KR20150105301A - Epoxy resin, epoxy resin composition and cured material - Google Patents

Abstract

The present invention provides an epoxy resin obtained by curing a resin having good optical characteristics and high toughness. A glycidyl group obtained by the reaction of a compound represented by the following formula (1) with epihalohydrin and having a surface area of 1 to 20% by area of triglycidyl ether in the measurement by GPC is represented by the following formula (A) Epoxy resin with alcohol moiety represented.

(In the above formula (A), R represents a hydrogen atom or an alkyl group, and * represents an oxygen atom.) The two Rs do not form a hydrogen atom or an alkyl group together)

Description

EPOXY RESIN, EPOXY RESIN COMPOSITION AND CURED MATERIAL "

The present invention relates to an epoxy resin, an epoxy resin composition, and a cured product thereof, which are suitable for use in electric and electronic materials, particularly optical materials.

BACKGROUND ART Conventionally, epoxy resin compositions have been employed in terms of balance between performance and economy in applications such as LED products and transparent substrate materials. Epoxy resin compositions using bisphenol A type epoxy resins having excellent balance among heat resistance, transparency and mechanical properties have been widely used (Patent Documents 1 to 3).

Japanese Patent Application Laid-Open No. 07-157536 Japanese Patent Application Laid-Open No. 2007-284680 Japanese Patent Application Laid-Open No. H06-067156

As described above, the bisphenol A type epoxy resin has general versatility as an optical resin, but these resins are generally in a liquid state and have problems such as sticking during sheeting or prepreging. In addition, although the molecular weight is increased and solidified, the cured product is excessively flexible since it is only extended in a straight line, so that heat resistance is hardly generated.

To such a problem, the epoxy resin of a trisphenol compound having a structure not having a benzylmethylene bond as in the case of the bisphenol A type epoxy resin, Printec Co., Ltd. VG3105 is used. However, since they have an initial coloration, a certain degree of transparency is required for use as an optical material. As a method for solving this problem, application of an epoxy resin having a silsesquioxane structure or an alicyclic epoxy resin has been studied, but an epoxy resin having a silsesquioxane structure has a high heat resistance, but tends to have a pronounced drift and a linear expansion rate . In addition, the refractive index is lowered. In addition, although alicyclic epoxy resins also have an improved heat resistance in the sense of glass transition point, they are problematic in terms of their solubility and low refractive index, and epoxy resins capable of obtaining cured products having good optical properties and high toughness are desired.

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above-mentioned facts and have completed the present invention.

That is,

(1) a compound obtained by the reaction of a compound represented by the following formula (1) with epihalohydrin and having a surface area of 1% by mass to 20% by area of the triglycidyl ether compound measured by GPC (gel permeation chromatography) An epoxy resin characterized in that the glycidyl group is an alcohol moiety represented by the following formula (A)

[In the above formula (A), each R independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and * bonds to an oxygen atom. And two R's do not together form a hydrogen atom or an alkyl group having 1 to 5 carbon atoms]

(2) In the above (1)

Wherein the reaction of the compound of formula (1) with epihalohydrin is carried out in a mixed solution of epihalohydrin and an alcohol having 1 to 5 carbon atoms,

(3) In the above (1) or (2)

After completion of the reaction of the compound of the above formula (1) with epihalohydrin, post-treatment with toluene or a solution of a ketone compound having 4 to 7 carbon atoms as a metal hydroxide aqueous solution.

(4) An epoxy resin composition comprising the epoxy resin according to any one of (1) to (3) as an essential component,

(5) In the above (4)

An epoxy resin composition characterized by containing a transition metal salt,

(6) In the above (4)

An epoxy resin composition comprising a quaternary phosphonium salt,

(7) In the above (4)

An epoxy resin composition characterized by containing a non-halogen quaternary ammonium salt,

(8) In any one of the above-mentioned (4) to (7)

An epoxy resin composition comprising at least one of an acid anhydride and a polycarboxylic acid as a curing agent,

(9) A cured product obtained by curing the epoxy resin composition according to any one of (4) to (8).

