TWI512016B - Polycarboxylic acid resin and its composition - Google Patents

Description

Polycarboxylic acid resin and its composition

The present invention relates to a polycarboxylic acid resin suitable for use in electrical and electronic materials, particularly in optical semiconductor applications, and a polycarboxylic acid composition containing the same.

Since the epoxy resin is cured by hardening to obtain a cured product excellent in adhesion, mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., it can be used in coatings, adhesives, composite materials, and molding materials. Used in a wide range of fields such as casting materials, various coating materials, and resists. Examples of the curing agent used in the epoxy resin include an amine compound, a carboxylic acid compound, a carboxylic acid anhydride, a phenol compound, a thiol compound, and the like. Among these hardeners, various carboxylic acid compounds or carboxylic anhydrides, especially liquids, are often used in applications where high transparency or heat resistance is required for the cured product or when a moderate service life is required. In the composition, a liquid carboxylic anhydride is usually used as the hardener. On the other hand, the hydrogen bond between the molecules of the carboxylic acid compound is strong, which 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 optical semiconductor sealing such as an LED (Light Emitting Diode), bisphenol epoxy resin, alicyclic epoxy resin, etc. have been used in terms of excellent mechanical strength and adhesion. The liquid epoxy resin composition (refer to Patent Document 1). In recent years, LEDs have been increasingly used in the field of high-intensity brightness such as automotive headlamps or lighting applications, and, in turn, are increasingly resistant to resins that seal optical semiconductor components. UV and heat resistance. However, it is difficult to say that the bisphenol type epoxy resin or the alicyclic epoxy resin as described above has sufficient UV resistance and heat resistance, and may not be used in a field requiring high brightness. Therefore, as a sealing material having high UV resistance, heat resistance and the like, a polyoxyxylene resin sealing material using an organic polyoxyalkylene having an unsaturated hydrocarbon group and an organic hydrogen polyoxyalkylene has been used (refer to the patent). Literature 2). However, the sealing material using such a polyoxymethylene 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 these problems, a condensate of a ruthenium compound having an epoxy group and a liquid carboxylic acid anhydride are used to promote the development of a sealing material which is excellent in UV resistance and heat resistance and has good adhesion (see Patent Document 3, Patent Literature). 4).

The carboxylic acid anhydride used in such a use is hexahydrophthalic anhydride or methylhexahydrophthalic acid because it is colorless and transparent, liquid at room temperature, and easy to handle. a carboxylic anhydride such as an acid anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride or the like a mixture of such. However, these carboxylic anhydrides are mostly low molecular weight compounds. Therefore, in the epoxy resin composition containing the carboxylic anhydride as a curing agent, volatilization of the carboxylic acid anhydride during thermal curing becomes a problem. The volatilization of the carboxylic anhydride not only causes a problem of poor curing of the epoxy resin composition due to the absence of a necessary amount of carboxylic anhydride (hardener) in the hardening reaction, but also adverse effects on the human body due to its harmfulness. The pollution of the production line and the air pollution have a greater impact on the environment.

Therefore, it has a low volatility and is a liquid polyoxygen skeleton at room temperature. Carboxylic acid compounds have been studied. However, since the strength of the cured product which is satisfactory can not be exhibited, there is a problem such as occurrence of cracks during lead-free reflow when used as an optical semiconductor sealing material (see Patent Document 5).

Patent Document 1: Japanese Patent Laid-Open Publication No. 2003-277473

Patent Document 2: Japanese Patent No. 4636242

Patent Document 3: Japanese Laid-Open Patent Publication No. 2008-174640

Patent Document 4: Japanese Laid-Open Patent Publication No. 2008-255295

Patent Document 5: International Publication No. 10/071168

The object of the present invention is to provide a liquid at room temperature, which is less volatile at high temperatures, especially when used as a hardener for epoxy resins, which has less volatility in the hardening step and provides transparency (colorless and transparent) ), a cured product excellent in hardenability, and a polycarboxylic acid resin excellent in mechanical strength of the cured product.

The inventors of the present invention have conducted intensive studies in view of the above-mentioned circumstances, and as a result, it has been found that by using a polyoxyl compound having a specific skeleton, a polyol compound having two or more hydroxyl groups in the molecule, and having two or more molecules in the molecule. The polycarboxylic acid resin obtained by reacting a carboxylic anhydride group-containing compound and, if necessary, a compound having a carboxylic anhydride group in a molecule, as a curing agent for an epoxy resin, solves the above problems, and completed the present invention.

That is, the present invention relates to

(1)

The polyvalent carboxylic acid resin (A) is a polyhydric alcohol compound (e) modified by a two-terminal methanol represented by the following formula (1), a polyol compound (e) having two or more hydroxyl groups in the molecule, and a compound (c) having two or more carboxylic acid anhydride groups in the molecule is obtained by an addition reaction,

(In the formula (1), R ₁ 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 R ₂ each independently represents a methyl group or a phenyl group, and n is average The value meter indicates 1~100);

(2)

A polyvalent carboxylic acid resin (A) is a polyhydric alcohol compound (e) having two or more hydroxyl groups represented by the following formula (1), a polyhydric alcohol compound (e) having two or more hydroxyl groups in the molecule, and a molecule The compound (c) having two or more carboxylic acid anhydride groups therein and the compound (d) having one carboxylic acid anhydride group in the molecule are obtained by an addition reaction.

(In the formula (1), R ₁ 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 R ₂ each independently represents a methyl group or a phenyl group, and n is average The value meter indicates 1~100);

(3)

a polycarboxylic acid resin (A) as in (1) or (2), wherein, in the molecule The polyol compound (e) having two or more hydroxyl groups is a terminal alcohol polyester compound (b);

(4)

a polycarboxylic acid resin (A) according to (3), wherein the terminal alcohol polyester compound (b) is represented by the formula (2),

(In the formula (2), R ₃ and R ₄ each independently represent an alkylene group having 1 to 10 carbon atoms, and m is represented by an average value of 1 to 100);

(5)

The polycarboxylic acid resin (A) according to (1) or (2), wherein the polyol compound (e) having two or more hydroxyl groups in the molecule is a hydrocarbon polyol compound (f);

(6)

The polycarboxylic acid resin (A) according to any one of (1) to (5), wherein the compound (c) having two or more carboxylic acid anhydride groups in the molecule is selected from the following formulas (3) to (5) More than one of the group,

(7)

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,

(8)

A polycarboxylic acid composition comprising the polycarboxylic acid resin (A) according to any one of (1) to (7), and an epoxy resin (B);

(9)

a hardened material obtained by hardening a polycarboxylic acid composition of (8);

(10)

A light-emitting diode having a cured product of (9).

According to the present invention, since the polyvalent carboxylic acid resin having a polysiloxane structure is in a liquid form, it is easy to handle, and a cured product excellent in heat resistance, hardness, transparency, and light resistance can be obtained, and thus the polycarboxylic acid of the present invention is contained. The polycarboxylic acid composition of the resin is useful in a wide range of applications such as electrical/electronic materials, molding materials, casting materials, laminate materials, coatings, adhesives, resists, and the like, especially as a material having necessary optical properties, such as It is extremely useful for an adhesive material or a sealing material for an optical semiconductor (such as an LED product).

The polyvalent carboxylic acid resin (A) of the present invention is a resin obtained by modifying a two-terminal methanol poly(oxygenated oil) (a), a polyol compound (e) having two or more hydroxyl groups in a molecule, and an intramolecular molecule. A compound (c) having two or more carboxylic anhydride groups (and a compound (d) having a carboxylic acid anhydride group in a molecule as needed) is obtained by an addition reaction, and has a polysiloxane structure in the molecule (by Si-O) The polyoxane composed of a bond is a main skeleton and an organic skeleton composed of C, H, and O, and has two or more carboxylic acids (carboxy groups) in the same molecule. The polyvalent carboxylic acid resin of the present invention can be modified in the molecule by modifying the two-terminal methanol described below with a polyoxyl oil (a) and an alcoholic hydroxyl group of a polyol compound (e) having two or more hydroxyl groups in the molecule. The carboxylic anhydride group of the compound (c) of two or more carboxylic anhydride groups (and the compound (d) which has one carboxylic anhydride group in a molecule as needed) is obtained by addition reaction. By having more than two molecules in the molecule The carboxylic anhydride group-containing compound (c) is subjected to an addition reaction, and the two-terminal methanol-modified polyoxo-oxygen oil (a) and the polyol compound (e) having two or more hydroxyl groups in the molecule, and/or Or the two-end methanol-modified polyoxyl oil (a) is polymerized into the same molecule as the polyol compound (e) having two or more hydroxyl groups in the molecule.

In the following, a methanol-modified polyfluorene oxide (a) which is a raw material of the polyvalent carboxylic acid resin (A), a polyol compound (e) having two or more hydroxyl groups in the molecule, and two or more carboxylic anhydrides in the molecule The compound (c) based on the group and the compound (d) having a carboxylic anhydride group in the molecule are explained.

First, the two-end methanol-modified polyoxyxane oil (a) will be described.

The both-end methanol-modified polyoxoic acid (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 ₁ 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 R ₂ each independently represents a methyl group or a phenyl group, and n is average Value meter indicates 1~100)

In the formula (1), specific examples of R ₁ include a methylene group, an exoethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and a octyl group. a linear alkylene group of ~10, a branched alkylene group having a carbon number of 1 to 10, such as an isopropyl group, an isobutyl group, an isoamyl group, an ethyl group having an alkyl group, a propoxy group, and an ethyl group. Propyloxypropyl, ethoxypropyl, etc. can be expressed by the following formula (11)

(In the above formula (11), R ₅ each independently represents an alkylene group having 1 to 5 carbon atoms)

An alkylene group having an ether bond of 1 to 10 carbon atoms is represented. Among them, preferred are propoxyethyl and ethoxypropyl.

Specific examples of R ₂ include a methyl 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 preferable to use a phenyl group. methyl.

In the formula (1), n is from 1 to 100, preferably from 2 to 80, more preferably from 5 to 30, in terms of an average value.

The two-terminal methanol-modified polyoxoic acid (a) represented by the formula (1) is, for example, a polyfluorene-based compound having an alcoholic hydroxyl group at both terminals. As a specific example, X-22-160AS, KF6001, KF6002, and KF6003 (both manufactured by Shin-Etsu Chemical Co., Ltd.) as a two-terminal methanol-modified polyoxygenated oil can be cited; BY16-201, BY16-004, and SF8427 (all manufactured by TORAY.DOWCORNING Co., Ltd.); XF42-B0970, XF42-C3294 (all manufactured by Momentive Performance Materials Japan Co., Ltd.), etc., are available from the market. The modified polyoxygenated oil having an alcoholic hydroxyl group at both ends may be used alone or in combination of two or more. Among these, X-22-160AS and KF6001 are preferred. KF6002, BY16-201 or XF42-B0970.

Next, a polyol compound (e) having two or more hydroxyl groups in the molecule will be described.

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 a terminal represented by the following formula (2).

(In the formula (2), R ₃ and R ₄ each independently represent an alkylene group having 1 to 10 carbon atoms, and m is an average value of 1 to 100)

In the formula (2), specific examples of R ₃ include a methyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and a octyl group. Branched alkylene, isopropylidene, ethylbutyl propyl, isobutyl, isopentyl, neopentyl, diethyl pentyl, etc. An alkylene group having a cyclic structure such as cyclopentane dimethylene or cyclohexane dimethylene. Among them, a branched alkylene group having a carbon number of 1 to 10 or an alkylene group having a cyclic structure is preferred, and ethyl butyl propyl group is particularly preferable from the viewpoint of heat-resistant transparency of the cured product. Stretching isobutyl, neopentyl, diethyl pentyl, cyclohexane dimethylene.

