TWI435896B - A carboxylic acid compound and an epoxy resin composition containing the same - Google Patents

Description

Carboxylic acid compound and epoxy resin composition containing same

The present invention relates to a carboxylic acid compound and a resin composition containing the same. More specifically, it has a specific structure and can be used as an epoxy resin hardener, a paint, an adhesive, a molded article, an optical material, a semiconductor, a resin for a sealing material for an optical semiconductor, and a resin for a die-shaped material for an optical semiconductor. a carboxylic acid compound such as a raw material or a modifying agent, a plasticizer, a lubricating oil raw material, a medical pesticide intermediate, a raw material for a coating resin, a resin for a toner, and a ring containing the same. Oxygen resin composition.

Since the epoxy resin is cured by hardening, it is possible to obtain a cured product excellent in adhesion, mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., and thus used for coatings, adhesives, composite materials, and molding materials. , casting materials, various coating materials, resists and other fields. Examples of the curing agent used for the epoxy resin include a usual curing agent such as an amine compound, a carboxylic acid compound, a carboxylic acid anhydride, a phenol compound, or a thiol compound. Among these hardeners, various carboxylic acid compounds or carboxylic anhydrides are often used in applications in which the cured product is required to have high transparency or heat resistance, or an appropriate service life is required, particularly in liquid compositions, usually A liquid carboxylic anhydride is used as the hardener. In fact, carboxylic acids are avoided because they have strong hydrogen bonds between molecules, which not only cause crystallization but also have poor compatibility with other resins.

As a resin for optical semiconductor sealing such as an LED (Light Emitting Diode), a liquid such as a bisphenol epoxy resin or an alicyclic epoxy resin is used in terms of excellent mechanical strength and adhesion. An epoxy resin composition (refer to Patent Document 1). In recent years, LEDs have been used in fields requiring high brightness such as automotive headlamps or lighting applications. Accordingly, the resin for sealing optical semiconductor elements particularly requires UV (ultraviolet) resistance and heat resistance. However, as described above, it is difficult to say that a bisphenol type epoxy resin or an alicyclic epoxy resin has sufficient UV resistance and heat resistance, and it may not be used in a field requiring high brightness. Therefore, as a sealing material having high UV resistance, heat resistance, etc., a polyfluorene resin sealing material using an organic polyoxyalkylene having a non-covalently bonded group and an organic hydrogenated diene polyoxyalkylene is currently used (refer to the patent) Literature 2). However, the sealing material using such a silicone 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 becomes sticky. In order to solve these problems, the industry is advancing the development of sealing materials which are excellent in UV resistance and heat resistance and have good adhesion by using a condensate of a ruthenium compound having an epoxy group and a liquid acid anhydride (see Patent Document 3). Patent Document 4). As an acid anhydride for such use, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydroortylene is used for reasons such as colorless and transparent, liquid at room temperature, easy handling, and the like. A carboxylic acid anhydride such as formic anhydride, methyltetrahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride or a mixture thereof. However, most of these carboxylic anhydrides are low molecular weight compounds. Therefore, in the epoxy resin composition containing the carboxylic anhydride as a curing agent, volatilization during thermal curing becomes a problem. The volatilization of the carboxylic anhydride not only causes the hardening of the epoxy resin composition due to insufficient carboxylic anhydride (hardener) in the hardening reaction, but also has adverse effects on the human body due to its harmfulness, and pollution to the production line. And air pollution, etc., has a greater impact on the environment. Further, in this case, since the hardening is insufficient, the remaining unreacted epoxy resin causes the sealing surface to become sticky, and the hardening of the epoxy resin due to the carboxylic anhydride which volatilizes during hardening, and also in terms of function. And environmental issues to consider.

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

Patent Document 2: Japanese Patent Laid-Open No. 2006-299099

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

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

SUMMARY OF THE INVENTION An object of the present invention is to provide a carboxylic acid compound which is liquid at room temperature and which is excellent in volatility at high temperatures, and particularly has low volatility in a hardening step as an epoxy resin hardener. A hardened, colorless, transparent surface that is not sticky.

In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that a polyfluorene-based compound having a specific skeleton is reacted with a compound having a specific skeleton and having a carboxylic anhydride group to obtain a carboxylic acid having a polyfluorene skeleton. The compound and the carboxylic acid compound are used as a curing agent for an epoxy resin, whereby the above problems can be solved, and the present invention has been completed.

That is, the present invention relates to the following:

(1) A carboxylic acid compound (A) which is subjected to an addition reaction with a polyoxosiloxane compound (a) represented by the following formula (1) and a compound having one or more carboxylic acid anhydride groups in the molecule. The compound having one or more carboxylic anhydride groups in the above molecule is at least one selected from the group consisting of compounds (c) represented by the following formulas (3) to (5):

(In the formula (1), R ₁ represents an alkylene group having a total carbon number of 1 to 10 which may have an ether group, R ₂ represents a methyl group or a phenyl group, and n is an average value, which represents 1 to 100).

(2) A carboxylic acid compound (A) which is subjected to an addition reaction with a polyoxosiloxane compound (a) represented by the following formula (1) and a compound having one or more carboxylic acid anhydride groups in the molecule. The compound obtained by the above formula (3) is a compound having one or more carboxylic anhydride groups in the above molecule:

(In the formula (1), R ₁ represents an alkylene group having a total carbon number of 1 to 10 which may have an ether group, R ₂ represents a methyl group or a phenyl group, and n is an average value, which represents 1 to 100).

(3) An epoxy resin hardener comprising the carboxylic acid compound (A) as described in (1) or (2) above and a hardening accelerator;

(4) An epoxy resin composition containing the carboxylic acid compound (A) according to (1) or (2) above or an epoxy resin hardener as described in (3) above and an epoxy resin;

(5) The epoxy resin composition according to (4) above, wherein the epoxy resin has an epoxy equivalent of 400 to 1500 g/eq., and a weight average molecular weight of 1,500 to 5,000;

(6) The epoxy resin composition according to (5) above, wherein the use of the epoxy resin composition is for the use of an optical semiconductor sealing material;

(7) The epoxy resin composition according to (5) above, wherein the use of the epoxy resin composition is for the use of an optical semiconductor die-bonding material;

(8) A cured product which is a cured product of the epoxy resin composition according to any one of the above (4) to (7).

The carboxylic acid compound (A) of the present invention is liquid at room temperature (25 ° C), and has extremely low volatility in a temperature range which is usually used for curing an epoxy resin. Further, the carboxylic acid compound (A) can be used as a curing agent for an epoxy resin, a coating material, an adhesive, a molded article, a resin for a sealing material for a semiconductor or an optical semiconductor, a resin for a die bonding material for an optical semiconductor, and a polyimide resin. Raw materials or modifiers, plasticizers, lubricant raw materials, medical pesticide intermediates, raw materials for coating resins, resins for colorants, especially the carboxylic acid compound (A) has hardening ability to epoxy resin Since the cured product obtained from the film has high transparency, it is extremely useful as a curing agent for an epoxy resin for sealing an optical semiconductor such as a high-intensity white LED.

