol, hydroquinone, pyrogallol, with diisoaluminum An epoxide such as a phenolic group of a propyl group, an anthracene, a fluorene-di- 4-hydroxyphenyl group, an epoxy resin having a glycidyl ether compound of a compound of a plurality of ages such as a skeletal age or a polybutylene. Examples of the epoxy resin of the glycidyl ether compound of various novolak resins include, for example, benzoquinone, carbamide, ethylbenzene, butylphthalide, octylbenzene, double expectant A, and double age. A phenolic varnish resin containing various phenols such as a double-looking type, a naphthol, and the like, a phenolic phenolic varnish resin containing a xylene skeleton, and a phenol novolak resin having a J-pentene skeleton. , with the joint button + ^ ^ ', the phenol novolak resin, containing the skeletal benzene age acid · varnish tree moon stalk female objects, etc.. The phenolic varnish resin glycidyl etherification as the above alicyclic epoxy ring? Nail enamel tree 舳For example, (3,4-epoxy) hexyl ketone... '4-cycloindole hexyl methacrylate, hexyl methyl ester), etc., and in the case of a furnace, the heart is double C 3 , and the 4% oxygen ring has a ruthenium ring. The alicyclic ring of the skeleton is t月t. As the above-mentioned fat surnamed s horns rolled tree sap. On the day of the month, the aliphatic epoxy resin was exemplified by 1,6-hexanediol, arm N, i, 4 j-oleole. The polycondensation of a polyhydric alcohol such as a diol or a neopentyl alcohol is, for example, a heterocyclic epoxy resin having a hetero-cyanide ring. 27 201245288 The above-mentioned glycidol vinegar-based epoxy resin is exemplified by an epoxy resin composed of a toxic acid such as hexahydro- ortho-carboxylic acid diglycolic acid. Examples of the glycidylamine-based epoxy resin include an epoxy resin obtained by glycidylating a benzene-based amine. Examples of the epoxy resin obtained by glycidylating the above-mentioned functional group include, for example, desertification double expectation A, desertified biguanide, desertified double expectation s, bismuth benzoate (four) varnish, and desertified hyperthyroidism. (4) Epoxy resin obtained by varnishing, gasification and double-seeking s 'gasification double age A and other functional phenol glycidylation. The condensate of the above-mentioned epoxy group-containing compound and the other compound of the cerium compound means, for example, a hydrolyzed condensate of a compound having an epoxy group, and a hydrolyzed condensate of a compound having a group of a condensate of an epoxy group-containing alkoxy compound and a polydimethyl oxalate having a zeolitar group, a polydidecyldiphenyl oxime having a phenolic alcohol group, or the like The condensed compound obtained in combination. Examples of the compound of the present invention include: 2-(3,4-epoxycyclohexyl)ethyltrimethoxyxanthine, 2-(3,4-epoxycyclohexyl)ethyl Triethoxy (tetra), 3-glycidoxypropyltrimethoxy sylvestre, 3' glycidoxypropylmethyl-methoxy (tetra), and the like. Examples of the compound of the oxyoxy group (tetra) having a methyl group or a styl group include, for example, methyltrimethoxy shixi, methyltriethoxy shixi, benzyl trimethoxy sulphur, and phenyltriethoxy sulphate. Burning, methyl methoxide, Xi Xuan 'diphenyldimethoxy ketone, Yin phenyl phenyl dimethoxy nucleus and the like. As a polydimethylene phenyloxyxy having a Shihsingol base, and a polydimethyldiphenyl sulphate having a Shi Xiyuan alcohol group, for example, a product available from the market 21 5841 KF 9701 (Shin-Etsu Chemical Industry Co., Ltd. 201245288 Manufacturing), ΒΥΙό — 873, PRX413 (Manufactured by TORAY.DOWCORNING Co., Ltd.), XC96-723, YF3804, YF3800, XF3905, YF3057 (Momentive Performance Materials Japan Co., Ltd.

Division), DMS-S12, DMS-S14, DMS-S15, DMS-S2, DMS-S27, DMS-S3 1, PDS- 0338, PDS-1615 (manufactured by Gelest). Examples of the copolymer of the polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds other than those which can be obtained from the market include Marproof G—0115S, Marproof G—0130S, Marproof G- 0250S ^ Marproof G- 1010S ^ Marproof G-0150M' Marproof G-2050M (manufactured by Nippon Oil Co., Ltd.), etc. Examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate and glycidyl methacrylate. ~Vinyl _ j - cyclohexene - 1,2 - epoxide, etc. X, as another polymerizable non-saturated compound, for example, (meth)propanoid acid series, (meth)acrylic acid vinegar, benzyl (meth) acrylate 1 lower axis I methyl) acrylate ring Hexyl ester, styrene, vinyl cyclohexane, and the like. These types are used above. It is possible to use one kind or mix 2 on the day of the month to use the carboxylic acid composition of the present invention from the carboxylic acid composition, especially in the case of the application of the light phoenix. Resin (Β), aid Saki County (using JISK-7236) T 'epoxy equivalent V, and preferably 35G~U ^)) preferably 15G~_ produces ~, then the hardened material will not Over-change: It is preferred that the epoxide equivalent is produced. If it is 15 (10) cracks and other cracks from the bottom, it is better to see the target. (1) The surface is not sticky. 29 201245288 Again, the weight, τ _~5000. When the amount of H is preferably from 250 to 10,000, and more preferably, the amount-average molecular weight is 250 or more, the toughness of the cured product is less likely to cause cracks such as cracks in the heat cycle test or the like, so that the amount is less than 1000 Å. Therefore, the viscosity is not easy to become high, and it is preferable because it is ambiguous. In the above, the % oxygen equivalent and the weight average molecular weight of the epoxy resin (Β) are worried, the heat-resistant transparency, the light-resistant transparency, the heat-resistant cycle, etc., and the 隹, 隹, y A condensate of an anthracene compound having an epoxy group and a ruthenium compound other than the above is preferred. Further, the weight average molecular weight in the present invention means a weight in a polystyrene equivalent of 帛GPC (condensation chromatography) measured under the following conditions: a molecular weight (Mw). GPC various conditions Manufacturer: Shimadzu Manufacturing Pipe column: Protection column SH0DEXGPCLF-GLF_8〇4 (3 ton flow rate: 1.0 ml / min Column temperature: 4 (TC solvent: THF (tetrahydrogen). Detector : RI (differential refractive index detector) The epoxy resin (Β) is preferably in the range of G. 5 to 3. G equivalent to the epoxy group with respect to the equivalent of the polyvalent carboxylic acid resin (α). When the amount is more than 0.5%, the heat-resistant transparency of the cured product is improved. Therefore, if it is 3.0 or less, the mechanical properties of the cured product are improved. Therefore, the multi-component grease of the present invention (A) It can be used alone as a 201245288 hardener for epoxy resins'. However, it is also preferred to use a polycarboxylic acid resin (A) mixed with a hardening accelerator as a hardener for epoxy resins. Any of the hardening accelerators in the resin (A) can be used as a hardening accelerator which can promote the hardening reaction of an epoxy group with a tickic acid and a m-anhydride, and an ammonium salt type hardening accelerator can be mentioned. , scale salt hardening accelerator, metal soap hardening accelerator, microphone A hardening accelerator, an amine-based hardening accelerator, a phosphine-based hardening accelerator, a phosphite-based hardening accelerator, a Lewis acid-based hardening accelerator, etc. Among these, in the case of optical semiconductor sealing such as high-brightness white LED In the use of the sclerosing agent for the multi-repulsive composition, the salt-based hardening accelerator, the scale salt-based hardening accelerator, and the metal soap-based hardening accelerator are particularly excellent in terms of transparency. Examples of the hardening accelerator include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium oxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, and trimethyl hydroxide. Propyl recording, trimethylbutyl hydride recording, trimethyl hexafluoride hydride recording, trioctylmethyl hydroxyhydroxide, tetramethyl chlorinated tetramethyl hydride, broken tetraf Base record 'tetramethyl acetate, trioctylmethyl acetate, etc. As a scaly salt (four), (4), for example, desertified ethyl triphenyl scale, tetraphenylboronic acid tetraphenyl scale, dimethyl Base plate acid methyltributyl scale, diethyl butyl methacrylate, etc. as gold Examples of the soap-based hardening accelerator include tin octylate, octyl (tetra), zinc octylate, octyl (10), octane:, acid detachment, etc. These hardening accelerators may be used alone or in combination of these hardening accelerators. A, preferably a tris-f-hexyl hexahydro hydride, a di-n-butyl butyl sulphate, a succinate, a octanoic acid, 31 201245288 manganese octoate. Among them, in order to obtain a cured product excellent in transparency and sulfidation resistance, It is especially preferred to use calcium stearate 'zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, rosin, zinc myristate) or zinc silicate (octyl zinc silicate, stearyl) A zinc compound such as zinc phosphate or the like. In addition to the above-mentioned ammonium salt-based hardening accelerator, sulfonium-based hardening accelerator, and metal soap-based hardening accelerator, a c-m β-stable curing accelerator may be used in other general-purpose applications. An amine-based hardening accelerator, a heterocyclic compound-based curing accelerator, a phosphine-based curing accelerator, a phosphite-based curing accelerator, a Lewis acid-based curing accelerator, and the like. Examples of the sodium beta sclerosing accelerator include 2-methylimidazole, 2-ethyl-4-methylammonium, 2-phenylimi, 2-|-- , 2--h-sodium pyridyl imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-mercaptoimidazole, fluorenyl cyanoethyl 2-methyl ° meter. Sit, 1-cyanoethyl-2-phenylene n-sodium, 1-cyanoethyl-2-oxanyl imidazole, 2,3-dihydro-indenyl-pyrrolo-[1,2-a] Benzimidazole, 2,4-diamino- 6 (2, monomethylimidazolium (1,)) ethyl-all-three-D well, 2,4-diamine- 6 (2'--1--院基米.Sit (1')) Ethyl mono-Hall well, 2,4-diamino- 6 (2,1-ethyl, 4-nonyl imidazole (1·)) Ethyl 2,4-diamino- 6 ( 2'-methylimidazolium (1,)) ethyl-all three wells / iso-cyanuric acid adduct, 2-methylimidazoisocyanuric acid 2 :3 adduct, 2-phenylimidazole isocyanurate adduct, 2_phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-indolyl-5-hydroxymethyl Imidazole or 1-cyanoethyl-2-phenyl- 3,5-dicyanoethoxymethylimidazole. 32 201245288 As the amine-based hardening accelerator, for example, a group of amines and -_____ can be used, such as triethylamine or tripropylenediamine. As a heterocyclic compound-based hardening accelerator, for example, pyridine, :...hetero-double--one,

