JP5745248B2 - Curing agent composition for epoxy resin, curable resin composition and cured product thereof - Google Patents

Description

  The present invention relates to a curing agent composition for an epoxy resin useful for preparing a curable resin composition useful for optical semiconductor encapsulation, etc., a curable resin composition containing the curing agent composition for an epoxy resin, The present invention relates to a cured product of a curable resin composition and an optical semiconductor device in which an optical semiconductor element is sealed with the cured product.

  An epoxy resin is used as a resin for sealing an optical semiconductor element such as a light emitting diode (LED), an optical sensor, a light emitting element for optical communication, and a light receiving element because of its high transparency.

  As a curing agent composition for an epoxy resin for curing such an epoxy resin, a curing agent composition comprising an acid anhydride curing agent and a curing accelerator such as a tertiary amine is generally used. However, when a mixture of an acid anhydride and a curing accelerator such as a tertiary amine is stored for a long period of time, there arises a problem that the mixture is colored or carbon dioxide is generated due to a decarboxylation reaction to swell the container. In Patent Document 1 (Japanese Patent Publication No. 55-30728), in order to solve such a problem, a specific amount of ethylene glycol or the like is contained in an acid anhydride containing 0 to 1% by weight of maleic anhydride and a tertiary amine. It has been proposed.

  On the other hand, in Patent Document 2 (Japanese Patent Laid-Open No. 2005-75915), in order to improve the storage stability of a mixture of an acid anhydride curing agent for epoxy resin and a tertiary amine curing accelerator, It has been proposed to incorporate a storage stability improver comprising a hydroxybenzoic acid ester.

Japanese Patent Publication No. 55-30728 JP 2005-75915 A

  However, as in Patent Document 1, when ethylene glycol is blended in a mixed solution of an acid anhydride and a curing accelerator such as a tertiary amine and stored for a long period of time, the generation of carbon dioxide is suppressed, but gradually precipitated. There arises a problem that a product (precipitate) is generated and the mixed solution becomes cloudy. In addition, the method described in Patent Document 2 requires the use of a special hydroxybenzoic acid ester that cannot be said to be easily available, resulting in a high cost.

Accordingly, an object of the present invention is to provide a curing agent composition for epoxy resins that is extremely low in carbon dioxide generation even when stored for a long period of time, is transparent without white turbidity due to precipitates, and can be prepared at low cost. And a curable resin composition containing the epoxy resin curing agent composition, a cured product of the curable resin composition, and an optical semiconductor device in which an optical semiconductor element is sealed with the cured product It is in.
In addition to the above, the other object of the present invention is to provide an epoxy resin curing agent composition capable of suppressing the generation of bubbles even during curing, a curable resin composition containing the epoxy resin curing agent composition, and It is in providing the hardened | cured material of this curable resin composition, and the optical semiconductor device by which the optical semiconductor element was sealed with this hardened | cured material.

  As a result of intensive studies to achieve the above object, the present inventor has formulated a specific compound into an acid anhydride curing agent and a curing accelerator. It was found that the production of the product can be remarkably suppressed, and furthermore, the generation of bubbles can be suppressed even when the epoxy resin is cured, and the present invention has been completed.

That is, the present invention is an acid anhydride curing agent (A), the curing accelerator (B), and contains at least one diol selected from neopentyl glycol and 1,3-butanediol (C) The ratio of the total amount of the acid anhydride curing agent (A), the curing accelerator (B) and the diol (C) to the epoxy resin curing agent composition is 50% by weight or more. An agent composition is provided.

  As a usage-amount of diol (C), the ratio of 0.5-15 weight part is preferable with respect to 100 weight part of acid anhydride type hardening | curing agents (A).

  The present invention also provides a curable resin composition comprising, as essential components, an epoxy compound (D) having two or more epoxy groups in the molecule and the epoxy resin curing agent composition.

  It is preferable to use at least one alicyclic epoxy compound as the epoxy compound (D).

  The present invention further provides a cured product obtained by curing the curable resin composition.

  The present invention further provides an optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable resin composition.

  According to the present invention, since a specific diol compound is blended with an acid anhydride curing agent and a curing accelerator, the storage stability is greatly improved, and even when the curing agent composition for epoxy resin is stored for a long period of time, The generation of carbon dioxide is extremely small, and white turbidity due to precipitates does not occur. Further, since an inexpensive and inexpensive compound is used, the cost is low. Furthermore, even when the epoxy resin is cured, the generation of bubbles can be remarkably suppressed. Therefore, an optical semiconductor device with extremely high reliability can be stably supplied, which is extremely valuable industrially.

  The curing agent composition for epoxy resin of the present invention comprises an acid anhydride curing agent (A), a curing accelerator (B), and at least one diol selected from neopentyl glycol and 1,3-butanediol. (C) is contained.

[Acid anhydride curing agent (A)]
As the acid anhydride-based curing agent (A), a curing agent generally used for curing an epoxy compound can be used, but a liquid one at room temperature is preferable. Specifically, for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, 2,4-diethylpentanedioic anhydride, cyclohexane-1,2, Examples include 4-tricarboxylic acid-1,2-anhydride. In addition, acid anhydrides that are solid at room temperature, such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride, and the like, can be used within a range that does not impair molding workability. When an acid anhydride that is solid at room temperature is used, it is preferably dissolved in a liquid acid anhydride at room temperature and used as a liquid mixture at room temperature. The acid anhydride curing agent (A) can be used alone or in combination of two or more.

  As the acid anhydride-based curing agent (A), the trade name “Ricacid MH-700” (manufactured by Shin Nippon Rika Co., Ltd.), the trade name “Rikacid MH” (manufactured by Shin Nippon Rika Co., Ltd.), the trade name “HN-5500” (Hitachi Commercial products such as those manufactured by Kasei Kogyo Co., Ltd. can also be used.

