JP5700759B2 - Curable resin composition and cured product thereof - Google Patents

Description

  The present invention relates to a curable resin composition having a specific structure, and relates to the curable resin composition suitable for electrical and electronic material applications, particularly for optical semiconductor applications, and a cured product.

Epoxy resins are generally cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., adhesives, paints, laminates, moldings It is used in a wide range of fields such as materials, casting materials and resists.
In the field of optoelectronics, especially in recent years, with advanced information technology, in order to smoothly transmit and process huge amounts of information, technology that utilizes optical signals has been developed instead of conventional signal transmission using electrical wiring. In the meantime, in the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, development of resins having excellent transparency is desired.

In particular, epoxy resin anhydrides are often used in fields requiring optical properties, such as LED products. Conventionally, as an epoxy resin used as a sealing material for an optical semiconductor element such as an LED product, a glycidyl ether type typified by a bisphenol A type epoxy resin excellent in balance of heat resistance, transparency and mechanical properties. The epoxy resin composition has been widely used.
However, as a result of the shortening of the emission wavelength of LED products (mainly blue emission of 480 nm or less), the sealing material is colored on the LED chip under the influence of short wavelength light, and finally as an LED product It has been pointed out that the illuminance will decrease.
Therefore, alicyclic epoxy resins represented by 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate are more transparent than glycidyl ether type epoxy resin compositions having an aromatic ring. Therefore, it has been actively studied as an LED sealing material. (Patent Documents 1 and 2)

  In recent years, LED products have become increasingly brighter for lighting, TV backlights, and the like, and when LEDs are turned on, they generate a lot of heat. Therefore, a resin composition using the alicyclic epoxy resin is used. Even an object causes coloring on the LED chip, and as a result, the illuminance is lowered as an LED product, leaving a problem in terms of durability.

JP-A-9-213997 Japanese Patent No. 3618238 JP 2008-285591 A International Publication No. 2005/100445

In general alicyclic epoxy resins, the hardness and brittleness of the cured product are regarded as problems. This also applies to the previous LED sealing material, and in particular, the LED sealing material requires the extraction of light, so that a larger amount of inorganic filler or the like can be mixed compared to a general sealing material. The mechanical strength cannot be reinforced. For this reason, a crack etc. are easy to arise and the high toughness is calculated | required by the sealing material. For this improvement, addition of alcohol such as trimethylolpropane has been studied (Patent Document 3). For example, when the alcohol is cured with an acid anhydride or the like, the alcohol and acid anhydride are added from room temperature. Since the reaction of the product proceeds, the storage stability has a significant demerit, or the stability of the cured product becomes very poor.
Moreover, in LED, the resin which introduce | transduced the siloxane frame | skeleton (specifically frame | skeleton which has Si-O bond) represented by a silicone resin, a silicone modified epoxy resin, etc. from the durability problem of the said epoxy resin. The use as a sealing material has been studied. (Patent Document 4)
In general, it is known that a resin incorporating a siloxane skeleton is more stable to heat and light than an epoxy resin. Therefore, when applied to the sealing material of LED products, it was said that it was superior to epoxy resin in terms of coloring on the LED chip. However, resins incorporating the siloxane skeleton are inferior in gas permeability resistance compared to epoxy resins. Therefore, when a silicone resin or a silicone-modified epoxy resin is used as the LED sealing material, the color on the LED chip does not matter, but the silver plated on the metal lead frame, which is a component in the LED package. There is a problem that the component (which is silver-plated to increase the reflectance) is discolored or blackened, and ultimately the performance as an LED product is lowered.
There is a demand in the market for an epoxy resin composition having a structure that has no problem with the gas permeation resistance and has a higher durability against light and heat as an optical material than the conventional alicyclic epoxy resin. It has been.

As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention
(1)
An epoxy resin having an epoxycyclohexane structure, a curable resin composition containing an alcohol having a tricyclodecane structure,
(2)
The curable resin composition according to item (1), wherein the epoxy resin having an epoxycyclohexane structure is an alicyclic epoxy resin,
(3)
The curable resin composition as described in (1) above, wherein the epoxy resin having an epoxycyclohexane structure is an epoxy resin having an epoxycyclohexane structure and a siloxane structure,
(4)
A curable resin composition comprising the curable resin composition according to any one of (1) to (3) above, a curing agent and / or a curing accelerator,
(5)
The curable resin composition according to item (4), wherein the curing agent is an acid anhydride,
(6)
A cured product obtained by curing the curable resin composition according to any one of (4) and (5),
(7)
An optical semiconductor device comprising the curable resin composition according to any one of (4) and (5),
About.

  Since the curable resin composition of the present invention is also excellent in resistance to coloring against light and heat, it is extremely useful as an adhesive material and sealing material for optical materials, particularly optical semiconductors (LED products and the like).

Hereinafter, it describes about the curable resin composition of this invention.
The epoxy resin in the present invention uses an epoxy resin having an epoxycyclohexane structure.
In the present invention, the epoxy resin having an epoxycyclohexane structure includes an alicyclic epoxy resin and an epoxy resin having an epoxycyclohexane structure and a siloxane structure.

The alicyclic epoxy resin is not particularly limited as long as it is a compound having two or more epoxy cyclohexane structures and has an alicyclic structure in the structure.
Specifically, esterification reaction between cyclohexene carboxylic acid and alcohols or esterification reaction between cyclohexene methanol and carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), etc.) And a compound obtained by oxidizing a compound that can be produced by a transesterification reaction of a cyclohexenecarboxylic acid ester (a method described in JP-A-2006-052187).
The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentane. Diol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol, etc. Diols, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, triols such as 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol, ditrimethylolpropane, etc. And the like. Examples of carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.

