WO2010071168A1 - Carboxylic acid compound and epoxy resin composition containing same - Google Patents

Abstract

Disclosed is a carboxylic acid compound which is liquid at room temperature, has little volatility at high temperatures, and provides a colorless, transparent hardened product with no surface stickiness as a hardening agent for an epoxy resin composition used particularly as a sealing material. This carboxylic acid compound is a carboxylic acid compound (A) obtained by causing an addition reaction between a silicone compound (a) represented by formula (1) and a compound such as that represented by the formula (3) having one or more carboxylic acid anhydride groups in the molecule. (In formula (1), R₁ represents an alkylene group with a total carbon number of 1-10 and which can include an ether group, R₂ represents a methyl group or a phenyl group, and n represents an average value of 1-100.)

Description

Carboxylic acid compound and epoxy resin composition containing the same

The present invention relates to a carboxylic acid compound and a resin composition containing the carboxylic acid compound. More specifically, it has a specific structure, epoxy resin curing agent, paint, adhesive, molded article, optical material, semiconductor, optical semiconductor encapsulant resin, optical semiconductor die bond material resin, polyimide resin, etc. The present invention relates to carboxylic acid compounds useful as raw materials and modifiers, plasticizers, lubricating oil raw materials, pharmaceutical and agrochemical intermediates, coating resin raw materials, toner resins and the like, and epoxy resin compositions containing the same.

Epoxy resins can be cured to obtain cured products with excellent adhesion, mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., so paints, adhesives, composite materials, molding materials It is used in a wide range of fields such as casting materials, various coating materials and resists. As a hardening | curing agent used for an epoxy resin, an amine compound, a carboxylic acid compound, a carboxylic acid anhydride, a phenol compound, a thiol compound etc. are mentioned as a general thing, for example. Among these curing agents, various carboxylic acid compounds and carboxylic acid anhydrides are used for applications such as when the cured product requires high transparency and heat resistance, or when an appropriate pot life is required. In particular, in a liquid composition, it has become common to use a liquid carboxylic acid anhydride as the curing agent. Carboxylic acid has a strong intermolecular hydrogen bond and is not only crystallized, but also has a very poor compatibility with other resins, so that its use is avoided.

A liquid epoxy resin composition using a bisphenol-type epoxy resin, an alicyclic epoxy resin, etc. as a resin for sealing an optical semiconductor such as an LED (Light Emitting Diode, light-emitting diode) is excellent in mechanical strength and adhesive strength. It was used (refer patent document 1). In recent years, LEDs have been used in fields that require high brightness, such as automotive headlamps and lighting applications. Accordingly, resins that encapsulate optical semiconductor elements are particularly resistant to UV and heat. It has come to be required. However, it is difficult to say that bisphenol-type epoxy resins and alicyclic epoxy resins have sufficient UV resistance and heat resistance as described above, and may not be used in fields where high luminance is required. Therefore, as a sealing material having high UV resistance, heat resistance, etc., a silicone resin sealing material using a noncovalent group-containing organopolysiloxane and an organohydrogenpolysiloxane is used (see Patent Document 2). ). However, although a sealing material using such a silicone resin has excellent UV resistance and heat resistance, it has problems such as low adhesion to the base material and sticking of the sealing surface. It was. In order to solve these problems, a condensate of a silicon compound having an epoxy group and a liquid acid anhydride are used to develop a sealing material that is excellent in UV resistance, heat resistance, and has good adhesion. (See Patent Document 3 and Patent Document 4). Acid anhydrides used in such applications include hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydroanhydride because they are colorless and transparent, are liquid at room temperature, and are easy to handle. Carboxylic anhydrides such as phthalic acid, methyltetrahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, and mixtures thereof are used. However, these carboxylic acid anhydrides are often low molecular weight compounds. Therefore, in the epoxy resin composition using the carboxylic acid anhydride as a curing agent, volatilization during thermal curing becomes a problem. The volatilization of the carboxylic acid anhydride is not only a problem that the epoxy resin composition is poorly cured due to the absence of the required amount of the carboxylic acid anhydride (curing agent) in the curing reaction, but also due to its harmfulness. The impact on the environment is also significant, such as adverse effects on the environment, production line contamination, and air pollution. In this case, since the curing becomes insufficient, stickiness of the sealing surface due to the remaining unreacted epoxy resin may occur, and the epoxy resin due to carboxylic acid anhydride that volatilizes during curing. Curing of the resin is regarded as a problem from the functional and environmental aspects.

Japanese Unexamined Patent Publication No. 2003-277473 Japanese Unexamined Patent Publication No. 2006-299099 Japanese Unexamined Patent Publication No. 2008-174640 Japanese Unexamined Patent Publication No. 2008-255295

The present invention is a carboxylic acid that is liquid at room temperature, has excellent volatility at high temperatures, and has a low volatility during the curing process as a curing agent for epoxy resins, and provides a cured product that is colorless and transparent and has no surface stickiness. The object is to provide a compound.

As a result of intensive studies to solve the above problems, the present inventors have obtained a silicone skeleton obtained by reacting a silicone compound having a specific skeleton with a compound having a carboxylic anhydride group having a specific skeleton. The present invention has been completed by finding that the above-mentioned problems can be solved by using a carboxylic acid compound having the above as a curing agent for an epoxy resin.

That is, the present invention
(1) A carboxylic acid compound obtained by subjecting a silicone compound (a) represented by the following formula (1) to a compound having one or more carboxylic anhydride groups in the molecule, The compound having one or more carboxylic acid anhydride groups in the molecule is at least one carboxylic acid compound (A) selected from compounds (c) represented by the following formulas (3) to (5):

(In Formula (1), R ₁ represents an alkylene group having 1 to 10 carbon atoms which may contain an ether group, R ₂ represents a methyl group or a phenyl group, and n represents an average value of 1 to 100).

(2) A carboxylic acid compound obtained by addition reaction of a silicone compound (a) represented by the following formula (1) and a compound having one or more carboxylic anhydride groups in the molecule, Carboxylic acid compound (A) in which the compound having one or more carboxylic anhydride groups in the molecule is a compound represented by the following formula (3)

(In Formula (1), R ₁ represents an alkylene group having 1 to 10 carbon atoms which may contain an ether group, R ₂ represents a methyl group or a phenyl group, and n represents an average value of 1 to 100).