(Effects of the Invention)

The epoxy resin of the present invention is excellent in transparency and heat resistance when used in an epoxy resin composition. Therefore, the present invention can be applied to an optical member requiring a high optical characteristic.

The epoxy resin of the invention is obtained by reacting the trisphenol compound of the compound of formula (1) with an epihalohydrin. A specific example of the production method of the epoxy resin of the present invention is shown below.

The trisphenol compound of the above formula (1) is a white crystalline phase, and does not undergo discoloration due to oxidation, but is slightly colored by long-term storage. The purity of the trisphenol compound to be used is preferably 96% or more, more preferably 98% or more, and particularly preferably 99% or more. The transmittance is preferably 95% or more, more preferably 96% or more, particularly preferably 90% or more in transmittance (1 cm cell width) at 400 nm when dissolved in tetrahydrofuran at a concentration of 30% It is more than 97%. The coloring of this raw material also affects the subsequent epoxidation process and becomes a coloring factor.

As the epihalohydrin in the reaction for obtaining the epoxy resin of the present invention, epichlorohydrin which is industrially available is preferable. The epihalohydrin is used in an amount of usually 4.0 to 10 mol, preferably 4.5 to 8.0 mol, more preferably 4.5 to 7.0 mol based on 1 mol of the hydroxyl group of the trisphenol compound. Addition of 0.5 to 10% by weight of alkyl glycidyl ether to the epihalohydrin is preferable in view of improvement in toughness of the obtained epoxy resin. The alkyl glycidyl ether is preferably an alkyl glycidyl ether having 1 to 5 carbon atoms such as methyl glycidyl ether, ethyl glycidyl ether, and propyl glycidyl ether.

In the above reaction, an alkali metal hydroxide may be used. As the alkali metal hydroxide which can be used in the above reaction, sodium hydroxide, potassium hydroxide and the like can be enumerated, and a solid material or an aqueous solution thereof may be used. In the present invention, in particular, Use of solids is preferred.

The amount of the alkali metal hydroxide to be used is generally from 0.90 to 1.5 mol, preferably from 0.95 to 1.25 mol, more preferably from 0.99 to 1.15 mol, per mol of the hydroxyl group of the trisphenol compound.

A quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride may be added as a catalyst in order to accelerate the reaction. The amount of the quaternary ammonium salt to be used is generally 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the trisphenol compound.

In the present reaction, an alcohol having 1 to 5 carbon atoms is preferably used in addition to the epihalohydrin. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol and isopropyl alcohol.

In the present invention, from the viewpoint of the solubility of the alkali metal hydroxide, alcohols having a smaller number of carbon atoms are preferable, and methanol is particularly preferable. The amount of alcohol to be used is usually 2 to 50% by weight, preferably 4 to 40% by weight, and particularly preferably 7 to 30% by weight based on the amount of epihalohydrin used. If the amount of the alcohol to be added is too small, the introduction rate of the alkoxy group may be lowered. If the amount of the alcohol is excessively large, the epoxy group may be excessively wasted.

The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. Particularly, in the present invention, the reaction is particularly preferably carried out at a temperature of 60 DEG C or higher, more preferably 65 DEG C or higher, and a reflux condition close to the refluxing temperature for epoxidation of higher purity. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 3 hours. If the reaction time is short, the reaction may not proceed to the end, and if the reaction time is prolonged, by-products may be generated.

Epihalohydrin, a solvent, and the like are removed from the reaction product of the epoxidation reaction after washing with water or without heating under reduced pressure. Further, the epoxy resin recovered in order to make the hydrolyzable halogen less epoxy resin can be used as a ketone compound having 4 to 7 carbon atoms (e.g., methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.) ) Is dissolved as a solvent, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to carry out the reaction, whereby the closed ring can be made definite. In this case, the amount of the alkali metal hydroxide to be used is generally 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 mol of the hydroxyl group of the trisphenol compound used for epoxidation. The reaction temperature is usually from 50 to 120 ° C, and the reaction time is usually from 0.5 to 2 hours.