The phosphine is a::------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------ As a Lewis acid-based hardening accelerator, for example, a 7-to-to-friend J is a gasification of a sulfhydrylamine, a bis-diethylamine, a triethylammonium trifluoride, a boron arsenylamine, and a tribasic amine. Boron fluoride, stearamine, trisamine difluoro-.οη ^ deuterated boron piperazine well, boron trifluoride piperidine, boron difluoride ethylamine, pentafluorinated turpentine tauamine pentafluoride The base neck, the phosphorus pentafluoride hexylamine, and the pentafluoride clock can be used in i or mixed with two kinds of m. Two or more kinds of the curing accelerators H are used. As to which of the hardening catalysts is used, for example, it can be appropriately selected according to the characteristics required for the transparent resin composition obtained by the transparency and the curing speed. 4 These hardenings are promoted (4) with respect to the plural (four) resin. It is used within the range of 5 parts by weight. Heavy Injury The composition of the polycarboxylate of the present invention is obtained by mixing the above ingredients at room temperature and adding 9 sentences. For example, by using an extruder, a kneading ring, a knowing, a preparation, a two-roller grinding machine, a universal mixer, a machine, a homogenizing machine, a land, a star-shaped type, Kunhe 7 to buy a mixer, homogenization The disperser and the bead mill are made uniform, and if necessary, the squeegee is kneaded until it is required to be SUS mesh or the like. 33 201245288 The non-inventive polycarboxylic acid resin (A) and the polybasic citric acid composition can be used as needed. Use other epoxy resin hardeners. Examples of the epoxy resin curing agent that can be used together include polycarboxylic acids, phthalic anhydrides, phenols, anthracenes, and mercaptans. The polyvalent carboxylic acid may, for example, be a polycyclic carboxylic acid, a cyclic fluorene polycarboxylic acid, an aromatic polycarboxylic acid or a heterocyclic polycarboxylic acid. As the above aliphatic polybasic acid, for example, it can be listed. Test & Ping. Early acid, C2 & L, butyric acid, glutaric acid, adipic acid, Geng Er-8-舻, Wenxin-acid, Azelaic acid, Liuyi, H3 - propane III, * 】 Shen tetracarboxylic acid and so on. = the above cyclic aliphatic polybasic acid, for example, hexahydroortho:: formazan, 1 > 3 - adamantane diacetic acid, adamantane dicarboxylic acid ortho-carboxylic acid, 2,3- enedicarboxylic acid ^ 1 0 C ^ , A4 ¥ 院 曱 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三Aromatic polycarboxylic acid, exemplified by x J. o-stanoic acid, m-formic acid, terephthalic acid, 1>2 1,8-naphthalene-methyl-capsule 夂1'4-naphthalene dicarboxylic acid 帒Monocarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2 dicarboxylic acid, 44, π-decanoic acid, 9,1 〇-蒽~ dimercapto ketone dicarboxylic acid, 2 w-linked dimethyl milk, 2,2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ a binaphthyl dicarboxylic acid, ^ 1,2,4 - stupid, the present dicarboxylic acid, the present monomethyl hydrazine, 1 > 3,5 - benzene tridecanoic acid - naphthalene = A touch, , 'Cai bismuth acid, 2 , 5,7 na-formic acid, 1,2,3,5-benzenetetracarboxylic acid, lithic acid, 3 3,4 4, , 2,3,4—the present tetracarboxylic acid, coke honey, 4,4 —two stupid Anthrone tetradecanoic acid, 2 2 _ oleic acid 2,3 3,4· , , a ketone tetramethyl, '~ dimercapto ketone tetradecanoic acid', J 4,4 -biphenyltetracarboxylic acid, 34 201245288 2,2,3,3 —Lian Ben 4 Tannic acid, 2,3,3,~. Bibenzic acid, 4,4, monooxydi-n-benzoic acid, 3,3,4,4, diphenylmethylm ^ ^ m T-alkane醆, 1,4,5,8-naphthalenetetramethyl hydrazine 1,2,5,6-naphthalenetetracarboxylic acid, 2,3, ό # .,. 'naphthalenetetracarboxylic acid, ruthenium tetracarboxylic acid, etc. as the above heterocyclic ring Examples of the polyvalent carboxylic acid, r2_^.r, may, for example, beocyanuric acid tris(2-carboxyethyl), iso-cyanuric acid, (3-carboxypropyl) or the like. I. _ .. ^ ^ • An aliphatic carboxylic acid anhydride, a cyclic aliphatic carboxylic acid, a hexanic anhydride, an aromatic carboxylic anhydride, etc. Examples of the aliphatic carboxylic acid anhydride include succinic anhydride and methyl group. Succinic anhydride, ethyl succinic anhydride, 23,3~ butane dicarboxylic anhydride, 2,4-pentane dicarboxylic anhydride, 3,5-heptane dicarboxylic acid hepatic butyl needle, 1,2,3,4 - butyl Alkane tetracarboxylic acid di-hepatic acid, cis-butane diacid liver, 12-yard diced diced acid, etc. As a cyclic aliphatic m-acid needle, hexahydro-o-phenylene Formic acid needle, decyl hexahydrophthalic anhydride, 13 - 3 law, 'long burned dicarboxylic acid needle, sputum to acid liver, hydrogenated methyl dying anhydride, double research AI ring [2, 2, 2] octane-2,3-dicarboxylic acid liver, 1,2,4-cyclohexylene dicarboxylic acid _] 9 a T 醆 I, 2 ~ anhydride, 1,2,3,4-cyclobutane tetracarboxylic acid Anhydride, 1,2,3,4 - 戌 戌 四 _ 衣 衣 衣 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐 酐Methyltetrahydrophthalic anhydride, citric acid needle, methyl-resistant material, 4,5-dimethyl-p-cyclohexyl _1>2_ dicarboxylic acid needle, double: fading [2.2.2 Bu 5 - Xin field ~ 2,3_ dicarboxylic acid needle and so on. "As the above aromatic carboxylic acid anhydride, for example, phthalic anhydride, m-formic acid Sf, Dong + cage - trial secrets, one-methyl anhydride, 1,2,4-stupoleic anhydride, and honey In addition, it can be exemplified by: 5_(2,5 per ^A ^ field ~ oxytetrahydrofuranyl) - 3 - fluorenyl 3-cyclohexene - i 2 -carboxylic acid monoterpene θ phthalic anhydride, 4» ( 2,5 - dioxane tetrahydrofuran 35 201245288 3 - group) - 1,2,3,4 - tetrahydronaphthalene - i, 〗 - an aliphatic carboxylic anhydride, a cyclic aliphatic carboxylic acid in the same compound such as phthalic anhydride Examples of the acid anhydride compound, etc. As the above-mentioned phenols, for example, bisphenol A, bisphenol ρ, bisphenol S, 4,4-biphenylphenol, tetramethylbisphenol a, dimethyl bisphenol a, and quaternary Bisphenol F, dimercaptobisphenol F, tetradecylbisphenol s 'dimethyl bisphenol s, tetradecyl-4,4, monobiphenol, dimethyl-4,4, _biphenylphenol , 丨-(4_hydroxyphenyl)-2-(4_(1,1-di-(4-hydroxyphenyl)ethyl)phenyl]propane, 2,2'-indenylene-double (4_ Mercapto-6-tert-butylphenol), 4,4, monobutylene-double (3-methyl-6) _ tertiary butyl phenol), trihydroxyphenyl decane, resorcinol, p-diphenol, pyrogallol, phenols having a diisopropylidene skeleton; 1,1 1-2 tetrahydroxy Phenylhydrazine and the like have the expectation of the first skeleton; expectant polybutadiene, stupid 'carbamidine, ethylphenanthene, butylphenol, octylphenol, bisphenol A, bisphenol F, (4) varnish resin, such as bisphenol S or naphthol, which is expected to be a raw material; phenol phenolic phenolic varnish resin containing a cyclopentadiene skeleton containing a xylene skeleton, and a phenolic phenolic resin containing a biphenyl skeleton. A varnish resin, a phenol aldehyde varnish resin containing a skeleton, a phenol varnish resin such as a varnish resin containing a furan, and a varnish resin, etc. The oxime is, for example, an isophthalic acid. Bismuth, diammonium adipate, azelaic acid, dioxane, dodecanedioic acid dioxime, 2,6-naphthalene diterpenic acid dioxime, etc. As the above mercaptans, such as sulfhydryl Acid ester), neopentyl alcohol tetrakis(6-(diyl-propionic acid vinegar), hetero-bis can be