In the formula (2), as a specific example of R ₄ , a carbon number of 1 to 10 such as an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an exooctyl group may be mentioned. Branched alkylene, isopropylidene, ethylbutyl propyl, isobutyl, isopentyl, neopentyl, diethyl pentyl, etc. An alkylene group having a cyclic structure such as cyclopentane dimethylene or cyclohexane dimethylene. Among them, a linear alkylene group having 1 to 10 carbon atoms is preferred, and from the viewpoint of adhesion between the cured product and the substrate, a propyl group, a butyl group, a pentyl group and a hexyl group are particularly preferable.

In the formula (2), m is from 1 to 100, preferably from 2 to 40, more preferably from 3 to 30, on the average.

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 500 or more, the hardness of the cured product of the polyvalent carboxylic acid composition is not excessively high, and there is no concern that cracks occur in the heat cycle test or the like, which is preferable. Further, when the weight average molecular weight is 20,000 or less, the stickiness of the cured product is not caused, which is preferable. 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 Permeation Chromatography).

Various conditions of GPC

Manufacturer: Shimadzu Manufacturing Co., Ltd.

Pipe column: protection column SHODEX GPC LF-G LF-804 (3 roots)

Flow rate: 1.0 ml/min.

Column temperature: 40 ° C

Use solvent: THF (tetrahydrofuran, tetrahydrofuran)

Detector: RI (differential refractive index detector)

The terminal alcohol polyester compound (b) represented by the formula (2) is, for example, a polyester polyol having an alcoholic hydroxyl group at its 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-2376, Polylite OD-X-2044, Polylite OD- X-688, 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-40M (all manufactured by Fengguo Oil Co., Ltd.), etc., all from the market Take. These polyester polyols can It is used in one type or in mixture of two or more types. Among these, KYOWAPOL 1000PA, Adeka New Ace Y9-10, and HS2N-221A 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 pentanediol. , neopentyl glycol, hexanediol, dimethyl butanediol, heptanediol, dimethyl pentanediol, diethyl propylene glycol, octanediol, dimethyl hexane diol, diethyl butanediol , decanediol, dimethyl heptanediol, diethyl pentanediol, decanediol, dimethyloctyl glycol, diethyl hexanediol, ethyl butyl propylene glycol, 3-hydroxymethyl-1 , a chain hydrocarbon polyol compound such as 5-pentanediol, diglycerin or dipentaerythritol, or cyclopentanediol, cyclopentane dimethanol, cyclohexanediol, cyclohexanedimethanol, tricyclic A cyclic hydrocarbon polyol compound such as decanediol, tricyclodecane dimethanol, norbornanediol or norbornane dimethanol. These hydrocarbon polyol compounds (f) can 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, decanediol, diethyl pentanediol, and tricyclodecane dimethanol are preferable.

Next, the terminal alcohol polycarbonate compound will be described.

The terminal alcohol polycarbonate compound is not particularly limited, and examples thereof include a polycarbonate compound having a hydroxyl group at the terminal represented by the following formula (12).

(In the formula (12), R ₆ represents an alkylene group having 1 to 10 carbon atoms, and p is represented by an average value of 1 to 100)

In the formula (12), specific examples of R ₆ include a methylene group, an exoethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and a octyl group. a linear alkylene group of ~10, having a carbon number of 1 to 10 such as an isopropyl group, an ethyl butyl propyl group, an isobutyl group, an isoamyl group, a neopentyl group, and a diethylamyl group. An alkylene group having a cyclic structure such as an alkylene group of a chain, a cyclopentane dimethylene group or a cyclohexane dimethylene group. 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 R ₆ present in the formula (12) may be the same or different.

In the formula (12), p is from 1 to 100, preferably from 2 to 40, more preferably from 3 to 30, in terms of an average value.

The weight average molecular weight (Mw) of the terminal alcohol polycarbonate compound 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 500 or more, the hardness of the cured product of the polyvalent carboxylic acid composition is not excessively high, and there is no concern that cracks occur in the heat cycle test or the like, which is preferable. Moreover, if the weight average molecular weight is 20,000 or less, then no It is preferable to produce a sticky feeling of the hardened material. 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 permeation chromatography).

Various conditions of GPC

Manufacturer: Shimadzu Manufacturing Co., Ltd.

Pipe column: protection column SHODEX GPC LF-G LF-804 (3 roots)

Flow rate: 1.0 ml/min.

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Detector: RI (differential refractive index detector)

The polyol compound (e) having two or more hydroxyl groups in the molecule may be used alone or in combination of two or more.

The amount of the polyol compound (e) having two or more hydroxyl groups in the molecule is not particularly limited, and is preferably from 0.5 to 200 parts by weight, based on 100 parts by weight of the methanol-modified polyoxyxane oil (a) at both ends. It is preferably 5 to 50 parts by weight, more preferably 10 to 30 parts by weight. When the amount is 0.5 parts by weight or more, the mechanical strength of the cured product is further improved. Therefore, when it is 200 parts by weight or less, the heat-resistant transparency of the cured product is further improved, or the viscosity of the obtained polycarboxylic acid resin (A) is further improved. It becomes more suitable and therefore preferred.

Next, the compound (c) having two or more carboxylic acid 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 or 1,2,3,4-cyclobutanetetracarboxylic acid Anhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, pyrogallic anhydride, 5-(2,5-dioxotetrahydrofuranyl )-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1 , 2-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 excessive increase in the viscosity of the polyvalent carboxylic acid resin (A) is less likely to occur, and therefore it is preferable from the viewpoint of viscosity control.

The compound (c) having two or more carboxylic anhydride groups in the molecule may be used alone or in combination of two or more. In addition, 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.). 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuranyl-3-yl)-1, 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, more preferably 1,2,3,4-butanetetracarboxylic dianhydride.

Next, the compound (d) having a carboxylic anhydride group in the molecule will be described.

Examples of the compound (d) having a carboxylic anhydride group in the molecule include succinic anhydride, methyl succinic anhydride, ethyl succinic anhydride, 2,3-butane dicarboxylic anhydride, 2,4-pentane dicarboxylic anhydride, a saturated aliphatic carboxylic anhydride such as 3,5-heptane dicarboxylic anhydride, an unsaturated aliphatic carboxylic anhydride such as maleic anhydride or dodecyl succinic anhydride, hexahydrophthalic anhydride or methylhexahydroortho Phthalic anhydride, 1,3-cyclohexanedicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, nadic acid anhydride , methylic acid anhydride, bicyclo[2,2,2]octane-2,3-dicarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic acid- a cyclic saturated aliphatic carboxylic anhydride such as 1,2-anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, ceric anhydride, methylic acid anhydride, 4,5-dimethyl- a cyclic unsaturated unsaturated carboxylic acid anhydride such as 4-cyclohexene-1,2-dicarboxylic anhydride or bicyclo[2.2.2]-5-octene-2,3-dicarboxylic anhydride, phthalic anhydride, and An aromatic carboxylic acid anhydride such as phthalic anhydride, terephthalic anhydride or 1,2,4-benzenetricarboxylic anhydride.

The compound (d) having one carboxylic anhydride group in the molecule may be used alone or in combination of two or more. In particular, the cured product obtained by curing the polyvalent carboxylic acid composition containing the polyvalent carboxylic acid resin (A) and the epoxy resin (B) is excellent in transparency (heat-resistant transparency, etc.), and is preferably hexahydrogen. Phthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride. More preferably, it is methylhexahydrophthalic anhydride or 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, and more preferably methylhexahydrophthalic anhydride.

The amount of the compound (d) having one carboxylic anhydride group in the molecule is not particularly limited, and is preferably from 5 to 1,500 parts by weight, based on 100 parts by weight of the compound (c) having two or more carboxylic anhydride groups in the molecule. It is preferably 50 to 1000 parts by weight, more preferably 100 to 800 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 the viscosity is not excessively increased, and the workability is further improved. The mechanical strength of the cured product becomes good, so it is preferable. The balance of the viscosity of the polyvalent carboxylic acid resin (A) and the mechanical strength of the cured product is particularly preferably from 150 to 700 parts by weight.

As for the two-terminal methanol-modified polyoxyl oil (a), a polyol compound (e) having two or more hydroxyl groups in the molecule, a compound (c) having two or more carboxylic anhydride groups in the molecule, and a carboxylic anhydride in the molecule. The compound (d) is used in an amount of 1 equivalent to the total alcoholic hydroxyl group of the methanol-modified polyoxyxane oil (a) having two or more hydroxyl groups in the molecule. The total carboxylic anhydride group of the compound (c) having two or more carboxylic anhydride groups and the compound (d) having one carboxylic anhydride group in the molecule is preferably from 0.5 to 2.0 equivalents, more preferably from 0.8 to 1.5 equivalents. When the amount is 0.5 equivalent or more, the mechanical strength of the cured product is good. Therefore, when the amount is 2.0 equivalent or less, the carboxylic anhydride group does not remain in a large amount and the storage stability is good, which is preferable.

The polycarboxylic acid resin (A) of the present invention can be produced by adding the above-mentioned two-terminal methanol-modified polyoxylized oil (a), a polyolized content (e) having two or more hydroxyl groups in the molecule, and two molecules in the molecule. The compound (c) having a carboxylic acid anhydride group or more is reacted, and it is preferred to carry out the addition of the compound (d) having one carboxylic anhydride group in the molecule. Here, the addition of the component (d) suppresses an excessive increase in the molecular weight of the polyvalent carboxylic acid resin (A), and therefore is preferable from the viewpoint of reaction control.

In this case, each of the above compounds may be simultaneously mixed and added to cause a reaction, and each of the above compounds may be added in a predetermined order to cause a reaction.

The production of the polyvalent carboxylic 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 polyhydric alcohol (a) which does not have a methanol modification with both ends, a polyhydric alcohol compound (e) having two or more hydroxyl groups in the molecule, and a compound (c) having two or more carboxylic anhydride groups in the molecule, Intramolecular The solvent having a reaction of the carboxylic anhydride group-containing compound (d) can be used without particular limitation. As a solvent which can be used, for example, an aprotic polar solvent such as dimethylformamide, dimethylacetamide, dimethyl hydrazine, tetrahydrofuran or acetonitrile such as methyl ethyl ketone or cyclopentane may be mentioned. A ketone or a ketone of methyl isobutyl ketone such as an aromatic hydrocarbon such as toluene or xylene, and the like, preferably an aromatic hydrocarbon or a ketone.

These solvents can be used alone or in combination of two or more. The use amount in the case of using a solvent is a polyol compound (e) having two or more hydroxyl groups in the molecule, a polyhydric alcohol compound (e) having two or more hydroxyl groups in the molecule, and two or more carboxylic anhydride groups in the molecule. The compound (c) and the compound (d) having one carboxylic anhydride group in the molecule are preferably 100 parts by weight, preferably 0.5 to 300 parts by weight.

Here, from the viewpoint of the easiness of production, it is preferably produced without a solvent.