  Furthermore, the acetal compound by the acetal reaction of a cyclohexene aldehyde derivative and alcohol is mentioned. As a reaction method, a general acetalization reaction may be applied. For example, a method in which a reaction is carried out while azeotropic dehydration using a solvent such as toluene or xylene (US Pat. No. 2,945,008), polyvalent to concentrated hydrochloric acid A method in which an alcohol is dissolved and a reaction is carried out while gradually adding aldehydes (Japanese Patent Laid-Open No. 48-96590), a method using water as a reaction medium (US Pat. No. 3,092,640), an organic solvent as a reaction medium And a method using a solid acid catalyst (Japanese Patent Laid-Open No. 2007-230992) and the like are disclosed. A cyclic acetal structure is preferable from the viewpoint of structural stability.

  Moreover, the thing etc. which oxidized cycloaliphatic polyolefin such as vinylcyclohexene, limonene, dicyclopentadiene, tricyclopentadiene, methyldicyclopentadiene, bicyclohexene, octadiene, etc. are mentioned.

  Specific examples of these epoxy resins include ERL-4221, ERL-4299 (all trade names, all manufactured by Dow Chemical), Eporide GT401, EHPE3150, EHPE3150CE (all trade names, all manufactured by Daicel Chemical Industries) and dicyclo Examples include, but are not limited to, pentadiene diepoxide (reference: review epoxy resin basic edition I p76-85). These may be used alone or in combination of two or more.

The epoxy resin having an epoxycyclohexane structure and a siloxane structure is not particularly limited as long as it is an organopolysiloxane having an epoxycyclohexane structure, but in the present invention, a sol-gel reaction using an alkoxysilane having an epoxycyclohexyl group as a raw material. The epoxy resin obtained by is mentioned.
Specifically, JP-A No. 2004-256609, JP-A No. 2004-346144, WO 2004/072150, JP-A 2006-8747, WO 2006/003990, JP-A 2006-104248. Three-dimensional networks described in Japanese Patent Laid-Open No. 2007/135909, Japanese Patent Laid-Open No. 2004-10849, Japanese Patent Laid-Open No. 2004-359933, International Patent Publication No. 2005/100445, Japanese Patent Laid-Open No. 2008-174640, and the like. Silsesquioxane type organopolysiloxane having the following structure.
The structure of the organopolysiloxane is not particularly limited. However, since a siloxane compound having a simple three-dimensional network structure is too hard, a structure that relaxes the hardness is desired.
In the present invention, a block structure having a silicone segment and the aforementioned silsesquioxane structure obtained by a sol-gel reaction in one molecule is particularly preferable. Examples of a method for producing such a compound include a production method and a structure as described in WO2010 / 026714.

  Examples of the alcohol having a tricyclodecane structure include tricyclodecane dimethanol, methyltricyclodecane dimethanol, and pentacyclopentadecane dimethanol. Examples of such a compound include a technique in which a polymer of cyclopentadiene or methylcyclopentadiene, for example, an olefin portion such as dicyclopentadiene, methyldicyclopentadiene, tricyclopentadiene, etc. is hydroformylated and reduced to an alcohol.

The curable resin composition of the present invention can be obtained by uniformly mixing the above-described epoxy resin having an epoxycyclohexane structure and an alcohol having a tricyclodecane structure at a predetermined ratio.
As a method for uniformly mixing, for example, a method in which these are uniformly melt-mixed while stirring within a range of 0 to 100 ° C., or after dissolving and homogenizing with an organic solvent, the solvent is distilled off, and the present invention is performed. It is also possible to use a technique of obtaining a curable resin composition.
As these compounding amounts, the alcohol having a tricyclodecane structure is 1.5 to 40% by weight, preferably 2 to 30% by weight, particularly preferably 2.25 to 25% by weight, based on the epoxy resin having an epoxycyclohexane structure. is there. An excessive amount of alcohol may cause a problem of poor curing, and is not preferable.

  The curable resin composition of the present invention not only improves toughness, transparency and gas permeation resistance, but in particular, when a thermosetting resin composition using an acid anhydride as a curing agent is used, volatilization during curing is prevented. There is an effect to suppress, release of compounds to the environment is also suppressed, and contributes to the safety of workers. This is particularly noticeable in applications such as surface mount LEDs that use only a small amount of resin, thin film coating materials, films, etc., and acid anhydrides volatilize, causing the balance between the curing agent and the epoxy to break, resulting in poor curing. It is useful for solving problems such as wake up and failure to obtain a proper cured product, and intense coloring.

  In the curable resin composition of the present invention, the epoxy resin having an epoxycyclohexane structure of the present invention can be used alone or in combination with other epoxy resins. When used in combination, the proportion of the epoxy resin in the total epoxy resin is preferably 70% by weight or more, particularly preferably 80% by weight or more.

  Other epoxy resins that can be used in the curable resin composition of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins, and the like. . Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetaldehyde Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols Solid or liquid epoxy resins such as chemical compounds, alicyclic epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins and the like are not limited thereto.

The curable resin composition of the present invention can contain a curing agent and / or a curing catalyst.
Hereinafter, thermal curing with a curing agent (curable resin composition A) and cationic curing with an acidic curing catalyst (curable resin composition B) will be described.

Thermal curing with a curing agent (curable resin composition A)
Examples of the curing agent contained in the curable resin composition A of the present invention include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, Bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid- 3, 4 Anhydride, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1 '-Biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol Alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, -Hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4 ' -Condensation products with bis (chloromethyl) benzene, 1,4'-bis (methoxymethyl) benzene and their modified products, halogenated bisphenols such as tetrabromobisphenol A, imidazole, trifluoroborane-amine complexes , Guanidine derivatives, condensates of terpenes and phenols, and the like, but are not limited thereto. These may be used alone or in combination of two or more.

  In the present invention, compounds having an acid anhydride structure and / or a carboxylic acid structure represented by the above-mentioned acid anhydrides and carboxylic acid resins are particularly preferable.

  Examples of the compound having an acid anhydride structure include methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2 , 1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride In particular, methylhexahydrophthalic anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride are particularly preferable.

As the compound having a carboxylic acid structure (hereinafter referred to as polycarboxylic acid), a bi- to tetra-functional polycarboxylic acid is particularly preferable, and a 2- to 4-functional polyhydric alcohol is preferably added to an acid anhydride. The polycarboxylic acid obtained by this is preferable.
The 2- to 4-functional polyhydric alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol. 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecanedi Diols such as methanol and norbornenediol; Kind, and the like.
As particularly preferred bifunctional to tetrafunctional polyhydric alcohols, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornene These are branched or cyclic alcohols such as diols.