The invention is described in detail below.

First, the polyfluorene oxide compound (a) of the present invention represented by the following formula (1) will be described.

(In the formula (1), R ₁ represents an alkylene group having a total carbon number of 1 to 10 which may have an ether group, R ₂ represents a methyl group or a phenyl group, and n is an average value, and represents 1 to 100.)

In the formula (1), specific examples of R ₁ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, and an isoamyl group. And an alkyl group such as a hexyl group, a heptyl group, a hexyl group, and an alkyl group which are interrupted by an ether represented by the following formulas (8) to (17); the total carbon number of the alkyl group is 1 to 10 . As a particularly preferred alkylene group, an alkylene group interrupted by an ether represented by the formula (12) can be enumerated. (The leftmost carbon atom in the formulae (8) to (17) is bonded to the ruthenium atom of the formula (1))

In the above formula (1), R ₂ represents a methyl group or a phenyl group, and may be the same or different. In order to make the carboxylic acid compound (A) liquid at room temperature, it is preferably a methyl group as compared with a phenyl group. .

In the formula (1), n is an average value, and represents 1 to 100, preferably 2 to 80, more preferably 5 to 50.

The polyfluorene oxide compound (a) represented by the formula (1) is, for example, a polyfluorene-based compound having an alcoholic hydroxyl group at both terminals. Specific examples thereof include X-22-160AS, KF6001, KF6002, and KF6003 (both manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-201, BY16-004, and SF8427, both of which are methanol-modified eucalyptus oils at both ends. It is manufactured by Toray Dow Corning Co., Ltd., XF42-B0970, XF42-C3294 (both manufactured by Momentive Performance Materials Inc.), etc., which are commercially available. The modified eucalyptus 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, KF6001, KF6002, BY16-201 or XF42-B0970 are preferred.

Next, the compound (c) having a carboxylic anhydride group represented by the formulas (3) to (5) will be described.

The compounds represented by the formulae (3) to (5) are methylhexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, respectively. A compound having a carboxylic anhydride group in a molecule. The carboxylic anhydride group is subjected to a ring-opening addition reaction with a functional group having an active hydrogen such as an alcoholic hydroxyl group, a phenolic hydroxyl group, an amine group, a carboxyl group or a stanol group to form an ester bond, a guanamine bond, etc., on the other hand, The acid anhydride group is opened to form a free carboxylic acid.

The carboxylic acid compound (A) of the present invention is an adduct of at least one selected from the group consisting of a polyoxosiloxane (a) and a compound (c) selected from the above formulas (3) to (5). The carboxylic acid anhydride group of the compound (c) represented by (3) to (5) may be subjected to an addition reaction with the alcoholic hydroxyl group of the polyfluorene oxide compound (a) to obtain a carboxylic acid compound (A).

In the addition reaction, in order to adjust the molecular weight and viscosity of the carboxylic acid compound (A), the compound (c) having a carboxylic anhydride represented by the formulas (3) to (5) and one or more carboxylic anhydride groups in the molecule may be used. Compound (b) is used to carry out an addition reaction.

Examples of the compound (b) having one or more carboxylic anhydride groups in the molecule include succinic anhydride, methyl succinic anhydride, ethyl succinic anhydride, 2,3-butane dicarboxylic anhydride, and 2,4-pentane. a saturated aliphatic carboxylic acid anhydride such as dicarboxylic anhydride, 3,5-heptane dicarboxylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride; maleic anhydride, dodecyl succinic anhydride, etc. a saturated aliphatic carboxylic acid anhydride; hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 1,3-cyclohexane dicarboxylic anhydride, nadic acid anhydride, methyl acid anhydride, Bicyclo[2.2.2]octane-2,3-dicarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1 a cyclic saturated aliphatic carboxylic anhydride such as 2,4,5-cyclohexanetetracarboxylic dianhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, ceric anhydride, methylic acid anhydride a cyclic unsaturated unsaturated carboxylic acid such as 4,5-dimethyl-4-cyclohexene-1,2-dicarboxylic anhydride or bicyclo[2.2.2]-5-octene-2,3-dicarboxylic anhydride Anhydride; aromatic carboxylic acid anhydride such as phthalic anhydride, isophthalic anhydride, terephthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, etc. Further, 5-(2,5-di-oxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4-(2,5-di-oxo-oxygen) The same compound such as tetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride has a saturated aliphatic carboxylic anhydride, a cyclic saturated carboxylic anhydride, and a cyclic unsaturated carboxylic anhydride. A polycarboxylic acid compound or the like.

When the compound (b) having one or more carboxylic anhydride groups in the molecule is used in combination with the compound (c) represented by the formulae (3) to (5), one type or two types may be used in addition to the compound (c). the above. In order to make the carboxylic acid compound (A) liquid at room temperature and to cure the carboxylic acid compound (A) and the epoxy resin, the cured product is excellent in transparency, and is preferably the following formula (2). , (6), (7), hexahydrophthalic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, 1,2,3,4-butanetetracarboxylic acid anhydride.

When the compound (b) is used, the compound (b) is preferably from 5 to 80 mol%, more preferably from 10 to 78 mol%, based on the total of the compound (b) and the compound (c).

The reaction of the polyoxygen compound (a) with the compound (c) (and optionally the compound (b)) can be carried out in a solvent or in the absence of a solvent. The solvent is not particularly limited as long as it is a solvent which does not react with the polyoxosiloxane (a) and the compound (c) (and optionally the compound (b)) represented by the formula (1). As the solvent which can be used, for example, dimethylformamide, dimethylacetamide, dimethylhydrazine, tetrahydrofuran, acetonitrile, methyl ethyl ketone, cyclopentanone, methyl isobutyl ketone can be mentioned. An aprotic polar solvent such as an aromatic hydrocarbon such as toluene or xylene, and the like is preferably an aromatic hydrocarbon. These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited, and the total weight of the compound (c) and the compound (c) (and the optional compound (b)) represented by the above formula (3) to formula (5) is 100. It is usually preferably used in an amount of from 0.1 to 300 parts by weight based on parts by weight.

A catalyst may be used for the reaction, and as the catalyst which can be used, for example, an acidic compound such as hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, nitric acid, trifluoroacetic acid or trichloroacetic acid may be mentioned. a metal hydroxide such as sodium hydroxide, potassium hydroxide, calcium hydroxide or magnesium hydroxide; an amine compound such as triethylamine, tripropylamine or tributylamine, pyridine or dimethylaminopyridine; 8-Diazabicyclo[5.4.0]undec-7-ene, imidazole, triazole, tetrazole and other heterocyclic compounds, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl hydroxide Ammonium, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylhexadecyl ammonium hydroxide, hydroxide a quaternary ammonium salt such as octylmethylammonium chloride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate or trioctylmethylammonium acetate. These catalysts may be used alone or in combination of two or more. Among these, triethylamine, pyridine, and dimethylaminopyridine are preferred.