The polyvalent carboxylic acid resin (A) of the present invention can be produced without a catalyst or can be produced by using a catalyst. In the case of using a catalyst, examples of the catalyst that can be used include acidic compounds such as hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid, and hydrogen peroxide. a metal hydroxide such as sodium, potassium hydroxide, calcium hydroxide or magnesium hydroxide; an amine compound such as triethylamine, tripropylamine or tributylamine, pyridine, dimethylaminopyridine, 1,8- Heterocyclic compound such as diazabicyclo[5.4.0]undec-7-ene, imidazole, triazole or tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethyl hydroxide Cetyl ammonium, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate, etc. Tertiary ammonium salts, orthotitanic acid such as tetraethyl orthotitanate, tetramethyl orthotitanate, metal soaps such as tin octoate, cobalt octoate, zinc octoate, manganese octoate, calcium octylate, sodium octoate and potassium octylate.

In the case of using a catalyst, one type or a mixture of two or more types may be used.

The amount of use in the case of using a catalyst is a polyol compound (e) having two or more hydroxyl groups in the molecule, and a polyhydric alcohol compound (e) having two or more hydroxyl groups in the molecule, and two or more carboxylic anhydrides in the molecule. The total amount of the compound (c) and the compound (d) having one carboxylic anhydride group in the molecule is 100 parts by weight, preferably 0.05 to 10 parts 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 anhydride groups in the unreacted molecule or the compound (d) having one carboxylic anhydride group in the molecule is reacted. It is better to avoid use.

In the present invention, from the viewpoint of improving corrosion resistance gas permeability and heat resistance in the cured product of the obtained polyvalent carboxylic acid composition, zinc carboxylate such as zinc octylate can be preferably used as a catalyst. From the viewpoint of reducing the coloration of the obtained polycarboxylic acid composition, it is preferred to carry out the reaction without a catalyst.

Among them, in order to obtain a cured product excellent in transparency and sulfidation resistance, calcium stearate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc laurate, zinc myristate) can be preferably used. Or zinc phosphate (zinc octyl phosphate, stearyl) A zinc compound such as zinc phosphate or the like.

The reaction temperature in the production of the polyvalent carboxylic acid resin (A) of the present invention is also dependent on the amount of the catalyst and the solvent to be used, but it is usually 20 to 160 ° C, preferably 50 to 150 ° C, and particularly preferably 60 to 145 ° C. Further, the total reaction time is usually from 1 to 20 hours, preferably from 3 to 18 hours. The reaction can also be carried out in two or more stages. For example, it can be reacted at 20 to 100 ° C for 1 to 8 hours, and then reacted at 100 to 160 ° C for 1 to 12 hours. In this case, in particular, the compound (d) having a carboxylic anhydride group in the molecule is mostly volatile, and in the case of using the compound, it is reacted at 20 to 100 ° C in advance, at 100 to 160. The reaction is carried out at ° C to suppress the volatilization. Thereby, not only the harmful substances can be suppressed from diffusing into the atmosphere, but also the polycarboxylic acid resin (A) designed according to the design can be obtained.

In the case of production using a catalyst, the catalyst may be removed by quenching and/or washing as needed, but may be left as a curing accelerator for the polycarboxylic acid composition.

In the case of performing the water washing step, it is preferred to add a solvent which can be separated from water depending on the kind of the solvent to be used. As a preferable solvent, for example, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone; esters such as ethyl acetate, butyl acetate, ethyl lactate, and isopropyl butyrate can be exemplified; Such as hexane, cyclohexane, toluene, xylene hydrocarbons and the like.

In the case where a solvent is used in the reaction or water washing, it can be removed by concentration under reduced pressure or the like.

The polycarboxylic acid resin (A) of the present invention obtained in this manner is usually a liquid having a fluidity at 25 °C. Also, its molecular weight is measured by GPC. The weight average molecular weight meter is preferably from 800 to 80,000, more preferably from 1,000 to 10,000, further preferably from 1,500 to 8,000, and particularly preferably from 3,000 to 8,000. When the weight average molecular weight is 800 or more, the fluidity at 25 ° C is improved, and the compatibility with the epoxy resin is also improved, which is preferable.

The weight average molecular weight is a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) under the following conditions.

Various conditions of GPC

Manufacturer: Shimadzu Manufacturing Co., Ltd.

Pipe column: protection column SHODEX GPC LF-G LF-804 (3 roots)

Flow rate: 1.0 ml/min.

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Detector: RI (differential refractive index detector)

The acid value (measured by the method described in JIS K-2501) of the polyvalent carboxylic acid resin (A) of the present invention produced is preferably 35 to 200 mgKOH/g, more preferably 50 to 180 mgKOH/g, particularly preferably It is 60~150 mgKOH/g. When the acid value is 35 mgKOH/g or more, the mechanical properties of the cured product are improved. Therefore, when the acid value is 150 mgKOH/g or less, the cured product is not excessively hardened, and the elastic modulus is moderate, so that it is preferable. .

Further, the functional group equivalent of the polycarboxylic acid resin (A) of the present invention is preferably from 280 to 1600 g/eq, more preferably from 350 to 1100 g/eq, still more preferably from 400 to 950 g/eq.

The viscosity of the polycarboxylic acid resin (A) of the present invention (E-type viscometer, measured at 25 ° C) is preferably 50 to 800,000 mPa. s, better for 500~ 100,000 mPa. s, especially good for 800~30,000 mPa. s. The viscosity is less than 50 mPa. In the case of s, there is a viscosity that is too low for use in the use of optical semiconductor sealing materials, in excess of 800,000 mPa. In the case of s, there is a case where the viscosity is too high and the workability is poor.

It is used to obtain the improvement of the storage stability of the polyvalent carboxylic acid resin (A) of the present invention, the low viscosity, and 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-resistant and transparent) A preferred embodiment of the present invention, which is excellent in the balance of curability and light resistance, is a (i) polycarboxylic acid resin (A) obtained by the following means: intramolecular The amount of the polyol compound (e) having two or more hydroxyl groups is 5 to 50 parts by weight based on 100 parts by weight of the two-terminal methanol-modified polyoxosiloxane (a), and a compound having a carboxylic anhydride group in the molecule is used. (d) is used in an amount of 50 to 1000 parts by weight based on 100 parts by weight of the compound (c) having two or more carboxylic acid anhydride groups in the molecule, and is modified with respect to the both ends of the methanol (a) and the molecule. a compound (c) having two or more carboxylic anhydride groups in the molecule and a compound having a carboxylic anhydride group in the molecule (d) having a total alcoholic hydroxyl group of the polyol compound (e) having two or more hydroxyl groups The total carboxylic anhydride group is set to be 0.8 to 1.5 equivalents.

Further, a more preferred embodiment is: (ii) setting the amount of the polyol compound (e) having two or more hydroxyl groups in the molecule to 100 parts by weight of the two-terminal methanol-modified polyoxyxane oil (a). 10 to 30 parts by weight of the polycarboxylic acid resin (A) obtained in (i); or (iii) having a compound (d) having a carboxylic anhydride group in the molecule, having two relative amounts in the molecule 100 parts by weight of the compound (c) of the above carboxylic anhydride group is set to 100 to 800 The polyvalent carboxylic acid resin (A) described in (i) is obtained in parts by weight.

Further, in a preferred embodiment, (iv) the amount of the polyol compound (e) having two or more hydroxyl groups in the molecule is used in an amount of 100 parts by weight relative to the two-terminal methanol-modified polyoxygenated oil (a). The amount of the compound (d) having one carboxylic anhydride group in the molecule is from 10 to 30 parts by weight, and 100 parts by weight to 100 parts by weight of the compound (c) having two or more carboxylic anhydride groups in the molecule. The polycarboxylic acid resin (A) (i) described in (i) is obtained (preferably 400 to 700 parts by weight).

Hereinafter, the polyvalent carboxylic acid composition of the present invention will be described.

The polyvalent carboxylic acid composition of the present invention contains the polyvalent carboxylic acid resin (A) and the epoxy resin (B) of the present invention as essential components.

Examples of the epoxy resin (B) include an epoxy resin which is a glycidyl ether compound of a phenol compound, an epoxy resin which is a glycidyl ether compound of various novolak resins, an alicyclic epoxy resin, and an aliphatic system. An epoxy resin, a heterocyclic epoxy resin, a glycidyl ester epoxy resin, a glycidylamine epoxy resin, an epoxy resin obtained by glycidylating a halogenated phenol, an anthracene compound having an epoxy group and A copolymer of a hydrazine compound other than the above, a copolymer of a polymerizable unsaturated compound having an epoxy group and a polymerizable unsaturated compound other than the above.

Examples of the epoxy resin of the glycidyl ether compound of the above phenol compound include 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-double [4-(2,3-hydroxy)phenyl]ethyl]phenyl]propane, bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenol, tetramethyl bisphenol A, dimethyl Bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl Bisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenol, 1-(4-hydroxyphenyl)-2-[4-(1,1-double -(4-hydroxyphenyl)ethyl)phenyl]propane, 2,2'-methylene-bis(4-methyl-6-tertiary butylphenol), 4,4'-butylene-double (3-methyl-6-tert-butylphenol), trihydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phloroglucinol, phenol with diisopropylidene skeleton An epoxy resin such as a glycidyl ether compound of a polyphenol compound such as a phenol having an anthracene skeleton or a phenolic polybutadiene or the like, such as a 1,1-di-4-hydroxyphenylhydrazine.

Examples of the epoxy resin of the glycidyl ether compound of the above-mentioned novolac resin include phenol, cresol, ethyl phenol, butyl phenol, octyl phenol, bisphenol A, and bisphenol F. A novolak resin containing various phenols such as bisphenols and naphthols as a raw material, a phenol novolak resin containing a xylene skeleton, a phenol novolak resin containing a dicyclopentadiene skeleton, and a phenol containing a biphenyl skeleton. A novolak resin, a glycidyl ether compound of various novolak resins, such as a phenol novolak resin containing an anthracene skeleton.

Examples of the alicyclic epoxy resin include 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexylcarboxylate and bis(3,4-epoxycyclohexylmethyl) adipate. An alicyclic epoxy resin having an aliphatic ring skeleton.

Examples of the aliphatic epoxy resin include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, and pentaerythritol.

Examples of the heterocyclic epoxy resin include heterocyclic epoxy resins having a heterocyclic ring such as a hetero-cyanuric ring or an intramethylene urea ring.

Examples of the glycidyl ester epoxy resin include an epoxy resin composed of a carboxylic acid ester such as hexahydrophthalic acid diglycidyl ester.

The glycidylamine-based epoxy resin is, for example, an epoxy resin obtained by glycidylating an amine such as aniline or toluidine.

Examples of the epoxy resin obtained by glycidylating the above halogenated phenol include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, and brominated cresol novolac. An epoxy resin obtained by glycidylating a halogenated phenol such as varnish, chlorinated bisphenol S or chlorinated bisphenol A.