exemplified: trihydroxymercaptopropane three (3 - (3) Mercaptopropionic acid g), dipentaerythritol polycyanate tris[(3 -mercaptopropoxycarbonyl) 36 201245288 -ethyl vinegar], ι,4-bis(3_mercaptobutyloxy) Butane, neopentyl alcohol tetradecyl-mercaptobutyrate) '1,3,5-tris(3-disylbutoxyethyl)__丨,^ 一二〇井一2,4,6 (1 ΐ, 3 Ι, 5 Η) - triketone, etc. These epoxy resin hardeners may be used in combination or in combination of two or more kinds. The polycarboxylic acid resin (Α) of the present invention is hardened as described above. In the case where the agent is used in combination, the ratio of the polycarboxylic acid resin (A) to the total hardener is 5% by weight or more, preferably 8% by weight or more. Next, a coupling agent, a phosphor, an inorganic filler, a highly thermally conductive fine particle, a phosphorus compound filler as a flame retardant, a binder resin, or the like may be added as needed in the polyvalent carboxylic acid composition of the present invention. As the coupling agent which can be used, for example, 3-glycidoxypropyldimethoxy zeoxi, 3-glycidoxypropylmercaptodimethoxyhydroalkane, 3-glycidoxypropane Methyl dimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy sulphur, N-(2-aminoethyl)3-aminopropyl fluorenyl dimethoxy Base decane, N —(2-aminoethyl) 3-aminopropyl decyl tridecyloxy sylvestre, 3-aminopropyl triethoxy sulphur, 3 mercaptopropyltrimethoxy decane , vinyl trimethoxy decane, N-(2-(ethylidenebenzylamino)ethyl) 3-aminopropyltrimethoxy oxalate hydrochloride, 3-methylpropoxypropyl propylate Trimethoxy zeshi, 3 - propyl propyl dimethyl oxime oxime, 3 - chloropropyl tributary oxy shirite, etc.; (N - ethylaminoethylamino) Isopropyl titanate, isopropyl triisostearate isopropyl titanate, bis(dioctyl pyrophosphate) oxyacetate, di(dioctyl phosphite) tetraisopropyl phthalate, neo-oxygenate (for an N- (/3 — Base 37 201245288 Titanium coupling agent such as ethyl)aminophenyl) titanate; zirconium acetonate pyruvate, zirconium methacrylate, zirconium propionate, neoalkoxy acid ester, neoalkoxy trisin Mercaptopurine, neoalkoxytris(dodecyl)phenylsulfonylhydrazine, neoalkoxybis(ethylideneethylamine) acid vinegar, new sulphur A ruthenium or an aluminum-based coupling agent, such as a zirconate, an ammonium carbonate, an aluminum phthalate, an aluminum methacrylate, or an aluminum propionate. The coupling agent may be used alone or in combination of two or more. The improvement of the adhesion to the substrate or the improvement of the hardness of the cured product can be expected by using the coupling agent. The coupling agent is usually contained in the polycarboxylic acid composition component of the invention in an amount of 0 to 05 to 20 parts by weight, preferably. It is contained in 〇丨~1〇 parts by weight. Examples of useful phosphors include YAG luminescence, ortho phthalate phosphor, thiogallate acid phosphor, sulfide phosphor, etc. By adding a labyrinth, it is possible to impart fluorescing property to the multi-read acid composition. As an inorganic filler that can be used, For example, crystalline Shishishi, fused vermiculite, alumina, smectite, calcium citrate, calcium carbonate, strontium carbide, gasified sputum, oxidized sputum cerium oxide, magnesium sapphire, block talc, Spinel, dioxotomy, slippery powder (4) Beads obtained by spheroidizing the material, etc. By adding an inorganic filler, heat resistance, light resistance, viscosity adjustment, etc. can be imparted. The content is used in an amount of ～95 parts by weight of the multi-repulsive composition of the present invention. Examples of the highly thermally conductive fine particles that can be used include gold, silver, copper, iron, brocade, tin, and rhodium. Metal particles such as diamonds and indium, or alloys thereof, 38 201245288 Metal oxides such as oxides, magnesium oxides, and titanium oxides, metal nitrides such as boron nitride and nitrided chains, and carbon compounds such as graphite, diamond, and carbon black, and resins. The metal is coated with a metal layer coated with a metal layer or the like. The thermal conductivity of the polycarboxylic acid composition can be improved by adding highly thermally conductive fine particles. As the phosphorus-containing compound which can be used, it may be either a reactive type or an additive type. Examples of the phosphorus-containing compound include tridecyl phosphate, diethyl acid dish, tricresyl acid ester, tris(xylene) acid ester, toluene diphenyl phthalate, and bismuth phthalate 2,6- Xylylene ester, 1,3 -phenylene bis(disodium benzoate), 1,4 phenyl bis(diphenylene phosphate), 4,4·-linked (phosphoric acid) Phosphate such as bis(diphenylene) ester, 9,1 fluorene dihydrogen-9-oxa-10, phenanthroline-10 oxide, 1 fluorene (2,5-dihydroxyphenyl) 10H-9-oxo-1〇-phosphaphenanthrene-10-oxide and other phosphines--containing epoxy resin, red phosphorus, etc. obtained by reacting epoxy resin with active hydrogen of the above phosphines Phosphate, phosphine or phosphorus-containing epoxy compound 'preferably 1,3 -phenylene bis(diphenylene phosphate), i,4 -extended bis(diphosphine) Benzene ester), 4,4.-biphenyl (di(dimethyl) phosphate) or phosphorus-containing epoxy compound. The content of the phosphorus-containing compound is preferably a phosphorus-containing compound/epoxy resin = 〇·1 to 0.6 (weight ratio). If it is 〇.丨 or more, the flame retardancy is sufficient, and therefore it is preferably 0-6 or less. It is preferred because it does not adversely affect the hygroscopicity and dielectric properties of the cured product. Examples of the binder resin that can be used include butyral resin, condensed resin, acrylic resin, epoxy-nylon resin, Nbr phenol resin, epoxy-NB R resin, and polyamine. Resin, polyimide tree 39 201245288, etc., but not limited to these. The binder resin is usually required to contain ο." to 5 parts by weight, preferably 〇〇5 to 2 parts by weight, of the polyvalent carboxylic acid composition component of the present invention. Further, the polycarboxylic acid composition of the present invention can be used. Adding a release agent such as stearic acid, palmitic acid, stearic acid or stearic acid, coloring T' antioxidant, light stabilizer, (four) improving agent, shaking imparting agent, and the like : agent, adhesion-imparting agent, impact modifier, ion trapping agent, anti-[π agent, lubricant, leveling agent, surface tension reducing agent, antifoaming agent, anti-lead agent, surfactant, ultraviolet absorber : Resin resin, various other resins. These may be added to the polycarboxylic acid composition of the present invention by itself. Method = light stabilizer which can be used, for example, carbonic acid double (pit gas base - 2,2'6,6-tetramethyl...4-yl)anthracene, tetrapentamethyl-4-n-negyl)=1,2,3,4-butylate tetracarboxylic acid vinegar,,,,~4 Base 4 - piperidinyl) = 1,2 4 - A: , 2'6,6-butane tetracarboxylic acid and 12,2,66-, 2,3,4 (2-exclusive, piperidinol and 3,9-double 1 base-, 1-dimethylethyl)__2,4,8-mixed esterified product of eleven-burning, bis-heterorubin [5,5] Nitrile: azelaic acid § Acrylic acid 2,2,μ- bismuth, azelaic acid bis(2,2,6,6-tetramethyl- 4-piperidinium 1 1 9 〇. bite base) g曰, azelaic acid ('Μ- Pentamethyl-4,yl), 4-phenyl-2,2,6,6-tetramethylpiperidine, j—[2_[3—(3,5 — _ — one-hole 丞~hydroxyphenyl)-propyl醯oxy]ethyl]_4-[3__(35-tert-butyl-4-yl-4-phenylphenyl)propanyloxy 2,2, 'some:: three-stage butyl wTm0 bottom bite, methyl