(3) An epoxy resin curing agent containing the carboxylic acid compound (A) according to the item (1) or (2) and a curing accelerator,
(4) An epoxy resin composition containing the carboxylic acid compound (A) according to (1) or (2) or the epoxy resin curing agent according to claim 3 and an epoxy resin,
(5) The epoxy equivalent of the epoxy resin is 400-1500 g / eq. The epoxy resin composition according to item (4), wherein the weight average molecular weight is 1500 to 5000,
(6) The epoxy resin composition according to the above (5), wherein the use of the epoxy resin composition is for an optical semiconductor sealing material,
(7) The epoxy resin composition according to (5), wherein the use of the epoxy resin composition is for an optical semiconductor die bond material,
(8) A cured product of the epoxy resin composition according to any one of (4) to (7),
About.

The carboxylic acid compound (A) of the present invention is liquid at room temperature (25 ° C.) and has very little volatility in a temperature range usually employed for curing an epoxy resin. Furthermore, this carboxylic acid compound (A) is used as a raw material for modified or modified raw materials such as epoxy resin curing agents, paints, adhesives, molded products, semiconductors, optical semiconductor encapsulant resins, optical semiconductor die bond material resins, and polyimide resins. It is useful as a quality agent, plasticizer, lubricant oil raw material, pharmaceutical and agrochemical intermediate, paint resin raw material, and toner resin, and in particular, the carboxylic acid compound (A) can be obtained from the ability to cure epoxy resin. Due to the high transparency of the cured product, it is extremely useful as a curing agent for epoxy resins for sealing high-luminance white LEDs and other optical semiconductors.

The present invention will be described in detail below.
First, the silicone compound (a) of the present invention represented by the following formula (1) will be described.

(In Formula (1), R ₁ represents an alkylene group having 1 to 10 carbon atoms which may contain an ether group, R ₂ represents a methyl group or a phenyl group, and n represents an average value of 1 to 100)

In the formula (1), specific examples of R ₁ include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene, hexylene, heptylene, octylene and other alkylene groups, and the following formulas (8) to (17) And the like, and the total number of carbon atoms of the alkylene group is 1 to 10. Particularly preferred is an alkylene group interrupted with an ether represented by the formula (12). (In the formulas (8) to (17), the leftmost carbon atom is the side bonded to the silicon atom of the formula (1).)

In the formula (1), R ₂ represents a methyl group or a phenyl group, and may be the same or different. However, since the carboxylic acid compound (A) is liquid at room temperature, the methyl group is preferable.

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

Examples of the silicone compound (a) represented by the formula (1) include silicone compounds having alcoholic hydroxyl groups at both ends. Specific examples include X-22-160AS, KF6001, KF6002, KF6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.); BY16-201, BY16-004, SF8427 (all Toray Dow Corning Co., Ltd.); XF42-B0970, XF42-C3294 (both manufactured by Momentive Performance Materials Japan GK), etc., are all available from the market. These modified silicone oils having alcoholic hydroxyl groups at both ends can be used alone or in combination of two or more. Among these, X-22-160AS, KF6001, KF6002, BY16-201, or XF42-B0970 is preferable.

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

The compounds represented by the formulas (3) to (5) are methylhexahydrophthalic anhydride, norbornane-2,3-dicarboxylic acid anhydride, methylnorbornane-2,3-dicarboxylic acid anhydride, respectively. Is a compound having a carboxylic acid anhydride group. Carboxylic anhydride groups react with functional groups having active hydrogen such as alcoholic hydroxyl groups, phenolic hydroxyl groups, amino groups, carboxyl groups and silanol groups to form ester bonds, amide bonds, etc. Ring opening of the anhydride group produces a free carboxylic acid.
The carboxylic acid compound (A) of the present invention is an adduct of the silicone compound (a) and at least one selected from the compounds (c) represented by the above formulas (3) to (5). The carboxylic acid compound (A) can be obtained by addition reaction of the carboxylic anhydride group of the compound (c) represented by (3) to (5) with the alcoholic hydroxyl group of the silicone compound (a).
For the addition reaction, in order to adjust the molecular weight and viscosity of the carboxylic acid compound (A), together with the compound (c) having a carboxylic acid anhydride represented by the formulas (3) to (5), one or more in the molecule An addition reaction can also be carried out using the compound (b) having a carboxylic anhydride group.

The compound (b) having one or more carboxylic anhydride groups in the molecule includes, for example, succinic anhydride, methyl succinic anhydride, ethyl succinic anhydride, 2,3-butanedicarboxylic anhydride, 2,4 -Saturated aliphatic carboxylic acid anhydrides such as pentanedicarboxylic acid anhydride, 3,5-heptanedicarboxylic acid anhydride, 1,2,3,4-butanetetracarboxylic dianhydride; maleic acid anhydride, dodecyl succinic acid Unsaturated aliphatic carboxylic acid anhydrides such as anhydrides; hexahydrophthalic acid anhydride, methylhexahydrophthalic acid anhydride, 1,3-cyclohexanedicarboxylic acid anhydride, nadic acid anhydride, methylnadic acid anhydride, bicyclo [2,2,2] octane-2,3-dicarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclo Cyclic saturated aliphatic carboxylic acid anhydrides such as tantalum tetracarboxylic dianhydride and 1,2,4,5-cyclohexanetetracarboxylic dianhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic acid anhydride Products, methyl nadic acid anhydride, 4,5-dimethyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, bicyclo [2.2.2] -5-octene-2,3-dicarboxylic acid anhydride, etc. Cyclic unsaturated aliphatic carboxylic anhydrides; phthalic anhydride, isophthalic anhydride, terephthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and other aromatic carboxylic anhydrides, etc. 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5-dioxothel, Lahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride and the like, saturated aliphatic carboxylic acid anhydride, cyclic saturated carboxylic acid anhydride, cyclic unsaturation A polycarboxylic acid compound having a carboxylic anhydride is also included.
When the compound (b) having one or more carboxylic acid anhydride groups in the molecule is used in combination with the compounds (c) represented by the formulas (3) to (5), in addition to the compound (c), Two or more kinds can be mixed and used. Among these, since the carboxylic acid compound (A) is liquid at room temperature and the cured product obtained by curing the carboxylic acid compound (A) and the epoxy resin is excellent in transparency, the following formulas (2), (6), Hexahydrophthalic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, and 1,2,3,4-butanetetracarboxylic dianhydride represented by (7) are preferred.