The amount of the catalyst to be used is not particularly limited, and is based on the polyoxonium compound (a) represented by the formula (1) and the compound (c) represented by the formulas (3) to (5) (and an optional compound (b). The total weight of 100% by weight of the)) is usually preferably 0.1 to 100 parts by weight as needed.

The reaction temperature at the time of the reaction is usually from 80 to 180 ° C, preferably from 110 to 140 ° C. Further, the reaction time is usually from 1 to 12 hours. The Mw (weight average molecular weight) of the reaction product can be determined by GPC (Gel Permeation Chromatography). After completion of the reaction, the heating is stopped, and when a solvent is used, the solvent can be removed under reduced pressure to obtain a target carboxylic acid compound. The Mw (weight average molecular weight) of the obtained carboxylic acid compound can also be confirmed by GPC.

The carboxylic acid compound (A) of the present invention has a specific structure and is liquid at room temperature (25 ° C), and has extremely low volatility in a temperature range which is usually used for curing an epoxy resin.

Further, since the carboxylic acid compound (A) is excellent in transparency, it can be used as a curing agent for an epoxy resin, a coating material, an adhesive, a molded article, a resin for a sealing material for a semiconductor or an optical semiconductor, and a resin for a die bonding material for an optical semiconductor. a raw material or a modifier, a plasticizer or a lubricant raw material, a pharmaceutical pesticide intermediate, a resin for a coating resin, a resin for a toner, and particularly a hardener for an epoxy resin, Since it is excellent in the hardening ability and the transparency of the hardened material is excellent, it is very useful as a hardener for epoxy resins for sealing an optical semiconductor such as a white LED of high brightness.

The carboxylic acid compound (A) of the present invention can be used alone as a curing agent for an epoxy resin, and it is also preferred to use the carboxylic acid compound (A) in combination with a curing accelerator as a curing agent for an epoxy resin. As the curing accelerator to be mixed in the carboxylic acid compound (A), any curing accelerator can be used as the curing accelerator which can be used as long as it has an ability to promote the curing reaction between the epoxy group and the carboxylic acid and the carboxylic acid anhydride. Examples of the examples include an ammonium salt-based hardening accelerator, an onium-based hardening accelerator, an imidazole-based curing accelerator, an amine-based curing accelerator, a phosphine-based curing accelerator, a phosphite-based curing accelerator, and a Lewis acid-based curing. Promoters, etc.

Among these, in the use of a curing agent for an epoxy resin composition for sealing an optical semiconductor such as a white LED having high brightness, an ammonium salt-based hardening accelerator and a cerium salt are particularly preferable in terms of excellent transparency. A 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. These hardening accelerators may be used alone or in combination of two or more. Among these hardening accelerators, trimethylhexadecyl ammonium hydroxide and methyl tributyl phosphonium dimethyl phosphate are preferred.

In addition to the above-mentioned ammonium salt-based hardening accelerator and the onium-based hardening accelerator, an imidazole-based hardening accelerator, an amine-based curing accelerator, a heterocyclic compound-based curing accelerator, and a phosphine-based curing may be used. An 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-pyrrole-[1.2-a]benzimidazole, 2,4-di Amino-6-(2'-methylimidazolium (1')) ethyl s-triazine, 2,4-diamino-6-(2'-undecylimidazolium (1')) ethyl Triazine, 2,4-diamino-6-(2'-ethyl, 4-methylimidazolium (1')) ethyl s-triazine, 2,4-diamino-6-(2'- Methylimidazolium (1')) ethyl s-triazine-iso-cyanuric acid adduct, 2-methylimidazoisocyanuric acid 2:3 adduct, 2-phenylimidazole isocyanocyanate Acid addition product, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole or 1-cyanoethyl-2-phenyl-3 , 5-dicyanoethoxymethylimidazole, and the like.

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 BF ₃ monoethylamine, BF ₃ diethylamine, BF ₃ triethylamine, BF ₃ benzylamine, BF ₃ aniline, BF ₃ piperazine, and BF _{3 .} Piperidine, PF ₅ ethylamine, PF ₅ butylamine, PF ₅ dodecylamine, PF ₅ benzylamine, AsF ₅ dodecylamine, and the like. These hardening accelerators may be used alone or in combination of two or more.

Each of the above-mentioned curing accelerators may be added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the carboxylic acid compound (A) of the present invention.

The epoxy resin composition of the present invention contains a carboxylic acid compound (A), an epoxy resin, an optional hardening accelerator, various additives, and the like.

Examples of the epoxy resin which can be used herein include, for example, 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, and an alicyclic epoxy resin. , an aliphatic epoxy resin, a heterocyclic epoxy resin, a glycidyl ester epoxy resin, a glycidylamine epoxy resin, an epoxy resin obtained by glycidylating a halogenated phenol, and an epoxy group. A condensate of a ruthenium compound and a ruthenium compound other than the compound, 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, tetramethylbisphenol 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-bis(4-hydroxyphenyl)ethyl)phenyl]propane, 2,2'-extension Bis(4-methyl-6-tert-butylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol , hydroquinone, pyrogallol, phloroglucinol, phenols having a diisopropylidene skeleton, 1,1-bis(4-hydroxyphenyl)fluorene, etc., phenolic compounds having an anthracene skeleton, phenolation A glycidyl ether compound of a polyphenol compound such as polybutadiene is an epoxy resin or the like.

Examples of the epoxy resin of the glycidyl ether compound of the above-mentioned novolac resin include phenol, cresol, ethylphenol, butylphenol, octylphenol, bisphenol A, and bisphenol F. A phenol novolak resin containing various phenols such as bisphenols and naphthols, a phenol novolak resin containing a benzene dimethyl skeleton, a phenol novolak resin containing a dicyclopentadiene skeleton, and a biphenyl skeleton A phenol novolak resin, a glycidyl ether compound of various novolac resins such as a phenol novolak resin containing an anthracene skeleton.

Examples of the alicyclic epoxy resin include 3,4-epoxycyclohexanecarboxylic acid-3,4-epoxycyclohexyl methyl ester and adipic acid bis(3,4-epoxycyclohexylmethyl ester). 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 a heterocyclic epoxy resin having a heterocyclic ring such as an iso-cyanocyanate ring or an intramethylene urea ring.

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

Examples of the glycidylamine-based epoxy resin include an epoxy resin obtained by glycidylating an amine such as aniline or toluidine.