40 201245288 Acrylic acid 1,2,2,6,6-pentamethyl- 4 - 〇 bottom bite, malonic acid bis (1,2,2,6,6-pentamethyl- 4-piperidinyl) [[3,5-bis(1,ι-dimethylethyl)_4-hydroxyphenyl]indolyl]butyl ester, decanedioic acid bis(2,2,6,6-tetradecyl- 1 ( Octyloxy)- 4-bendylene ester, reaction product of 1,1-dimethylethylhydroperoxide and octane, N,N',N",N'" one four (4, 6—Double (butyl-(N-fluorenyl-2,2·6,6-tetradecyl)> Chenbita-4~yl)amino)—three wells—2—base)_4,7 — Diazepines-1,1〇-diamine, dibutylamine-1,3,5—three wells, Ν·—double (2,2,6,6-tetramethyl-4) Bottom base __ ι,6 - hexamethylenediamine and 1''!_(2,2,6,6-tetradecyl-4-pyrene) butylamine polycondensate, poly[( 6-( 1,1,3,3 -tetramethylbutyl)amino _ 135 — two wells _2,4 — a base)[(2,2,6,6 —tetramethyl _ 4 — brig Olefin]imido]hexamethylene[(2,2,6,6-tetramethyl-4-indanyl)imido]], dimethyl succinate and 4-hydroxyl a polymer of 2,2,6,6-tetradecyl-1 monopiperidinyl alcohol, 2,2,4,4-tetramethyl-20-(anthracene-lauroyloxycarbonyl)ethyl-7-oxo Miscellaneous 3,20 —. A heterozygous snail [5,1,11,2] twenty-one pit _ 21 ketone, /3 - alanine, Ν - ( 2,2,6,6 - tetradecyl —4 — 〇 bottom bite base — twelve burning base vinegar / fourteen burning vinegar, Ν - 乙 一 a 3 - twelve dazzling _ ι_ (2,2,6,6 - four 曱基_4 a bite Base) 〇 ratio <7 each 0 __25 - bismuth, 2,2,4,4-tetramethyl-7-oxa- 3,20-diazabispiro[5 ill 2] twenty-one Alkane-21-ketone, 2,2,4,4_tetradecyl-21-oxa-3 2〇-diaza·1%· — [5,1,11,2] —11烧一一20 - propionic acid 12 yards g / tetradecyl ester, malonic acid [(4-methoxyphenyl) - fluorenylene] - bis (1, 2, 2, 6, 6 - quinone Higher 4-fattyl ester of 2,2,6,6-tetramethyl-4 piperidinol, 1,3 - benzodiazepine, N, N, _ double 41 201245288 Blocky ketone and other dibasic) -4 - fluorenyl (2,2,6,6-tetradecyl-4-piperidyl) and other hindered amines, benzophenone , 2 - ( 2H - stupid and tris - 2 (1,1,3,3-tetramethylbutyl) cumbersome, 2-, 2-amino)benzotriazole, 2 - [2 - Hydroxy- 3~ quinone imine monomethyl)-5-nonylphenyl] benzotriazole_本一甲(3 - dibutylbutyl-2-carbo-5-methylphenyl b-5-gas Stupid and triterpene, Bu_hydroxy_3,5-di-p-pentylpentylphenyl)benzotriazole, 2-acid 2~yl)-benzotriazole-2-yl)_5_tributyl The reaction product of 4-hydroxydioxime oxime ester and polyethylene glycol, 2-(2Η-poor and ν η, 并三啥~2—j _6-dodecyl _ 4-methylphenol, etc. Compound, 2 7 - di-tert-butylphenyl-3,5-di-tertiary butyl-"hydroxybenzoic acid vinegar-specific formic acid S"-2 (4,6-diphenyl-135 ~~—,, two d wells—2 _ groups) Three-d well compounds such as 5-[(hexyl)oxy]phenol. When the polyvalent carboxylic acid composition of the present invention is used for an optical material, particularly β for a photo-semiconductor encapsulant, it is particularly preferred to contain a phosphorus-based compound as an antioxidant. The phosphorus-based compound is not particularly limited, and examples thereof include, for example, I,1'3-di(2-methyl-1,4-yield-di-tert-triester)-~5-=-butylbenzene Butane, distearyl neopentyl alcohol diphosphite, bis(24-di-tert-butylphenyl) neodecyl diamine di squarate, bis (26- _ a third grade —4-mercaptophenyl) pentaerythritol diphosphite, phenyl bisphenol A neopentyl glycol di ternary acid ester, dicyclohexyl neopentyl alcohol diphosphoric acid, phosphorous acid tris(II) Ethyl phenyl ester), tris(di-isopropylbenzene vinegar) phosphite, tris(di-n-butylphenyl) phosphite, and tris(2,4-di-three-level 201245288 basic S) Sub-salt tris (2,6-di-tert-butyl butyl vinegar), sub-disc tris[2,6-di-tert-butyl butyl phenyl ester], 2,2, mono-indenyl bis (4, 6_di-tert-butyl butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2,monodecyl bis (4,6-di-terphenyl) (2)-tert-butyl- 4-nonylphenyl phosphite, 2,2'-methylenebis(4-indolyl-6-tertiary Phenyl) (2-tertiary butyl-4-ylphenyl) phosphite, 2,2, monoethyl bis(4-methyl-6-triphenyl) (2 - 3) Butyl-4-methylphenyl)phosphite, tetrakis(2,4,2,3,3-butylphenyl)-4,4, diphenylene diphosphite, tetra (2,4 Di-tertiary butylphenyl)- 4,3'-extended biphenyl diphosphite, tetrakis(2,4,2,3-triphenyl)- 3,3'~-diphenylene Phosphite, tetrakis(2,6-di-tertiary butylphenyl) 4'4 extended intrinsic dimercapic acid vinegar, tetrakis(2,6-di-tertiary butylphenyl)-4' 3'-extended biphenyl diphosphite, tetrakis (2,6-di-tert-butyl butyl) -3,3'~ extended biphenyl di sulphate, sub-acid double (2,4 1-2 butyl phenyl)~4 phenyl-phenyl ester, bis(2,4,2,3-tri-butylphenyl)-3-phenyl-phenyl phosphite, bisphosphite (2,6-di-n-butylphenyl)~3~phenyl-p-phenyl ester, bis(2,6-di-tri-butylphenyl)phenyl monophenyl phosphite, double phosphorous (2,6 one two one three Butylphenyl)-3-phenyl-phenyl ester, tetrakis(2,4,2,3-tris-butyl-5-methylphenyl)-4,4'-biphenyldiphosphite, Tributyl phosphate, tridecyl phosphate, tridecyl phenyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, toluene diphenyl phosphate, mono-o-phenyl diphenyl phosphate, phosphoric acid Butoxyethyl ester, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like. 43 201245288 A commercially available product can also be used as the above phosphorus compound. The commercially available phosphorus-based compound is not particularly limited. For example, as ADEKA, Adekastab PEP-4C ' Adekastab PEP- 8 ' Adekastab PEP-246 ' Adekastab PEP- 36 ' Adekastab HP- l〇. Adekastab 2112 Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, Adekastab TPP 〇 Here, the ratio of the phosphorus compound is 0.005 to 5 by weight relative to the polycarboxylic acid resin (A). The weight ❶/〇 is more preferably 〜1 to 4% by weight, still more preferably 0.1 to 2% by weight. The multi-repulsive acid composition of the present invention may contain an anthraquinone compound as an antioxidant material other than a carbon-based compound. The phenolic compound is not particularly limited, and examples thereof include 2,6 _ di-tertiary butyl-4-methylphenol and 3 _(3,5-di-tri-butyl-4-cyclohydroxy) N-octadecyl propionate, tetrakis[methylene-3-(35-mono-tert-butyl-4-hydroxyphenyl)propionate]decane, 2,4-di-tertiary butyl a 6-nonylphenol, hexanediol_bis_[3_(3,5-di-tri-butyl-4-hydroxyphenyl)propionate], iso-cyanide tris(3,5 — 1-3 butyl-hydroxybenzyl ester trimethyl- 2,4,6-two (3'5-mono-butyl-4-hydroxybenzyl)benzene, neopentyl alcohol ~ four [3 one (3 , 5-2-3 tributyl-4-ylhydroxyphenyl)propionate], 3,9-double _ [2—[3—(3-tris-butyl-4-hydroxy-5-fluorenyl) Base) — oxime]1,1-mercaptoethyl]-2,4,8,1 0—tetraoxaspiro[5 5]undecane, triethylene glycol—double [3—(3— Tertiary butyl-5-indenyl~4-hydroxy 201245288 phenyl)propionate], 2,2'-butylene bis (4,61-2 di-butyl acyl), 4,4 — Butylene bis(3-indenyl-6-tertiary butylbenzene) ), 2,2'--indenyl bis(4-methyl-6-tert-butylbenzene), 2,2--methylenebis(4-methyl-6-tert-butylbenzene ), 2-tertiary butyl-6-(3-tertiary butyl-2-trans-benzyl-5-methylbenzyl)-4-methylphenol acrylate vinegar, 2-[1—(2— Substituting 3,5-di-3,3 pentylphenyl)ethyl]-4,6-di-p-pentylphenyl propyl acrylate, 4,4·-thiobis(3-indenyl) a 6-tertiary butyl phenol), 4,4'-butylidene bis(3-methyl-6-tertiary butyl phenol), 2-tertiary butyl 4-nonyl phenol, 2,4 Di-tert-butyl butyl phenol, 2,4-di-p-pentyl pentyl phenol, 4,4'-thiobis(3-methyl-6-tertiary butyl phenol), 4,4'-butylene Bis(3-methyl-6-tertiary butylphenylhydrazine), bis-[3,3-di-(41-yl-amino-3'-tert-butylphenyl)-butyric acid]-glycol, 2,4,213, butyl phenol, 2,4,2,3,3,pentyl phenol, 2-[1—(2-hydroxy-3,5-di-p-pentylphenyl)ethyl] —4,6—two-three-grade pentyl phenyl propyl Alkenoic acid ester, di-[3,3-di-mono(41-hydroxy-3,3-tert-butylphenyl)-butyric acid]-glycol ester, and the like.