When the compound (b) is used, the compound (b) is desirably 5 to 80 mol%, more preferably 10 to 78 mol%, of the total of the compound (b) and the compound (c).
The reaction between the silicone compound (a) and the compound (c) (and optionally the compound (b)) can be performed in a solvent or without a solvent. As the solvent, any solvent that does not react with the silicone compound (a) and the compound (c) (and optionally the compound (b)) represented by the formula (1) can be used without any particular limitation. Examples of the solvent that can be used include aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, methyl ethyl ketone, cyclopentanone, and methyl isobutyl ketone, and aromatic hydrocarbons such as toluene and xylene. Of these, aromatic hydrocarbons are preferred. These solvents may be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, but the total weight of the silicone compound (a) and the compound (c) represented by the formulas (3) to (5) (and the compound (b) if necessary) is 100 wt. It is usually preferable to use 0.1 to 300 parts by weight per part.

A catalyst may be used for the reaction. Examples of usable catalysts include hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acid and other acidic compounds, water Metal hydroxides such as sodium oxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, amine compounds such as triethylamine, tripropylamine, tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4. 0] heterocyclic compounds such as undec-7-ene, imidazole, triazole, tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, Methyl ethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium Examples include quaternary ammonium salts such as acetate and trioctylmethylammonium acetate. These catalysts may be used alone or in combination of two or more. Of these, triethylamine, pyridine, and dimethylaminopyridine are preferred.

The amount of the catalyst used is not particularly limited, but the silicone compound (a) represented by the formula (1) and the compound (c) represented by the formulas (3) to (5) (and optionally the compound (b) In general, 0.1 to 100 parts by weight is preferably used if necessary.

The reaction temperature in the reaction is usually 80 to 180 ° C, preferably 110 to 140 ° C. The reaction time is usually 1 to 12 hours. Mw (weight average molecular weight) of the reaction product can be measured by GPC (gel permeation chromatography). When the reaction is completed, heating is stopped, and when a solvent is used, the solvent can be removed under reduced pressure to obtain the target carboxylic acid compound. The Mw (weight average molecular weight) of the obtained carboxylic acid compound can be similarly confirmed by GPC.

The carboxylic acid compound (A) of the present invention has a specific structure, is liquid at room temperature (25 ° C.), and has extremely low volatility in a temperature range usually employed for curing an epoxy resin.
Furthermore, since this carboxylic acid compound (A) is excellent in transparency, epoxy resin curing agents, paints, adhesives, molded products, semiconductors, optical semiconductor encapsulant resins, optical semiconductor die bond material resins, polyimides It is useful as a raw material for resins and modifiers, a raw material for plasticizers and lubricants, an intermediate for medicines and agricultural chemicals, a raw material for paint resins, and a resin for toners. Since it is excellent and the transparency of the cured product is excellent, it is extremely useful as a curing agent for epoxy resin used for sealing an optical semiconductor such as a white LED with high brightness.

The carboxylic acid compound (A) of the present invention can be used alone as a curing agent for an epoxy resin, but as a curing agent for an epoxy resin by mixing the carboxylic acid compound (A) and a curing accelerator. It is also a preferred embodiment to use. As the curing accelerator to be mixed with the carboxylic acid compound (A), any one having the ability to accelerate the curing reaction between an epoxy group and a carboxylic acid and a carboxylic anhydride can be used. Examples of the ammonium salt curing accelerator, phosphonium salt curing accelerator, imidazole curing accelerator, amine curing accelerator, phosphine curing accelerator, phosphite curing accelerator, Lewis acid curing Examples include accelerators.

Among these, for the curing agent use for epoxy resin compositions used for sealing optical semiconductors such as high-intensity white LEDs, an ammonium salt-based curing accelerator and a phosphonium salt-based curing accelerator include an excellent transparency. Especially excellent. Examples of the ammonium salt curing accelerator include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide. , Trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate and the like. Examples of the phosphonium salt curing accelerator include ethyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium dimethylphosphate, methyltributylphosphonium diethylphosphate, and the like. These curing accelerators may be used alone or in combination of two or more. Among these curing accelerators, trimethyl cetyl ammonium hydroxide and methyl tributyl phosphonium dimethyl phosphate are preferable.

Other general-purpose applications include the above ammonium salt-based curing accelerators, phosphonium salt-based curing accelerators, imidazole-based curing accelerators, amine-based curing accelerators, heterocyclic compound-based curing accelerators, phosphine-based curing accelerators, A phosphite type hardening accelerator, a Lewis acid type hardening accelerator, etc. can be used.

Examples of the imidazole curing accelerator include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,3-dihydro -1H-pyrrolo- [1,2-a] benzimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2'- Undecylimidazole (1 ′)) ethyl-s-triazine, 2 4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl-s-triazine, Isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxy Examples thereof include methylimidazole and 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole.

Examples of the amine curing accelerator include triethylamine, tripropylamine, tributylamine and the like.
Examples of the heterocyclic compound type curing accelerator include pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, imidazole, triazole, tetrazole and the like.
Examples of the phosphine curing accelerator include triethylphosphine, tributylphosphine, triphenylphosphine, and the like.
Examples of the phosphite curing accelerator include trimethyl phosphite and triethyl phosphite.
Examples of the Lewis acid curing accelerator include BF ₃ monoethylamine, BF ₃ diethylamine, BF ₃ triethylamine, BF ₃ benzylamine, BF ₃ aniline, BF ₃ piperazine, BF ₃ piperidine, PF ₅ ethyl amine, PF ₅ butyl amine, and PF ₅ Examples include laurylamine, PF ₅ benzylamine, AsF ₅ laurylamine and the like. These curing accelerators may be used alone or in combination of two or more.

Each of the curing accelerators may be added in an amount of 0.1 to 10 parts by weight with respect to 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) and an epoxy resin, and, if necessary, a curing accelerator and various additives.
Examples of epoxy resins that can be used here include, for example, epoxy resins that are glycidyl etherification products of phenolic compounds, epoxy resins that are glycidyl etherification products of various novolak resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic types Epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, condensates of silicon compounds having an epoxy group with other silicon compounds, polymerizable groups having an epoxy group Examples include a copolymer of a saturated compound and other polymerizable unsaturated compound.

Examples of the epoxy resin that is a glycidyl etherified product of the phenol compound include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [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, 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'-me Ren-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phloroglucinol, Examples thereof include phenols having a diisopropylidene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, and epoxy resins which are glycidyl etherified products of polyphenol compounds such as phenolized polybutadiene.