[Curing accelerator (B)]
The curing accelerator (B) is not particularly limited as long as it is a curing accelerator generally used for accelerating the curing of epoxy compounds. For example, tertiary amines, tertiary amine salts, imidazoles, organophosphorus compounds Quaternary ammonium salts, quaternary phosphonium salts, organometallic salts, boron compounds, and the like can be used. A hardening accelerator (B) can be used individually by 1 type or in combination of 2 or more types.

  Examples of the tertiary amine include lauryl dimethylamine, N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline, (N, N-dimethylaminomethyl) phenol, 2,4. , 6-Tris (N, N-dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 ( DBN).

  Examples of the tertiary amine salt include carboxylates, sulfonates, and inorganic acid salts of the tertiary amine. Examples of the carboxylate include salts of carboxylic acids having 1 to 30 carbon atoms (particularly 1 to 10 carbon atoms) such as octylates (particularly salts of fatty acids). Examples of the sulfonate include p-toluenesulfonate, benzenesulfonate, methanesulfonate, and ethanesulfonate. Typical examples of the tertiary amine salt include salts of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) (for example, p-toluenesulfonate, octylate). .

  Examples of imidazoles include 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2,4-diamino-6- (2-methylimidazolylethyl) -1,3,5-triazine, 2,4-diamino-6- (2-Undecylimidazolyl ethi ) -1,3,5-triazine, 2,4-diamino-6- (2-ethyl-4-methylimidazolylethyl) -1,3,5-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, Examples include 2-phenyl-4-methyl-5-hydroxymethylimidazole.

  Examples of the organic phosphorus compound include triphenylphosphine and triphenyl phosphite.

  Examples of the quaternary ammonium salt include tetraethylammonium bromide and tetrabutylammonium bromide.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴は、同一又は異なって、炭素数１〜１６の炭化水素基を示す。Ｘはカルボン酸又は有機スルホン酸のアニオン残基を示す）
で表される化合物などが挙げられる。 As a quaternary phosphonium salt, for example, the following formula (1)

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrocarbon group having 1 to 16 carbon atoms. X represents an anion residue of carboxylic acid or organic sulfonic acid)
The compound etc. which are represented by these are mentioned.

  Examples of the hydrocarbon group having 1 to 16 carbon atoms include linear chains such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl, decyl, and dodecyl groups. Or branched alkyl group; linear or branched alkenyl group such as vinyl, allyl, crotyl group; aryl group such as phenyl, toluyl, xylyl, naphthyl, anthryl, phenanthryl group; benzyl, phenethyl group, etc. And aralkyl groups. Among these, a linear or branched alkyl group having 1 to 6 carbon atoms, particularly a butyl group is preferable.

  Examples of the “carboxylic acid” in the “anionic residue of carboxylic acid or organic sulfonic acid” include aliphatic monocarboxylic acids having 1 to 20 carbon atoms such as octanoic acid, decanoic acid, lauric acid, myristic acid, and palmitic acid. 1,2,4,5-cyclohexanetetracarboxylic acid, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, etc. Examples thereof include alicyclic carboxylic acids (monocyclic alicyclic mono- or polycarboxylic acids, cross-linked cyclic mono- or polycarboxylic acids). The alicyclic ring of the alicyclic carboxylic acid includes a linear or branched alkyl group having 1 to 4 carbon atoms such as a methyl group, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, and a chlorine atom. A substituent such as a halogen atom may be bonded. As the carboxylic acid, an aliphatic monocarboxylic acid having 10 to 18 carbon atoms and an alicyclic polycarboxylic acid having 8 to 18 carbon atoms are preferable.

  Examples of the “organic sulfonic acid” in the “anionic residue of carboxylic acid or organic sulfonic acid” include methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 2-propanesulfonic acid, 1-butanesulfonic acid, Aliphatic sulfonic acids such as 1-pentanesulfonic acid, 1-hexanesulfonic acid, 1-octanesulfonic acid, 1-decanesulfonic acid and 1-dodecanesulfonic acid (for example, aliphatic sulfonic acids having 1 to 16 carbon atoms) Benzenesulfonic acid, p-toluenesulfonic acid, 4-ethylbenzenesulfonic acid, 3- (linear or branched octyl) benzenesulfonic acid, 4- (linear or branched octyl) benzenesulfonic acid, 3 -(Linear or branched dodecyl) benzenesulfonic acid, 4- (linear or branched dodecyl) benzene Sulfonic acid, 2,4-dimethylbenzene sulfonic acid, 2,5-dimethylbenzene sulfonic acid, 4-methoxy benzenesulfonic acid, 4-ethoxy-benzenesulfonic acid, 4-chlorobenzene sulfonic acid.

  Representative examples of quaternary phosphonium salts include tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, tetrabutylphosphonium myristate, tetrabutylphosphonium palmitate, tetrabutylphosphonium cation and bicyclo [2.2. .1] Salts of heptane-2,3-dicarboxylic acid and / or methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid with anions, tetrabutylphosphonium cation and 1,2,4,5- Salt of cyclohexanetetracarboxylic acid anion, salt of tetrabutylphosphonium cation and anion of methanesulfonic acid, salt of tetrabutylphosphonium cation and anion of benzenesulfonic acid, anion of tetrabutylphosphonium cation and p-toluenesulfonic acid Salts with a salt of the anion of tetrabutylphosphonium cation and 4-chlorobenzene sulfonic acid, and salts with anions of tetrabutylphosphonium cation and dodecylbenzenesulfonic acid.

  Examples of the organic metal salt include tin octylate, zinc octylate, dibutyltin dilaurate, and aluminum acetylacetone complex.

  Examples of the boron compound include boron trifluoride and triphenyl borate.

  As the curing accelerator (B), commercially available products such as trade names “U-CAT SA-506”, “U-CAT SA-102”, “U-CAT 5003” (manufactured by San Apro) may be used. it can.