In the reaction with epihalohydrin, it is preferable to carry out the reaction while blowing an inert gas such as nitrogen into the liquid or the liquid. If there is no blowing of the inert gas, the resultant resin may be colored. The blowing amount of the inert gas differs depending on the volume of the reaction vessel, but it is preferable to blow the inert gas in an amount capable of displacing the volume of the reaction vessel to 0.5 to 10 hours.

After completion of the reaction, the resulting salt is removed by filtration, washing with water, and the solvent is distilled off under reduced pressure and heating to obtain the epoxy resin of the present invention.

The epoxy resin thus obtained is a resin having excellent transparency. A softening point of 55 to 90 占 폚, and an epoxy equivalent of 205 to 250 g / eq. The result of measurement by gel permeation chromatography is 1 to 20% by area of the epoxy resin having the structure of the following formula (3) with respect to the structure of the following formula (2).

(Wherein G represents a glycidyl group)

(B) or (c), at least one of the three groups is represented by the formula (a), the formula (b) or the formula (c) *, And R represents an alkyl group having 1 to 5 carbon atoms)

In the measurement results of the gel permeation chromatography, the epoxy resin having the structure of the formula (3) is contained in an amount of 1 to 20% by area, preferably 2 to 20% by area, Is 5 to 20% by area, particularly preferably 5 to 17% by area. R is preferably an alkyl group having 1 to 3 carbon atoms, and a methyl group is particularly preferable.

The epoxy equivalent of such an epoxy resin is preferably 210 to 240 g / eq. More preferably from 215 to 235 g / eq. And more preferably from 215 to 230 g / eq.

The softening point is preferably 55 to 90 占 폚, more preferably 55 to 85 占 폚, particularly preferably 55 to 80 占 폚. The preferable epoxy equivalent and the preferable softening point are effective for the heat resistance of the cured product and the handling property when the epoxy resin composition is used.

The epoxy equivalent of the epoxy resin to the theoretical epoxy equivalent weight of the epoxy resin (theoretical epoxy equivalent calculated from the compound obtained by adding epihalohydrin to the entire phenolic hydroxyl group of the phenol compound of formula (1) Is preferably 1.06 or more, more preferably 1.10 or more, and particularly preferably 1.10 to 1.18. In this range, it means that a structure in which an epoxy group in the epoxy resin is ring-opened (a structure similar to the formulas (b) and (c) in the formula (3)) is contained in a certain amount or more. It is also important that the amount of halogen is preferably 1500 ppm or less, particularly preferably 1200 ppm or less at the same time. When the amount of halogen is large, this ratio tends to increase, but it becomes important in terms of lowering the electrical reliability in use for electronic materials applications.

When the compound represented by the formula (2) as measured by gel permeation chromatography (GPC) in the epoxy resin obtained by the reaction of the compound of the formula (1) of the present invention with epihalohydrin is 40 The area is preferably 80% by area to 80% by area, particularly preferably 55% by area to 75% by area.

The epoxy resin composition of the present invention contains the epoxy resin of the present invention as an essential component. Further, it is preferable that another epoxy resin or a curing agent is contained as an optional component.

In the present invention, the structure of the above formula (1) is dimerized, trimerized and further increased in mass (hereinafter, also simply referred to as a multimer), but the introduction ratio of the alkoxy group The introduction rate of the alkoxy group will be discussed in the structures of the above-mentioned formulas (2) and (3) which can be separated because the measurement is difficult in the permeation chromatography.

By including the structure of the formula (3) in the structure of the formula (2), it is possible to suppress the rise of the free volume due to the over-functional groups, thereby reducing the drift (improving the mechanical properties).