  Examples of acid anhydrides for producing polycarboxylic acids include methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [ 2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3, 4-anhydrides and the like are preferred.

  Although there is no particular designation as a condition for the addition reaction, as one of the specific reaction conditions, an acid anhydride and a polyhydric alcohol are reacted while heating at 40 to 150 ° C. under non-catalytic and solvent-free conditions, It is a technique of taking out as it is after completion of the reaction. However, it is not limited to this reaction condition.

  The acid anhydride and polycarboxylic acid can be used alone or in combination of two or more. In that case, the weight ratio of the acid anhydride to the polycarboxylic acid is 90/10 to 20/80, particularly preferably 80/20 to 30/70.

  In the curable resin composition of the present invention, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents in terms of functional group equivalent to 1 equivalent of epoxy group of the epoxy resin. More preferably, it is 0.7-1.1 equivalent, Most preferably, it is 0.8-1.0 equivalent. When less than 0.5 equivalent or more than 1.5 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete, and good cured properties may not be obtained.

  In the curable resin composition A of the present invention, a curing accelerator (curing catalyst) may be used in combination with the curing agent. Specific examples of the curing accelerator that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole. 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 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-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole imidazoles, and imidazoles and phthalic acid , Salts with polyvalent carboxylic acids such as isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4) 0.0) diaza compounds such as undecene-7 and their Salts such as traphenylborate and phenol novolac, salts with the above polyvalent carboxylic acids or phosphinic acids, ammonium salts such as tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, triphenylphosphine, tri (toluyl) ) Phosphines such as phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, phosphonium compounds, phenols such as 2,4,6-trisaminomethylphenol, metal compounds such as amine adducts, tin octylate, and the like, and Examples thereof include a microcapsule type curing accelerator obtained by making these curing accelerators into microcapsules. Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, or working conditions. A hardening accelerator is normally used in 0.001-15 weight part with respect to 100 weight part of epoxy resins.

  The curable resin composition A of the present invention may contain a phosphorus-containing compound as a flame retardant imparting component. The phosphorus-containing compound may be a reactive type or an additive type. Specific 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 ( Phosphoric acid esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes A phosphorus-containing product obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned, and phosphoric esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The phosphorus-containing compound content is preferably phosphorus-containing compound / total 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.

  Furthermore, binder resin can also be mix | blended with the curable resin composition A of this invention as needed. Examples of the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is not limited to these. The blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts per 100 parts by weight of the resin component. Part by weight is used as needed.

  An inorganic filler can be added to the curable resin composition A of the present invention as necessary. Examples of inorganic fillers include 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. However, the present invention is not limited to these. These may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the curable resin composition of the present invention. Furthermore, the curable resin composition of the present invention includes a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate and calcium stearate, various compounding agents such as pigments, zinc carboxylate (2-ethyl Zinc compounds such as zinc hexanoate, zinc stearate, zinc behenate, zinc myristate) and zinc phosphate esters (such as zinc octyl phosphate and zinc stearyl phosphate) and various thermosetting resins can be added.

  When the curable resin composition A of the present invention is used for an optical material, particularly an optical semiconductor encapsulant, the particle size of the inorganic filler used is transparent by using a nano-order level filler. It is possible to supplement the mechanical strength without impairing the properties. As a standard for the nano-order level, it is preferable from the viewpoint of transparency to use a filler having an average particle size of 500 nm or less, particularly an average particle size of 200 nm or less.

When using the curable resin composition A of this invention for an optical material, especially an optical semiconductor sealing agent, a fluorescent substance can be added as needed. For example, the phosphor has a function of forming white light by absorbing part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in the curable resin composition, the optical semiconductor is sealed. There is no restriction | limiting in particular as fluorescent substance, A conventionally well-known fluorescent substance can be used, For example, rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated. More specifically, phosphors such as a YAG phosphor, a TAG phosphor, an orthosilicate phosphor, a thiogallate phosphor, and a sulfide phosphor can be mentioned, and YAlO ₃ : Ce, Y ₃ A ₁₅ O ₁₂ : Ce, Y _{4 Al 2 O 9: Ce,} Y 2 O 2 S: Eu, Sr 5 (PO 4) 3 Cl: Eu, (SrEu) O · A l2 O 3 and the like. As the particle size of the phosphor, those having a particle size known in this field are used, and the average particle size is preferably 1 to 250 μm, particularly preferably 2 to 50 μm. When using these fluorescent substance, the addition amount is 1-80 weight part with respect to 100 weight part with respect to the resin component, Preferably, 5-60 weight part is preferable.

  When the curable resin composition A of the present invention is used for an optical material, particularly an optical semiconductor encapsulant, for the purpose of preventing sedimentation during curing of various phosphors, silica fine powder (also called Aerosil or Aerosol) is used. An agent for imparting thixotropic properties can be added. Examples of such silica fine powder include Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil Aerosil R805, RY200, RX200 (made by Nippon Aerosil Co., Ltd.), etc. are mentioned.

When the curable resin composition A of the present invention is used for an optical material, particularly an optical semiconductor encapsulant, for the purpose of preventing coloring, an amine compound as a light stabilizer, or a phosphorus compound or phenol as an antioxidant. Compounds can be included.
Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-6- Tetramethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed ester, decanedioic acid bis (2,2, 6,6-tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6, -tetramethyl -4-piperidyl methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy- 2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis ( 1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] buty Malonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, N, N ′, N ", N"'-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl)- 4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexa Polycondensate of methylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-triazine-2, 4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], dimethyl succinate and Polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7-oxa-3 , 20-diazadispiro [5 · 1 · 11 · 2] heneicosan-21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl) -dodecyl ester / tetradecyl ester, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3 , 20-diazadispiro [5,1,11,2] heneicosan-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11,2]- Heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 2 , 2,6,6-tetramethyl-4-piperidinol higher fatty acid ester, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl), etc. Hindered amine series, benzophenone series compounds such as octabenzone, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3- Tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimido-methyl) -5-methylphenyl] Benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole, methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol reaction product, 2- (2H-benzotriazol-2-yl)- Benzotriazole compounds such as 6-dodecyl-4-methylphenol, 2,4- Benzoate type such as tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [ (Hexyl) oxy] triazine compounds such as phenol and the like can be mentioned, and hindered amine compounds are particularly preferable.