  Although the compounding quantity of a hardening accelerator (B) changes also with the kind of acid anhydride type hardening | curing agent (A), it is 0.01-15 normally with respect to 100 weight part of acid anhydride type hardening | curing agents (A). Parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight.

[Diol (C)]
In the present invention, at least one diol (C) selected from neopentyl glycol and 1,3-butanediol is used as an essential component. By blending neopentyl glycol and / or 1,3-butanediol, the long-term storage stability of the curing agent composition is remarkably improved, and carbon dioxide is generated even when the curing agent composition is stored for a long period of time. There is almost no white turbidity due to precipitates, and transparency can be maintained.

  The blending amount of the diol (C) varies depending on the type of the acid anhydride curing agent (A), but is usually 0.5 to 15 parts by weight with respect to 100 parts by weight of the acid anhydride curing agent (A). The amount is preferably 1 to 10 parts by weight, more preferably 1.5 to 8 parts by weight. If the amount of the diol (C) is too small, the effect of addition becomes small. On the other hand, if the amount is too large, the viscosity increases when the curable resin composition is prepared, and the pot life tends to be shortened.

  The epoxy resin curing agent composition of the present invention may be composed of only the acid anhydride curing agent (A), the curing accelerator (B), and the diol (C). Other components may be included as long as the effects of the invention are not hindered. The proportion of the total amount of the acid anhydride curing agent (A), curing accelerator (B) and diol (C) in the curing agent composition for epoxy resin of the present invention is, for example, 50% by weight or more, preferably 80% by weight. As mentioned above, More preferably, it is 95 weight% or more.

[Curable resin composition]
The curable resin composition of this invention contains the epoxy compound (D) which has 2 or more of epoxy groups in a molecule | numerator, and the said hardening | curing agent composition for epoxy resins of this invention as an essential component.

[Epoxy compound having two or more epoxy groups in the molecule (D)]
It does not specifically limit as an epoxy compound (D) which has two or more epoxy groups in a molecule | numerator, For example, an alicyclic epoxy compound, a bisphenol-type diepoxy compound, an aliphatic polyhydric alcohol polyglycidyl ether, etc. can be used. An epoxy compound (D) can be used individually by 1 type or in combination of 2 or more types.

  The alicyclic epoxy compound is not particularly limited as long as it is a compound having a cycloaliphatic skeleton and two or more epoxy groups in the molecule. (I) Adjacent one in which the epoxy group constitutes the cycloaliphatic skeleton An epoxy compound having two or more alicyclic epoxy groups formed containing two carbon atoms is preferred. Examples of such alicyclic epoxy compounds include compounds represented by the following formula (2).

  The alicyclic epoxy compound represented by the general formula (2) is produced by oxidizing a corresponding alicyclic olefin compound with an aliphatic percarboxylic acid or the like. What was manufactured using it is preferable at the point which has a high epoxidation rate (Unexamined-Japanese-Patent No. 2002-275169 etc.).

  In the general formula (2), Y represents a single bond or a linking group, and examples of the linking group include a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), and an ester bond. (-COO-), an amide bond (-CONH-), a carbonate bond (-OCOO-), and a group in which a plurality of these are linked. Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms (particularly 1 to 6) and a divalent alicyclic hydrocarbon group (particularly a divalent cycloalkylene group). And the like are preferably exemplified. Examples of the linear or branched alkylene group include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene groups. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, Examples include 1,4-cyclohexylene and cyclohexylidene groups.

  Specific examples of the compound described above include the following compounds.

  In said formula, n is an integer of 1-30.

  As the alicyclic epoxy compound, in addition to the above, (ii) only one of the two epoxy groups is an alicyclic epoxy group formed by including two adjacent carbon atoms constituting the cycloaliphatic skeleton. An epoxy compound (for example, limonene diepoxide), (iii) an epoxy compound in which a carbon atom constituting an epoxy group is bonded to a carbon atom constituting a cyclic aliphatic skeleton by a single bond, (iv) a glycidyl ether compound (for example, Also, a glycidyl ether type epoxy compound having a cyclic aliphatic skeleton and a glycidyl ether group can be used. Specific examples of the above compound include the following compounds.

In the above formula, R is a group obtained by dividing q OH from a q-valent alcohol [R— (OH) _q ], p is an integer of 1 to 50, and q is an integer of 1 to 10. In the groups in q parentheses, p may be the same or different. As the q-valent alcohol [R- (OH) _q ], monovalent alcohols such as methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol; ethylene glycol, 1,2-propanediol, 1,3- Divalent alcohols such as propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polypropylene glycol; glycerin, diglycerin, erythritol , Trivalent or higher alcohols such as trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol. The alcohol may be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, or the like. As said alcohol, C1-C10 aliphatic alcohol (especially aliphatic polyhydric alcohols, such as a trimethylol propane), is preferable.

  In addition, (v) a polyfunctional epoxy compound having 3 or more epoxy groups can also be used. Specifically, the following compounds are exemplified.

  In the above formula, a, b, c, d, e and f are integers of 0 to 30.

  As the bisphenol diepoxy compound, known compounds can be used, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin.

  The aliphatic polyhydric alcohol polyglycidyl ether is not particularly limited. Examples of the “aliphatic polyhydric alcohol” in the aliphatic polyhydric alcohol polyglycidyl ether include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4- Divalent alcohols such as butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol; glycerin, di Examples include trivalent or higher alcohols such as glycerin, polyglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, and dipentaerythritol.

  Representative examples of the aliphatic polyhydric alcohol polyglycidyl ether include 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol Examples include diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polyethylene glycol diglycidyl ether.

  In the present invention, the epoxy compound (D) is preferably in the form of a liquid from the viewpoint of improving workability during preparation and casting. However, even if it is a solid epoxy compound as a simple substance, it can be used as long as the viscosity (25 ° C.) of the curable resin composition after blending each component is, for example, 20000 mPa · s or less. The viscosity (25 ° C.) of the epoxy compound (D) (a mixture of all epoxy compounds used) is, for example, 50 to 50000 mPa · s, preferably 100 to 30000 mPa · s, and more preferably 200 to 20000 mPa · s. When this viscosity is too large, molding workability such as casting workability tends to be lowered.