Commercially available products can also be used as the phenolic compound. The commercially available phenolic compound is not particularly limited. For example, as Ciba Specialty Chemicals, IRGANOX 1010, IRGANOX 1 035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295 can be cited. , IRGANOX 3114, IRGANOX 1098, IRGANOX 1520L; manufactured as ADEKA, can be cited as: Adekastab AO

20' Adekastab AO — 30, Adekastab AO — 40, Adekastab AO — 50, Adekastab AO — 60, Adekastab AO — 70, Adekastab AO 45 201245288

- 80, Adekastab AO- 90, Adekastab AO-330; as Sumitomo Chemical Industry's manufacture, Sumilizer GA-80, Sumilizer MDP-S' Sumilizer BBM-S, Sumilizer GM, SumiUzer GS (F),

Semilizer GP, etc. In addition, commercially available additive materials can be used as the anti-coloring agent for the resin. For example, as Ciba refined manufacturing, THINUVIN 328, THINUVIN 234, THINUVIN 326, THINUVIN 120, THINUVIN 477, THINUVIN 479, CHIMASSORB 2020 FDL, CHIMASSORB 119FL, and the like can be cited. In the case where the phenolic compound is added, the amount of the phenolic compound to be added is not particularly limited, and is preferably in the range of from 5 to 5.0% by weight based on the polyvalent carboxylic acid composition of the present invention. When the polycarboxylic acid composition of the present invention is used for an optical material, particularly in the case of an optical semiconductor encapsulant, a phosphor may be added as needed. The fluorescent system has, for example, a function of absorbing white light emitted from a blue LED element and emitting wavelength-converted yellow light to form white light. The photo-semiconductor is sealed by dispersing the phosphor in advance in the polycarboxylic acid composition. The phosphor is not particularly limited, and a known phosphor can be used, and examples thereof include an aluminate of a rare earth element, a sulphur gallate, and a protophos. More specifically, a phosphor such as a YAG phosphor, a TAG phosphor, a protonate phosphor, a thiogallate phosphor, or a sulfide phosphor can be exemplified as YA103:Ce, Y3Al5Ol2: Ce, Y4Al2〇9:Ce> Y2〇2S: Eu' Sr5(P04) 3C1:Eu>(SrEu) O-Al2〇3 and the like. As the particle diameter of the above phosphor, a particle diameter known in the art can be used.

S 46 201245288 As the average particle diameter, it is preferably 2 centimeters m, and the illusion is 2 to 5 〇". In the case of using the phosphors, the amount of addition is relative to the weight of the (4) component (10) by weight. Preferably, it is 5 to 6 parts by weight. When the polycarboxylic acid composition of the present invention is used for an optical material, particularly in the case of an optical semiconductor encapsulant, & As a fine powder of such a vermiculite, for example, Aerosil 50, Aerosil 9〇, Aer〇sil 13〇, and VIII can be added to the shovel. ...State 2〇〇, 300 > Aerosil 380 > Aerosil 0X50 . Aerosil TT600 > Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R812, Aer〇sil R812S, Aerosil R805, RY200, RX2〇〇 (Japan Aer〇sU The polycarboxylic acid composition of the present invention may also be used in the form of a varnish or an ink in the case where a solvent is mixed as needed. The solvent is only the polycarboxylic acid tree ruthenium (A), the % oxygen resin (b) of the present invention, Hardening accelerator, other additives If the components have high solubility and are not reactive with the above, they can be used. Specific examples thereof include alcohols such as decyl alcohol, ethanol, propanol and butanol; and ethyl alcohol as early as ethylene glycol. Ethylene glycol, ethylene glycol monobutyl ether, glycol ether monoglycol, propylene glycol monomethyl ether, 3_nonoxybutanol, 3-methyl-3-indolyl butanol, glycol ethers, ethylene glycol monoethyl ether acetate, Ethylene glycol monobutyl ether acetate, propylene glycol monomethyl acetate, propylene glycol monoethyl ether acetate '3-methoxybutyl butyl acetate, 3-methyl-3-methoxybutyl acetate, ethoxylate An alkylene glycol oxime acetate such as ethyl propyl propionate; an aromatic hydrocarbon such as benzene, toluene or xylene; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentane嗣, 4__ 47 201245288 Ketones such as hydroxy_4_methyl-2-pentanone; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl 2-hydroxy-2-methylpropionate, 2 Monohydroxy _ 2 _ethyl propionate ethyl ester, methyl hydroxyacetate, hydroxyacetic acid acetonitrile, hydroxyacetic acid butyl I, lactic acid methyl vinegar, lactic acid ethyl vinegar, lactic acid butyl vinegar, 3 bismuth citrate Ester, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, propyl 2-hydroxy-3-mercaptobutyrate, ethoxyacetic acid Propyl ester, methyl ethoxyacetate, ethoxyacetic acid ethyl acetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , 2 - propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate , 2 - butyl ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl acetoacetate , 3 - ethoxy propionate, g-ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate; diethyl ether 'tetrahydrofuran, etc. Ethers, etc. Further, as the aprotic polar solvent, dimethyl decylamine 'dimethylammonium amide, dimercapto sulfoxide, acetonitrile or the like can also be used. These solvents are usually contained in an amount of 2 to 98 parts by weight in the polycarboxylic acid composition component of the present invention. The polycarboxylic acid composition of the present invention in the case of using a solvent to form a varnish or an ink may be subjected to microfiltration, for example, using a filter of 〇〇5 to 2 m. Next, the case where the polyvalent carboxylic acid composition of the present invention is used as a sealing material or a solid crystal material of a photo-semiconductor will be described in detail. "In the case where the polycarboxylic acid composition of the present invention is used as a sealing material or material of a high-brightness white optical film such as Le 〇, in addition to the present invention, the polyacid resin (A) and the epoxy resin (A) In addition to b), an additive such as another hardener, a hardening accelerator, a coupling material, an antioxidant, a light stabilizer, a mortar, a vermiculite fine powder, or the like may be sufficiently mixed, thereby preparing a poly- & carboxylic acid composition, and Used as a sealing material or as both a solid crystal material and a sealing material. As a mixing method, a kneader, a three-roll mill, a universal mixer, a planetary mixer, a homomixer, a disperser, a bead mill can be used. The machine is mixed at room temperature or by heating. The optical semiconductor element such as a white LED is usually made of an adhesive (solid crystal material) to laminate GaAs on a substrate such as sapphire, spinel, Sic, Si, or Zn0. A semiconductor wafer such as GaP, GaA1As, GaAsp, AiGa, Inp, GaN, or AIN InGaN is packaged on a lead frame or a heat sink. In order to allow current to flow, there is also a type in which a gold wire or the like is connected. Subject to Or a moisture and functioning as a lens function to seal with a sealing material such as an epoxy resin. The multi-component (four) composition of the present invention can be used as the sealing material or the solid crystal material. The polycarboxylic acid composition is used for both a solid crystal material and a sealing material. In the method of using the present invention; #z, Λ IΛ 凡 羧酸 carboxylic acid composition to make the semiconductor wafer adhere to the substrate, , > Twist, it knife, device, infusion, screen printing After applying the composition of the hair (4), a semiconductor wafer is mounted and heat-hardened to carry out the wafer. The heating can be carried out by using a hot air circulation type, an infrared ray, or a high heating condition, for example, preferably at 8 Torr to (10) for about Μ minutes to Μ hours. In order to reduce the internal stress generated by the j 4 π 1匕 temple during heat hardening, for example, 49 201245288 is pre-hardened at 80 to 120 C for 30 minutes to 5 hours, at 120 to 180 C, 30 minutes to 丨〇 hours. Post-hardening under conditions. As a molding method of the sealing material, an injection method in which a sealing material is injected into a mold frame in which a substrate on which a semiconductor wafer is fixed is inserted as described above, and then heat-hardened and formed is used; a sealing material is injected into the mold in advance. A semiconductor wafer that is fixed on a substrate is subjected to a compression molding method in which a semiconductor wafer is heat-hardened and then released from a mold. Examples of the injection method include a dispenser, transfer molding, and injection molding. For heating, a hot air circulation type, an infrared ray, a high frequency, or the like can be used. The heating conditions are, for example, preferably from 80 to 23 Torr. Your majesty carries out i minutes ~ 24 hours: right. In order to reduce the internal stress generated during heat curing, for example, it can be pre-hardened at 8 〇 to 120 ° C for 30 minutes to 5 hours, and then carried out under conditions of 12 Torr to 8 〇〇 c for 30 minutes to 1 hour. After hardening. The polybasic acid-reducing resin (A) of the present invention has a specific structure and is liquid at room temperature (25. under the enamel, and the hardening property of the epoxy resin is excellent [the volatility in the temperature range usually used for hardening the epoxy resin) The polycarboxylic acid composition containing the polycarboxylic acid resin (A) of the present invention can be used in various applications typified by optical component materials using a usual epoxy resin composition. The so-called optical material, letterhead + a & β η is not commonly used for the purpose of allowing visible light, infrared rays, ultraviolet rays, X-rays, lasers, etc. to pass through the material. More specifically, 'light-type, fine-type, etc. Other than the optical semiconductor solid crystal material, the following may be mentioned. In the field of liquid crystal display, the base plate #, the light guide plate', the deflector, the retardation plate, the 201245288 viewing angle correction film, the adhesive, and the polarizing element protective film 4 A liquid crystal display device such as a U-film is not used as a peripheral material, and a sealing material, an anti-reflection film, and an optical repair of a PDP (Plasma Display Panel) which is expected as a next-generation flat panel display. Positive film, cover material, protective film for front glass, front plate glass substitute material, adhesive, LED mold material used in LED display device, LED sealing material, front plate glass protective film, front plate glass instead Material, adhesive material, substrate material in plasma address liquid crystal display (PALC), light guide plate prism sheet, deflecting plate, phase difference plate 1 angle correction film, adhesive, polarizing element 4 film, organic EL (electr〇lumineseence, electroluminescent) protective film for front glass, front glass replacement material, adhesive, and various film substrates and front glass in field emission display (FED, field emissi〇n -1) Protective film, front glass replacement material, adhesive. In the field of optical recording 'has VD (vide〇disk, video CD), cd /CD-ROM ^ CD-R/rW , DVD-R/DVD-RAM &gt MO / MD, PD (Phase Change Disc), optical disc substrate material, disc pickup lens (pickUp Lens), protective film, sealing material, adhesive, etc. In the field of optical equipment In the middle, it is the material for the lens of the static camera, the finder prism, the target prism, the viewfinder cover (finderC〇Ver), and the light sensor. Also, the video camera is ~ lens It is a projection lens, a protective film, a sealing material, an adhesive, etc. of a projection television, a lens material for a light sensing device, a sealing material, an adhesive, a film, and the like. In the optical component collar 51 201245288 domain, the fiber material around the optical converter in the optical communication system, the lens, the sealing material of the waveguide element, the adhesive, and the like. Further, it is an optical fiber material, a ferrule, a sealing material, an adhesive or the like around the optical connector. Further, in the passive components and optical circuit components, the lens, the waveguide, the sealing material for the LED, the sealing material for the CCD, and the adhesive are used. A substrate material, a fiber material, a sealing material for an element, an adhesive, and the like surrounding the IC Optics Electronic Integrated Circuit. In the field of optical fiber, it is used for illumination, light guide, etc., for industrial use, 15 types of display, display/identification, etc., as well as communication infrastructure and digital in the home. Also equipped with A fiber for connection. In the material surrounding the semiconductor integrated circuit, LS [, a resist material for lithography used in super LSI materials. In the field of automobiles/transports, the lamp reflectors, bearing retainers, gear parts, touch-resistant coatings, switch parts, headlights, engine parts, xenon parts, internal and external parts, and drive engines , brake oil tanks, anti-recording steel plates for automobiles, interior panels, interior materials, harnesses for protection/tying, fuel hoses, car lights, glass substitutes. In addition, the injury broadcast. Lao A ± is a laminated glass for railway vehicles. In addition, it is known as the structural material of the aircraft, _ pre-agent, engine peripheral components, protection / set of things :: two things. In the field of construction, there is interior/force: two materials. For agricultural use oli:: instead of °. °, the surrounding material of the solar cell is τ糸, and the wind is used for covering. As the next generation of 弁 / lei functional organic materials, is #I _ pieces, as a light (four) 1 piece of peripheral materials, organic light refracting element as a first-first conversion component of the optical amplifier solar cell periphery of a dry; ^ transport ^ Pieces, with adhesives, etc. Material, fiber material, sealing material for components,