The following commercially available products can be used as the amine compound that is the light stabilizer.
The commercially available amine compound is not particularly limited, and for example, TINUVIN 765, TINUVIN 770DF, TINUVIN 144, TINUVIN 123, TINUVIN 622LD, TINUVIN 152, CHIMASSORB 944, and ADEKA, LA-52, LA-57, LA-, manufactured by Ciba Specialty Chemicals. 62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like.

  The phosphorus compound is not particularly limited, and for example, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Dicyclohexylpentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) Hosuf Ite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butyl) Phenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-ethylidenebis (4-methyl-6-tert-butyl) Phenyl) (2-tert-butyl-4-methylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl)- , 4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3 '-Biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'- Biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite Bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di -N-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl Examples include phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc. It is.

  A commercial item can also be used for the said phosphorus compound. It does not specifically limit as a phosphorus compound marketed, For example, as a product made from ADEKA, Adeastab PEP-4C, Adeastab PEP-8, Adeastab PEP-24G, Adeastab PEP-36, Adeastab HP-10, Adeastab 2112, Adeastab 260 ADEASTAB 522A, ADEASTAB 1178, ADEASTAB 1500, ADEASTAB C, ADEASTAB 135A, ADEASTAB 3010, and ADEASTAB TPP.

  The phenol compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol and n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,4-di-tert-butyl-6-methylphenol, 1,6-hexanediol-bis -[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythrine Lithyl-tetrakis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis- [2- [3- (3-tert-butyl-4-hydroxy-5] -Methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol-bis [3- (3-t-butyl- 5-methyl-4-hydroxyphenyl) propionate], 2,2′-butylidenebis (4,6-di-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 2, 2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butyl) Phenol), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenol acrylate, 2- [1- (2-hydroxy-3,5-di-) tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6) -Tert-butylphenol), 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,4-di-tert-pentylphenol, 4,4'-thiobis (3-methyl-6) -Tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) Bis- [3,3-bis- (4′-hydroxy-3′-tert-butylphenyl) -butanoic acid] -glycol ester, 2,4-di-tert-butylphenol, 2,4-di- tert-pentylphenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, bis- [3,3-bis- (4′-hydroxy-3′-tert-butylphenyl) -butanoic acid] -glycol ester and the like.

  A commercial item can also be used for the said phenolic compound. There are no particular limitations on the commercially available phenolic compounds. For example, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114 IRGANOX 1098, Adekas 1520L AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330, SUMITOMO CHEMICAL CO., LTD., Sumilizer GA-80, Sumizer MDP-S, Sumili er BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, and the like.

  In addition, commercially available additives can be used as an anti-coloring agent for the resin. For example, TINUVIN 328, TINUVIN 234, TINUVIN 326, TINUVIN 120, TINUVIN 477, TINUVIN 479, CHIMASSORB 2020FDL, CHIMASSORB 119FL and the like are manufactured by Ciba Specialty Chemicals.

  It is preferable to contain at least one of the above phosphorus compounds, amine compounds, and phenol compounds, and the amount of the compound is not particularly limited, but is 0.005 to 5 with respect to the curable resin composition. The range is 0.0% by weight.

  The curable resin composition A of the present invention is obtained by uniformly mixing each component. The curable resin composition A of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the curable resin composition of the present invention, a curing agent and, if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent are uniformly used using an extruder, a kneader, a roll, or the like as necessary. Thoroughly mix to obtain a curable resin composition, melt the curable resin composition after molding using a casting or transfer molding machine, and further heat at 80 to 200 ° C. for 2 to 10 hours Thus, the cured product of the present invention can be obtained.

  Further, the curable resin composition A of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone to obtain a curable resin composition varnish, and glass fiber. The curable resin composition A of the present invention is cured by hot press molding a prepreg obtained by impregnating a base material such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating. It can be a thing. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent. Moreover, the epoxy resin hardened | cured material which contains a carbon fiber by a RTM system with a liquid composition can also be obtained.

  Moreover, the curable resin composition A of this invention can be used also as a modifier of a film type composition. Specifically, it can be used to improve the flexibility characteristics in the B stage. In such a film-type resin composition, the curable resin composition A of the present invention is applied onto a release film as the curable resin composition varnish, the solvent is removed under heating, and then B-stage is performed. Thus, it is obtained as a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

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

  When the curable resin composition A of the present invention is used as a sealing material or die bond material for an optical semiconductor such as a high-intensity white LED, a curing agent or coupling containing the epoxy resin of the present invention, a polyvalent carboxylic acid, or the like. An epoxy resin composition is prepared by thoroughly mixing additives such as a material, an antioxidant, and a light stabilizer, and used as a sealing material, or both a die bond material and a sealing material. 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. A semiconductor chip such as 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 to play a role of a lens function. The curable resin composition A of the present invention can be used as this sealing material or die bond material. For the convenience of the process, the curable resin composition A of the present invention is preferably used for both the die bond material and the sealing material.

  As a method of adhering the semiconductor chip to the substrate using the curable resin composition A of the present invention, the curable resin composition A of the present invention is applied by dispenser, potting, or screen printing, and then the semiconductor chip is placed thereon. Then, the semiconductor chip can be bonded by heat curing. For the heating, methods such as hot air circulation, infrared rays and high frequency can be used. The heating condition is preferably about 80 to 230 ° C. and about 1 minute to 24 hours, for example. 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 condition is preferably 80 to 230 ° C. and 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.