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

The condensate of the above-mentioned oxime compound having an epoxy group and a ruthenium compound other than the above, for example, 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 condensate of an epoxy alkoxydecane compound with a polydimethyl methoxyalkane 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. As a polydimethyl methoxy oxane having a decyl alcohol group and a polydimethyl phenyl siloxane having a stanol group, for example, as a commercially available product, X-21-5841, KF can be cited. -9701 (manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-873, PRX413 (manufactured by Toray-Dow Corning Co., Ltd.), XC96-723, YF3804, YF3800, XF3905, YF3057 (Momentive Performance Materials Inc.), DMS-S12 , DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S31 (manufactured by Gelest), and the like.

As a copolymer of a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds, commercially available products include Marproof G-0115S, Marproof G-0130S, and Marproof G-0250S. For example, 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 methacrylic acid shrinkage Glyceride, 4-vinyl-1-cyclohexene-1,2-epoxide, and the like. Moreover, examples of the copolymer of the other polymerizable unsaturated compound include methyl (meth)acrylate, ethyl (meth)acrylate, benzyl (meth)acrylate, and cyclohexyl (meth)acrylate. Styrene, vinyl cyclohexane, and the like. These epoxy resins may be used alone or in combination of two or more.

In particular, when the epoxy resin composition of the present invention is used for an optical semiconductor sealing material, it is preferred that the epoxy resin has an epoxy equivalent (measured by the method described in JIS K-7236) of 400 to 400. It is more preferably 1500 g/eq., and the epoxy equivalent is 450 to 1100 g/eq. When the epoxy equivalent is less than 400 g/eq., the cured product tends to be too hard, and cracks and the like tend to be broken. When the epoxy equivalent is more than 1500 g/eq., the surface tends to be sticky.

Further, the weight average molecular weight is preferably from 1,500 to 10,000, more preferably from 1800 to 5,000. When the weight average molecular weight is less than 1,500, the toughness of the cured product tends to be inferior, and for example, there is a fear that cracks such as cracks may occur in a heat cycle test or the like. When the weight average molecular weight is more than 10,000, the viscosity tends to be high, which tends to deteriorate workability.

In the epoxy resin 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, etc., it is more preferable to have an epoxy group-containing oxime compound and the like. a condensate of the compound.

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

Various conditions of GPC

Manufacturer: Shimadzu Corporation

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

Flow rate: 1.0ml/min.

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Detector: RI (differential refraction detector)

As for the content of each of the above components in the epoxy resin composition of the present invention, the polyoxonium compound (a) represented by the formula (1) and the compound represented by the formula (3) to (5) of the present invention ( c) (and optionally the compound (b) having a carboxylic anhydride group) The carboxylic acid compound (A) obtained by an addition reaction is 5 to 95 parts by weight, preferably 20 to 80 parts by weight, as described above. The epoxy resin is 5 to 95 parts by weight, preferably 20 to 80 parts by weight, and if necessary, the curing accelerator is 0.005 to 10 parts by weight, preferably 0.05 to 5 parts by weight.

The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components at normal temperature or under heating. For example, it can be prepared by using an extruder, a kneader, a three-roller, a universal mixer, a planetary mixer, a homomixer, a homogenizer, a bead mill, etc., to thoroughly mix until uniform, and if necessary Filtration treatment is performed using a SUS sieve or the like.

In the epoxy resin hardener and the epoxy resin 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, and sebacic acid. 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-. Norbornene dicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2,3-cyclohexanetricarboxylic acid, 1,2,4,6-cyclohexane Tetraformic acid, etc.

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, Hemimellitic acid, trimellitic acid, trimesic acid, 1,2,4-naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,3,5-benzenetetracarboxylic acid ( Mellophanic acid), 1,2,3,4-benzenetetracarboxylic acid (prehnitic acid), pyromellitic acid, 3,3'4,4'-benzophenonetetracarboxylic acid, 2,2'3,3'- Benzophenone tetracarboxylic acid, 2,3,3',4'-benzophenonetetracarboxylic acid, 3,3'4,4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyl Tetracarboxylic 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-cyclobutanetetracarboxylic acid Anhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic acid Anhydride, benzoic acid 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, trimellitic anhydride, and pyromellitic dianhydride.

Further, 5-(2,5-di-oxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4-(2,5-di-tertiary tetrahydrofuran) 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′-biphenol, tetramethyl bisphenol A, dimethyl bisphenol A, and tetramethyl bisphenol F. Dimethylbisphenol F, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenol, 1-(4- Hydroxyphenyl)-2-[4-(1,1-bis(4-hydroxyphenyl)ethyl)phenyl]propane, 2,2'-extended methyl bis(4-methyl-6-third Butyl phenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, a phenol having a diisopropylidene skeleton; a phenol having an anthracene skeleton such as 1,1-bis(4-hydroxyphenyl)anthracene; a phenolated polybutadiene, a phenol, a cresol, an ethylphenol, Phenolic varnish resin containing various phenols such as butyl phenol, octyl phenol, bisphenol A, bisphenol F, bisphenol S, naphthol, etc., phenol novolac resin containing benzene dimethyl skeleton, containing two rings Phenolic novolak resin of pentadiene skeleton, phenol novolak resin containing biphenyl skeleton, phenol novolak resin containing ruthenium skeleton, phenol novolac containing furan skeleton Novolac resins and other resins.

Examples of the above-mentioned anthraquinones include isophthalic acid, hexamethylene dioxime, fluorene dioxime, dinonyl dodecanoate, and 2,6-naphthoquinone.

Examples of the above mercaptans include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), and iso-trisole. Tris[(3-decylpropenyloxy)ethyl]cyanate, 1,4-bis(3-mercaptobutyloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3, 5-tris(3-mercaptobutoxyethyl)-1,3,5-s-triazine-2,4,6-(1H,3H,5H)trione and the like.

These epoxy resin hardeners may be used alone or in combination of two or more. When the carboxylic acid compound (A) of the present invention is used in combination with the above-mentioned curing agent, the amount used is adjusted so that the proportion of the carboxylated content (A) in the total curing agent is 50% by weight or more. It is preferably 80% by weight or more.

In the epoxy resin composition of the present invention, 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.

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, vinyltrimethoxy Baseline, N-(2-(vinylbenzylamino)ethyl)-3-aminopropyltrimethoxydecane hydrochloride, 3-methylpropenyloxypropyltrimethoxydecane, 3 - decane coupling agent such as chloropropylmethyldimethoxydecane or 3-chloropropyltrimethoxydecane; (N-ethylaminoethylamino) isopropyl titanate, triisostearate Isopropyl titanate, titanium (dioctyl pyrophosphate) titanium glycol, di(dioctylphosphite) tetraisopropyl titanate, neoalkoxy three (for N-(β-amino group) a titanium coupling agent such as ethyl)aminophenyl) titanate; zirconium acetonate pyruvate, zirconium methacrylate, zirconium propionate, Neoalkoxy zirconate, neoalkoxy triindenyl zirconate, neoalkoxytris(taudecyl)benzenesulfonyl zirconate, neoalkoxytris(ethylenediamine) Zirconium such as ethyl)zirconate, neoalkoxytris(m-aminophenyl)zirconate, ammonium zirconium carbonate, aluminum acetylacetonate, aluminum methacrylate or aluminum propionate, or aluminum coupling agent .