In the formula (A), R represents an alkyl group having 1 to 5 carbon atoms, but in the present invention, a lower alkyl group such as a methyl group, an ethyl group, and an isopropyl group is preferable.

The epoxy resin composition of the present invention may contain an epoxy resin other than the epoxy resin of the present invention. The proportion of the epoxy resin of the present invention in the whole epoxy resin is preferably 20% by weight or more, more preferably 30% by weight or more, and particularly preferably 40% by weight or more.

Examples of other epoxy resins which can be used in combination with the epoxy resin of the present invention include novolak type epoxy resins, bisphenol type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins and phenol aralkyl type epoxy resins. Specific examples thereof include bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpenediphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'- (1,1'-biphenyl) -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis Hydroxyphenyl) ethane, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene and the like) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o- Benzoyl peroxide, benzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'- (Methoxymethyl) -1,1'-biphenyl, 1,4-bis (chloromethyl) benzene or 1,4-bis (methoxymethyl) benzene and their modifications, tetrabromobisphenol A Halogenated bisphenols such as Alicyclic epoxy resins, glycidylamine epoxy resins, glycidyl ester epoxy resins, silsesquioxane epoxy resins (chain-like, cyclic, ladder-like, or a mixture thereof) derived from alcohols, alicyclic epoxy resins, glycidylamine- Or an epoxy resin having a glycidyl group and / or an epoxycyclohexane structure in a siloxane structure having at least two or more mixed structures), and the like, but is not limited thereto.

In particular, when the epoxy resin composition of the present invention is used for optical use, it is preferable to use the epoxy resin of the present invention in combination with an alicyclic epoxy resin or an epoxy resin having a silsesquioxane structure. Especially, in the case of alicyclic epoxy resin, a compound having an epoxy cyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is particularly preferable.

Examples of the compound having a cyclohexene structure include an esterification reaction of a cyclohexenecarboxylic acid and an alcohol or an esterification reaction of a cyclohexene methanol and a carboxylic acid (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980) (The method described in JP-A-2003-170059, JP-A-2004-262871, etc.) of cyclohexene aldehyde and the transesterification reaction of cyclohexenecarboxylic acid ester Japanese Patent Application Laid-Open No. 2006-052187 and the like).

The alcohols are not particularly limited as long as they are compounds having an alcoholic hydroxyl group, and examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4- butanediol, Diols and cyclohexane dimethanol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol and the like, and tetraols such as pentaerythritol . The carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, cyclohexanedicarboxylic acid and the like.

Other than the above, compounds having a cyclohexene structure include acetal compounds obtained by an acetal reaction between a cyclohexene aldehyde derivative and an alcohol compound. As a reaction method, a general acetalization reaction can be applied. For example, there is a method in which a reaction is carried out while azeotropically dehydrating a reaction medium using a solvent such as toluene or xylene (US Pat. No. 2,945,008), a method of dissolving a polyhydric alcohol in concentrated hydrochloric acid (Japanese Patent Application Laid-Open No. 48-96590), a method of using water as a reaction medium (U.S. Patent No. 3092640), a method of using an organic solvent as a reaction medium (Japanese Patent Application Laid-Open No. 7-215979), and a method using a solid acid catalyst (Japanese Patent Application Laid-Open No. 2007-230992). From the stability of the structure, a cyclic acetal structure is preferable.

Specific examples of these epoxy resins include ERL-4221, UVR-6105 and ERL-4299 (all manufactured by The Dow Chemical Company), Celloxide 2021P, Epolead GT401, EHPE 3150 and EHPE 3150CE Dicyclopentadiene epoxide, and the like, but the present invention is not limited thereto (References: General-use Epoxy Resin Foundation I p76-85).

These may be used alone or in combination of two or more.