Curable resin composition B (cationic curing with acidic curing catalyst)
The curable resin composition B of the present invention that is cured using an acidic curing catalyst contains a photopolymerization initiator or a thermal polymerization initiator as an acidic curing catalyst. Furthermore, you may contain various well-known compounds, materials, such as a diluent, a polymerizable monomer, a polymerizable oligomer, a polymerization start adjuvant, a photosensitizer. Moreover, you may contain various well-known additives, such as an inorganic filler, a color pigment, a ultraviolet absorber, antioxidant, a stabilizer, as needed.

As the acidic curing catalyst, a cationic polymerization initiator is preferable, and a photocationic polymerization initiator is particularly preferable. Examples of the cationic polymerization initiator include those having an onium salt such as an iodonium salt, a sulfonium salt, and a diazonium salt, and these can be used alone or in combination of two or more.
Examples of the active energy ray cationic polymerization initiator include metal fluoroboron complex and boron trifluoride complex (US Pat. No. 3,379,653), bis (perfluoroalkylsulfonyl) methane metal salt (US Pat. No. 3,586,616). ), Aryldiazonium compounds (US Pat. No. 3,708,296), aromatic onium salts of group VIa elements (US Pat. No. 4,058,400), aromatic onium salts of group Va elements (US Pat. No. 4,0690,055) Dicarbonyl chelates of group IIIa-Va elements (US Pat. No. 4068091), thiopyrylium salts (US Pat. No. 4,139,655), group VIb elements in the form of MF6-anions (US Pat. No. 4,161,478) M is selected from phosphorus, antimony and arsenic). Lille sulfonium complex salts (US Pat. No. 4,231,951), aromatic iodonium complex salts and aromatic sulfonium complex salts (US Pat. No. 4,256,828), and bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluoro Metal salt (Journal of Polymer Science, Polymer Chemistry, Vol. 2, paragraph 1789 (1984)). In addition, mixed ligand metal salts of iron compounds and silanol-aluminum complexes can also be used.
As specific examples, “Adekaoptomer SP150”, “Adekaoptomer SP170” (all manufactured by Asahi Denka Kogyo Co., Ltd.), “UVE-1014” (manufactured by General Electronics Co., Ltd.), “CD-1012” (Sartomer Company) Product), “RP-2074” (manufactured by Rhodia), and the like.
The amount of the cationic polymerization initiator used is preferably 0.01 to 50 parts by weight and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin component.

  Furthermore, it is possible to simultaneously use one or two or more of these photocationic polymerization initiators, known polymerization initiation assistants and photosensitizers. Examples of the polymerization initiation aid include, for example, benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinolpropan-1-one, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1- Chloroanthraquinone, 2-amylanthraquinone, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone di Chiruketaru, benzophenone, 4-methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis-diethylamino benzophenone, and a photo-radical polymerization initiator such as Michler's ketone. The usage-amount of polymerization start adjuvants, such as radical photopolymerization initiator, is 0.01-30 weight part with respect to 100 weight part of components in which radical photopolymerization is possible, Preferably it is 0.1-10 weight part. .

  Specific examples of the photosensitizer include anthracene, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acridine orange, acridine yellow, phosphine R, benzo Examples include flavin, cetoflavin T, perylene, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, triethylamine and the like. The usage-amount of a photosensitizer is 0.01-30 weight part with respect to 100 weight part of all the epoxy resin components, Preferably it is 0.1-10 weight part.

  Furthermore, various compounding agents such as inorganic fillers, silane coupling materials, mold release agents, pigments, and various thermosetting resins can be added to the curable resin composition B of the present invention as necessary. . Specific examples are as described above.

  The curable resin composition B of the present invention can be obtained by uniformly mixing each component. It is also possible to dissolve in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or γ-butyrolactone and make it uniform, and then use it after removing the solvent by drying. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition B of the present invention and the solvent. The curable resin composition B of the present invention can be cured by irradiating with ultraviolet rays, but the amount of ultraviolet irradiation varies depending on the blending of the curable resin composition, and thus is determined by the respective curing conditions. What is necessary is just the irradiation amount which a curable resin composition hardens | cures, and should just satisfy | fill the hardening conditions with which the adhesive strength of hardened | cured material is favorable. Since it is necessary for light to be transmitted through the details during the curing, the epoxy resin and the curable resin composition B of the present invention are desired to be highly transparent. In addition, these epoxy resin-based photocuring is difficult to be completely cured only by light irradiation, and in applications requiring heat resistance, it is necessary to complete reaction curing by heating after light irradiation.

  When heating is performed after light irradiation, the heating can be performed in a normal curing temperature range of the curable resin composition B. For example, the range of 30 minutes to 7 days at room temperature to 150 ° C. is suitable. Although it changes depending on the blending of the curable resin composition B, the higher the temperature range, the more effective the curing is after light irradiation, and the short heat treatment is effective. Further, the lower the temperature, the longer the heat treatment. By performing such heat after-curing, an effect of aging treatment is obtained.

  Moreover, since the shape of the cured product obtained by curing these curable resin compositions B can be variously selected depending on the application, it is not particularly limited. For example, a film shape, a sheet shape, a bulk shape, or the like can be used. . Although the molding method varies depending on the applicable part and member, for example, molding methods such as casting method, casting method, screen printing method, spin coating method, spray method, transfer method, dispenser method, etc. can be applied, It is not limited to these. As the mold, polishing glass, hard stainless steel polishing plate, polycarbonate plate, polyethylene terephthalate plate, polymethyl methacrylate plate, or the like can be applied. In addition, a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyimide film, or the like can be applied in order to improve releasability from the mold.

  For example, when used for a cationically curable resist, first, the photocationic curable resin composition B of the present invention dissolved in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or γ-butyrolactone is copper-clad. A coating film is formed on a substrate such as a laminated plate, a ceramic substrate, or a glass substrate with a film thickness of 5 to 160 μm by a method such as screen printing or spin coating. The coating film is preliminarily dried at 60 to 110 ° C., and then irradiated with ultraviolet rays (for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a laser beam, etc.) through a negative film having a desired pattern. Then, post-exposure baking is performed at 70 to 120 ° C. Thereafter, the unexposed part is dissolved and removed (developed) with a solvent such as polyethylene glycol monoethyl ether, and if necessary, sufficient by irradiation with ultraviolet rays and / or heating (for example, at 100 to 200 ° C. for 0.5 to 3 hours). Curing is performed to obtain a cured product. In this way, it is also possible to obtain a printed wiring board.