  Among the above epoxy compounds, alicyclic epoxy compounds (particularly, epoxy compounds having an alicyclic epoxy group formed by including two adjacent carbon atoms in which the epoxy group constitutes a cycloaliphatic skeleton) Although the cured resin is excellent in transparency and heat resistance, bubbles are easily generated during curing. Therefore, the present invention is particularly useful when the curable resin composition contains an alicyclic epoxy compound. In the present invention, an alicyclic epoxy compound in the epoxy compound (D) (in particular, an epoxy compound having an alicyclic epoxy group in which the epoxy group is formed to include two adjacent carbon atoms constituting the cycloaliphatic skeleton) ) Is preferably 30% by weight or more, more preferably 50% by weight or more, and particularly preferably 80% by weight or more.

  In the curable resin composition of the present invention, the blending ratio of the epoxy compound (D) having two or more epoxy groups in the molecule and the epoxy resin curing agent composition of the present invention is selected in consideration of curability and the like. it can. For example, the amount of the acid anhydride-based curing agent (A) in the curable resin composition is 0.5 to 1.5 equivalents per equivalent of epoxy groups of all epoxy compounds contained in the curable resin composition. It is preferable to mix | blend the said epoxy compound (D) and the said hardening | curing agent composition for epoxy resins so that it may become. When the amount of the acid anhydride-based curing agent (A) used is too small, the curing becomes insufficient, and the toughness of the cured product tends to decrease. On the other hand, when the amount is too large, the cured product is colored and the hue deteriorates. There is.

  In the curable resin composition of the present invention, the amount of the curing accelerator (B) is, for example, 0.01 to 15 parts by weight, preferably 0.1 to 10 parts per 100 parts by weight of the epoxy compound (D). Part by weight, more preferably 0.5 to 8 parts by weight. When the blending amount of the curing accelerator is too small, the curing accelerating effect may be insufficient, and when it is too large, the hue in the cured product may be deteriorated.

[Other ingredients]
You may add various additives to the curable resin composition of this invention as needed. For example, when a compound having a hydroxyl group (polyhydric alcohol or the like) such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin is used as the additive, the reaction can be allowed to proceed gently. The amount of such a hydroxyl group-containing compound (polyhydric alcohol or the like) used is, for example, 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the epoxy compound (D). is there. As described above, when ethylene glycol or the like is added to the curing agent composition, white turbidity occurs during storage. Therefore, it may be mixed with the epoxy compound (D) in advance or the curable resin composition. It is preferable to add at the time of preparation.

  Further, when an ester (such as a diester) of a polyhydric carboxylic acid anhydride (such as an alicyclic polycarboxylic acid anhydride) and a polyhydric alcohol (such as a polyalkylene glycol) is used as an additive, the flexibility of the cured product can be improved. Can be improved. The amount of the ester used is, for example, 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the epoxy compound (D) contained in the curable resin composition of the present invention. is there.

  In addition, if necessary, silicone-based or fluorine-based antifoaming agent, leveling agent, silane coupling agent, surfactant, inorganic, as long as the viscosity of the curable resin composition and the transparency of the cured product are not impaired. Fillers, organic rubber particles, flame retardants, colorants, plasticizers, antistatic agents, mold release agents, antioxidants, UV absorbers, light stabilizers, ion adsorbers, pigments, dyes, phosphors, etc. It can also be used. The compounding quantity of these various additives is 5 weight% or less with respect to the whole curable resin composition, for example. The curable resin composition of the present invention may contain a solvent, but if the amount of the solvent is too large, bubbles may be formed in the cured resin, and preferably 10% by weight or less based on the entire curable composition. In particular, it is 1% by weight or less.

  In the curable resin composition of the present invention, the ratio of the epoxy compound (D) to the total amount of the acid anhydride-based curing agent (A), the curing accelerator (B), the diol (C), and other components is epoxy. The total amount of the acid anhydride curing agent (A), the curing accelerator (B), the diol (C) and other components is preferably 70 to 200 parts by weight with respect to 100 parts by weight of the compound (D). More preferably, it is 80-160 weight part. Moreover, the ratio for which the total amount of an acid anhydride type hardening | curing agent (A), a hardening accelerator (B), diol (C), and an epoxy compound (D) accounts for the curable resin composition of this invention is 50 weight, for example. % Or more, preferably 70% by weight or more, and more preferably 90% by weight or more.

  The viscosity (25 degreeC) of the curable resin composition of this invention is 50-5000 mPa * s, for example, Preferably it is 100-4000 mPa * s, More preferably, it is 200-3000 mPa * s. When this viscosity is too large, it is difficult for bubbles to escape, and molding workability such as sealing workability and casting workability tends to deteriorate.

  The curable resin composition of the present invention is prepared, for example, by mixing an epoxy compound (D) and other components added as necessary to prepare an agent A (that is, an epoxy resin composition), and an acid anhydride. A B agent (that is, a curing agent composition for epoxy resin) is prepared by mixing the system curing agent (A), the curing accelerator (B), the diol (C), and other components added as necessary. Subsequently, it manufactures by stirring and mixing A agent and B agent in a predetermined | prescribed ratio, and degas | defoaming under vacuum as needed. The order of addition of each component at the time of preparation of the B agent (curing agent composition for epoxy resin) is not particularly limited. First, the acid anhydride curing agent (A) and the curing accelerator (B) are mixed, The diol (C) may be added and mixed. First, the acid anhydride curing agent (A) and the diol (C) are mixed, and then the curing accelerator (B) is added and mixed. As a result, a uniform composition can be efficiently prepared. The temperature at the time of stirring and mixing at the time of preparing A agent (when comprised with 2 or more components) is 30-150 degreeC, for example, Preferably it is 35-130 degreeC. The temperature at the time of stirring and mixing at the time of preparing B agent is 30-100 degreeC, for example, Preferably it is 35-80 degreeC. For stirring and mixing, a known apparatus such as a rotation / revolution mixer, a planetary mixer, a kneader, a dissolver, or the like can be used.