S 52 201245288 As a sealant, a condenser, an electro-crystal, a photo-electrode, an IC, an L-SI, etc., and a *-a-** polar body are used for smelting, sub-cracking, and transfer molding. LSI class c〇B, COF, TAB, leisure, male, +~ 1C, TAB, perfusion seal, inverted primer, BGA, CSP, etc. κ: package type _ glue). Sealing (the use of the base material for reinforcement), examples of the epoxy resin group include an adhesive, a coating material, a coating agent, a molding method (including a sheet, a film, an FRP, etc.), an insulating material (including a printed substrate, and The t-line coating, etc., and the sealant 'other than this' may be an additive to other resins, etc. The material-adhesive' may be used as an adhesive for civil engineering, Jianhua, gas, general office, and medical use. In addition, an adhesive for an electronic material may be used. Examples of the bonding agent for the electronic material include an interlayer adhesive such as a multilayer substrate, a bonding agent, and a semiconductor such as a primer. An adhesive, a BGA-reinforced primer, an anisotropic conductive film (ACF, Anisotropic Conductive Film), an anisotropic conductive paste (ACP 'Anisotropic Conductive Paste), etc., etc., especially the hardened material obtained thereby Since it has excellent transparency, it is extremely useful as a hardener for epoxy resin for sealing high-brightness white LEDs or other optical semiconductors. In other applications, it is used as a raw material for polyimide or other polyimide resins. A chemical agent, a plasticizer, a lubricating oil raw material, a cyanate resin composition for a substrate, or an additive for other resins, a raw material for a coating resin, and a colorant are particularly useful for tree riding and medical pesticide intermediates. EXAMPLES Hereinafter, the present invention will be described in more detail by way of Synthesis Examples and Examples. Further, the present invention is not limited to the above-described synthesis examples and examples. Further, the physical property values in the examples are as follows. Here, the parts are by weight unless otherwise limited. '', 〇 Weight average molecular weight: The weight average molecular weight is calculated by the GPC method by conversion of polystyrene measured under the following conditions. 〃 GPC Various conditions Manufacturer: Shimadzu Manufacturing Pipe column. Protection column SHODEX GPC LF- G LF — 804 (3) Flow rate: 1.0 ml/min Column temperature: 40eC Solvent: THF (tetrahydrofuran) Detector: RI (differential Refractive index detector: Citrate value: Measured by the method described in JIS κ-2501. 〇 Epoxy equivalent: measured by the method described in JIS K-7236. 〇 Viscosity: E-type viscometer was used at 251 〇 Heat weight reduction: TG / DTA6200 ' manufactured by Shimadzu Corporation was used, and the temperature was raised at 20 ° C / min from 30 ° C, heated to 120 ° C, and the weight reduction rate after holding at 120 ° C for 60 minutes was measured. The air flow rate was carried out at 200 ml/min. Example 1 In a glass separable flask equipped with a stirring device, a Dairy condenser, and a thermometer, a two-terminal sterol-modified polyoxo X22-160AS (Shin-Etsu Chemical) was added. 47.1 parts of Adeka New Ace Y9 — 1 〇 as a polyester polyol (made by ADEKA CORPORATION 54 201245288) In the above formula (2), R3 is a neopentyl group and R4 is a butyl group. Ester polyol) 1 1_8 parts, RIKACID TDA — 1〇〇( 4—( 2,5-dihydrotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene _ L2 phthalic anhydride, new 7.4 parts, rikaCID MH (Nippon hexahydrophthalic acid needle 'manufactured by Nippon Chemical Co., Ltd.), 12 parts, reacted at 14 ° C for 10 hours to obtain the present invention. The polycarboxylic acid resin (a _ 1 ) was 78.5 parts. At this time, the peaks of rIKACID TDA-100 and RIKACID 消失 disappeared in the GPC measurement. The obtained compound had an acid value of 86 8 mgKOH/g, a weight average molecular weight of 3,483, a viscosity of 2〇48 〇 mpa.s, and a colorless transparent liquid. Example 2 In a glass separable flask provided with a stirrer, a Daimler condenser, and a thermometer, a two-terminal sterol-modified polyfluorene oxide 22_l6〇AS (manufactured by Shin-Etsu Chemical Co., Ltd.) 47 i was added. AdekaNewAceY9-l〇 as a polyester polyol (manufactured by ADEKA Co., Ltd., Rs is a neopentyl group in the above formula (2) and < butyl polyester polyol) "8 injury RIKACID BT-1 〇〇 (Ding Xuan tetradecanoic acid dianhydride, manufactured by New Japan Physical and Chemical Co., Ltd.) 2.5 parts, 16 parts of RIKACID MH (methyl hexahydro phthalic anhydride 'Nippon Chemical Co., Ltd.), 16 parts, The polycarboxylic acid resin (a-2) of the present invention was obtained by reacting at (4) C for 1 hr. At this time, in the Gpc measurement, ^丁一](8) and the RIKACID ΜΗ are slightly less, and are lost by Λ Α & The polycarboxylic acid resin was a colorless and transparent liquid at the end of the reaction, and 彳θ was lowered from the temperature of the #-reacting reaction liquid, and the appearance became a liquid of white 4. The obtained compound has an acid value of $76 7 , 55 201245288, a weight average molecular weight of 3452, and a viscosity of 5730 mPa·s β. Example 3 is in a glass separable flask equipped with a stirring device, a Dairy condenser, and a thermometer. Adding 471 parts of a two-terminal sterol-modified polyfluorene oxime 22_i6〇as (manufactured by Shin-Etsu Chemical Co., Ltd.) as Adeka New Ace Y9_1〇 (produced by ADEKA Co., Ltd., in the above formula (2) & is a neopentyl group and I is a butyl polyester polyol) 11.8 parts, RIKACID BT - 100 (butane tetraphthalic acid dianhydride, manufactured by New Japan Physical and Chemical Co., Ltd.) 4.9 parts, RIKACID MH (methyl six 125 parts of hydrogen phthalic anhydride (manufactured by Nippon Chemical and Chemical Co., Ltd.) was reacted at 140 ° C for 10 hours to obtain 74.0 parts of the polycarboxylic acid resin (A-3) of the present invention. At this time, in the Gpc measurement, the peaks of RIKACID Βτ_ 1〇〇 and RIKACID 消失 disappear. The obtained compound had an acid value of 79 9 mgKOH/g' weight average molecular weight of 6,960, a viscosity of 18,600 mPa.s, and a colorless transparent liquid. Example 4