The condensate of the above-mentioned oxime compound having an epoxy group and the ruthenium compound other than the above is a hydrolyzed condensate of an alkoxy decane compound having an epoxy group and an alkoxy decane having a methyl group or a phenyl group, or a ring. a condensate of an alkoxy alkane compound of an oxy group with a polydimethyl methoxy oxane having a stanol group, a polydimethyldiphenyl siloxane having a stanol group, or a condensation obtained by using the same Compound. Examples of the alkoxydecane compound having an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane and 2-(3,4-epoxycyclohexyl)ethyl three. Ethoxy decane, 3-glycidoxypropyl trimethoxy decane, 3-glycidoxy propyl methyl dimethoxy decane, and the like. Examples of the alkoxydecane compound having a methyl group or a phenyl group include methyltrimethoxydecane, methyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, and dimethyl. Dimethoxy decane, diphenyl dimethoxy decane, methyl phenyl dimethoxy decane, and the like. Examples of the polydimethyl methoxyoxane having a stanol group and the polydimethyldiphenyl siloxane having a stanol group include, for example, X-21-5841 and KF-9701 which are commercially available. (Xin Yue Chemical Industry Co., Ltd. Manufacturing), BY16-873, PRX413 (manufactured by TORAY.DOWCORNING Co., Ltd.), XC96-723, YF3804, YF3800, XF3905, YF3057 (Momentive Performance Materials Japan Co., Ltd.), DMS-S12, DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S31, PDS-0338, PDS-1615 (manufactured by Gelest), and the like. 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, and Marproof. G-1010S, Marproof G-0150M, Marproof G-2050M (manufactured by Nippon Oil Co., Ltd.), etc., as the polymerizable unsaturated compound having an epoxy group, for example, glycidyl acrylate or glycidyl methacrylate may be mentioned. , 4-vinyl-1-cyclohexene-1,2-epoxide, and the like. Further, examples of the other polymerizable unsaturated compound include methyl (meth)acrylate, ether (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, and styrene. Vinyl cyclohexane and the like. These epoxy resins can be used alone or in combination of two or more.

In the case where the polyvalent carboxylic acid composition of the present invention is used in particular in the use of a photo-semiconductor sealing material, the epoxy equivalent (measured by the method described in JIS K-7236) in the above epoxy resin (B) is preferred. It is 150 to 1500 g/eq, and more preferably 350 to 1100 g/eq. When the epoxy equivalent is 300 g/eq or more, the cured product is not excessively hardened, and cracks such as cracks can be suppressed, which is preferable. If it is 1500 g/eq or less, the stickiness of the surface is not easy to occur, so it is preferable.

Further, the weight average molecular weight is preferably from 250 to 10,000, more preferably from 300 to 5,000. When the weight average molecular weight is 250 or more, the toughness of the cured product is improved, and for example, cracks such as cracks are less likely to occur in a heat cycle test or the like, which is preferable. When the weight average molecular weight is 10,000 or less, the viscosity is not easily increased, and workability is improved, which is preferable.

Among the epoxy resins (B) having the above epoxy equivalent weight and weight average molecular weight, from the viewpoints of transparency, heat-resistant transparency, light-resistant transparency, heat cycle resistance, and the like, an anthracene compound having an epoxy group is further preferred. a condensate of a compound other than the oxime compound.

In addition, the weight average molecular weight in the present invention means a weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography) under the following conditions.

Various conditions of GPC

Manufacturer: Shimadzu Manufacturing Co., Ltd.

Pipe column: protection column SHODEX GPC LF-G LF-804 (3 roots)

Flow rate: 1.0 ml/min.

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Detector: RI (differential refractive index detector)

The epoxy resin (B) is preferably used in an amount of from 0.5 to 3.0 equivalents based on 1 equivalent of the carboxylic acid group in the polyvalent carboxylic acid resin (A). When the amount is 0.5 equivalent or more, the heat-resistant transparency of the cured product is improved. Therefore, when it is 3.0 or less, the mechanical properties of the cured product are improved, which is preferable.

The polycarboxylic acid resin (A) of the present invention can be used alone as an epoxy resin. A hardener, but it is also preferable to use a polycarboxylic acid resin (A) in combination with a hardening accelerator as a hardener for an epoxy resin. As the hardening accelerator to be mixed in the polyvalent carboxylic acid resin (A), any one having an ability to promote a hardening reaction between an epoxy group and a carboxylic acid and a carboxylic acid anhydride can be used, and examples of the hardening accelerator which can be used include, for example, Ammonium salt-based hardening accelerator, cerium salt-based hardening accelerator, metal soap-based hardening accelerator, imidazole-based hardening accelerator, amine-based curing accelerator, phosphine-based curing accelerator, phosphite-based curing accelerator, Lewis acid system Hardening accelerator, etc.

Among these, in the use of a curing agent for a polyvalent carboxylic acid composition used for sealing an optical semiconductor such as a high-intensity white LED, an ammonium salt-based hardening accelerator and an anthracene are particularly excellent in terms of transparency. A salt-based hardening accelerator and a metal soap-based hardening accelerator. Examples of the ammonium salt-based hardening accelerator include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, and hydrogen. Trimethylpropylammonium oxide, trimethylbutylammonium hydroxide, trimethylhexadecyl ammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide And tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate, and the like. Examples of the onium salt-based hardening accelerator include ethyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium dimethyl phosphate, and methyltributylphosphoric acid. Hey. Examples of the metal soap-based hardening accelerator include tin octylate, cobalt octoate, zinc octylate, manganese octoate, calcium octylate, sodium octylate, and potassium octylate. These hardening accelerators can be used alone or in combination of two or more. Among these hardening accelerators, preferred are trimethylhexadecyl ammonium hydroxide, methyl tributyl phosphonium dimethyl phosphate, tin octylate, zinc octoate, Manganese octoate.

Among them, in order to obtain a cured product excellent in transparency and sulfidation resistance, calcium stearate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc laurate, zinc myristate) can be preferably used. Or a zinc compound such as zinc phosphate (zinc octyl phosphate, stearyl zinc phosphate, etc.).

In addition to the above-mentioned ammonium salt-based hardening accelerator, cerium salt-based hardening accelerator, and metal soap-based hardening accelerator, an imidazole-based hardening accelerator, an amine-based hardening accelerator, or a heterocyclic compound-based hardening may be used. An accelerator, a phosphine-based hardening accelerator, a phosphite-based hardening accelerator, a Lewis acid-based hardening accelerator, and the like.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, and 2-heptadecylimidazole. 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyano Ethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,3-dihydro-1H-pyrrolo-[1,2-a]benzimidazole, 2,4 -diamino-6(2'-methylimidazolium(1'))ethyl-all three 2,4-Diamino-6(2'-undecylimidazolium (1')) ethyl-all three 2,4-Diamino-6(2'-ethyl, 4-methylimidazolium (1')) ethyl-all three 2,4-Diamino-6(2'-methylimidazolium(1'))ethyl-all three /Iso-cyanuric acid adduct, 2:3 adduct of 2-methylimidazoisocyanuric acid, 2-phenylimidazole isocyanurate adduct, 2-phenyl-3,5 -dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole or 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole .

Examples of the amine-based curing accelerator include triethylamine, tripropylamine, and tributylamine.

Examples of the heterocyclic compound-based curing accelerator include pyridine, dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, imidazole, triazole, tetrazole, and the like. .

Examples of the phosphine-based curing accelerator include triethylphosphine, tributylphosphine, and triphenylphosphine.

Examples of the phosphite-based curing accelerator include trimethyl phosphite and triethyl phosphite.

Examples of the Lewis acid-based hardening accelerator include boron trifluoride monoethylamine, boron trifluoride diethylamine, boron trifluoride triethylamine, boron trifluoride benzylamine, and trifluoride. Boron aniline, boron trifluoride , boron trifluoride piperidine, boron trifluoride ethylamine, phosphorus pentabutylamine, phosphorus pentafluoride, benzylamine pentafluoride, arsenic pentafluoride, and the like. These hardening accelerators can be used alone or in combination of two or more. As for the use of such a hardening catalyst, for example, it can be appropriately selected depending on the properties required for the transparent resin composition obtained by transparency, curing speed, working conditions and the like.

The curing accelerator is used in an amount of usually 0.001 to 15 parts by weight based on 100 parts by weight of the polyvalent carboxylic acid resin (A).

The polycarboxylic acid composition of the present invention can be obtained by uniformly mixing the above components at normal temperature or under heating. For example, it is prepared by using an extruder, a kneader, a three-roll mill, a universal mixer, a planetary mixer, a homomixer, a homogenizer, a bead mill, etc., until it is sufficiently mixed, Filtration treatment is performed by a SUS mesh or the like as needed.

In the polyvalent carboxylic acid resin (A) and the polyvalent carboxylic acid composition of the present invention, other epoxy resin hardeners may be used in combination as needed.

Examples of the epoxy resin curing agent that can be used together include polyvalent carboxylic acids, carboxylic anhydrides, phenols, anthraquinones, and mercaptans.

Examples of the polyvalent carboxylic acid include aliphatic polycarboxylic acids, cyclic aliphatic polycarboxylic acids, aromatic polycarboxylic acids, and heterocyclic polycarboxylic acids.

Examples of the aliphatic polycarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, sebacic acid, and 1,2. 3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, and the like.

Examples of the cyclic aliphatic polycarboxylic acid include hexahydrophthalic acid, 1,3-adamantane diacetic acid, 1,3-adamantane dicarboxylic acid, tetrahydrophthalic acid, and 2,3-. Decalene dicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2,3-cyclohexanetricarboxylic acid, 1,2,4,6- Cyclohexane tetracarboxylic acid and the like.

Examples of the aromatic polycarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, 1,2-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, and 1,8-naphthalene dicarboxylic acid. , 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 9,10-decanedicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, 2,2'-diphenylic acid, 3,3 '-Diphenyl phthalic acid, 4,4'-diphenyl phthalic acid, 3,3'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-binaphthalene dicarboxylic acid, 1 , 2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1 , 2,3,5-benzenetetracarboxylic acid, 1,2,3,4-benzenetetracarboxylic acid, pyroic acid, 3,3'4,4'-benzophenonetetracarboxylic acid, 2,2'3, 3'-benzophenonetetracarboxylic acid, 2,3,3'4'-benzophenonetetracarboxylic acid, 3,3'4,4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 4,4'-oxydiphthalic acid, 3,3'4,4' - Diphenylmethanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, perylenetetracarboxylic acid, and the like.

Examples of the heterocyclic polycarboxylic acid include tris(2-carboxyethyl) isocyanurate and tris(3-carboxypropyl) isocyanurate.

Examples of the carboxylic acid anhydrides include aliphatic carboxylic anhydrides, cyclic aliphatic carboxylic anhydrides, and aromatic carboxylic anhydrides.

Examples of the aliphatic carboxylic acid anhydride include succinic anhydride, methyl succinic anhydride, ethyl succinic anhydride, 2,3-butane dicarboxylic anhydride, 2,4-pentane dicarboxylic anhydride, and 3,5. - heptane dicarboxylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, maleic anhydride, dodecyl succinic anhydride, and the like.

Examples of the cyclic aliphatic carboxylic anhydride include hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 1,3-cyclohexanedicarboxylic anhydride, hydrogenated acid anhydride, and hydrogenated methylation resistance. Anhydride, bicyclo[2,2,2]octane-2,3-dicarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, 1,2,3,4-cyclobutane Tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, tetrahydrophthalic anhydride, methyltetrahydroortho Phthalic anhydride, ceric anhydride, methyl benzoic anhydride, 4,5-dimethyl-4-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]-5-octene-2 , 3-Dicarboxylic anhydride, and the like.

Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, isophthalic anhydride, terephthalic anhydride, 1,2,4-benzenetricarboxylic anhydride, and pyrogalic anhydride.

Further, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4-(2,5-dioxotetrahydrofuran) A compound having an aliphatic carboxylic anhydride or a cyclic aliphatic carboxylic acid anhydride in the same compound such as -3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride.