Examples of epoxy resins that are glycidyl etherified products of various novolak resins include phenols, cresols, ethylphenols, butylphenols, octylphenols, bisphenols such as bisphenol A, bisphenol F and bisphenol S, and various phenols such as naphthols. And glycidyl etherified products of various novolac resins such as a novolak resin, a phenol novolac resin containing a xylylene skeleton, a phenol novolak resin containing a dicyclopentadiene skeleton, a phenol novolak resin containing a biphenyl skeleton, and a phenol novolac resin containing a fluorene skeleton.

Examples of the alicyclic epoxy resin include alicyclic rings having an aliphatic ring skeleton such as 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate. An epoxy resin is mentioned.
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 an isocyanuric ring and a hydantoin ring.
Examples of the glycidyl ester-based epoxy resin include epoxy resins made of carboxylic acid esters such as hexahydrophthalic acid diglycidyl ester.
Examples of the glycidylamine-based epoxy resin include epoxy resins obtained by glycidylating amines such as aniline and toluidine.
Examples of epoxy resins obtained by glycidylating halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, chlorinated bisphenol A, and the like. An epoxy resin obtained by glycidylating any of the halogenated phenols.

The condensate of the silicon compound having an epoxy group and the other silicon compound is, for example, a hydrolysis condensate of an alkoxysilane compound having an epoxy group and an alkoxysilane having a methyl group or a phenyl group, or an alkoxy group having an epoxy group. It is a condensate of a silane compound and a polydimethylsiloxane having a silanol group, a polydimethyldiphenylsiloxane having a silanol group, or a condensate obtained by combining them. Examples of the alkoxysilane compound having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and 3-glycidoxypropyltrimethoxysilane. , 3-glycidoxypropylmethyldimethoxysilane and the like. As polydimethylsiloxane having a silanol group and polydimethyldiphenylsiloxane having a silanol group, for example, X-21-5841, KF-9701 (manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-873 are commercially available products. , PRX413 (Toray Dow Corning) XC96-723, YF3804, YF3800, XF3905, YF3057 (Momentive Performance Materials Japan GK), 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, Marproof G-0115S, G-0130S and G-0250S are commercially available products. G-1010S, G-0150M, G-2050M (manufactured by NOF Corporation), and the like. Examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, 4 -Vinyl-1-cyclohexene-1,2-epoxide and the like. Examples of other polymerizable unsaturated compound copolymers include methyl (meth) acrylate, ether (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, and vinylcyclohexane. These epoxy resins may be used alone or in combination of two or more.

When the epoxy resin composition of the present invention is used particularly for an optical semiconductor encapsulant, the epoxy equivalent (measured by the method described in JIS K-7236) is 400 to 1500 g / eq. And preferably 450 to 1100 g / eq. Is more preferable. Epoxy equivalent is 400 g / eq. If it is less than 1, the cured product tends to be too hard and cracks such as cracks tend to occur, and 1500 g / eq. If it is larger than the range, surface stickiness tends to occur.
The weight average molecular weight is preferably 1500 to 10,000, more preferably 1800 to 5000. If the weight average molecular weight is less than 1500, the toughness of the cured product tends to be inferior. For example, cracks such as cracks may occur in a heat cycle test or the like. If the weight average molecular weight is greater than 10,000, the viscosity tends to be high and workability tends to be poor.
Among the epoxy resins having the epoxy equivalent weight and the weight average molecular weight, condensation of a silicon compound having an epoxy group with other silicon compounds from the viewpoints of transparency, heat-resistant transparency, light-resistant transparency, heat cycle resistance, etc. More preferred are.
In addition, the weight average molecular weight in this invention is a polystyrene conversion and a weight average molecular weight (Mw) measured on condition of the following etc. using GPC (gel permeation chromatography).
Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

The content of each component in the epoxy resin composition of the present invention includes the silicone compound (a) represented by the formula (1) of the present invention and the compound (c) represented by the formulas (3) to (5) (and 5 to 95 parts by weight, preferably 20 to 80 parts by weight of the carboxylic acid compound (A) obtained by addition reaction with the compound (b)) having a carboxylic acid anhydride group, if necessary, the epoxy resin 5 as described above ~ 95 parts by weight, preferably 20 to 80 parts by weight, if necessary, curing accelerator, 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 room temperature or under heating. For example, mix thoroughly until uniform using an extruder, kneader, three rolls, universal mixer, planetary mixer, homomixer, homodisper, bead mill, etc., and if necessary, filter with SUS mesh etc. Prepared.

The epoxy resin curing agent and the epoxy resin composition of the present invention can be used in combination with other epoxy resin curing agents as necessary.
Examples of the epoxy resin curing agent that can be used in combination include polyvalent carboxylic acids, carboxylic anhydrides, phenols, hydrazines, and mercaptans.