Adding a two-terminal methanol-modified polyoxonium 22-16〇As (manufactured by Shin-Etsu Chemical Co., Ltd.) in a separable flask made of glass with a mixing device, a Dairy condenser, and a thermometer. 1,10-decanediol η·8 parts as hydrocarbon polyol, RIKACID BT-100 (butane tetradecanoic acid dianhydride manufactured by Nippon Chemical Co., Ltd.) 9.8 parts, rikacid μη (mercaptohexahydro-ortho-benzene) 24.9 parts of diacetic anhydride, manufactured by Nippon Chemical Co., Ltd., was reacted at 140 ° C for 1 hour to obtain 90.8 parts of the polycarboxylic acid resin (A-4) of the present invention. At this time, in the GPC measurement, the peaks of RIKACID 56 201245288 ΒΤ-100 and RIKACID MH disappeared. The obtained compound had an acid value of 89.3 mgKOH/g, a weight average molecular weight of 5,604, a viscosity of 23,296 mPa's, and a colorless transparent liquid. Example 5 In a glass separable flask provided with a stirring device, a Dairy condenser, and a thermometer, 'addition of two-terminal sterol-modified polysulfide X22 _ 16 〇 As (manufactured by K Yue Chemical Industry Co., Ltd.) 47.1 parts, 118 parts of tricyclodecane dimethanol as a hydrocarbon polyol, rIKACID bt - 1 〇〇 (butane tetracarboxylic dianhydride 'manufactured by New Japan Physical and Chemical Co., Ltd.) 8.7 parts, RIKACID MH (mercaptohexahydrogen neighbor) 2,0 parts of phthalic anhydride, manufactured by Nippon Chemical and Chemical Co., Ltd., at 14〇. (: The next reaction was carried out for 1 hour, and 87.1 parts of the polybasic acid resin (A-5) of the present invention was obtained. At this time, the peaks of RIKACID BT-1〇〇 and RIKACm MH disappeared in the GPC measurement. The acid value is 79.1 mgKOH/g', the weight average molecular weight is 4777, and the appearance is a colorless transparent liquid, but the viscosity is not determined because of the high viscosity. Example 6 is made of glass with a stirring device, a Dairy condenser, and a thermometer. In a separable flask, 'addition of two-terminal sterol-modified polyfluorene oxime 22-16 〇 (manufactured by Shin-Etsu Chemical Co., Ltd.) 47.1 parts, as a hydrocarbon polyol 2,4-diethylpentane-1,5 - 11.8 parts of diol, RIKACID BT -

1 〇〇 (butane tetraphthalic acid dianhydride, manufactured by New Japan Physicochemical Co., Ltd.) 9.7 parts, RIKACID ΜΗ (mercapto hexahydrophthalic anhydride, manufactured by New Japan Physicochemical Co., Ltd.) 24 9 parts, at l4 When the reaction was carried out under 〇«c, 90.7 parts of the polycarboxylic acid resin (A-6) of the present invention was obtained. At this time, the peaks of ' RIKACIDBT-100 and RIKACIDMH disappeared in the measurement of GPC 57 201245288. The obtained compound had an acid value of 81.1 mgKOH/g, a weight average molecular weight of 5203, a viscosity of 593920 mPa·s, and a colorless transparent liquid. Physical properties test The polycarboxylic acid resins a-1 to A-6 obtained in Examples 1 to 6 and RIKACID MH as a liquid acid anhydride compound in Comparative Example 1 (methylhexahydro-ortho-formic acid Sf' New Japan Physical and Chemical Co., Ltd. The traits of the company's manufacturing are summarized in Table 1. [Table 1] Table 1 Physical properties Test Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Compound Φ Amount Average molecular weight Acid value (mgICOH/g) Dot (25 ° C, mPa -s) Reduction of heat quantity (%) A-1 3483 86.8 20480 -1.0 A-2 3452 76.7 5730 -1.1 A-3 6960 79.9 18600 A 1.3 A-4 5604 89.3 23296 -1.9 A-5 4777 79.1 -1.5 A — 6 5203 81.1 593920 -1.4 RIKACID ΜΗ 60 -42.8 Synthesis Example 1 Synthesis of a condensate of an oxime compound having an epoxy group and a ruthenium compound other than the ruthenium compound 2 - (3,4 epoxycyclohexyl)ethyltrimethoxy 394 parts of decane, molecular weight 1700 (GPC measured value) of decyl alcohol-based polydidecyldiphenyl siloxane 475 parts '〇·5% ΚΟΗ methanol solution 4 parts, isopropyl alcohol 36 parts added to the reaction vessel Medium's temperature rise to 751. After the temperature was raised, the reaction was carried out under reflux for 10 hours. After the reaction, 656 parts of decyl alcohol was added, and then 172.8 parts of a 50% distilled water sterol solution was added dropwise over 60 minutes, and further reacted under reflux for 10 hours. After the completion of the reaction, the mixture was neutralized with a 5% aqueous solution of disodium hydrogen phosphate, and then distilled at 10,000 ° C to carry out distillation. Thereafter, methyl isobutyl is added for washing.

S 58 201245288 _ ( MIBK ) After 780 parts, wash it 3 times. Then, 4 doses were removed from the organic phase at 100 C under reduced pressure, whereby 73 parts of an alkoxylated a substance (Β ~ 1 ) having an epoxy group was obtained. The obtained compound had an epoxy equivalent of 491 g/eq, a weight average molecular weight of 2〇9〇, and a colorless and transparent appearance. Synthesis Example 2 (Synthesis of a condensate of an oxime compound having an epoxy group and a ruthenium compound other than the oxime compound) 197 parts of 2-(3'4 epoxycyclohexyl)ethyltrimethoxy shixiyuan, molecular weight 1700 (GPC measurement value) 534 parts of polydimethyl dimethyl oxane having a base of Shi Xiyuan, 〇·5% sterol solution, 4 parts of isopropanol, and added to the reaction vessel, and heating up i 75〇c . After the temperature was raised, the reaction was carried out under reflux for 10 hours. After the reaction, after adding 576 parts of decyl alcohol, 86 parts of a 50% distilled water methanol solution was added dropwise over 6 minutes, and further reacted under reflux for 1 hour. After completion of the reaction, the mixture was neutralized with a 5% aqueous solution of disodium hydrogen phosphate, and then subjected to distillation distillation at 8 ° <>>c. Thereafter, after washing and adding MIBK 66 aliquots, the mixture was washed three times with water. Then, the solvent was removed from the organic phase under reduced pressure at i 〇〇 <>c, whereby 648 parts of the oxoxane compound (B-2) having an epoxy group was obtained. The obtained compound had an epoxy equivalent of 857 g/eq, a weight average molecular weight of 1,860, and a colorless and transparent appearance. Synthesis Example 3 (Liquid carboxylic acid compound having a polyfluorene skeleton) 50 parts of a methanol modified polyoxyxylene X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), RIKACID MH (methylhexahydroortho-benzene) 154 parts of diacetic anhydride, manufactured by Nippon Chemical Co., Ltd., was added to the reaction vessel, and the temperature was raised to 80 ° C. After 4 hours, GPC was measured, and the peak of RIKACID MH disappeared. Thereafter, the reaction was further carried out for 2 hours, whereby 65.0 parts of a carboxylic acid compound (A-7) was obtained from 59 201245288. The obtained compound had an acid value of 80.0 mgKOH/g, a weight average molecular weight of 17 Å, and a viscosity of 75 〇mPa-s. Example 7 The polycarboxylic acid resin (A-1) obtained in Example 1 was added. 71 parts of an oxirane compound (B-1) having an epoxy group obtained in Synthesis Example 1 as an epoxy resin, and an oxy-oxygen compound having an epoxy group obtained in Synthesis Example 2 (B-2) 71 parts were mixed and defoamed for 5 minutes to obtain a polycarboxylic acid composition. Example 8 The polyvalent carboxylic acid resin (a - 2 ) obtained in Example 2 was added in an amount of 1 part by weight, and the epoxy group-containing aziridine compound (B-1) obtained in Synthesis Example 1 as an epoxy resin H0 The mixture was mixed and defoamed for 5 minutes to obtain a polycarboxylic acid composition. Example 9

The carboxylic acid compound (A-3) obtained in Example 3 and the liquid carboxylic acid compound (A-7) obtained in Synthesis Example 3 were added as a oxime resin in Synthesis Example 1. 220 parts of the epoxy group-containing oxoxane compound (B-1) were obtained, mixed and defoamed for 5 minutes to obtain a polybasic citric acid composition. Example 1 0 100 parts of the polycarboxylic acid resin (A-4) obtained in Example 40, a liquid carboxylic acid compound (A-7) obtained in Synthesis Example 3, and a synthesis example of an 'oxygen resin' Obtained in 1 and ancient $ a々a & ^ ”', ring