Examples of the phenols include bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenylphenol, tetramethylbisphenol A, dimethyl bisphenol A, and tetramethyl bisphenol F. , dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenylphenol, 1-( 4-hydroxyphenyl)-2-[4-(1,1-bis-(4-hydroxyphenyl)ethyl)phenyl]propane, 2,2'-methylene-bis(4-methyl- 6-tertiary butyl phenol), 4,4'-butylene-bis(3-methyl-6-tertiary butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, neighbor Pyrogallol, phenol having a diisopropylidene skeleton; phenol having an anthracene skeleton such as 1,1-di-4-hydroxyphenylhydrazine; phenolated polybutadiene, phenol, cresol, B Phenolic varnish resin containing various phenols such as phenols, butyl phenols, octyl phenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc.; phenol novolak resin containing xylene skeleton, containing a phenol novolak resin of a dicyclopentadiene skeleton, a phenol novolak resin containing a biphenyl skeleton, a phenol novolak resin containing an anthracene skeleton, and a furan bone The phenol novolac resin and other novolac resins.

Examples of the above hydrazines include diammonium isophthalate, diammonium adipate, diterpene sebacate, dinonyl dodecanoate, and diammonium 2,6-naphthalene dicarboxylate. Wait.

Examples of the above mercaptans include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and dipentaerythritol hexa(3-decylpropionate). Acid ester), trisuccinic acid [(3-decylpropenyloxy)-ethyl ester], 1,4-bis(3-mercaptobutyloxy)butane, neopentyl alcohol tetrakis(3- Mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione and the like.

These epoxy resin hardeners can be used alone or in combination of two or more. When the polyvalent carboxylic acid resin (A) of the present invention is used in combination with the above-mentioned curing agent other than the above, the ratio of the polyvalent carboxylic acid resin (A) to the total curing agent is 50% by weight or more. The amount of use is preferably adjusted so as to be 80% 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.

Examples of the coupling agent which can be used include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, and 3-glycidoxypropylmethyl. Dimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, N-(2-aminoethyl)3-aminopropylmethyldimethoxydecane, N -(2-Aminoethyl) 3-aminopropylmethyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, vinyltrimethoxydecane , N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxydecane hydrochloride, 3-methylpropenyloxypropyltrimethoxydecane, 3-chloropropane a decane coupling agent such as methyl dimethoxy decane or 3-chloropropyl trimethoxy decane; (N-ethylaminoethylamino) isopropyl titanate, triisostearate titanic acid Isopropyl ester, bis(dioctyl pyrophosphate) titanium oxyacetate, di(dioctyl phosphite) tetraisopropyl titanate, neoalkoxy tris(p-N-(β-amino group) Titanium coupling agent such as ethyl)aminophenyl) titanate; zirconium acetonate pyruvate, zirconium methacrylate, zirconium propionate, neoalkoxy zirconate, neoalkoxytrimethylene zirconium , neoalkoxytris(dodetodecyl)benzenesulfonyl zirconium, neoalkoxytris(ethylideneethylamino)zirconate, neoalkoxytris(m-aminophenyl) A zirconium or aluminum coupling agent such as zirconate, zirconium ammonium carbonate, aluminum acetylacetonate, aluminum methacrylate or aluminum propionate.

These coupling agents can be used alone or in combination of two or more.

By using a coupling agent, it is expected that the adhesion to the substrate is improved or the hardness of the cured product is improved. The coupling agent is usually contained in an amount of 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on the polyvalent carboxylic acid composition of the present invention.

Examples of the phosphor that can be used include a phosphor such as a YAG phosphor, a TAG phosphor, an orthophthalate phosphor, a thiopentate phosphor, or a sulfide phosphor. Fluorescence can be imparted to the polyvalent carboxylic acid composition by adding a phosphor.

Examples of the inorganic filler which can be used include crystalline vermiculite, molten vermiculite, alumina, zircon, calcium silicate, calcium carbonate, tantalum carbide, tantalum nitride, boron nitride, zirconium oxide, and magnesium. Powders such as olivine, talc, spinel, titanium dioxide, talc, or beads which are spheroidized. By adding an inorganic filler, heat resistance, light resistance, viscosity adjustment, and the like can be imparted. The content of the inorganic fillers is from 0 to 95 parts by weight based on the polycarboxylic acid composition of the present invention.

Examples of the highly thermally conductive fine particles that can be used include metal particles such as gold, silver, copper, iron, nickel, tin, aluminum, cobalt, and indium, or alloys thereof. A metal oxide such as alumina, magnesia or titanium oxide; a metal nitride such as boron nitride or aluminum nitride; a carbon compound such as graphite, diamond or carbon black; and a metal coated metal particle coated with a metal layer on the resin particle. 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 a reactive type or an additive type. Examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tris(xylylene) phosphate, toluene diphenyl phosphate, toluene-2,6-xylylene phosphate, and 1 , 3-phenylphenyl bis(xylylene phosphate), 1,4-phenylene bis(xylylene phosphate), 4,4'-biphenyl (bis(xylene) phosphate) Phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10(2,5-dihydroxyphenyl)-10H-9-oxa-10- a phosphorus-containing epoxy compound obtained by reacting an epoxy resin with an active hydrogen of the above phosphine, a red phosphorus or the like, preferably a phosphate, a phosphine or a phosphorus Epoxy compound, preferably 1,3-phenylene bis(di(xylylene) phosphate), 1,4-phenylene bis(diphenyl)phosphate, 4,4'-biphenyl (bis(xylene) phosphate) or phosphorus-containing epoxy compound.

The content of the phosphorus-containing compound is preferably a phosphorus-containing compound/epoxy resin = 0.1 to 0.6 (weight ratio). When the amount is 0.1 or more, the flame retardancy is sufficient, and if it is 0.6 or less, it is preferable since it does not adversely affect the moisture absorption property and dielectric properties of the cured product.

Examples of the binder resin that can be used include a butyraldehyde resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, an NBR-phenol resin, an epoxy-NBR resin, and a polyamide resin. Polyimine tree A fat, a polysiloxane resin, or the like is not limited thereto. The binder resin is usually contained in an amount of 0.05 to 50 parts by weight, preferably 0.05 to 20 parts by weight, based on the polyvalent carboxylic acid composition of the present invention.

Further, a polyamic acid composition of the present invention may be added with a release agent such as stearic acid, palmitic acid, zinc stearate or calcium stearate, a coloring agent such as a dye or a pigment, an antioxidant, a light stabilizer, and a moisture resistance. Improver, shake imparting agent, antifoaming agent, adhesion imparting agent, impact modifier, ion trapping agent, antistatic agent, lubricant, leveling agent, surface tension reducing agent, antifoaming agent, antiprecipitant Additives such as surfactants and UV absorbers, various thermosetting resins, and various other resins. These may be added to the polycarboxylic acid composition of the present invention by a method known per se.

As a light stabilizer which can be used, for example, bis(1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, four (1, 2, 2) can be mentioned. ,6,6-pentamethyl-4-piperidinyl) = 1,2,3,4-butane tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl ) 1,2,3,4-butane tetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and Mixed esterified product of 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, decanedioic acid Bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, azelaic acid (2,2,6,6-tetramethyl-4-piperidinyl) ester, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 4- Benzyl oxime-2,2,6,6-tetramethylpiperidine, 1-[2-[3-(3,5-di-tri-tert-butyl-4-hydroxyphenyl)propoxyloxy Ethyl]-4-[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propanoxy]-2,2,6,6-tetramethylpiperidine, methyl 1,2,2,6,6-pentamethyl-4-piperidinyl acrylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) [[3, 5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl ester, decanedioic acid bis(2,2,6,6-tetramethyl-1(octyloxy) )-4-piperidinyl)ester, reaction product of 1,1-dimethylethylhydroperoxide and octane, N,N',N",N'''-tetra(4,6-double -(butyl-(N-methyl-2,2.6,6-tetramethylpiperidin-4-yl)amino)-three -2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-three -N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl) Polycondensate of poly-4-(piperidinyl)butylamine, poly[(6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-tri -2,4-diyl)[(2,2,6,6-tetramethyl-4-piperidinyl)imido]hexamethylene[(2,2,6,6-tetramethyl- 4-piperidinyl)imido]], dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol polymer, 2, 2, 4, 4-tetramethyl-20-(β-lauroyloxycarbonyl)ethyl-7-oxa-3,20-diazaspiro[5,1,11,2]icosane-21-one , β-alanine, N-(2,2,6,6-tetramethyl-4-piperidinyl)-dodecyl ester/tetradecyl ester, N-acetylindole-3-dodecane 1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa- 3,20-diazabispiro[5,1,11,2]icosane-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diaza Heterobicyclo-[5,1,11,2]-docosane-20-propionic acid lauryl ester/tetradecyl ester, malonic acid [(4-methoxyphenyl)- sub Methyl]-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol a hindered amine system such as 1,3-phthalimide or N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl) or a benzophenone such as benzophenone Compound, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2-hydroxy-5-methylbenzene Benzotriazole, 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimido-methyl)-5-methylphenyl]benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-triamylphenyl) Reaction product of benzotriazole, methyl 3-(3-(2H-benzotriazol-2-yl)-5-tributyl-4-hydroxyphenyl)propanoate and polyethylene glycol, 2 a benzotriazole compound such as (2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, 2,4-di-tertiary butylphenyl-3,5 a benzoate such as di-tertiary butyl-4-hydroxybenzoate, 2-(4,6-diphenyl-1,3,5-three -2-yl)-5-[(hexyl)oxy]phenol, etc. A compound or the like.

When the polyvalent carboxylic acid composition of the present invention is used for an optical material, particularly in the case of an optical semiconductor encapsulant, it is particularly preferred to contain a phosphorus-based compound as an antioxidant material.

The phosphorus compound is not particularly limited, and examples thereof include 1,1,3-tris(2-methyl-4-phosphite di-tridecyl ester-5-tributylphenyl) Alkane, distearyl neopentyl alcohol diphosphite, bis(2,4-di-tert-butylphenyl)neopentitol diphosphite, bis(2,6-di-tridecyl) Benzyl 4-methylphenyl) neopentyl alcohol diphosphite, phenyl bisphenol A neopentyl alcohol diphosphite, dicyclohexyl neopentyl alcohol diphosphite, phosphorous tris (diethyl) Phenyl phenyl ester), tris(di-isopropylphenyl) phosphite, tris(di-n-butylphenyl) phosphite, tris(2,4-di-tridecyl phosphite) Phenyl phenyl ester), tris(2,6-di-tert-butylphenyl) phosphite, tris[2,6-di-tert-butylphenyl phosphite], 2,2'-methylene double (4,6-di-tertiary butylphenyl)(2,4-di-tertiary butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-tris Butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-methylenebis(4-methyl-6-tributylphenyl) (2 -Tris-butyl-4-methylphenyl)phosphite, 2,2'-ethylenebis(4-methyl-6-tributylphenyl) (2-tert-butyl-4) -Methylphenyl)phosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-extended biphenyl diphosphite, tetrakis (2,4-di-tris Butylphenyl)-4,3'-extended biphenyl diphosphite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-extended biphenyl diphosphite, Tetrakis(2,6-di-tert-butylphenyl)-4,4'-extended biphenyl diphosphite, tetrakis(2,6-di-triphenylphenyl)-4,3' - extended biphenyl diphosphite, tetrakis(2,6-di-tributylphenyl)-3,3'-extended biphenyl diphosphite, bisphosphite bis(2,4-di- Tert-butyl phenyl)-4-phenyl-phenyl ester, bis(2,4-di-tri-butylphenyl)-3-phenyl-phenyl phosphite, phosphorous Bis(2,6-di-n-butylphenyl)-3-phenyl-phenyl ester, bis(2,6-di-tri-butylphenyl)-4-phenyl-phenyl phosphite , bis(2,6-di-tri-butylphenyl)-3-phenyl-phenyl phosphite, tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4 , 4'-Exbiphenyl bisphosphite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, toluene diphenyl phosphate, Mono-o-phenyl diphenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like.