These coupling agents may 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 increased. 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 epoxy resin component of the present invention.

Examples of the phosphor that can be used include YAG (yttrium aluminum garnet) phosphor, TAG (terbium aluminum garnet) phosphor, orthosilicate phosphor, sulfur. A phosphor such as a gallate phosphor or a sulfide phosphor. The epoxy resin composition can be imparted with fluorescing properties by adding a phosphor.

Examples of the inorganic filler which can be used include crystalline cerium oxide, molten cerium oxide, aluminum oxide, zircon, calcium silicate, calcium carbonate, cerium carbide, cerium nitride, boron nitride, zirconia, and magnesium. A powder such as forsterite, steatite, spinel, titanium dioxide or talc, or particles obtained by spheroidizing the particles. By adding an inorganic filler, heat resistance, light resistance, viscosity, or the like can be imparted. The content of the inorganic filler is from 0 to 90 parts by weight based on the epoxy resin 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, and metal oxides such as alumina, magnesia, and titania. 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 epoxy resin composition can be improved by adding highly thermally conductive fine particles.

The phosphorus-containing compound which can be used may be either 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, and toluene-2,6-bis(xylene) phosphate. Ester, 1,3-benzenedi(di(xylylene) phosphate), 1,4-benzenedi(di(dimethyl)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 a phosphine such as a phenanthrene-10-oxide, an epoxy resin with an active hydrogen of the above phosphine, a red phosphorus or the like, preferably a phosphate ester, a phosphine or a phosphorus-containing ring. Oxygen compound, preferably 1,3-benzenedi(di(xylylene) phosphate), 1,4-benzenedi(di(xylylene) phosphate), 4,4'-biphenyl (phosphoric acid di(II) Toluene) or phosphorus-containing epoxy compounds. The content of the phosphorus-containing compound is preferably a phosphorus-containing compound/epoxy resin = 0.1 to 0.6 (weight ratio). If it is less than 0.1, the flame retardancy is insufficient, and if it exceeds 0.6, there is a fear that the hygroscopic property and dielectric properties of the cured product are adversely affected.

Examples of the binder resin that can be used include a butyral resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, a NBR (nitrile butadiene rubber)-phenol resin, and an epoxy-NBR. The resin, the polyamine resin, the polyamidene resin, the polyoxyn resin, etc. are not limited thereto. The binder resin is usually contained in an epoxy resin composition of the present invention in an amount of 0.05 to 50 parts by weight, preferably 0.05 to 20 parts by weight, as needed.

Further, in the curable resin composition of the present invention, 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 may be added. Lifting agent, thixotropic agent, antifoaming agent, tackifier, impact modifier, ion trapping agent, antistatic agent, lubricant, leveling agent, surface tension reducing agent, defoaming agent Additives such as anti-precipitant, surfactant, UV absorber, various thermosetting resins, and various other resins. These are added to the epoxy resin composition of the present invention by a method known per se.

The epoxy resin composition of the present invention may be used by mixing a solvent or a varnish or an ink as needed. The solvent can be used as long as it has high solubility in each component such as the carboxylic acid compound (A), the epoxy resin, the curing accelerator, and other additives of the present invention, and does not react with the above, and 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, 3-methoxybutanol, 3-methyl Glycol ethers such as -3-methoxybutanol, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, acetic acid Alkyl glycol ether acetates such as 3-methoxybutyl ester, acetic acid-3-methyl-3-methoxybutyl ester, ethyl ethoxypropionate; aromatic hydrocarbons such as benzene, toluene and xylene Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone; methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, lactic acid Methyl ester, lactate B Ester, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, propyl 2-hydroxy-3-methylbutanoate Ethyl methoxyacetate, propyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, 2-methoxypropionic acid Methyl ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid Ethyl ester, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid Propyl ester, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3-ethoxypropionic acid Esters such as butyl ester; ethers such as diethyl ether and tetrahydrofuran. Further, as the aprotic polar solvent, dimethylformamide, dimethylacetamide, dimethylhydrazine, acetonitrile or the like can also be used.

These solvents are contained in the epoxy resin component of the present invention, and are usually contained in an amount of 2 to 90 parts by weight as needed. The epoxy resin composition of the present invention in the case of using a solvent to form a varnish or an ink can be precisely filtered, for example, using a filter of 0.05 to 2 μm.

Hereinafter, the case where the epoxy resin composition of the present invention is used as a sealing material or a die bonding material of a photo-semiconductor will be described in detail.

When the epoxy resin composition of the present invention is used as a sealing material or a die-bonding material for an optical semiconductor such as a high-brightness white LED, the carboxylic acid compound (A) of the present invention and an epoxy resin, and other hardeners are used. An additive such as a hardening accelerator, a coupling material, an antioxidant, a light stabilizer, or the like is sufficiently mixed to prepare an epoxy resin composition, which can be used as a sealing material or both for a die-bonding material and a sealing material. As a mixing method, a kneader, a three-roller, a universal mixer, a planetary mixer, a homomixer, a homogenizer, and a bead mill are used, and it mixes at normal temperature or heating.

Optical semiconductor elements such as high-brightness white LEDs are usually GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN laminated on a substrate such as sapphire, spinel, SiC, Si, or ZnO using an adhesive (a die-bonding material). A semiconductor wafer of InN, AlN, InGaN or the like is formed by a lead frame, a heat release plate, and a package. There is also a type in which a wire such as a metal wire is connected in order to pass current. In order to prevent the semiconductor wafer from being heated or damp, and to function as a lens, it is sealed with a sealing material such as an epoxy resin. The epoxy resin composition of the present invention can be used as the sealing material or the die bonding material. In terms of steps, it is convenient to use the epoxy resin composition of the present invention for both the die-bonding material and the sealing material.

As a method of attaching a semiconductor wafer to a substrate using the epoxy resin composition of the present invention, the following method can be employed; the epoxy resin composition of the present invention is applied by dispenser printing, potting printing, screen printing, The semiconductor wafer is then placed and heat hardened to cause the semiconductor wafer to follow the substrate. The heating can be performed by a hot air circulation type, an infrared ray, a high frequency or the like.

The heating condition is preferably, for example, heating 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 may be pre-hardened at 80 to 120 ° C for 30 minutes to 5 hours, and then post-cured at 120 to 180 ° C for 30 minutes to 10 hours.