Examples of the polyvalent carboxylic acids include aliphatic polyvalent carboxylic acids, cycloaliphatic polyvalent carboxylic acids, aromatic polyvalent carboxylic acids, and heterocyclic polyvalent carboxylic acids.
Examples of the aliphatic polycarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,2,3-propanetricarboxylic acid, 1, Examples include 2,3,4-butanetetracarboxylic acid.
Examples of the cycloaliphatic polyvalent carboxylic acid include hexahydrophthalic acid, 1,3-adamantane diacetic acid, 1,3-adamantane dicarboxylic acid, tetrahydrophthalic acid, 2,3-norbornene dicarboxylic acid, 1,2,4 -Cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2,3-cyclohexanetricarboxylic acid, 1,2,4,6-cyclohexanetetracarboxylic acid and the like.
Examples of the aromatic polyvalent carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid. Acid, 2,6-naphthalenedicarboxylic acid, 9,10-anthracene dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, 2,2′-biphenyl dicarboxylic acid, 3,3′-biphenyl dicarboxylic acid, 4,4′- Biphenyl dicarboxylic acid, 3,3′-biphenyl ether dicarboxylic acid, 4,4′-biphenyl ether dicarboxylic acid, 4,4′-binaphthyl dicarboxylic acid, hemimellitic acid, trimellitic acid, trimesic acid, 1,2,4- Naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, merophanic acid, plani Acid, pyromellitic acid, 3,3′4,4′-benzophenone tetracarboxylic acid, 2,2′3,3′-benzophenone tetracarboxylic acid, 2,3,3 ′, 4′-benzophenone tetracarboxylic acid, 3,3′4,4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 4,4′-oxydiphthalate Acid, 3,3'4,4'-diphenylmethanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7- Naphthalene tetracarboxylic acid, anthracene tetracarboxylic acid and the like can be mentioned.
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 acid anhydrides, cycloaliphatic carboxylic acid anhydrides, and aromatic carboxylic acid anhydrides.
Examples of the aliphatic carboxylic acid anhydride include succinic acid anhydride, methyl succinic acid anhydride, ethyl succinic acid anhydride, 2,3-butanedicarboxylic acid anhydride, 2,4-pentanedicarboxylic acid anhydride, 3,5- Examples include heptane dicarboxylic acid anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, maleic acid anhydride, dodecyl succinic acid anhydride and the like.
Cyclic aliphatic carboxylic acid anhydrides include hexahydrophthalic acid anhydride, methyl hexahydrophthalic acid anhydride, 1,3-cyclohexanedicarboxylic acid anhydride, hydrogenated nadic acid anhydride, hydrogenated methyl nadic acid anhydride, Bicyclo [2,2,2] octane-2,3-dicarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic acid Anhydride, methyl nadic anhydride, 4,5-dimethyl-4-cyclohexene-1,2-dicarboxylic anhydride, bicyclo [2.2 .2] -5-octene-2,3-dicarboxylic acid anhydride and the like.
Examples of the aromatic carboxylic anhydride include phthalic anhydride, isophthalic anhydride, terephthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like.
In addition, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1, Examples thereof include compounds having an aliphatic carboxylic acid anhydride and a cyclic aliphatic carboxylic acid anhydride in the same compound such as 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride.

Examples of the phenols include bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenylphenol, 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′-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) Phenyl] propane, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorci Phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene; phenolic polybutadiene, phenol, cresols, ethylphenols, butylphenol , Octylphenols, bisphenol A, bisphenol F, bisphenol S, novolac resins made from various phenols such as naphthols; xylylene skeleton-containing phenol novolac resins, dicyclopentadiene skeleton-containing phenol novolac resins, biphenyl skeleton-containing phenol novolac resins, Examples include various novolak resins such as a fluorene skeleton-containing phenol novolac resin and a furan skeleton-containing phenol novolac resin.

Examples of the hydrazines include isophthalic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, and 2,6-naphthalenedicarboxylic acid dihydrazide.

Examples of the mercaptans include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tris [(3 -Mercaptopropionyloxy) -ethyl], isocyanurate 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyl And oxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione.

These epoxy resin curing agents 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 other curing agents as described above, the proportion of the carboxylic acid compound (A) in the total curing agent is 50% by weight or more, preferably 80%. Adjust the usage so that it is at least wt%.

Next, a coupling agent, a phosphor, an inorganic filler, highly heat conductive fine particles, a phosphorus compound filler as a flame retardant, a binder resin, etc. are added to the epoxy resin composition of the present invention as necessary. Can do.
Examples of coupling agents that can be used include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl. Trimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltri Methoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloro Silane coupling agents such as propyltrimethoxysilane; isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate, Titanium coupling agents such as neoalkoxytri (pN- (β-aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneodeca Noyl zirconate, neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxytris (ethylenediaminoethyl) zirconate, neoalco Examples thereof include zirconium such as xylitol (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, Al-propionate, and aluminum coupling agents.
These coupling agents may be used alone or in combination of two or more.
The use of a coupling agent can be expected to improve the adhesion to the substrate and the hardness of the cured product. 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, if necessary, in the epoxy resin composition of the present invention.

Examples of phosphors that can be used include phosphors such as YAG phosphors, TAG phosphors, orthosilicate phosphors, thiogallate phosphors, and sulfide phosphors. Fluorescence can be imparted to the epoxy resin composition by adding a phosphor.

Examples of inorganic fillers that can be used include powders of crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc and the like. Or a bead obtained by spheroidizing these. By adding an inorganic filler, heat resistance and light resistance can be imparted, viscosity can be adjusted, and the like. The content of these inorganic fillers is used in an amount of 0 to 90 parts by weight in the epoxy resin composition of the present invention.

Examples of the high thermal conductive fine particles that can be used include metal particles such as gold, silver, copper, iron, nickel, tin, aluminum, cobalt, and indium, and alloys thereof, metal oxides such as aluminum oxide, magnesium oxide, and titanium oxide, Examples thereof include metal nitrides such as boron nitride and aluminum nitride, carbon compounds such as graphite, diamond and carbon black, and metal-coated particles obtained by coating a resin layer with a metal layer. By adding the high thermal conductive fine particles, the thermal conductivity of the epoxy resin composition can be improved.

The phosphorus-containing compound that can be used may be a reactive type or an additive type. Examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis (dixylyl). Phosphoric esters such as lenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate), 9,10-dihydro-9-oxa-10 -Phosphanphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, and other phosphanes, epoxy resin and active hydrogen of the phosphanes Phosphorus-containing ester obtained by reaction Xyl compounds, red phosphorus, and the like. Phosphoric esters, phosphanes, or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are preferred. The content of the phosphorus-containing compound is preferably 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 concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.

Binder resins that can be used include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. Although it is mentioned, it is not limited to these. 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, if necessary, in the epoxy resin composition of the present invention.

Further, the curable resin composition of the present invention includes a release agent such as stearic acid, palmitic acid, zinc stearate, calcium stearate, a coloring agent such as a dye and a pigment, an antioxidant, a light stabilizer, and a moisture resistance improver. , Thixotropy imparting agent, antifoaming agent, tackifier, impact resistance improving agent, ion trapping agent, antistatic agent, lubricant, leveling agent, surface tension reducing agent, antifoaming agent, antisettling agent, surfactant, ultraviolet ray Additives such as an absorbent, various thermosetting resins, and various other resins can be added. 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 can be used as a varnish or ink by mixing a solvent as necessary. The solvent can be used as long as it has a high solubility in each component such as the carboxylic acid compound (A), epoxy resin, curing accelerator, and other additives of the present invention and does not react with them. As alcohols such as methanol, ethanol, propanol, butanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, etc. Glycol ethers, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Alkylene glycol ether acetates such as 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate and ethyl ethoxypropiolate; aromatic hydrocarbons such as benzene, toluene and xylene; acetone, methyl ethyl ketone, methyl isobutyl Ketones such as ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy -2-ethyl ethyl propionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3- Propyl roxypropionate, butyl 3-hydroxypropionate, propyl 2-hydroxy-3-methylbutanoate, ethyl methoxyacetate, propyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, 2-methoxypropion Acid methyl, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, 2-ethoxypropionic acid Butyl, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropyl Examples thereof include esters such as ethyl lopionate, propyl 3-ethoxypropionate and butyl 3-ethoxypropionate, and ethers such as diethyl ether and tetrahydrofuran. In addition, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile and the like can be used as the aprotic polar solvent.
These solvents are usually contained in an amount of 2 to 90 parts by weight in the epoxy resin composition of the present invention as required. If necessary, the epoxy resin composition of the present invention in the case of using a solvent as a varnish or ink may be subjected to microfiltration using, for example, a 0.05 to 2 μm filter.