Commercially available products can also be used as the phosphorus compound. The commercially available phosphorus-based compound is not particularly limited. For example, as ADEKA, Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-24G, Adekastab PEP-36, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, Adekastab TPP.

Here, the ratio of the phosphorus compound is 0.005 to 5% by weight, more preferably 0.01 to 4% by weight, still more preferably 0.1 to 2% by weight, based on the weight of the polyvalent carboxylic acid resin (A).

The polyvalent carboxylic acid composition of the present invention may contain a phenolic compound as an antioxidant material other than the phosphorus compound.

The phenolic compound is not particularly limited, and examples thereof include 2,6-di-tertiarybutyl-4-methylphenol and 3-(3,5-di-tertiarybutyl-4-hydroxyphenyl). n-Octadecyl propionate, tetrakis[methylene-3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate]methane, 2,4-di-three Butyl-6-methylphenol, 1,6-hexanediol-bis-[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate], iso-cyanuric acid Tris(3,5-di-tert-butyl-4-hydroxybenzyl ester), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tertiary butyl-4 -hydroxybenzyl)benzene, pentaerythritol-tetrakis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate], 3,9-bis-[2-[3 -(3-tertiary butyl-4-hydroxy-5-methylphenyl)-propenyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro [5,5]undecane, triethylene glycol-bis[3-(3-tri-butyl-5-methyl-4-hydroxyl) Phenyl phenyl) propionate], 2,2'-butylene bis(4,6-di-tertiary butyl phenol), 4,4-butylene bis(3-methyl-6-tertiary butyl Phenol), 2,2'-methylenebis(4-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl-6-tertiary butylphenol) 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenol acrylate, 2-[1-(2-hydroxy-3, 5-di-tertiary amylphenyl)ethyl]-4,6-di-triamylpentyl phenyl acrylate, 4,4'-thiobis(3-methyl-6-tertiary butyl Phenol), 4,4'-butylene bis(3-methyl-6-tertiary butylphenol), 2-tributyl-4-methylphenol, 2,4-di-tertiary butylphenol , 2,4-di-tripentylphenol, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 4,4'-butylene bis(3-methyl- 6-tertiary butyl phenol), bis-[3,3-bis-(4'-hydroxy-3'-tertiary butylphenyl)-butyric acid]-diol ester, 2,4-di-three Butyl phenol, 2,4-di-tripentylphenol, 2-[1-(2-hydroxy-3,5-di-tri-pentylphenyl)ethyl]-4,6-di- Tertiary pentyl phenyl acrylate, bis-[3,3-bis-(4'-hydroxy-3'-tris-butylphenyl)-butyric acid]-diol 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 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114, IRGANOX 1098, IRGANOX 1520L; manufactured as ADEKA, may be listed as: Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO -80, Adekastab AO-90, Adekastab AO-330; manufactured by Sumitomo Chemical Industries, including Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), Semilizer GP, and the like.

Further, commercially available additive materials can be used as the colorant of 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 blending amount thereof is not particularly limited, and is preferably in the range of 0.005 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 in 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 forming white light by absorbing a portion of the blue light emitted from the blue LED element and emitting wavelength-converted yellow light. The photo-semiconductor is sealed after the phosphor is previously dispersed in the polycarboxylic acid composition. The phosphor is not particularly limited, and a conventionally known phosphor can be used, and examples thereof include an aluminate of a rare earth element, a thiogallate, a protoporate, and the like. More specifically, a phosphor such as a YAG phosphor, a TAG phosphor, a protonate phosphor, a thiogallate acid phosphor, or a sulfide phosphor can be exemplified, and YAlO ₃ :Ce can be exemplified. Y ₃ Al ₅ O ₁₂ :Ce, Y ₄ Al ₂ O ₉ :Ce, Y ₂ O ₂ S:Eu, Sr ₅ (PO ₄ ) ₃ Cl:Eu, (SrEu)O-Al ₂ O ₃ or the like. As the particle diameter of the above-mentioned phosphor, a particle diameter known in the art can be used, and the average particle diameter is preferably from 1 to 250 μm, particularly preferably from 2 to 50 μm. In the case of using these phosphors, the amount thereof is from 1 to 80 parts by weight, preferably from 5 to 60 parts by weight, per 100 parts by weight of the resin component.

When the polycarboxylic acid composition of the present invention is used for an optical material, particularly in the case of an optical semiconductor encapsulant, in order to prevent precipitation of various phosphors upon hardening, a fine powder of vermiculite (also known as Aerosil) may be added. Or Aerosol) is a representative of the shake imparting agent. As such a vermiculite fine powder, for example, Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R812, Aerosil R812S , Aerosil R805, RY200, RX200 (manufactured by Japan Aerosil Co., Ltd.).

The polycarboxylic acid composition of the present invention may also be used in the form of a varnish or an ink, if necessary, by mixing a solvent. The solvent can be used as long as it has high solubility in each component such as the polyvalent carboxylic acid resin (A), the epoxy resin (B), the curing accelerator, and other additives of the present invention, and does not react with such a solvent. Specific examples thereof include alcohols such as methanol, ethanol, propanol and butanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and 3-methoxybutyl Alcohol, glycol ethers such as 3-methyl-3-methoxybutanol, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Alkylene glycol ether acetates such as acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl ethoxypropionate; benzene, toluene, Aromatic hydrocarbons such as toluene; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 4- Ketones such as hydroxy-4-methyl-2-pentanone; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2- Ethyl methacrylate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, Propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, propyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, propyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxylate, propyl ethoxyacetate, butyl ethoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate , butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate , methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate An ester such as ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate or butyl 3-ethoxypropionate; an ether such as diethyl ether or tetrahydrofuran; and the like. Further, as the aprotic polar solvent, dimethylformamide, dimethylacetamide, dimethylhydrazine, acetonitrile or the like can also be used.

These solvents usually contain 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 also be subjected to microfiltration using, for example, a filter of 0.05 to 2 μm as needed.

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.

When the polycarboxylic acid composition of the present invention is used as a sealing material or a solid crystal material of an optical semiconductor such as a high-brightness white LED, in addition to the present invention In addition to the carboxylic acid resin (A) and the epoxy resin (B), other additives such as a curing agent, a curing accelerator, a coupling material, an antioxidant, a light stabilizer, a phosphor, and a vermiculite fine powder may be sufficiently mixed. Thereby, a polycarboxylic acid composition is prepared and used as a sealing material or both for a die bonding material and a sealing material. As a mixing method, a kneader, a three-roll mill, a universal mixer, a planetary mixer, a homomixer, a homogenizer, and a bead mill may be used, which are mixed at room temperature or heated.

Optical semiconductor elements such as high-brightness white LEDs are usually laminated on GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, etc. on a substrate such as sapphire, spinel, SiC, Si, or ZnO using an adhesive (solid crystal material). A semiconductor wafer such as InN, AlN, or InGaN is then packaged on a lead frame or a heat sink. In order to make the current flow, there is also a type of wire connecting the gold wire. In order to protect the semiconductor wafer from heat or moisture and function as a lens, a sealing material such as an epoxy resin is used for sealing. The polycarboxylic acid composition of the present invention can be used as the sealing material or the solid crystal material. In terms of steps, it is preferred to use the polycarboxylic acid composition of the present invention for both the die bonding material and the sealing material.

As a method of adhering a semiconductor wafer to a substrate using the polyvalent carboxylic acid composition of the present invention, the polyvalent carboxylic acid composition of the present invention can be applied by a dispenser, infusion, or screen printing, and then a semiconductor wafer is mounted and heat-hardened. The semiconductor wafer is followed. 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 carried out at 80 to 230 ° C for about 1 minute to 24 hours. In order to reduce the internal stress generated during heat hardening, for example After pre-hardening at 80-120 ° C for 30 minutes to 5 hours, post-hardening is carried out at 120-180 ° C for 30 minutes to 10 hours.

As a method of forming 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, and then heat-hardened and molded is formed as described above; a sealing material is injected into the mold in advance. A semiconductor wafer that is immersed and fixed on a substrate is subjected to heat-hardening, and is subjected to a compression molding method such as demolding 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 carried out at 80 to 230 ° C for about 1 minute to 24 hours. In order to reduce the internal stress generated during heat curing, for example, it can be pre-hardened at 80 to 120 ° C for 30 minutes to 5 hours, and then post-hardened at 120 to 80 ° C for 30 minutes to 10 hours.

The polycarboxylic acid resin (A) of the present invention has a specific structure and is liquid at room temperature (25 ° C), and the epoxy resin is excellent in hardening property, and the volatility in the temperature region which is usually used for hardening the epoxy resin Very few. 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 material for optics is a material which is generally used for applications in which visible light, infrared rays, ultraviolet rays, X-rays, and laser light are passed through the material. More specifically, in addition to the optical semiconductor sealing material such as a lamp type or an SMD type, and the optical semiconductor solid crystal material, the following may be mentioned. Substrate materials, light guide plates, cymbals, deflecting plates, phase difference plates, A material for a liquid crystal display device such as a liquid crystal film such as a viewing angle correction film, an adhesive, or a polarizing element protective film. Further, as a next-generation flat panel display, a sealing material for a PDP (Plasma Display Panel), an antireflection film, an optical correction film, a cover material, a protective film for a front glass, and a front glass substitute material are used. Agent, LED mold material used in LED display device, LED sealing material, front plate glass protective film, front plate glass substitute material, adhesive, plasma address liquid crystal (PALC) display Substrate material, light guide plate, cymbal sheet, deflecting plate, phase difference plate, viewing angle correction film, adhesive, polarizing element protective film, protective film for front plate glass and front plate glass in organic EL (electroluminescence) display Materials, adhesives, and various film substrates in a field emission display (FED), a protective film for front glass, a front glass substitute material, and an adhesive. In the field of optical recording, there are VD (video disk), CD/CD-ROM, CD-R/RW, DVD-R/DVD-RAM, MO/MD, PD (Phase Change Disc). , optical disc substrate material, optical pickup lens (Pickup Lens), protective film, sealing material, adhesive, etc.