  The cured product obtained by curing the curable resin composition A and the curable resin composition B of the present invention can be used for various applications including optical component materials. 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 LED sealing material such as lamp type or SMD type, 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 polarizing 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 optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Pickup lenses, protective films, sealing materials, adhesives and the like.

  In the optical equipment field, they are still camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor sections. 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 are materials for lenses of optical sensing devices, sealing materials, adhesives, films, and the like. 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 material, ferrule, sealing material, adhesive, etc. around the optical connector. For optical passive components and optical circuit components, they 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 industrial use sensors, display / signs, etc. for illumination / light guides for decorative displays, and for communication infrastructure and home digital equipment connection. As 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 organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.

  As sealing agents, potting for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, dipping, transfer mold sealing, pottings for ICs, LSIs such as COB, COF, TAB, etc., flip chip For example, underfill for IC packaging such as QFP, BGA, and CSP (reinforcing underfill).

  Other uses of the optical material include general uses in which the curable resin composition A and the curable resin composition B are used. For example, adhesives, paints, coating agents, molding materials (sheets, films) , FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.), sealants, cyanate resin compositions for substrates, acrylic ester resins as resist curing agents, other resins, etc. And the like. 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).

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples. In the examples, the epoxy equivalent was measured using an E-type viscometer at JIS K-7236 and the viscosity at 25 ° C. The analytical conditions in gas chromatography (hereinafter referred to as GC) were HP5-MS (0.25 mm ID x 15 m, film thickness 0.25 μm) for the separation column, and the column oven temperature was set to an initial temperature of 100 ° C. The temperature was raised at a rate of 15 ° C. per minute and held at 300 ° C. for 25 minutes. Helium was used as a carrier gas. Furthermore, in the measurement of gel permeation chromatography (hereinafter referred to as GPC), it is as follows. The column is a Shodex SYSTEM-21 column (KF-803L, KF-802.5 (× 2), KF-802), the linking eluent is tetrahydrofuran, and the flow rate is 1 ml / min. The column temperature was 40 ° C., the detection was performed by RI, and the standard curve made by Shodex was used for the calibration curve.

Synthesis example 1
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen, 10 parts of water, 2.0 parts of 12-tungstophosphoric acid, 3.0 parts of sodium tungstate, 3.2 parts of disodium hydrogen phosphate 2.9 parts of trioctylmethylammonium acetate (50% by weight xylene solution manufactured by Lion Akzo, TOMAA-50), 130 parts of toluene, 220 parts of 3-cyclohexenemethyl = 3-cyclohexenecarboxylate, and the solution is brought to 48 ° C. While warming and stirring vigorously, 220 parts of 35 wt% hydrogen peroxide solution was added in 30 minutes, and the mixture was stirred at 48 ° C. for 14 hours.
After completion of the reaction, the mixture was neutralized with a 20 wt% aqueous sodium hydroxide solution, added with 45 parts of a saturated aqueous sodium thiosulfate solution, stirred for 30 minutes, and allowed to stand. The organic layer separated into two layers was taken out, 20 parts of activated carbon (CP2 manufactured by Ajinomoto Fine-Techno) and 20 parts of montmorillonite (Kunimine Industries Kunipia F) were added thereto, and the mixture was stirred at room temperature for 3 hours and filtered. The obtained filtrate was washed with 100 parts of water three times, and toluene was distilled off from the obtained organic layer to obtain 222 parts of a colorless liquid epoxy resin (EP-1) at room temperature. The epoxy equivalent of the obtained epoxy resin is 130 g / eq. The viscosity was 205 mPa · s (25 ° C.).

Synthesis example 2
β- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane 106 parts, weight average molecular weight 1700 (GPC measured value) silanol-terminated methylphenyl silicone oil 234 parts (silanol equivalent 850, weight average molecular weight 1 measured using GPC) ), 18 parts of 0.5% potassium hydroxide (KOH) methanol solution was charged into the reaction vessel, the bath temperature was set to 75 ° C., and the temperature was raised. After raising the temperature, the reaction was carried out under reflux for 8 hours.
Next, after adding 305 parts of methanol, 86.4 parts of a methanol solution of distilled water (concentration: 50% by weight) was added dropwise over 60 minutes and reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and about 90% of methanol was recovered by distillation at 80 ° C. 380 parts of methyl isobutyl ketone was added, and washing with 200 parts of water was repeated three times. Subsequently, the organic phase was removed using a rotary evaporator at 100 ° C. under reduced pressure to obtain 300 parts of an epoxy resin (EP-2) having a siloxane structure. The epoxy equivalent of the obtained compound was 729 g / eq, the viscosity was 1090 mPa · s (25 ° C.), the weight average molecular weight was 2200, and the appearance was colorless and transparent.

Synthesis example 3
A flask equipped with a stirrer, a reflux condenser, a stirrer, and a Dean-Stark tube was purged with nitrogen, and 140 parts of dimethyl 1,4-cyclohexanedicarboxylate (DMCD-p manufactured by Iwatani Gas Co., Ltd.), cyclohexene-4-methanol 314 And 0.07 part of tetrabutoxytitanium were added, and the reaction was carried out at 120 ° C. for 1 hour, 150 ° C. for 1 hour, 170 ° C. for 1 hour and 190 ° C. for 12 hours while removing methanol produced by the reaction. After reacting by gas chromatography (GC), it was cooled to 50 ° C.
After cooling, 347 parts of toluene was added and homogenized, and then the reaction solution was washed 3 times with 80 parts of a 10 wt% aqueous sodium hydroxide solution, and further washed with water until the wastewater became neutral at 100 parts / time of water. , Liquid at room temperature mainly composed of bis (3-cyclohexenylmethyl) = 1,4-cyclohexanedicarboxylic acid by distilling off toluene and unreacted 3-cyclohexene-1-methanol under reduced pressure by heating with a rotary evaporator 240 parts of the compound (D-1) was obtained.