[Cured product]
A cured product is obtained by injecting the curable resin composition of the present invention into a desired place or mold and curing it. Curing temperature is 45-200 degreeC, for example, Preferably it is 80-190 degreeC, More preferably, it is 100-180 degreeC. The curing time is, for example, 30 to 1440 minutes, preferably 45 to 900 minutes, and more preferably 60 to 600 minutes. Curing can also be performed in multiple stages.

  From the viewpoint of heat resistance, the glass transition temperature of the cured product is preferably 90 ° C. or higher, more preferably 110 ° C. or higher.

[Optical semiconductor device]
In the optical semiconductor device of the present invention, the optical semiconductor element is sealed with a cured product of the curable resin composition of the present invention.

  Examples of the optical semiconductor element include a light emitting diode, an optical sensor, a light emitting element for optical communication, a light receiving element, and the like. The optical semiconductor element is sealed by, for example, injecting the curable resin composition into a predetermined mold in which the optical semiconductor element is installed (or injecting the curable resin composition into the mold, It can be performed by installing a semiconductor element) and heating and curing under predetermined conditions. The curing conditions are the same as above.

  According to the present invention, even when the curable composition for epoxy resins is stored for a long period of time, generation of bubbles and generation of precipitates are extremely small. In addition, the generation of bubbles during curing is extremely small. For this reason, an optical semiconductor device with extremely high reliability can be stably supplied.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
The curing agent Rikacid MH-700 (manufactured by Shin Nippon Rika Co., Ltd .; 4-methylhexahydrophthalic anhydride: hexahydrophthalic anhydride = 70: 30) was added to 100 parts by weight of the curing accelerator 2-ethyl-4-methyl. 1 part by weight of imidazole was added and dissolved by heating and stirring at 60 ° C. for 30 minutes, then cooled to 50 ° C., and further 3.2 parts by weight of neopentyl glycol was added and dissolved by heating and stirring for 4 hours at 50 ° C. Then, it cooled to room temperature and obtained the transparent liquid hardening | curing agent liquid (hardening agent composition) at normal temperature.

Example 2
To 100 parts by weight of the curing agent Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; the main component is 4-methylhexahydrophthalic anhydride), 1 part by weight of the curing accelerator 2-ethyl-4-methylimidazole is added, and 60 After stirring and dissolving at 30 ° C. for 30 minutes, the mixture was cooled to 50 ° C., and further 3.2 parts by weight of neopentyl glycol was added and dissolved by heating and stirring for 4 hours at 50 ° C., followed by cooling to room temperature. A transparent liquid curing agent solution was obtained.

Example 3
The curing agent Rikacid MH-700 (manufactured by Shin Nippon Rika Co., Ltd .; 4-methylhexahydrophthalic anhydride: hexahydrophthalic anhydride = 70: 30) was added to 100 parts by weight of the curing accelerator 2-ethyl-4-methyl. Add 1 part by weight of imidazole, dissolve with heating and stirring at 60 ° C. for 30 minutes, cool to 50 ° C., add 2.8 parts by weight of 1,3-butanediol, and heat and stir at 50 ° C. for 4 hours. After dissolution, the mixture was cooled to room temperature to obtain a transparent liquid curing agent liquid at room temperature.

Example 4
To 100 parts by weight of the curing agent Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; the main component is 4-methylhexahydrophthalic anhydride), 1 part by weight of the curing accelerator 2-ethyl-4-methylimidazole is added, and 60 After stirring and dissolving at 30 ° C. for 30 minutes, the mixture was cooled to 50 ° C., and 2.8 parts by weight of 1,3-butanediol was further added and dissolved by heating and stirring for 4 hours at 50 ° C., followed by cooling to room temperature. Then, a transparent liquid curing agent liquid was obtained at room temperature.

Example 5
Curing agent Ricacid MH-700 (manufactured by Shin Nippon Rika Co., Ltd .; 4-methylhexahydrophthalic anhydride: hexahydrophthalic anhydride = 70: 30) is added to 100 parts by weight of curing accelerator N, N-dimethylbenzylamine. Add 1 part by weight, dissolve by heating and stirring at 60 ° C. for 30 minutes, then cool to 50 ° C. Add 3.2 parts by weight of neopentyl glycol and dissolve by heating and stirring at 50 ° C. for 4 hours. Then, it was cooled to room temperature to obtain a transparent liquid curing agent liquid at room temperature.

Example 6
Add 1 part by weight of N, N-dimethylbenzylamine, a curing accelerator, to 100 parts by weight of curing agent Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; main component is 4-methylhexahydrophthalic anhydride), and The mixture was dissolved by heating and stirring for 30 minutes, and then cooled to 50 ° C. Further, 3.2 parts by weight of neopentyl glycol was added and dissolved by heating and stirring for 4 hours at 50 ° C, and then cooled to room temperature. A transparent liquid curing agent solution was obtained.

Example 7
Curing accelerator Rikacid MH-700 (manufactured by Shin Nippon Rika Co., Ltd .; 4-methylhexahydrophthalic anhydride: hexahydrophthalic anhydride = 70: 30) was added to 100 parts by weight of curing accelerator “U-CAT 5003” ( 1 part by weight of San Apro Co., Ltd. (quaternary phosphonium bromide) was added, dissolved by heating and stirring at 60 ° C. for 30 minutes, cooled to 50 ° C., and further added with 3.2 parts by weight of neopentyl glycol. The mixture was dissolved by heating and stirring for 4 hours while maintaining the temperature, and then cooled to room temperature to obtain a transparent liquid curing agent liquid at room temperature.