Next, the case where the epoxy resin composition of the present invention is used as an optical semiconductor sealing material or die bonding material will be described in detail.

When the epoxy resin composition of the present invention is used as a sealing material for an optical semiconductor such as a high-intensity white LED, or a die bond material, in addition to the carboxylic acid compound (A) of the present invention and the epoxy resin, other curing agents Prepare an epoxy resin composition by thoroughly mixing additives such as curing accelerators, coupling materials, antioxidants, light stabilizers, etc., as a sealing material, or as both a die bond material and a sealing material used. As a mixing method, a kneader, a three-roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill or the like is used to mix at room temperature or warm.

Optical semiconductor elements such as high-intensity white LEDs are generally GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN laminated on a substrate of sapphire, spinel, SiC, Si, ZnO or the like. Such a semiconductor chip is bonded to a lead frame, a heat sink, or a package using an adhesive (die bond material). There is also a type in which a wire such as a gold wire is connected to pass an electric current. The semiconductor chip is sealed with a sealing material such as an epoxy resin in order to protect it from heat and moisture and play a role of a lens. The epoxy resin composition of the present invention can be used as this sealing material or die bond material. From the viewpoint of the process, it is advantageous to use the epoxy resin composition of the present invention for both the die bond material and the sealing material.

As a method of adhering a semiconductor chip to a substrate using the epoxy resin composition of the present invention, the epoxy resin composition of the present invention is applied by a dispenser, potting, or screen printing, and then the semiconductor chip is placed and heat-cured. Yes, the semiconductor chip can be bonded. For the heating, methods such as hot air circulation, infrared rays and high frequency can be used.
For example, the heating conditions are preferably 80 to 230 ° C. for about 1 minute to 24 hours. For the purpose of reducing internal stress generated during heat-curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.

As a molding method of the sealing material, as described above, an injection method in which the sealing material is injected into the mold frame in which the substrate on which the semiconductor chip is fixed is inserted and then heat-cured and molded, and the sealing material is formed on the mold. A compression molding method or the like in which a semiconductor chip fixed on a substrate is immersed therein and heat-cured and then released from a mold is used.
Examples of the injection method include dispenser, transfer molding, injection molding and the like.
For the heating, methods such as hot air circulation, infrared rays and high frequency can be used.
For example, the heating conditions are preferably 80 to 230 ° C. for about 1 minute to 24 hours. For the purpose of reducing internal stress generated during heat-curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.

The carboxylic acid compound (A) of the present invention has a specific structure, is liquid at room temperature (25 ° C.), has excellent epoxy resin curability, and is usually employed in a temperature range for curing the epoxy resin. Is very volatile. The epoxy resin composition containing the carboxylic acid compound (A) of the present invention can be used for various applications including optical component materials in which ordinary epoxy resin compositions are used.
The optical material refers to general materials used for applications that allow light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material. More specifically, in addition to the optical semiconductor sealing material such as lamp type and SMD type, and the optical semiconductor die bond material, the following may be mentioned. It is a peripheral material for liquid crystal display devices such as a substrate material, a light guide plate, a prism sheet, a deflection plate, a retardation plate, a viewing angle correction film, an adhesive, and a film for a liquid crystal such as a polarizer protective film in the liquid crystal display field. In addition, color PDP (plasma display) sealing materials, antireflection films, optical correction films, housing materials, front glass protective films, front glass replacement materials, adhesives, and LED displays that are expected as next-generation flat panel displays LED molding materials, LED sealing materials, front glass protective films, front glass substitute materials, adhesives, and substrate materials for plasma addressed liquid crystal (PALC) displays, light guide plates, prism sheets, deflection plates , Phase difference plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass substitute material, adhesive, and various in field emission display (FED) Film substrate Front glass protective films, front glass substitute material, an adhesive. In the field of optical recording, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate materials for optical cards, Pickup lenses, protective films, sealing materials, adhesives and the like.

In the field of optical equipment, they are steel camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor parts. It is also a photographic lens and viewfinder for video cameras. Projection lenses for projection televisions, protective films, sealing materials, adhesives, and the like. These include lens materials, sealing materials, adhesives, and films for optical sensing devices. In the field of optical components, they are fiber materials, lenses, waveguides, element sealing materials, adhesives and the like around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. For optical passive components and optical circuit components, there are lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, and the like. These are substrate materials, fiber materials, device sealing materials, adhesives, etc. around an optoelectronic integrated circuit (OEIC). In the field of optical fiber, it is an optical fiber for lighting, light guides for decorative displays, sensors for industrial use, displays / signs, etc., and for communication infrastructure and home digital equipment connection. In the semiconductor integrated circuit peripheral material, it is a resist material for microlithography for LSI and VLSI material. In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Rusted steel plate, interior panel, interior material, wire harness for protection / bundling, fuel hose, automobile lamp, glass substitute. In addition, it is a multilayer glass for railway vehicles. Further, they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wire harnesses, and corrosion resistant coatings. In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film. Next generation optical / electronic functional organic materials include peripheral materials for organic EL elements, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical computing elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.

As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, underfill for sealing, and sealing (reinforcing underfill) when mounting IC packages such as BGA and CSP.

Other uses of optical materials include general uses in which epoxy resin compositions are used. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials In addition to the sealant (including printed circuit boards and wire coatings), additives to other resins and the like can be mentioned. Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP). In particular, since the transparency of the cured product obtained therefrom is excellent, it is extremely useful as a curing agent for epoxy resins for sealing high-luminance white LEDs and other optical semiconductors. Other uses include raw materials such as polyimide resins, modifiers, plasticizers, lubricating oil raw materials, cyanate resin compositions for substrates, additives to other resins, raw materials for paint resins, toner resins, medicines, etc. Useful as an agrochemical intermediate.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following, “part” means part by weight, and “%” means weight%. Moreover, the measurement method of the test in an Example is as follows.