Synthesis example 4
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 15 parts of water, 0.95 parts of 12-tungstophosphoric acid, 0.78 parts of disodium hydrogen phosphate, and 50% xylene trioctylammonium while purging with nitrogen. 2.7 parts of a solution, 180 parts of toluene, and 118 parts of the compound (D-1) obtained in Synthesis Example 3 were added, and this solution was heated to 60 ° C. and stirred vigorously while 35 wt% aqueous hydrogen peroxide. 70 parts were added in 1 hour, and it stirred at 60 degreeC as it was for 13 hours. When the progress of the reaction was confirmed by gas chromatography, the raw material peak disappeared.
Next, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 25 parts of a 20% by weight aqueous sodium thiosulfate solution was added, stirred for 30 minutes, and allowed to stand. The organic layer separated into two layers was taken out, 20 parts of activated carbon (CP1 manufactured by Ajinomoto Fine Techno) and 20 parts of bentonite (Bengel SH manufactured by Hojun) were added thereto, and the mixture was stirred for 1 hour at room temperature and then filtered. The obtained filtrate was washed with 100 parts of water three times, and toluene was distilled off from the obtained organic layer to obtain 119 parts of a liquid epoxy resin (EP-3) at room temperature. The epoxy equivalent of the obtained epoxy resin was 217 g / eq. The viscosity was 7520 mPa · s (25 ° C.).

Examples 1 and 2 and Comparative Examples 1 and 2
As an example, the epoxy resin (EP-1), tricyclodecane dimethanol (AL-1) obtained in Synthesis Example 1 and trimethylolpropane (AL-2) as a comparative example are shown in Table 1 below. It mixed uniformly by quantity and obtained the curable resin composition (F-1) (F-2) for an Example, and the curable resin composition (F-3) (F-4) for a comparative example.

Examples 3, 4, 5 and Comparative Examples 3, 4, 5
With respect to the obtained curable resin composition (F-1) (F-2) (F-3) (F-4) and the epoxy resin (EP-1), an acidic curing accelerator (cationic polymerization initiator) ( Sanshin Chemical Industries, Ltd., Sun Aid SI-60, hereinafter referred to as C-1) was blended in the blending amounts shown in Table 2 below to obtain a curable resin composition.

Furthermore, the storage stability and curability of the obtained compound were evaluated. The results are also shown in Table 2.
(Evaluation method)
・ Storage stability:
Storage stability when the curable resin composition is stored at room temperature for 24 hours. If it gelled in 24 hours, it was marked as x, and if it was kept liquid, it was marked as ◯.
・ Curing property:
Curability when cured at 80 ° C. for 1 hour. The cured product was marked with ◯, and the cured product (flowable or semi-solid) was marked with ×.

From the above results, in the case of an alcohol such as trimethylolpropane, the storage stability is poor when an amount in a range with good curability is added, and the curability is poor when storage stability is obtained (Comparative Examples 3 and 4). Moreover, if alcohol is not added, sclerosis | hardenability and storage stability are securable (Comparative Example 5).

Examples 6 and 7 and Comparative Examples 6 and 7
With respect to the obtained curable resin composition (F-1) and epoxy resin (EP-1), an acidic hardening accelerator (C-1) is mix | blended with the compounding quantity described in Table 3 below, and curable resin composition I got a thing.

Further, the moisture permeability of the obtained compound was evaluated. The results are also shown in Table 3.
(Evaluation method)
Humidity and moisture permeability conditions 60 ° C 90% 24 hours Curing conditions 80 ° C 1 hour

  From the above results, it can be seen that the curable resin composition of the present invention is effective in moisture permeation resistance.

Example 8 and Comparative Example 8
With respect to the obtained curable resin composition (F-1) and epoxy resin (EP-1), an acidic hardening accelerator (C-1) is mix | blended with the compounding quantity described in Table 4 below, and curable resin composition I got a thing.

Further, the obtained compound was evaluated for adhesive shear strength. The results are also shown in Table 4.
(Evaluation method)
-Adhesive shear strength curing conditions: 80 ° C for 1 hour, moisture absorption test conditions, 60 ° C, 90%, 63 hours

From the above results, it can be seen that the curable resin composition of the present invention has not only excellent adhesiveness but also high moisture resistance.

Examples 9 and 10, Comparative Examples 9 and 10
In the same manner as in Example 1, curable resin compositions (F-1) and (F-5) for Examples and curable resin compositions (F-3) and (F-6) for Comparative Examples were used. Created. The composition is shown in Table 5.
About the obtained curable resin composition, methylhexahydrophthalic anhydride (manufactured by Shin Nippon Chemical Co., Ltd., Rikacid MH, hereinafter referred to as H-1) as a curing agent, and quaternary phosphonium salt (Hishicolin, manufactured by Nippon Chemical Industry Co., Ltd.) as a curing accelerator. PX4MP, hereinafter referred to as C-2), and the following blending amounts shown in Table 5 were obtained to obtain curable resin compositions.

Furthermore, the storage stability of the obtained compound was evaluated. The results are also shown in Table 5.
(Evaluation method)
・ Storage stability:
The increase in viscosity when left at room temperature for 4 hours was compared with the initial viscosity and the viscosity after 4 hours. The greater the viscosity increase, the worse the storage stability.

From the above results, it can be seen that the curable resin composition using the curable resin composition of the present invention is excellent in storage stability.

Examples 11 and 12, Comparative Example 11
Curing accelerators using acid anhydrides (H1) as curing agents for the curable resin compositions (F-1) and (F-5) for the examples and the epoxy resin (EP-1) for the comparative examples. Hexadecyltrimethylammonium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd., 25% methanol solution, hereinafter referred to as C-3) was blended at the blending ratio (parts by weight) shown in Table 6 below and removed for 20 minutes. Foaming was performed to obtain a curable resin composition.