Example 8
Curing agent Rikacid MH (manufactured by Shin Nippon Rika Co., Ltd .; main component is 4-methylhexahydrophthalic anhydride) and curing accelerator “U-CAT 5003” (manufactured by San Apro Co., Ltd .; No. 4) 1 part by weight of phosphonium bromide) was added, dissolved by heating and stirring at 60 ° C. for 30 minutes, cooled to 50 ° C., and further 3.2 parts by weight of neopentyl glycol was added and kept at 50 ° C. for 4 hours. After dissolving by heating and stirring, the solution was cooled to room temperature, and a transparent liquid curing agent solution was obtained at room temperature.

Example 9
Curing agent Ricacid MH-700 (manufactured by Shin Nippon Rika Co., Ltd .; 4-methylhexahydrophthalic anhydride: hexahydrophthalic anhydride = 70: 30) was added to 1,8-diazabicyclo [5 4.0] 1 part by weight of p-toluenesulfonic acid salt of undecene-7 was added, dissolved by heating and stirring at 60 ° C. for 30 minutes, then cooled to 50 ° C., and further 3.2 parts by weight of neopentyl glycol. In addition, the mixture was dissolved by heating and stirring for 4 hours at 50 ° C., and then cooled to room temperature to obtain a transparent liquid curing agent liquid at room temperature.

Example 10
Curing agent Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; main component is 4-methylhexahydrophthalic anhydride) and curing accelerator 1,8-diazabicyclo [5.4.0] undecene-7 1 part by weight of p-toluenesulfonic acid salt was added, dissolved by heating and stirring at 60 ° C. for 30 minutes, then cooled to 50 ° C., and further 3.2 parts by weight of neopentyl glycol was added and left at 50 ° C. for 4 hours. After dissolving by heating and stirring, the solution was cooled to room temperature, and a transparent liquid curing agent solution was obtained at room temperature.

Example 11
Add 100 parts by weight of the curing agent Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; the main component is 4-methylhexahydrophthalic anhydride) and add 1 part by weight of the curing accelerator tetrabutylphosphonium decanoate at 60 ° C. After stirring and dissolving for 30 minutes, cooling to 50 ° C, adding 3.2 parts by weight of neopentyl glycol, dissolving by heating and stirring for 4 hours at 50 ° C, cooling to room temperature, and transparent at room temperature A liquid curing agent liquid was obtained.

Example 12
Add 100 parts by weight of the curing agent Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; the main component is 4-methylhexahydrophthalic anhydride), 1 part by weight of a curing accelerator, tetrabutylphosphonium laurate, at 60 ° C. After stirring and dissolving for 30 minutes, cooling to 50 ° C, adding 3.2 parts by weight of neopentyl glycol, dissolving by heating and stirring for 4 hours at 50 ° C, cooling to room temperature, and transparent at room temperature A liquid curing agent liquid was obtained.

Example 13
Add 100 parts by weight of the curing agent Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; the main component is 4-methylhexahydrophthalic anhydride) and add 1 part by weight of the curing accelerator tetrabutylphosphonium myristate at 60 ° C. After stirring and dissolving for 30 minutes, cooling to 50 ° C, adding 3.2 parts by weight of neopentyl glycol, dissolving by heating and stirring for 4 hours at 50 ° C, cooling to room temperature, and transparent at room temperature A liquid curing agent liquid was obtained.

Example 14
Add 100 parts by weight of the curing agent Rikacid MH (manufactured by Shin Nippon Rika Co., Ltd .; the main component is 4-methylhexahydrophthalic anhydride) and add 1 part by weight of the curing accelerator tetrabutylphosphonium palmitate at 60 ° C. After stirring and dissolving for 30 minutes, cooling to 50 ° C, adding 3.2 parts by weight of neopentyl glycol, dissolving by heating and stirring for 4 hours at 50 ° C, cooling to room temperature, and transparent at room temperature A liquid curing agent liquid was obtained.

Example 15
To 100 parts by weight of a 40% by weight aqueous solution of tetrabutylphosphonium hydroxide, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid / methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid ( Weight ratio 1/4) Neutralization was performed by adding 42 parts by weight of the mixture, and the resulting reaction mixture was dehydrated by using a vacuum distillation method to obtain a curing accelerator, that is, tetrabutylphosphonium cation and bicyclo [2.2. .1] 80 parts by weight of a salt with a mixed anion residue derived from a mixture of heptane-2,3-dicarboxylic acid / methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid (weight ratio 1/4) Obtained. 1 part by weight of this curing accelerator is added to 100 parts by weight of the curing agent Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; the main component is 4-methylhexahydrophthalic anhydride) and dissolved by heating and stirring at 80 ° C. for 30 minutes. After cooling to 50 ° C., 3.2 parts by weight of neopentyl glycol was further added and dissolved by heating and stirring for 4 hours at 50 ° C., followed by cooling to room temperature to obtain a transparent liquid curing agent solution at room temperature. It was.

Example 16
Neutralizing by adding 38 parts by weight of 1,2,4,5-cyclohexanetetracarboxylic acid to 100 parts by weight of a 40% by weight aqueous solution of tetrabutylphosphonium hydroxide, and dehydrating the resulting reaction mixture by using a vacuum distillation method As a result, 76 parts by weight of a curing accelerator, that is, a salt of a tetrabutylphosphonium cation and an anion residue of 1,2,4,5-cyclohexanetetracarboxylic acid was obtained. 1 part by weight of this curing accelerator is added to 100 parts by weight of the curing agent Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; the main component is 4-methylhexahydrophthalic anhydride) and dissolved by heating and stirring at 80 ° C. for 30 minutes. After cooling to 50 ° C., 3.2 parts by weight of neopentyl glycol was further added and dissolved by heating and stirring for 4 hours at 50 ° C., followed by cooling to room temperature to obtain a transparent liquid curing agent solution at room temperature. It was.