In the field of optical devices, it is a lens material for a static camera, a finder prism, a target prism, a finder cover, and a light receiving sensor portion. Also, it is a movie lens and viewfinder of a video camera. Further, it is a projection lens, a protective film, a sealing material, an adhesive, and the like of a projection television. A lens material, a sealing material, an adhesive, a film, or the like of a light sensing device. In the optical parts collar In the domain, it is a fiber material, a lens, a waveguide, a sealing material for an element, an adhesive, and the like around the optical converter in the optical communication system. 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 LED sealing material, the CCD sealing material, and the adhesive are used. A substrate material, a fiber material, a sealing material for an element, an adhesive, and the like surrounding the OEIC (Optics Electronic Integrated Circuit). In the field of optical fibers, it is a lighting/light guide for decorative displays, sensors for industrial use, display/identification, and the like, and optical fibers for digital connection of communication infrastructure and home use. Among the materials surrounding the semiconductor integrated circuit, there are resist materials for lithography for LSI and super LSI materials. In the field of automobile/transporter, it is a lamp reflector for automobile, bearing retainer, gear part, corrosion resistant coating film, switch part, headlight, engine parts, electrical parts, various internal and external parts, drive engine, brake Fuel tanks, anti-rust steel plates for automobiles, interior panels, interior materials, wiring harnesses for protection/stuffing, fuel hoses, automobile lamps, glass substitutes. In addition, it is a laminated glass for railway vehicles. In addition, it is a toughness imparting agent for structural materials of an aircraft, a peripheral member for an engine, a wire harness for protection/tying, and a corrosion-resistant coating film. In the field of construction, there are interior/processing materials, lampshades, sheets, glass interlayer films, glass substitutes, and solar cell peripheral materials. In agriculture, it is a film for greenhouse coating. As a next-generation optical/electronic functional organic material, it is an organic EL element peripheral material, an organic light refractive element, an optical amplification element as a light-to-light conversion element, an optical operation element, a substrate material around an organic solar cell, a fiber material, and a component. Sealing material, adhesive, and the like.

Examples of the sealant include perfusion, immersion, and transfer mold sealing for condensers, transistors, diodes, light-emitting diodes, ICs, and LSIs, and COB, COF, TAB, etc. for ICs and LSIs. Sealing, flip-chip and other primers, BGA, CSP and other IC packages such as sealing (strengthening primer).

Examples of other uses of the optical material include a general use of an epoxy resin composition, and examples thereof include an adhesive, a coating material, a coating agent, a molding material (including a sheet, a film, and an FRP), and an insulating material (including a printed substrate). In addition to the sealant, an additive such as another resin or the like may be mentioned. Examples of the adhesive agent include an adhesive for civil engineering, construction, automotive, general office use, and medical use, and an adhesive for electronic materials. Among these, examples of the adhesive for the electronic material include an interlayer adhesive for a multilayer substrate such as a build-up substrate, a semiconductor adhesive such as a die bond or a primer, a BGA reinforcing primer, and an anisotropic conductive film. (ACF, Anisotropic Conductive Film), an adhesive for mounting such as an anisotropic conductive paste (ACP), and the like. In particular, since the cured product thus obtained is excellent in transparency, it is extremely useful as a curing agent for a high-brightness white LED or an epoxy resin for sealing other photo-semiconductors. In other applications, a raw material or a modifier, a plasticizer, a lubricant raw material, a cyanate resin composition for a substrate, or an additive for other resins or a resin for a coating resin, The toner is very useful for resin and medical pesticide intermediates.

Example

Hereinafter, the present invention will be described in more detail by way of Synthesis Examples and Examples. again The present invention is not limited to the above-described synthesis examples and examples. Further, each physical property value in the examples was measured by the following method. Here, the parts represent parts by weight unless otherwise specified.

○ Weight average molecular weight: The weight average molecular weight was calculated by a GPC method by polystyrene conversion measured under the following conditions.

Various conditions of GPC

Manufacturer: Shimadzu Manufacturing Co., Ltd.

Pipe column: protection column SHODEX GPC LF-G LF-804 (3 roots)

Flow rate: 1.0 ml/min.

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Detector: RI (differential refractive index detector)

○ Acid value: Measured by the method described in JIS K-2501.

○ Epoxy equivalent: measured by the method described in JIS K-7236.

○ Viscosity: Measured at 25 ° C using an E-type viscometer.

○ Thermal 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

Adding 47.1 parts of methanol modified polyxanthene X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.) as a polyester polyol to a glass separable flask equipped with a stirring device, a Dairy condenser, and a thermometer Adeka New Ace Y9-10 (manufactured by ADEKA Co., Ltd., 11.3 parts of the above formula (2) wherein R ₃ is a neopentyl group and R ₄ is a butyl polyester polyol), RIKACID TDA-100 (4-(2) , 5-dihydrotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, manufactured by Nippon Chemical and Chemical Co., Ltd.) 7.4 parts, RIKACID MH (methylhexahydrogen) 12.5 parts of phthalic anhydride (manufactured by Nippon Chemical and Chemical Co., Ltd.) was reacted at 140 ° C for 10 hours to obtain 78.5 parts of the polycarboxylic acid resin (A-1) of the present invention. At this time, the peaks of RIKACID TDA-100 and RIKACID MH disappeared in the GPC measurement. The obtained compound has an acid value of 86.8 mgKOH/g, a weight average molecular weight of 3,48, and a viscosity of 20,480 mPa. s, the appearance is a colorless transparent liquid.

Example 2

In a separable flask made of glass equipped with a stirring device, a Dairy condenser, and a thermometer, 47.1 parts of methanol modified polyxanthene x22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a polyester polyol. Adeka New Ace Y9-10 (manufactured by ADEKA Co., Ltd., 11.3 parts of the above formula (2) wherein R ₃ is a neopentyl group and R ₄ is a butyl polyester polyol), RIKACID BT-100 (butane tetracarboxylic acid) Diamine, manufactured by Nippon Chemical Co., Ltd.), 2.5 parts of RIKACID MH (methylhexahydrophthalic anhydride, manufactured by Nippon Chemical Co., Ltd.), 16.6 parts, and reacted at 140 ° C for 10 hours to obtain the present invention. The polyvalent carboxylic acid resin (A-2) was 77.5 parts. At this time, the peaks of RIKACID BT-100 and RIKACID MH disappeared in the GPC measurement. The polycarboxylic acid resin is a colorless and transparent liquid at the end of the reaction, but the appearance becomes a cloudy liquid as the temperature of the reaction liquid decreases. The obtained compound has an acid value of 76.7 mgKOH/g, a weight average molecular weight of 3452 and a viscosity of 5730 mPa. s.

Example 3

Adding 47.1 parts of methanol modified polyxanthene X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.) as a polyester polyol to a glass separable flask equipped with a stirring device, a Dairy condenser, and a thermometer Adeka New Ace Y9-10 (manufactured by ADEKA Co., Ltd., 11.3 parts of the above formula (2) wherein R ₃ is a neopentyl group and R ₄ is a butyl polyester polyol), RIKACID BT-100 (butane tetracarboxylic acid) Diacetate, manufactured by Nippon Chemical Co., Ltd., 4.9 parts, 12.5 parts of RIKACID MH (methylhexahydrophthalic anhydride, manufactured by Nippon Chemical Co., Ltd.), and reacted at 140 ° C for 10 hours to obtain the present invention. The polycarboxylic acid resin (A-3) was 74.0 parts. At this time, the peaks of RIKACID BT-100 and RIKACID MH disappeared in the GPC measurement. The obtained compound has an acid value of 79.9 mgKOH/g, a weight average molecular weight of 6,960, and a viscosity of 18,600 mPa. S, the appearance is a colorless transparent liquid.

Example 4

In a separable flask made of glass equipped with a stirring device, a Dairy condenser, and a thermometer, 47.1 parts of a methanol-modified polyoxo X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a hydrocarbon polyol. 11.8 parts of 1,10-decanediol, RIKACID BT-100 (butane tetracarboxylic dianhydride, manufactured by Nippon Chemical and Chemical Co., Ltd.) 9.8 parts, RIKACID MH (methylhexahydrophthalic anhydride, New Japan Physical and Chemical Co., Ltd.) 24.9 parts of the product was produced and reacted at 140 ° C for 10 hours to obtain 90.8 parts of the polycarboxylic acid resin (A-4) of the present invention. At this time, in the GPC measurement, RIKACID The peaks of BT-100 and RIKACID MH disappeared. The obtained compound has an acid value of 89.3 mgKOH/g, a weight average molecular weight of 5,604, and a viscosity of 23,296 mPa. s, the appearance is a colorless transparent liquid.

Example 5

In a separable flask made of glass equipped with a stirring device, a Dairy condenser, and a thermometer, 47.1 parts of a methanol-modified polyoxo X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a hydrocarbon polyol. 11.8 parts of tricyclodecane dimethanol, RIKACID BT-100 (butane tetracarboxylic dianhydride, manufactured by Nippon Chemical and Chemical Co., Ltd.) 8.7 parts, RIKACID MH (methyl hexahydrophthalic anhydride, New Japan Physicochemical Co., Ltd.) 22.2 parts of the company was reacted at 140 ° C for 10 hours to obtain 87.1 parts of the polycarboxylic acid resin (A-5) of the present invention. At this time, the peaks of RIKACID BT-100 and RIKACID MH disappeared in the GPC measurement. The obtained compound had an acid value of 79.1 mgKOH/g and a weight average molecular weight of 4,777. The appearance was a colorless transparent liquid, but the viscosity was not measured because of the high viscosity.

Example 6

In a separable flask made of glass equipped with a stirring device, a Dairy condenser, and a thermometer, 47.1 parts of a methanol-modified polyoxo X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a hydrocarbon polyol. 11.8 parts of 2,4-diethylpentane-1,5-diol, RIKACID BT-100 (butane tetracarboxylic dianhydride, manufactured by Nippon Chemical and Chemical Co., Ltd.) 9.7 parts, RIKACID MH (methylhexahydroortene) 24.9 parts of phthalic anhydride (manufactured by Nippon Chemical and Chemical Co., Ltd.) was reacted at 140 ° C for 10 hours to obtain 90.7 parts of the polycarboxylic acid resin (A-6) of the present invention. At this time, in GPC In the measurement, the peaks of RIKACID BT-100 and RIKACID MH disappeared. The obtained compound has an acid value of 81.1 mgKOH/g, a weight average molecular weight of 5203, and a viscosity of 593920 mPa. s, the appearance is a colorless transparent liquid.

Physical property test

The polycarboxylic acid resins A-1 to A-6 obtained in Examples 1 to 6 and RIKACID MH (methylhexahydrophthalic anhydride), a new Japanese physicochemical company as a liquid acid anhydride compound in Comparative Example 1. The properties of the manufacturing) are summarized in Table 1.

Synthesis Example 1 (Synthesis of a condensate of an oxime compound having an epoxy group and a ruthenium compound other than the oxime)

394 parts of 2-(3,4 epoxycyclohexyl)ethyltrimethoxydecane, molecular weight 1700 (GPC measured value) of dimethylol diphenyl decane having stanol groups, 475 parts, 0.5% KOH 4 parts of a methanol solution and 36 parts of isopropyl alcohol were added to a reaction container, and the temperature was raised to 75 °C. After the temperature was raised, the reaction was carried out under reflux for 10 hours. After the reaction, 656 parts of methanol was added, and then 172.8 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was further reacted under reflux for 10 hours. After completion of the reaction, the mixture was neutralized with a 5% aqueous solution of disodium hydrogen phosphate, and then distilled under methanol at 80 °C. Thereafter, methyl isobutyl is added for washing. After 780 parts of ketone (MIBK), it was washed three times with water. Then, the solvent was removed from the organic phase at 100 ° C under reduced pressure, whereby 731 parts of a cyclooxyl compound (B-1) having an epoxy group was obtained. The obtained compound had an epoxy equivalent of 491 g/eq, a weight average molecular weight of 2090, 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)

197 parts of 2-(3,4 epoxycyclohexyl)ethyltrimethoxydecane, molecular weight 1700 (GPC measured value) of dimethylol diphenyl decane having decyl alcohol group 534 parts, 0.5% KOH 4 parts of a methanol solution and 36 parts of isopropyl alcohol were added to a reaction container, and the temperature was raised to 75 °C. After the temperature was raised, the reaction was carried out under reflux for 10 hours. After the reaction, after adding 576 parts of methanol, 86.4 parts of a methanol solution of 50% distilled water was added dropwise over 60 minutes, and the mixture was further reacted for 10 hours under reflux. After completion of the reaction, the mixture was neutralized with a 5% aqueous solution of disodium hydrogen phosphate, and then distilled under methanol at 80 °C. Thereafter, 660 parts of MIBK was added for washing, and then washed three times with water. Then, the solvent was removed from the organic phase at 100 ° C under reduced pressure, whereby 648 parts of a cyclooxyl 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 methanol-modified polyoxo X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.) and 15.4 parts of RIKACID MH (methylhexahydrophthalic anhydride, manufactured by Nippon Chemical Co., Ltd.) were added to the reaction. In the vessel, the temperature was raised to 80 ° C, and GPC was measured after 4 hours, and the peak of RIKACID MH disappeared. Thereafter, the reaction is further carried out for 2 hours. 65.0 parts of a carboxylic acid compound (A-7) was obtained. The obtained compound has an acid value of 80.0 mgKOH/g, a weight average molecular weight of 1,700, and a viscosity of 750 mPa. s.