  Using the obtained curable resin composition, a volatilization test was conducted in the following manner, and the results are shown in Table 6. The curing conditions are 150 ° C. × 5 hours after preliminary curing at 120 ° C. × 2 hours.

(Volatilization test)
The curable resin compositions obtained in Examples and Comparative Examples were subjected to vacuum defoaming for 20 minutes, and then gently cast on a glass substrate on which a dam was created with heat-resistant tape so as to be 30 mm × 20 mm × height 1 mm. . After accurately measuring the weight of the cast resin, the cast was cured under the conditions described above.
The weight of the cured product thus obtained was measured to confirm the weight reduction during curing. (Examples and comparative examples were cured in the same oven in the same manner)

  When Examples 11 and 12 are compared with Comparative Example 11, the curable resin composition of the present invention has a small volatilization amount. It turns out that the curable resin composition of this invention has the effect which suppresses volatilization at the time of hardening.

Examples 13 and 14 and Comparative Example 12
Using the organopolysiloxane compound (EP-2) obtained in Synthesis Example 1 as an epoxy resin, curable resin compositions (F-7) and (F-8) were prepared according to the formulation shown in Table 7. The acid anhydride (H-1) is used as the curing agent, the curing accelerator (C-2) is used as the curing accelerator, blended at the blending ratio (parts by weight) shown in Table 7 below, and defoamed for 20 minutes. The curable resin composition for the present invention or for comparison was obtained.

(Corrosion gas permeability test)
Using the obtained curable resin composition, filling into a syringe and using a precision discharge device, an outer diameter 5 mm square surface-mount LED package (with an inner diameter of 4.4 mm and an outer wall height of 1) on which a chip having a central emission wave of 465 nm is mounted. .25 mm). The cast product was put into a heating furnace and cured at 120 ° C. for 1 hour, further at 150 ° C. for 3 hours, and an LED package was prepared. The LED package was left in a corrosive gas under the following conditions, and the color change of the silver-plated lead frame part inside the seal was observed. The results are shown in Table 7.

Measurement conditions Corrosion gas: 20% aqueous solution of ammonium sulfide (discolors black when sulfur component reacts with silver)
Contact method: A container of an ammonium sulfide aqueous solution and the LED package were mixed in a wide-mouth glass bottle, and the wide-mouth glass bottle was covered to bring the volatilized ammonium sulfide gas into contact with the LED package in a sealed state.
Judgment of corrosion: The time when the lead frame inside the LED package was discolored black (referred to as blackening) was observed, and it was determined that the longer the discoloration time, the better the corrosion gas resistance.
Observations were taken out after 10 minutes, 30 minutes and 1 hour, and confirmed, evaluation was ○ for those with no discoloration, Δ for those where discoloration began, × for brown to brown, completely blackened Items were marked XX.

  From the above results, it is clear that the curable resin composition of the present invention is superior in corrosion gas resistance because the silver plating of the lead frame is not discolored as compared with the curable resin composition of the comparative example. It is.

Examples 15 and 16
Using the epoxy resins (EP-1) and (EP-3) obtained in Synthesis Examples 1 and 4, curable resin compositions (F-9) and (F-10) were prepared according to the formulation shown in Table 8. As the curing agent, acid anhydride (H-1), 1,3,4-cyclohexanetricarboxylic acid 3,4-anhydride (H-TMAn manufactured by Mitsubishi Gas Chemical Co., Ltd., hereinafter referred to as H-2) is used as a curing accelerator. As a curing accelerator (C-2), it was blended at a blending ratio (parts by weight) shown in Table 8 below, defoamed for 20 minutes, and a curable resin composition of the present invention was obtained.
(Transmissivity test)
The obtained curable resin composition was vacuum-defoamed for 20 minutes, and then gently cast on a glass substrate on which a dam was created with a heat-resistant tape so as to be 30 mm × 20 mm × height 1 mm. 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. The transmittance of each cured product at 400 nm was measured.
(LED lighting test)
The obtained curable resin composition is filled into a syringe and a 5 mm outer diameter surface mount LED package (inner diameter: 4.4 mm, outer wall height: 1.25 mm) mounted with a chip having a central emission wave of 465 nm using a precision discharge device. ). The cast product was put into a heating furnace and cured at 120 ° C. for 1 hour, further at 150 ° C. for 3 hours, and an LED package was prepared. After mounting the LED, the LED was turned on under the following conditions to measure the illuminance, and the results are shown in Table 8.
Detailed lighting conditions Light emission wavelength: 465nm
Drive system: constant current system, 60 mA (light emitting element regulation current is 30 mA)
Driving environment: 85 ° C, 85%
Driving time: 200 hours Evaluation: Illuminance retention after lighting for 200 hours

  From the above results, it was found that the curable resin composition of the present invention is a compound useful for an optical material having excellent optical properties and excellent properties such as corrosion gas resistance. Moreover, it became clear that it has the characteristic outstanding also in the characteristic at the time of setting it as a curable resin composition from the little volatile matter at the time of storage stability and hardening.

Claims (7)

A thermosetting resin composition comprising an epoxy resin having an epoxycyclohexane structure, an alcohol having a tricyclodecane structure, a curing accelerator, and a curing agent having an acid anhydride structure or a carboxylic acid structure , the tricyclodecane structure A thermosetting resin composition in which the alcohol having is selected from tricyclodecane dimethanol, methyltricyclodecane dimethanol or pentacyclopentadecane dimethanol . The thermosetting resin composition according to claim 1, wherein the epoxy resin having an epoxycyclohexane structure is an alicyclic epoxy resin. The thermosetting resin composition according to claim 1, wherein the epoxy resin having an epoxycyclohexane structure is an epoxy resin having an epoxycyclohexane structure and a siloxane structure. The thermosetting resin composition for optical semiconductors as described in any one of Claims 1-3. The thermosetting resin composition according to any one of claims 1 to 4, curing agent, characterized in that an acid anhydride. Hardened | cured material obtained by hardening | curing the thermosetting resin composition as described in any one of Claims 4 and 5. The optical semiconductor device containing the thermosetting resin composition as described in any one of Claims 4 and 5.