As a molding method of the sealing material, an injection method in which a sealing material is injected into a template in which a substrate on which a semiconductor wafer is fixed as described above is inserted and then heat-hardened is performed to form a molding; and a sealing material is previously injected onto the metal mold. And a semiconductor wafer to be fixed on the substrate is immersed therein and heat-hardened, and then a compression molding method for releasing the mold from the metal mold.

Examples of the injection method include a dispenser, transfer molding, and injection molding.

For heating, a hot air circulation type, an infrared ray, a high frequency, or the like can be used.

The heating condition is preferably, for example, heating 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 may be pre-hardened at 80 to 120 ° C for 30 minutes to 5 hours, and then post-cured at 120 to 180 ° C for 30 minutes to 10 hours.

The carboxylic acid compound (A) of the present invention has a specific structure and is liquid at room temperature (25 ° C), and the epoxy resin has excellent hardening ability, and the volatility in the temperature range which is usually used for curing the epoxy resin is extremely small. . The epoxy resin composition containing the carboxylic acid compound (A) of the present invention can be used for various purposes represented by optical component materials using a usual epoxy resin composition.

The material for optics generally means a material for allowing light such as visible light, infrared rays, ultraviolet rays, X-rays, and lasers to pass through itself. More specifically, in addition to an optical semiconductor sealing material such as a lamp type or a SMD (Surface Mounted Devices) type, or an optical semiconductor die bonding material, the following may be mentioned: a substrate material, a light guide plate, a ruthenium film, and a liquid crystal display device. A material for a liquid crystal display device such as a liquid crystal film such as a deflecting plate, a retardation plate, a viewing angle correction film, an adhesive, or a polarizing element protective film. In addition, it can be used as a sealing material for a PDP (plasma display), an anti-reflection film, an optical correction film, a casing material, a protective film for a front glass, a front glass substitute material, and a high-precision color plate. Subsequent agent; LED mold material used for LED display device, LED sealing material, front glass protective film, front glass substitute material, adhesive; substrate material in plasma address liquid crystal (PALC) display , light guide plate, cymbal sheet, deflecting plate, phase difference plate, viewing angle correction film, adhesive, polarizer protective film; protective film for front glass in organic EL (electro luminescence) display, front glass instead of material, Next agent; various film substrates in a field emission display (FED), a protective film for the front glass, a front glass substitute material, and an adhesive. In the field of optical recording, VD (video disk), CD/CD-ROM, CD-R/RW, DVD-R/DVD-RAM, MO/MD, PD (phase change disc), optical disc Substrate material, optical disk drive head, protective film, sealing material, adhesive, and the like.

In the field of optical equipment, it can be used for: lens materials for still cameras, finder finder, target finder, viewfinder cover, and light receiving sensor. In addition, a camera lens and a viewfinder of the camera can be cited. In addition, it can be used for projection lenses, protective films, sealing materials, adhesives, etc. of projection televisions. And it can be used for: lens materials for light sensing devices, sealing materials, adhesives, films, and the like. In the field of optical components, it can be used for fiber materials around the optical switch of optical communication systems, lenses, optical waveguides, sealing materials for components, and adhesives. And can be used for: optical fiber material around the optical connector, ferrule, sealing material, adhesive, and the like. In the light passive parts and optical circuit parts, it can be used for: lenses, optical waveguides, LED sealing materials, CCD (Charge-Coupled Device) sealing materials, adhesives, and the like. Moreover, it can be used for a substrate material, a fiber material, a sealing material for an element, an adhesive, and the like around the OEIC (Optoelectronic Integrated Circuit). In the field of optical fibers, it can be used for: decorative lighting for decorative displays, light pipes, industrial sensors, display-markers, etc., and other optical fiber for connecting digital devices in the home. The material for the semiconductor integrated circuit can be used for LSI (large scale integrated circuit) or lithographic resist material for super LSI materials. In the field of automobiles and conveyors, it can be used for: lamp reflectors for automobiles, bearing retainers, gear parts, corrosion resistant coatings, switch parts, headlights, engine parts, motor parts, various interior and exterior decorations. , drive engine, brake fuel tank, automotive rust-proof steel plate, interior decorative panel, interior decoration materials, protection-end harness, fuel pipe, lamp, glass substitute. Also available for: multi-layer glass for rail vehicles. In addition, it can be used for toughness imparting agents for structural materials of aircraft, engine peripheral members, protective-end harnesses, and corrosion-resistant coatings. In the field of construction, it can be used for: interior decoration, processing materials, electrical masks, sheets, glass interlayer films, glass substitutes, solar cell peripheral materials. It can be used as a film for greenhouse coating in agricultural applications. As a next-generation light-electron-functional organic material, it can be used for: organic EL element peripheral materials, organic light-refracting elements, optical amplifying elements as optical-optical conversion devices, optical arithmetic elements, substrate materials around organic solar cells, and fiber materials. , sealing material for components, adhesives, etc.

The sealing agent is used for filling, dipping, and transfer molding of capacitors, transistors, diodes, light-emitting diodes, ICs (integrating circuits), LSIs, etc., for ICs, LSIs, and the like. Infusion sealing of COB (Chip-on-Board), COF (Chip On Film), TAB (Tape Automated Bonding), etc., for bottom layer of flip chip For sealing applications, it is used for sealing (enhanced underfill) for mounting IC packages such as BGA (Ball Grid Array) and CSP (Chip Scale Package).

As other uses for the optical material, general use of the epoxy resin composition can be cited, for example, in addition to an adhesive, a coating, a coating agent, a molding material (including sheets, films, FRP (Fiber Reinforced Plastics)). In addition to the insulating material (including a printed circuit board, a wire coating, etc.) and a sealant, additives such as other resins may be mentioned. As the adhesive, in addition to the adhesive for civil engineering, construction, automotive, general affairs, and medical use, an adhesive for electronic materials may be mentioned. In the above, examples of the adhesive for the electronic material include an interlayer adhesive for a multilayer substrate such as a build-up substrate, an adhesive for a semiconductor such as an adhesive, an underfill, and an underfill for BGA, and an anisotropic conductivity. An adhesive for mounting such as a film (ACF, Anisotropic Conductive Film) or an anisotropic conductive paste (ACP). In particular, since the cured product obtained therefrom is excellent in transparency, it is extremely useful as a curing agent for an epoxy resin for sealing an optical semiconductor such as a high-intensity white LED. For other uses, it can be used as a raw material or a modifier, a plasticizer, a lubricating oil raw material, a cyanate resin composition for a substrate, or an additive for other resins or a resin for coating, such as a polyimide resin. Raw materials, resins for resins, medical pesticides and intermediates.

Example

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the examples. Hereinafter, "parts" means parts by weight, and "%" means weight%. In addition, the measuring method of the test in the Example is as follows.