Example 17
14 parts by weight of methanesulfonic acid (a reagent manufactured by Kanto Chemical Co., Inc.) was added to 100 parts by weight of a 40% by weight aqueous solution of tetra n-butylphosphonium hydroxide for neutralization. After neutralization, the resulting reaction mixture was dehydrated using a vacuum distillation method to obtain 51 parts by weight of a curing accelerator, that is, a salt of a tetra n-butylphosphonium cation and an anion of methanesulfonic acid. 1.3 parts by weight of this curing accelerator is added to 100 parts by weight of the curing agent Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; the main component is 4-methylhexahydrophthalic anhydride), and heated and stirred at 60 ° C. for 30 minutes. After dissolution, the mixture is cooled to 50 ° C., 3.2 parts by weight of neopentyl glycol is further added, and the mixture is dissolved by heating and stirring for 4 hours at 50 ° C., and then cooled to room temperature. Got.

Example 18
To 100 parts by weight of a 40% by weight aqueous solution of tetra n-butylphosphonium hydroxide, 23 parts by weight of benzenesulfonic acid (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was added for neutralization. After neutralization, the resulting reaction mixture was dehydrated using a vacuum distillation method to obtain 61 parts by weight of a curing accelerator, that is, a salt of a tetra n-butylphosphonium cation and an anion of benzenesulfonic acid. 1.3 parts by weight of this curing accelerator is added to 100 parts by weight of the curing agent Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; the main component is 4-methylhexahydrophthalic anhydride), and heated and stirred at 60 ° C. for 30 minutes. After dissolution, the mixture is cooled to 50 ° C., 3.2 parts by weight of neopentyl glycol is further added, and the mixture is dissolved by heating and stirring for 4 hours at 50 ° C., and then cooled to room temperature. Got.

Example 19
25 parts by weight of p-toluenesulfonic acid monohydrate (reagent manufactured by Kanto Chemical Co., Inc.) was added to 100 parts by weight of a 40% by weight aqueous solution of tetra n-butylphosphonium hydroxide for neutralization. After neutralization, the resulting reaction mixture was dehydrated using a vacuum distillation method to obtain 57 parts by weight of a curing accelerator, that is, a salt of a tetra n-butylphosphonium cation and an anion of p-toluenesulfonic acid. . Add 1.3 parts by weight of this curing accelerator to 100 parts by weight of Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; the main component is 4-methylhexahydrophthalic anhydride) and stir at 60 ° C. for 30 minutes. After dissolution, the mixture is cooled to 50 ° C., 3.2 parts by weight of neopentyl glycol is further added, and the mixture is dissolved by heating and stirring for 4 hours at 50 ° C., and then cooled to room temperature. Got.

Example 20
To 100 parts by weight of a 40% by weight aqueous solution of tetra n-butylphosphonium hydroxide, 28 parts by weight of 4-chlorobenzenesulfonic acid / n hydrate (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was added for neutralization. After neutralization, the obtained reaction mixture was dehydrated using a vacuum distillation method to obtain 60 parts by weight of a curing accelerator, that is, a salt of tetra n-butylphosphonium cation and 4-chlorobenzenesulfonic acid anion. . Add 1.3 parts by weight of this curing accelerator to 100 parts by weight of Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; the main component is 4-methylhexahydrophthalic anhydride) and stir at 60 ° C. for 30 minutes. After dissolution, the mixture is cooled to 50 ° C., 3.2 parts by weight of neopentyl glycol is further added, and the mixture is dissolved by heating and stirring for 4 hours at 50 ° C., and then cooled to room temperature. Got.

Example 21
120 parts by weight of methanol was added to 100 parts by weight of a 40% by weight aqueous solution of tetra-n-butylphosphonium hydroxide and neutralized by adding 52 parts by weight of n-dodecylbenzenesulfonic acid (purity 90%, manufactured by Kanto Chemical Co., Inc.). . After neutralization, the obtained reaction mixture was subjected to removal of methanol water using a vacuum distillation method to obtain a curing accelerator, that is, a salt of tetra n-butylphosphonium cation and n-dodecylbenzenesulfonic acid anion 85 wt. Got a part. 1.3 parts by weight of this curing accelerator is added to 100 parts by weight of the curing agent Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; the main component is 4-methylhexahydrophthalic anhydride), and heated and stirred at 60 ° C. for 30 minutes. After dissolution, the mixture is cooled to 50 ° C., 3.2 parts by weight of neopentyl glycol is further added, and the mixture is dissolved by heating and stirring for 4 hours at 50 ° C., and then cooled to room temperature. Got.

Comparative Example 1
The curing agent Rikacid MH-700 (manufactured by Shin Nippon Rika Co., Ltd .; 4-methylhexahydrophthalic anhydride: hexahydrophthalic anhydride = 70: 30) was added to 100 parts by weight of the curing accelerator 2-ethyl-4-methyl. Add 1 part by weight of imidazole, dissolve by heating and stirring at 60 ° C. for 30 minutes, cool to 50 ° C., dissolve by heating and stirring for 4 hours at 50 ° C., cool to room temperature, A curing agent solution was obtained.

Comparative Example 2
To 100 parts by weight of the curing agent Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; the main component is 4-methylhexahydrophthalic anhydride), 1 part by weight of the curing accelerator 2-ethyl-4-methylimidazole is added, and 60 After dissolving by heating and stirring at 30 ° C. for 30 minutes, the solution was cooled to 50 ° C., dissolved by heating and stirring for 4 hours at 50 ° C., and then cooled to room temperature to obtain a transparent liquid curing agent solution at room temperature.

Comparative Example 3
Add 100 parts by weight of the curing agent Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; the main component is 4-methylhexahydrophthalic anhydride) and add 1 part by weight of the curing accelerator tetrabutylphosphonium decanoate at 60 ° C. After dissolving by heating and stirring for 30 minutes, the mixture was cooled to room temperature to obtain a transparent liquid curing agent liquid at room temperature.