Example 7

100 parts of the polyvalent carboxylic acid resin (A-1) obtained in Example 1 and 71 parts of the epoxy group-containing oxirane compound (B-1) obtained in Synthesis Example 1 of the epoxy resin, Synthesis Example 2 71 parts of the epoxy group-containing oxoxane compound (B-2) obtained by mixing and defoaming for 5 minutes gave a polyvalent carboxylic acid composition.

Example 8

100 parts of the polyvalent carboxylic acid resin (A-2) obtained in Example 2, 110 parts of the epoxy group-containing oxoxane compound (B-1) obtained in Synthesis Example 1 of the epoxy resin, and mixed Defoaming was carried out for 5 minutes to obtain a polycarboxylic acid composition.

Example 9

100 parts of the polycarboxylic acid resin (A-3) obtained in Example 3, 100 parts of the liquid carboxylic acid compound (A-7) obtained in Synthesis Example 3, and the obtained in Synthesis Example 1 as an epoxy resin were obtained. 220 parts of an epoxy group-containing oxoxane compound (B-1), which was mixed and defoamed for 5 minutes to obtain a polyvalent carboxylic acid composition.

Example 10

100 parts of the polycarboxylic acid resin (A-4) obtained in Example 4, 100 parts of the liquid carboxylic acid compound (A-7) obtained in Synthesis Example 3, and the obtained in Synthesis Example 1 as an epoxy resin were obtained. Epoxy alkoxylate compound (B -1) 121.5 parts of 121.5 parts of the epoxy group-containing oxirane compound (B-2) obtained in Synthesis Example 2, which were mixed and defoamed for 5 minutes to obtain a polyvalent carboxylic acid composition.

Example 11

100 parts of the polycarboxylic acid resin (A-5) obtained in Example 5, 100 parts of the liquid carboxylic acid compound (A-7) obtained in Synthesis Example 3, and the obtained in Synthesis Example 1 as an epoxy resin were obtained. 206 parts of the epoxy group-containing oxoxane compound (B-1), which were mixed and defoamed for 5 minutes to obtain a polyvalent carboxylic acid composition.

Example 12

100 parts of the polycarboxylic acid resin (A-6) obtained in Example 6, 100 parts of the liquid carboxylic acid compound (A-7) obtained in Synthesis Example 3, and the obtained in Synthesis Example 1 as an epoxy resin were obtained. 210 parts of an epoxy group-containing oxoxane compound (B-1), which was mixed and defoamed for 5 minutes to obtain a composition of a polyvalent carboxylic acid composition.

Comparative example 2

100 parts of the liquid carboxylic acid compound (A-7) obtained in Synthesis Example 3, 100 parts of the epoxy group-containing oxoxane compound (B-1) obtained in Synthesis Example 1 of the epoxy resin, and mixed Defoaming was carried out for 5 minutes to obtain an epoxy resin composition.

Evaluation test

The blend ratio of the polycarboxylic acid compositions obtained in Examples 7 to 12 and Comparative Example 2 and the duometer hardness of the cured product, the transmittance, the depression of the cured product accompanying the volatilization of the cured product, and the surface stickiness Sexual outcome Shown in Table 2. The tests in Table 2 were carried out in the following manner.

(1) Viscosity after mixing:

The polycarboxylic acid compositions obtained in Examples 7 to 12 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 compositions obtained in Examples 7 to 12 and Comparative Example 2 were subjected to vacuum defoaming for 5 minutes, and then cast into a mold using aluminum foil so as to have a diameter of 30 mm and a height of 70 mm. The cast material was pre-cured at 120 ° C for 1 hour, and then hardened at 150 ° C for 3 hours to obtain a test piece for hardness tester having a thickness of 7 mm. The hardness of the obtained test piece was measured by the method described in JIS K-6253 (type A).

(3) Hardened material transmittance:

The polycarboxylic acid compositions obtained in Examples 7 to 12 and Comparative Example 2 were subjected to vacuum defoaming for 5 minutes, and then slowly cast into a barrier of 30 mm × 20 mm × height 0.8 mm by using heat-resistant tape. On the glass substrate. The cast material was pre-cured at 120 ° C for 1 hour, and then hardened at 150 ° C for 3 hours to obtain a test piece for transmittance of 0.8 mm in thickness. The obtained test piece was measured for light transmittance at 400 nm under the following conditions.

Spectrophotometer measurement conditions

Manufacturer: Hitachi High-Technologies Co., Ltd.

Model: U-3300

Slit width: 2.0 nm

Scanning speed: 120 nm/min

(4) Depression test

The polycarboxylic acid composition obtained in each of Examples 7 to 12 and Comparative Example 2 was subjected to vacuum defoaming for 5 minutes, and then filled in a syringe, and the opening was flattened so that the opening was flat with a micro-injection device. A surface mount type LED of a light-emitting element having an emission wavelength of nm. After pre-hardening at 120 ° C for 1 hour, the surface-mounted LED was sealed by hardening at 150 ° C for 3 hours. 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 evaluated. In the table, ○: no depression was confirmed; Δ: a small depression was confirmed; ×: a large number of depressions were confirmed.

(5) Surface viscosity:

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, ○: no sticky; ×: sticky.

As clear from the results shown in Table 1, as a comparison of liquid carboxylic anhydrides In the case of RIKACID MH of Example 1, the thermal weight was greatly reduced at 120 ° C. In contrast, the polycarboxylic acid resins A-1 to A-6 of Examples 1 to 6 were liquid and 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 cured product in Comparative Example 2 was small (A type), and the strength was inferior. In contrast, in Examples 7 to 12, the hardness of the durometer was relatively small. High and excellent strength. Further, there is no depression and the surface is sticky. Further, the polyhydric carboxylic acid resin A-2 used in Example 8 was white turbid at room temperature, but was excellent in transmittance similar to those of Examples 7 and 9 to 12.

The present invention has been described in detail above with reference to the specific embodiments thereof. It is understood that various changes and modifications may be made without departing from the spirit and scope of the invention.

In addition, the present application is based on a Japanese patent application filed on Apr. 7, 2011 (Japanese Patent Application No. 2011-85067). Further, all references cited herein are hereby incorporated by reference in their entirety.

[Industrial availability]

The polyvalent carboxylic acid resin of the present invention can be used as a hardener for epoxy resins by being contained together with an epoxy resin. Further, the composition containing a polyvalent carboxylic acid resin and an epoxy resin is useful in a wide range of applications such as electric/electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, and resists, especially as a A material which is indispensable for optical characteristics and adhesion to a machine member, for example, an adhesive material for an optical semiconductor (such as an LED product) and a sealing material is extremely useful.

Claims (10)

A polyvalent carboxylic acid resin (A) modified by a two-terminal methanol represented by the following formula (1), which is selected from the group consisting of a terminal alcohol polyester compound (b) and a hydrocarbon polyol compound ( f) and a polyol compound having at least two hydroxyl groups in one or more of the group consisting of terminal alcohol polycarbonate compounds, and a polyol compound (e) having two or more hydroxyl groups selected from 1, 2, 3, 4-butane tetracarboxylic dianhydride, 1 , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, pyromellite Anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)- a compound (c) having two or more carboxylic acid anhydride groups in one or more molecules of a group consisting of 1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride obtained by an addition reaction, (In the formula (1), R ₁ 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 R ₂ each independently represents a methyl group or a phenyl group, and n is average The value meter indicates 1~100). A polyvalent carboxylic acid resin (A) modified by a two-terminal methanol represented by the following formula (1), which is selected from the group consisting of a terminal alcohol polyester compound (b) and a hydrocarbon polyol compound ( And a polyhydric alcohol compound (e) having two or more hydroxyl groups in the group of the terminal alcohol polycarbonate compound, selected from the group consisting of 1,2,3,4-butanetetracarboxylic dianhydride, 1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, pyroic anhydride 5-(2,5-Dioxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1 a compound (c) having two or more carboxylic anhydride groups in one or more molecules of the group consisting of 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, and selected from the group consisting of succinic anhydride and methyl butyl Diacid anhydride, ethyl succinic anhydride, 2,3-butane dicarboxylic anhydride, 2,4-pentane dicarboxylic anhydride, 3,5-heptane dicarboxylic anhydride, maleic anhydride, dodecyl butyl Diacid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 1,3-cyclohexanedicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane -2,3-Dicarboxylic anhydride, nadic acid anhydride, methyl acid anhydride, bicyclo[2,2,2]octane-2,3-dicarboxylic anhydride, 1,2,4-ring Hexanetricarboxylic acid-1,2-anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, acid anhydride, methylic acid anhydride, 4,5-dimethyl-4- Cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]-5-octene-2,3-dicarboxylic anhydride, phthalic anhydride, isophthalic anhydride, terephthalic anhydride and a compound (d) having one or more carboxylic anhydride groups in one or more molecules of the group consisting of 1,2,4-benzenetricarboxylic anhydride, obtained by an addition reaction, (In the formula (1), R ₁ 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 R ₂ each independently represents a methyl group or a phenyl group, and n is average The value meter indicates 1~100). The polyvalent carboxylic acid resin (A) according to claim 1 or 2, wherein the polyol compound (e) having two or more hydroxyl groups in the molecule is a terminal alcohol polyester compound (b). The polycarboxylic acid resin (A) according to claim 3, wherein the terminal alcohol polyester compound (b) is represented by the formula (2), (In the formula (2), R ₃ and R ₄ each independently represent an alkylene group having 1 to 10 carbon atoms, and m is an average value of 1 to 100). The polyvalent carboxylic acid resin (A) according to claim 1 or 2, wherein the polyol compound (e) having two or more hydroxyl groups in the molecule is a hydrocarbon polyol compound (f). The polycarboxylic acid resin (A) according to claim 1 or 2, wherein the compound (c) having two or more carboxylic acid anhydride groups in the molecule is selected from the group consisting of the following formulas (3) to (5) One or more of them, The polycarboxylic acid resin (A) according to the second aspect of the invention, wherein the compound (d) having a carboxylic anhydride group in the molecule is one or more selected from the group consisting of the formulae (6) to (10), A polycarboxylic acid composition comprising the polyvalent carboxylic acid resin (A) and the epoxy resin (B) according to any one of claims 1 to 7. A cured product obtained by hardening a polycarboxylic acid composition of claim 8 of the patent application. A light-emitting diode having a cured product of claim 9th.