○ Epoxy equivalent: The measurement was carried out by the method described in JIS K-7236.

○ Acid value: Measurement was carried out using an AT-610 type potential difference titration apparatus of Kyoto Electronics Industry Co., Ltd. Specifically, the measurement sample was dissolved in methyl ethyl ketone and ethanol, and titrated with a 0.1 mol/L sodium hydroxide aqueous solution.

○ Viscosity: The measurement was carried out at 25 ° C using an E-type viscometer.

○ Weight average molecular weight: It was measured using GPC (gel permeation chromatography) manufactured by Shimadzu Corporation. The column is protected by SHODEX GPC LF-G LF-804 (3), the flow rate is 1.0ml/min, the column temperature is 40°C, the solvent is THF (tetrahydrofuran), and the detector is RI (differential refraction detection). Device). The calibration curve used standard polystyrene made by Shodex.

○ Thermal weight reduction: TG/DTA6200 manufactured by Shimadzu Corporation was used, and the temperature was raised from 30° C. at 20° C./min. and 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.

○ Transmittance: The light transmittance at 400 nm was measured using U-3300 manufactured by Hitachi, Ltd.

The MH700G used in the examples is a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride produced by New Japan Physical and Chemical Co., Ltd., and the mixing ratio is methylhexahydrophthalic anhydride accounting for 70% by weight. % (68 mol%).

Similarly, HNA-100 is a mixture of methyl norbornane-2,3-dicarboxylic anhydride and norbornane-2,3-dicarboxylic anhydride manufactured by New Japan Physical and Chemical Co., Ltd., and the mixing ratio is methyl norbornene. The alkane-2,3-dicarboxylic anhydride accounts for 80% by weight (79 mol%).

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

59.1 parts of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane and 130.6 parts of polydimethyldiphenyloxane having a stanol group having a molecular weight of 1700 (GPC measured value), 0.5 10.0 parts of a %KOH methanol solution was added to the reaction vessel and the temperature was raised to 75 °C. After the temperature was raised, the mixture was reacted at 75 ° C for 8 hours under reflux. After adding 135 parts of methanol after the reaction, 25.9 parts of a 50% distilled water methanol solution was added dropwise thereto over 60 minutes, and the mixture was further reacted at 75 ° C for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with a 5% aqueous sodium dihydrogen phosphate solution, and then methanol was distilled at 80 ° C to recover. Then, after adding 170 parts of MIBK for washing, the washing was repeated 3 times. Then, the solvent of the organic phase was removed under reduced pressure at 100 ° C to obtain 162 parts of a cyclooxyl compound (B-1) having an epoxy group. The obtained compound had an epoxy equivalent of 707 g/eq., a weight average molecular weight of 2,680, and a colorless and transparent appearance.

Example 1

50 parts of methanol modified polyoxyxylene X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), RIKACID MH (methylhexahydrophthalic anhydride, manufactured by Nippon Chemical & Chemical Co., Ltd.), 15.4 parts, toluene 10 The fraction was added to a reaction vessel, and the temperature was raised to 130 ° C. After 3 hours, GPC measurement was performed, and the peak of RIKACID MH disappeared. Thereafter, the reaction was further carried out for 2 hours. After completion of the reaction, the solvent was removed under reduced pressure, whereby 65.0 parts of a carboxylic acid compound (A-1) was obtained. The weight average molecular weight of the obtained carboxylic acid compound was 1,700.

Example 2

50 parts of methanol modified polyoxyxylene X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), RIKACID MH700G (mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, New Japan Physical and Chemical) (manufactured by the company) 16.8 parts and 10 parts of toluene were placed in a reaction vessel, and the temperature was raised to 130 ° C. After 3 hours, GPC measurement was performed, and the peak of RIKACID MH700G disappeared. Thereafter, the reaction was further carried out for 2 hours. After completion of the reaction, the solvent was removed under reduced pressure, whereby 66.8 parts of the carboxylic acid compound (A-2) was obtained. The weight average molecular weight of the obtained carboxylic acid compound was 1,700.

Example 3

50 parts of methanol modified polyoxyxylene X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), HTMAn (1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, Mitsubishi Gas Chemical Co., Ltd.) 9.9 parts, RIKACID MH700G (a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, manufactured by Nippon Chemical & Chemical Co., Ltd.), 8.4 parts, and 10 parts of toluene were added to the reaction vessel, and the temperature was raised to The GPC measurement was carried out at 130 ° C after 3 hours, and the peaks of HTMAn and RIKACID MH700G disappeared. Thereafter, the reaction was further carried out for 2 hours. After completion of the reaction, the solvent was removed under reduced pressure, whereby 68.2 parts of a carboxylic acid compound (A-3) was obtained. The weight average molecular weight of the obtained carboxylic acid compound was 1900.

Example 4

50 parts of methanol modified polyoxyxylene X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), 9.2 parts of RIKACID MH (methyl hexahydrophthalic anhydride, manufactured by Nippon Chemical & Chemical Co., Ltd.), RIKACID BT -100 (1,2,3,4-butane tetracarboxylic dianhydride, manufactured by Nippon Chemical and Chemical Co., Ltd.) 4.0 parts, 10 parts of toluene was added to the reaction vessel, and the temperature was raised to 130 ° C, and was carried out after 3 hours. As a result of GPC measurement, the peaks of RIKACID MH and RIKACID BT-100 disappeared. Thereafter, the reaction was further carried out for 2 hours. After completion of the reaction, the solvent was removed under reduced pressure, whereby 63.0 parts of a carboxylic acid compound (A-4) was obtained. The weight average molecular weight of the obtained carboxylic acid compound was 4,640.

Example 5

50 parts of methanol modified polyoxyxylene X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), RIKACID HNA-100 (norbornane-2,3-dicarboxylic anhydride and methylnorbornane-2,3) 17.0 parts of a mixture of dicarboxylic anhydride and Nippon Chemical and Chemical Co., Ltd., and 10 parts of toluene were placed in a reaction vessel, and the temperature was raised to 130 ° C. After 3 hours, GPC measurement was performed, and the peak of RIKACID HNA-100 disappeared. Thereafter, the reaction was further carried out for 2 hours. After completion of the reaction, the solvent was removed under reduced pressure, whereby 66.8 parts of a carboxylic acid compound (A-5) was obtained. The weight average molecular weight of the obtained carboxylic acid compound was 1,730.

Example 6

100 parts of the carboxylic acid compound (A-1) obtained in Example 1 and 108 parts of the oxirane compound (B-1) having an epoxy group obtained in Synthesis Example 1 of the epoxy resin were mixed and mixed. And defoaming for 20 minutes to obtain an epoxy resin composition.

Example 7

An epoxy resin composition was obtained in the same manner as in Example 6 except that the carboxylic acid compound in Example 6 was changed from A-1 to A-2.