Comparative Example 4
To 100 parts by weight of a 40% by weight aqueous solution of tetrabutylphosphonium hydroxide, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid / methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid ( Weight ratio 1/4) Neutralization was performed by adding 42 parts by weight of the mixture, and the resulting reaction mixture was dehydrated by using a vacuum distillation method to obtain a curing accelerator, that is, tetrabutylphosphonium cation and bicyclo [2.2. .1] 80 parts by weight of a salt with a mixed anion residue derived from a mixture of heptane-2,3-dicarboxylic acid / methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid (weight ratio 1/4) Obtained. 1 part by weight of this curing accelerator is added to 100 parts by weight of the curing agent Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; the main component is 4-methylhexahydrophthalic anhydride) and dissolved by heating and stirring at 80 ° C. for 30 minutes. After cooling to room temperature, a transparent liquid curing agent liquid was obtained at room temperature.

Comparative Example 5
120 parts by weight of methanol was added to 100 parts by weight of a 40% by weight aqueous solution of tetra-n-butylphosphonium hydroxide and neutralized by adding 52 parts by weight of n-dodecylbenzenesulfonic acid (purity 90%, manufactured by Kanto Chemical Co., Inc.). . After neutralization, the obtained reaction mixture was subjected to removal of methanol water using a vacuum distillation method to obtain a curing accelerator, that is, a salt of tetra n-butylphosphonium cation and n-dodecylbenzenesulfonic acid anion 85 wt. Got a part. 1.3 parts by weight of this curing accelerator is added to 100 parts by weight of the curing agent Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; the main component is 4-methylhexahydrophthalic anhydride), and heated and stirred at 60 ° C. for 30 minutes. After dissolution, the mixture was cooled to room temperature to obtain a transparent liquid curing agent liquid at room temperature.

Comparative Example 6
120 parts by weight of methanol was added to 100 parts by weight of a 40% by weight aqueous solution of tetra-n-butylphosphonium hydroxide and neutralized by adding 52 parts by weight of n-dodecylbenzenesulfonic acid (purity 90%, manufactured by Kanto Chemical Co., Inc.). . After neutralization, the obtained reaction mixture was subjected to removal of methanol water using a vacuum distillation method to obtain a curing accelerator, that is, a salt of tetra n-butylphosphonium cation and n-dodecylbenzenesulfonic acid anion 85 wt. Got a part. 1.3 parts by weight of this curing accelerator is added to 100 parts by weight of the curing agent Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd .; the main component is 4-methylhexahydrophthalic anhydride), and heated and stirred at 60 ° C. for 30 minutes. After dissolution, the mixture was cooled to 50 ° C., 1.9 parts by weight of ethylene glycol was further added, dissolved by heating and stirring for 4 hours at 50 ° C., then cooled to room temperature, and a transparent liquid curing agent solution was added at room temperature. Obtained.

<Evaluation test>
The following evaluations 1 to 3 were performed using the curing agent liquids obtained in Examples and Comparative Examples. The results are shown in Tables 1-3.

Evaluation 1
The obtained hardener solution was filled in 300 g in a 500 ml steel can and sealed with nitrogen gas. After the can was stored for 6 months in an environment of 30 ° C., the appearance of the can was visually observed. If the can was swollen, it was judged as “failed”, and if it was not swollen, it was judged as “good”.

Evaluation 2
30 g of the obtained curing agent solution was filled in a 50 ml glass container, and nitrogen gas was sealed in a sealed manner. After storing this container in an environment of 23 ° C. for one month, the curing agent solution is visually observed. If the precipitate is generated and becomes cloudy, it is rejected “x”, and if it remains transparent, it is “accepted”. ○ ”.

Evaluation 3
100 parts by weight of Daicel Chemical Industries, Ltd., trade name “Celoxide 2021P” [3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate], with respect to 125 parts by weight of the obtained curing agent liquid, Using “Shintaro Awatori” manufactured by Shinky Corporation, the mixture was uniformly mixed (2000 rpm, 5 minutes) to obtain an optical semiconductor sealing resin composition (curable resin composition). The obtained resin composition for encapsulating an optical semiconductor was cast into a lead frame with an optical semiconductor element (InGaN) and cured by heating to produce an optical semiconductor device. Curing was performed by the procedure of heating at 110 ° C. for 2 hours, once removing from the mold, and post-curing at 150 ° C. for about 3 hours. The optical semiconductor device was observed with a microscope, and the case where the ratio of bubbles remaining in the sealed portion of the optical semiconductor device exceeded 20% was judged as “Fail”, and the case where it was 20% or less was judged as “◯”.

  In addition, as a comprehensive evaluation, all evaluations of evaluations 1 to 3 are “pass” if one evaluation is “good”, “fail” if there is even one “×”, and “pass / fail judgment” column in each table Filled in.

Claims (6)

An acid anhydride-based curing agent (A), a curing accelerator (B), and at least one diol (C) selected from neopentyl glycol and 1,3-butanediol , The hardening | curing agent composition for epoxy resins whose ratio to the hardening | curing agent composition for epoxy resins of the total amount of a hardening | curing agent (A), the said hardening accelerator (B), and the said diol (C) is 50 weight% or more .   The hardening | curing agent composition for epoxy resins of Claim 1 which contains a diol (C) in the ratio of 0.5-15 weight part with respect to 100 weight part of acid anhydride type hardening | curing agents (A).   A curable resin composition comprising, as essential components, an epoxy compound (D) having two or more epoxy groups in a molecule and the epoxy resin curing agent composition according to claim 1 or 2.   The curable resin composition according to claim 3, wherein at least one alicyclic epoxy compound is used as the epoxy compound (D).   A cured product obtained by curing the curable resin composition according to claim 3.   An optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable resin composition according to claim 5.