○ Epoxy equivalent: Measured by the method described in JIS K-7236.
O Acid value: Measured using an AT-610 potentiometric titrator manufactured by 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: Measured using an E-type viscometer at 25 ° C.
-Weight average molecular weight: It measured using GPC (gel permeation chromatography) by Shimadzu Corporation. The column used was a guard column SHODEX GPC LF-G LF-804 (3), flow rate 1.0 ml / min, column temperature 40 ° C., solvent THF (tetrahydrofuran), detector RI (differential refraction detector). . The standard curve made from Shodex was used for the calibration curve.
○ Decrease in thermal weight: Using TG / DTA6200 manufactured by Shimadzu Corporation, the temperature was increased from 30 ° C. at 20 ° C./minute, heated to 120 ° C., and held at 120 ° C. for 60 minutes to measure the weight reduction rate. The air flow rate was 200 ml / min.
○ Transmittance: Using a U-3300 manufactured by Hitachi, Ltd., a light transmittance of 400 nm was measured.

MH700G used in the examples is a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride manufactured by Shin Nippon Rika Co., Ltd., and the mixing ratio is 70 wt.% Of methylhexahydrophthalic anhydride. % (68 mol%).
Similarly, HNA-100 is a mixture of methylnorbornane-2,3-dicarboxylic acid anhydride and norbornane-2,3-dicarboxylic acid anhydride manufactured by Shin Nippon Chemical Co., Ltd., and the mixing ratio is methylnorbornane-2. , 3-dicarboxylic acid anhydride is 80 wt% (79 mol%).

Synthesis Example 1 (Synthesis of a condensate between a silicon compound having an epoxy group and another silicon compound)
29.1 parts of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 130.6 parts of polydimethyldiphenylsiloxane having a silanol group having a molecular weight of 1700 (measured by GPC), 10.0 parts of 0.5% KOH methanol solution Was charged into a reaction vessel and heated to 75 ° C. After raising the temperature, the reaction was carried out at 75 ° C. under reflux for 8 hours. After the reaction, 135 parts of methanol was added, 25.9 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was further reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium hydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. Thereafter, for washing, 170 parts of MIBK was added, and washing with water was repeated three times. Then, the solvent was removed from the organic phase at 100 ° C. under reduced pressure to obtain 162 parts of a siloxane compound (B-1) having an epoxy group. The epoxy equivalent of the obtained compound was 707 g / eq. The weight average molecular weight was 2680, and the appearance was colorless and transparent.

Example 1
Reaction of 50 parts of carbinol-modified silicone X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), 15.4 parts of Ricacid MH (methylhexahydrophthalic anhydride, Shin Nippon Rika Co., Ltd.), and 10 parts of toluene When the vessel was charged, heated to 130 ° C., and GPC was measured after 3 hours, the peak of Ricacid MH disappeared. Thereafter, the reaction was further continued for 2 hours. After completion of the reaction, the solvent was removed under reduced pressure to obtain 65.0 parts of carboxylic acid compound (A-1). The weight average molecular weight of the obtained carboxylic acid compound was 1700.

Example 2
50 parts of both ends carbinol-modified silicone X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), Ricacid MH700G (mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, manufactured by Shin Nippon Rika Co., Ltd.) 16 .8 parts and 10 parts of toluene were charged into a reaction vessel, heated to 130 ° C., and GPC was measured after 3 hours. As a result, the peak of Ricacid MH700G disappeared. Thereafter, the reaction was further continued for 2 hours. After completion of the reaction, the solvent was removed under reduced pressure to obtain 66.8 parts of carboxylic acid compound (A-2). The weight average molecular weight of the obtained carboxylic acid compound was 1700.

Example 3
8. 50 parts of both ends carbinol-modified silicone X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), HTAn (1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 9 parts, licacid MH700G (mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, made by Shin Nippon Rika Co., Ltd.) 8.4 parts, 10 parts of toluene were charged in a reaction vessel, and the temperature was raised to 130 ° C. When GPC was measured after 3 hours, the peaks of HTAn and Ricacid MH700G disappeared. Thereafter, the reaction was further continued for 2 hours. After completion of the reaction, the solvent was removed under reduced pressure to obtain 68.2 parts of carboxylic acid compound (A-3). The weight average molecular weight of the obtained carboxylic acid compound was 1900.

Example 4
50 parts of both ends carbinol-modified silicone X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), ricacid MH (methylhexahydrophthalic anhydride, Shin Nippon Rika Co., Ltd.) 9.2 parts, ricacid BT-100 ( 4.0 parts of 1,2,3,4-butanetetracarboxylic dianhydride (manufactured by Shin Nippon Rika Co., Ltd.) and 10 parts of toluene were charged into a reaction vessel, heated to 130 ° C., and GPC was added after 3 hours. When measured, the peaks of Ricacid MH and Ricacid BT-100 disappeared. Thereafter, the reaction was further continued for 2 hours. After completion of the reaction, the solvent was removed under reduced pressure to obtain 63.0 parts of a carboxylic acid compound (A-4). The weight average molecular weight of the obtained carboxylic acid compound was 4640.

Example 5
50 parts of both-end carbinol-modified silicone X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), Ricacid HNA-100 (a mixture of norbornane-2,3-dicarboxylic acid anhydride and methylnorbornane-2,3-dicarboxylic acid anhydride) (Manufactured by Shin Nippon Rika Co., Ltd.) 17.0 parts and 10 parts of toluene were charged in a reaction vessel, heated to 130 ° C., and GPC was measured after 3 hours. The peak of Ricacid HNA-100 disappeared. Thereafter, the reaction was further continued for 2 hours. After completion of the reaction, the solvent was removed under reduced pressure to obtain 66.8 parts of carboxylic acid compound (A-5). The obtained carboxylic acid compound had a weight average molecular weight of 1,730.

Example 6
100 parts of the carboxylic acid compound (A-1) obtained in Example 1 and 108 parts of the siloxane compound (B-1) having an epoxy group obtained in Synthesis Example 1 were added as an epoxy resin, mixed, and defoamed for 20 minutes. And an epoxy resin composition was obtained.