Example 8

An epoxy resin composition was obtained in the same manner as in Example 6 except that the carboxylic acid compound in Example 6 was changed from A-1 to A-3.

Example 9

An epoxy resin composition was obtained in the same manner as in Example 6 except that the carboxylic acid compound in Example 6 was changed from A-1 to A-4.

Example 10

An epoxy resin composition was obtained in the same manner as in Example 6 except that the carboxylic acid compound in Example 6 was changed from A-1 to A-5.

Example 11

The epoxy resin of Example 6 was changed to ERL-4221 (3,4-epoxycyclohexanecarboxylic acid-3,4-epoxycyclohexylmethyl ester, manufactured by Dow Chemical), and in addition to Example 6, The epoxy resin composition was obtained in the same manner.

Comparative example 1

841 parts of a cyclooxyl compound (B-1) having an epoxy group obtained in Synthesis Example 1 of an epoxy resin, RIKACID MH700G (methylhexahydroortholine) as a liquid carboxylic anhydride of an epoxy resin hardener 100 parts of a mixture of phthalic anhydride and hexahydrophthalic anhydride, manufactured by Nippon Chemical and Chemical Co., Ltd., and PX-4MP (an alkali salt-based hardening accelerator, manufactured by Nippon Chemical Industry Co., Ltd.) as a curing accelerator. 0.8 parts were mixed and defoamed for 20 minutes to obtain an epoxy resin composition.

Comparative example 2

The epoxy resin of Comparative Example 1 was changed to ERL-4221 (3,4-epoxycyclohexanecarboxylic acid-3,4-epoxycyclohexylmethyl ester, manufactured by Dow Chemical), and Comparative Example 1 was used. The epoxy resin composition was obtained in the same manner.

An attempt to use an epoxy resin composition as an optical semiconductor sealing material

The curable resin compositions obtained in Examples 6 to 11 and Comparative Example 1-2 were filled in a syringe, and cast into a surface mount type LED in which a light-emitting element having an emission wavelength of 405 nm was mounted using a precision discharge device. After hardening at 120 ° C for 3 hours, it was hardened at 150 ° C for 1 hour to seal the surface-mounted LED.

○ physical property test

The properties of the carboxylic acid compounds A-1 to A-5 obtained in Examples 1 to 5 and RIKACID MH700G as a liquid carboxylic anhydride as a comparative example are summarized in Table 1.

[Table 1]

MH700G: a mixture of methyl hexahydrophthalic anhydride and hexahydrophthalic anhydride, manufactured by New Japan Physical and Chemical Co., Ltd.

○ Evaluation test

The results of the blending ratio of the epoxy resin composition obtained in Examples 6 to 11 and Comparative Examples 1 and 2, the transmittance of the cured product, and the depression and surface viscosity of the cured product accompanying the volatilization of the cured product are shown in Table 2. The tests in Table 2 were carried out in the following manner.

(1) Hardened material transmittance:

The epoxy resin compositions obtained in Examples 6 to 11 and Comparative Examples 1 and 2 were subjected to vacuum defoaming for 20 minutes, and then slowly cast to a barrier of heat-resistant tape so as to reach 30 mm × 20 mm × height 1 mm. On the glass substrate. The cast material was subjected to preliminary hardening at 120 ° C for 3 hours, and then hardened at 150 ° C for 1 hour to obtain a test piece for transmittance of 1 mm in thickness.

(2) Depression test:

The epoxy resin compositions obtained in Examples 6 to 11 and Comparative Examples 1 and 2 were subjected to vacuum defoaming for 20 minutes, filled in a syringe, and cast into a flat surface by using a precision discharge device. A surface mount type LED in which a light-emitting element having an emission wavelength of 405 nm is mounted. After preliminary hardening at 120 ° C for 3 hours, hardening was performed at 150 ° C for 1 hour to seal the surface-mounted LED. The surface of the resin accompanying the volatilization of the hardener sealed in this manner was visually evaluated. In the table, ○: no depression was observed, △: slight depression, ×: more depressions were observed.

(3) Surface adhesion:

A test piece similar to the above test for the transmittance of the cured product was produced, and the surface adhesion (degree of stickiness of the surface) of the test piece was confirmed by contact with a finger. In the table, ○: no sticky, ×: sticky.

[Table 2]

As is apparent from the results shown in Table 1, the comparative example of RIKACID MH700G showed a large degree of thermal weight loss at 120 ° C. In contrast, the carboxylic acid compounds A-1 to A of Examples 1 to 5 -5 is liquid, and almost no weight loss is seen. Further, as is apparent from the results shown in Table 2, a large number of hardened material depressions were observed in Comparative Examples 1 and 2. On the other hand, in Examples 6 to 11, almost no depression was observed, and the transmittance of the cured product was excellent. The surface is not sticky.

The present invention has been described in detail 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 Japanese Patent Application No. 2008-324305, filed on Dec. In addition, all references cited herein are hereby incorporated by reference in their entirety.

Claims (7)

An epoxy resin composition comprising a carboxylic acid compound and an epoxy resin, wherein the carboxylic acid compound has one or more carboxylic anhydrides in the molecule by a polyoxonium compound (a) represented by the following formula (1) The compound obtained by the addition reaction of the group is obtained, and the compound having one or more carboxylic anhydride groups in the molecule is at least one selected from the group consisting of the compounds (c) represented by the following formulas (3) to (5): (In the formula (1), R ₁ represents an alkylene group having a total carbon number of 1 to 10 which may have an ether group, R ₂ represents a methyl group or a phenyl group, and n is an average value, which represents 1 to 100) The epoxy resin has an epoxy equivalent of 400 to 1500 g/eq. and a weight average molecular weight of 1,500 to 10,000. The epoxy resin is a condensate of a ruthenium compound having an epoxy group and a ruthenium compound other than the epoxy group. An epoxy resin composition according to claim 1, wherein the carboxylic acid compound is a compound having a polyoxonium compound (a) represented by the following formula (1) and a compound having one or more carboxylic anhydride groups in the molecule. A compound obtained by performing an addition reaction and having one or more carboxylic anhydride groups in the molecule is a compound represented by the following formula (3): (In the formula (1), R ₁ represents an alkylene group having a total carbon number of 1 to 10 which may have an ether group, R ₂ represents a methyl group or a phenyl group, and n is an average value, which represents 1 to 100) The epoxy resin composition of claim 1, further comprising a hardening accelerator. The epoxy resin composition of claim 2, further comprising a hardening accelerator. The epoxy resin composition according to any one of claims 1 to 4, which is used for an optical semiconductor sealing material. The epoxy resin composition according to any one of claims 1 to 4, which is used for an optical semiconductor die-bonding material. A cured product obtained from the epoxy resin composition according to any one of claims 1 to 6.