121.5 parts of an epoxy group-containing oxoxane compound (B 201245288-1), and an epoxy group-containing oxime compound (B-2) 121.5 parts obtained in Synthesis Example 2 were mixed and carried out for 5 minutes. Defoaming is carried out to obtain a polycarboxylic acid composition. Example 11 The polycarboxylic acid resin (A-5) obtained in Example 5 was added in an amount of 1 part by weight, and the liquid carboxylic acid compound (A - 7 ) obtained in Synthesis Example 3 was used as an epoxy resin. The epoxy group-containing oxoxane compound (B-1) obtained in Synthesis Example 1 was mixed, and defoamed for 5 minutes to obtain a polyvalent decanoic acid composition. Example 12 The polycarboxylic acid resin (a-6) obtained in Example 6 was added in 10 parts by weight, and the liquid carboxylic acid compound (A-7) obtained in Synthesis Example 3 was used as an epoxy resin. The epoxy group-containing oxoxane compound -1 ) obtained in Example 1 was made up of 10 parts, mixed and defoamed for 5 minutes to obtain a composition of a polybasic phthalic acid composition. Comparative Example 2 100 parts of the liquid acid compound (a-7) obtained in Synthesis Example 3, and an epoxy group-containing compound (B-1) obtained as an epoxy resin in Synthesis Example 1. 00 parts were mixed and defoamed for 5 minutes to obtain an epoxy resin composition. Evaluation Test The blend ratio of the polyvalent carboxylic acid compositions obtained in Examples 7 to 12 and Comparative Example 2, and the Durometer Hardness of the cured product, the transmittance, the depression of the cured product accompanying the volatilization of the cured product, The results of surface tackiness 201245288 are shown in Table 2. The tests in Table 2 were carried out in the following manner. (1) Post-mixing viscosity: The polycarboxylic acid compositions obtained in Examples 7 to 2 and Comparative Example 2 were subjected to vacuum defoaming for 5 minutes, and then measured at 25 ° C using an E-type viscometer. (2) Hardness tester hardness: The polycarboxylic acid composition obtained in Comparative Example 2 of Examples 7 to 12' was vacuum defoamed for 5 minutes, and then cast into a mold having a diameter of 3 mm and a height of 7 mm. Inside the mold of aluminum foil. The cast material was pre-hardened for ι hours and then hardened at 15 Ot X 3 hours to obtain a test piece for hardness tester having a thickness of 7 mm. The obtained test piece was measured for durometer hardness (type A) by the method described in JIS κ-6253. (3) Hardened material transmittance: The polycarboxylic acid composition obtained in Examples 7 to 12 and Comparative Example 2 was subjected to vacuum defoaming for 5 minutes, and then slowly cast at a height of 3 mm mmOO mm x 0.8 mm. A heat-resistant adhesive tape is used to form a glass substrate having a barrier. The cast material was subjected to pre-hardening at 12 ° C for 1 hour and then hardened at 150 ° C for 3 hours to obtain a test piece having a thickness of 〇 and a transmittance of 8 mm. The light transmittance of 4 〇〇 nm was measured on the obtained test piece under the following conditions. Spectrophotometer measurement conditions Manufacturer: Hitachi High-Technologies Co., Ltd. Model: U-3300 Slit width: 2.0 nm Knowing speed: 12 0 nm/ miri 62 201245288 (4) Example of depression test 7 to 12, the polycarboxylic acid composition obtained in Comparative Example 2, and the knife-knife vacuum defoaming, and then filled in a syringe, using a micro-injection device, so that the opening portion is flat, and it is expected to be equipped with a 45 Grm. A surface mount type LED of a light emitting element having an emission wavelength. 12Gt: xl hours 〇 Moxibustion is hardened by l5〇C χ3 hours, and the surface mount type is sealed. The presence or absence of the depression of the surface of the resin accompanying the vulcanization of the hardener after sealing in this manner was visually observed. In the table, 〇: not sure 5 endured to the depression, △: confirmed a little depression; X: confirmed a large number of depressions. (5) Surface tackiness: A test piece having the same test as the above-mentioned cured product transmittance was produced, and the surface tackiness (stickiness of the surface) of the test piece was confirmed by a finger touch. In the table, 〇: no sticky; X: sticky. [Table 2] Table 2 - Production price test polycarboxylated compound Α-1 Α-2 Α-3 Α-4 Α-5 Α-6 Example 7 100 Example 8 100 Example 9 100 Example 10 100 Implementation Example 11 100 Example 12 100 Comparative Example 2 Carboxylic acid compound Α-7 — Epoxy resin epoxy resin (Β-1) Epoxy resin (Β-2) 71 71 110 220 100 121.5 121.5 100 206 100 210 100 100 Physical properties Evaluation (1) Post-mudiness viscosity (mPa.s) (2) Hardness tester hardness (3) Hardened material transmittance (%) (4) Depression (5) Surface viscosity 3686 A-57 92 〇〇3891 A-53 91 〇〇3789 A-55 92 〇〇Ϊ971 A-48 91 〇〇7168 A-65 92 〇-〇6592 A-61 92 〇〇1560 A-4I 91 As shown by the results shown in Table 1, As a comparison of the liquid carboxylic anhydrides 63 201245288 The RIKACID of Example 1 is at 12 (the thermal weight is greatly reduced under the condition of TC). In contrast, the polycarboxylic acid resins A-1 to A-6 of Examples 1 to 6 are In the liquid state, almost no weight loss was observed. Further, as is clear from the results shown in Table 2, it was found that the hardness of the hardened material (type A) of the cured product in Comparative Example 2 was small and the strength was poor. In the examples 7 to 12, the hardness meter has a high hardness and excellent strength. Further, 'there is no depression and the surface is sticky. Moreover, the polycarboxylic acid resin A-2 used in Example 8 is turbid at room temperature, but it is turbid at room temperature. In the same manner as in the examples 7 and 9 to 12, the transmittance of the cured product is excellent. The present invention has been described in detail above with reference to the specific embodiments, but it will be understood by those skilled in the art that various changes can be made without departing from the spirit and scope of the invention. Furthermore, this application is based on the patent application filed on April 7, 2011 (the patent application No. 2011_85〇67), the entire contents of which are hereby incorporated by reference. All of the references herein are as follows. I. Industrial Applicability] The multi-strength resin of the present invention is composed of a hardener for an epoxy resin together with an epoxy resin. It is useful for electrical/electronic materials, oxygen-deposited materials for forming materials, coatings, adhesives, anti-surname materials, and especially for essential light H. For example, optical semiconductors (10), etc.)::::: Material, extremely use. ; Sealing material and [Simple description] 64 201245288 None [Main component symbol description

Claims (1)

201245288 VII. Patent application scope: 1 . A polyvalent carboxylic acid resin (A) which has two or more methanol-modified polyoxosulfuric acid (a) represented by the following formula (i) and has two or more molecules in the molecule. The hydroxyl group polyol compound (e) and the compound (c) having two or more carboxylic acid anhydride groups in the molecule are obtained by an addition reaction. (In the formula (1), 'R, each independently represents an alkylene group having 1 to 1 carbon atom or an alkylene group having an ether bond having 1 to 10 carbon atoms, and each independently represents a methyl group or a phenyl group, and η The average value indicates 1 to 1 〇〇). 2. A polycarboxylic acid resin (Α) which is a polyol compound (e) having a molecular weight of two or more hydroxyl groups in the molecule by the following formula (〇) a compound (c) having two or more carboxylic acid anhydride groups in the molecule, and a compound (d) having one carboxylic anhydride group in the molecule are obtained by an addition reaction. (In the formula (1), 'Ri each independently represents a alkylene group having a carbon number of 1 to 1 Å or an alkylene group having an ether bond having 1 to 10 carbon atoms, and each independently represents a fluorenyl group or a S 66 201245288 stupid group, η is expressed as an average value !00 ). 3. The polyol compound (e) having two or more hydroxyl groups in the molecule, as in the polyvalent carboxylic acid resin (a) of the invention of claim 2 or 2, is a terminal alcohol polyester compound (b). 4. The polycarboxylic acid resin (A) according to claim 3, wherein the terminal alcohol polyester compound (b) is represented by the formula (2), A, Han 3, and R4 each independently represent a carbon number base, and ni is expressed as an average value of 1 to 1 〇〇). Among them, 5. "Please request the multi-acid sour resin (4) of the patent range..., the polyol has two 4-group polyol compounds (e) as hydrocarbons (A) 6, such as; 7 patent range 1st to The multi-domain acid resin of any of the five items is one or more selected from the group consisting of: (1) " (5) having the following two = more than two groups, 67 201245288 7. The polycarboxylic acid resin (A) of any one of claims 2 to 6, wherein the compound (") having a phthalic anhydride group in the molecule is selected from the formula (6) to (1). More than one of the group, 8. A polycarboxylic acid composition comprising the multi-drug resistant resin (A) and the epoxy resin (b) according to any one of claims 1-6. A hardened material obtained by hardening a polycarboxylic acid composition of claim 8 of the patent application. S 68 » 201245288 9 hardening 1 〇. A kind of light-emitting diode with the scope of patent application. 69