Example 7
An epoxy resin composition was obtained in the same manner as in Example 6 except that the carboxylic acid compound was changed from A-1 to A-2 in Example 6.

Example 8
An epoxy resin composition was obtained in the same manner as in Example 6 except that the carboxylic acid compound was changed from A-1 to A-3 in Example 6.

Example 9
An epoxy resin composition was obtained in the same manner as in Example 6 except that the carboxylic acid compound was changed from A-1 to A-4 in Example 6.

Example 10
An epoxy resin composition was obtained in the same manner as in Example 6 except that the carboxylic acid compound was changed from A-1 to A-5 in Example 6.

Example 11
An epoxy resin composition was prepared in the same manner as in Example 6 except that the epoxy resin in Example 6 was changed to ERL-4221 (3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate, manufactured by Dow Chemical). I got a thing.

Comparative Example 1
841 parts of the epoxy group-containing siloxane compound (B-1) obtained in Synthesis Example 1 as an epoxy resin, and Ricacid MH700G (methyl hexahydrophthalic anhydride and hexahydrophthalic acid) which is a liquid carboxylic acid anhydride as an epoxy resin curing agent 100 parts of a mixture of acid anhydrides (manufactured by Shin Nippon Rika Co., Ltd.) and 0.8 parts of PX-4MP (phosphonium salt-based curing accelerator, manufactured by Nippon Chemical Industry Co., Ltd.) as a curing accelerator are mixed for 20 minutes. Foaming was performed to obtain an epoxy resin composition.

Comparative Example 2
The epoxy resin composition was the same as in Comparative Example 1 except that the epoxy resin of Comparative Example 1 was changed to ERL-4221 (3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate, manufactured by Dow Chemical). I got a thing.

Example of trial use of epoxy resin composition as optical semiconductor encapsulant The curable resin compositions obtained in Examples 6 to 11 and Comparative Examples 1 and 2 were filled in a syringe, and the emission wavelength was measured using a precision discharge device. A surface-mounted LED mounted with a light-emitting element having a wavelength of 405 nm was cast, and pre-cured at 120 ° C. for 3 hours and then cured at 150 ° C. for 1 hour to seal the surface-mounted LED.

Physical Properties Test Table 1 summarizes the properties of the carboxylic acid compounds A-1 to A-5 obtained in Examples 1 to 5 and Ricacid MH700G, which is a liquid carboxylic acid anhydride, as a comparative example.

MH700G: A mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, manufactured by Shin Nippon Rika Co., Ltd.

○ Evaluation test Table 2 shows the compounding ratio of the epoxy resin compositions obtained in Examples 6 to 11 and Comparative Examples 1 and 2, the transmittance of the cured product, the dent of the cured product accompanying the volatilization of the cured product, and the results of surface tack. Shown in The test in Table 2 was performed as follows.

(1) cured product 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 on a glass substrate on which a dam was formed with heat-resistant tape so as to be 30 mm × 20 mm × height 1 mm. I cast it gently. The cast was cured at 120 ° C. for 1 hour after pre-curing at 120 ° C. for 3 hours to obtain a test piece for transmittance having a thickness of 1 mm.
(2) dent test;
The epoxy resin compositions obtained in Examples 6 to 11 and Comparative Examples 1 and 2 were vacuum degassed for 20 minutes, filled into a syringe, and mounted with a light emitting element having an emission wavelength of 405 nm using a precision discharge device. The surface-mounted LED was cast so that the opening was flat. After pre-curing at 120 ° C. for 3 hours, curing was performed at 150 ° C. for 1 hour to seal the surface-mounted LED. The presence or absence of dents on the resin surface accompanying the volatilization of the curing agent after sealing in this way was visually evaluated. In the table, ◯: no dent is observed, Δ: some dent is observed, x: many dents are observed (3) surface tack;
A test piece similar to the cured product transmittance test was prepared, and the surface tackiness (stickiness of the surface) of the test piece was confirmed by finger touch. In the table, ○: no stickiness, x: stickiness

As is apparent from the results shown in Table 1, the ricacid MH700G of the comparative example shows a significant decrease in thermogravimetricity at 120 ° C., whereas the carboxylic acid compounds A-1 to A-5 of Examples 1 to 5 In the case of liquid, the weight was hardly decreased. Further, as is clear from the results shown in Table 2, in Comparative Examples 1 and 2, there are many dents in the cured product, while in Examples 6 to 11, almost no dents are observed, and further, the transmittance of the cured product. And the surface was not sticky.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2008-324305) filed on December 19, 2008, and is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

Claims (8)

1. A carboxylic acid compound obtained by addition reaction of a silicone compound (a) represented by the following formula (1) and a compound having one or more carboxylic anhydride groups in the molecule, The compound having at least one carboxylic acid anhydride group is at least one carboxylic acid compound (A) selected from the compounds (c) represented by the following formulas (3) to (5).
   

   

   
   (In Formula (1), R ₁ represents an alkylene group having 1 to 10 carbon atoms which may contain an ether group, R ₂ represents a methyl group or a phenyl group, and n represents an average value of 1 to 100)
   

   
2. A carboxylic acid compound obtained by addition reaction of a silicone compound (a) represented by the following formula (1) and a compound having one or more carboxylic anhydride groups in the molecule, A carboxylic acid compound (A) in which the compound having one or more carboxylic acid anhydride groups is a compound represented by the following formula (3).
   

   

   
   (In Formula (1), R ₁ represents an alkylene group having 1 to 10 carbon atoms which may contain an ether group, R ₂ represents a methyl group or a phenyl group, and n represents an average value of 1 to 100)
   

   
3. An epoxy resin curing agent containing the carboxylic acid compound (A) according to claim 1 or 2 and a curing accelerator.
4. An epoxy resin composition comprising the carboxylic acid compound (A) according to claim 1 or 2, or an epoxy resin curing agent according to claim 3 and an epoxy resin.
5. The epoxy equivalent of the epoxy resin is 400-1500 g / eq. The epoxy resin composition according to claim 4, wherein the weight average molecular weight is 1500 to 10,000.
6. The epoxy resin composition according to claim 5, wherein the epoxy resin composition is used for an optical semiconductor encapsulant.
7. The epoxy resin composition according to claim 5, wherein the use of the epoxy resin composition is for an optical semiconductor die bond material.
8. A cured product of the epoxy resin composition according to any one of claims 4 to 7.