The epoxy resin composition of the present invention may contain a curing accelerator (curing catalyst). Specific examples of the curing accelerator that can be used in the present invention include amine compounds such as triethylamine, tripropylamine, and tributylamine; amines such as pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undeca- 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, Benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino- (2'-ethyl, 4-methylimidazole (1 ')) ethyl-s-triazine, Triazine, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2 : 3 adduct, 2-phenylimidazole 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl -3,5-dicyanoethoxymethylimidazole, and various heterocyclic compounds such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, Salts of polycarboxylic acids such as maleic acid and oxalic acid, amides such as dicyandiamide, diaza compounds such as 1,8-diazabicyclo (5.4.0) undecene-7 and their tetraphenylborates, Phenol novolak and the like, polycarboxylic acids or salts of phosphinic acids, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethyl Ammonium hydroxide, trimethylpropylammonium hydroxide, trimethyl An ammonium salt such as triethylammonium hydroxide, tetramethylammonium hydroxide, tetramethylammonium hydroxide, tetramethylammonium hydroxide, tetramethylammonium hydroxide, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate and trioctylmethylammonium acetate , Phosphines such as triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium and tetraphenylborate, and phenols such as 2,4,6-trisaminomethylphenol (Zinc salts such as stearic acid, behenic acid, myristic acid and the like, tin salts, zirconium salts), phosphoric acid ester metals (such as zinc salts such as octylphosphoric acid and stearylphosphoric acid) Salts), alkoxy metal salts (tributyl aluminum, tetrapropyl zirconium etc.), acetylacetone salts (acetylacetone zirconium chelate, acetyl acetone titanium There may be mentioned metal compounds such as acrylate, etc.), transition metal salts, quaternary phosphonium salts, quaternary ammonium salts, such as halogen. In the present invention, phosphonium salts, ammonium salts, and metal compounds are particularly preferable in terms of coloration upon curing and changes thereof. Further, when a quaternary salt is used, a salt with a halogen causes a halogen to remain in the cured product, which is undesirable from the viewpoint of electrical reliability and environmental problems.

The curing accelerator is used in an amount of 0.01 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin.

The epoxy resin composition of the present invention preferably contains a curing agent. Examples of the curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Examples of the curing agent include nitrogen-containing compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a polyamide resin synthesized from dimer of linolenic acid and ethylenediamine (Amines, amide compounds); There may be mentioned phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Carboxylic acid 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; Various alcohols, carboxylic acid resins obtained by addition reaction of carbinol-modified silicone with the acid anhydrides described above; Bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpendiphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1 (4-hydroxyphenyl) -4,4'-diol, hydroquinone, resorcin, naphthalene diol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis Ethane, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene and the like) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o- Bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) biphenyl, dihydroxyacetophenone, dicyclopentadiene, furfural, Polycondensates such as 1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene or 1,4'-bis (methoxymethyl) benzene and their modified products, tetrabromobisphenol A Halogenated bisphenols, terpenes and phenols Of polyphenols such as a condensate; But are not limited to, compounds such as imidazoles, trifluoroborane-amine complexes, and guanidine derivatives. These may be used alone, or two or more of them may be used.

In the present invention, a compound having an acid anhydride-based compound, an acid anhydride structure typified by a carboxylic acid-based compound, and / or a carboxylic acid structure is particularly preferable.

The amount of the curing agent to be used in the epoxy resin composition of the present invention is preferably 0.7 to 1.2 equivalents based on 1 equivalent of the epoxy group of the epoxy resin. When the amount is less than 0.7 equivalents or more than 1.2 equivalents based on one equivalent of the epoxy group, curing is incomplete in all cases and good curing properties may not be obtained.

The carboxylic acid compound is preferably a polycarboxylic acid. Specific preferred polyvalent carboxylic acids are compounds having at least two carboxyl groups and having an aliphatic hydrocarbon group as a main skeleton, and are preferably 2 to 6 functional carboxylic acids, and more preferably 2 to 6 functional polyvalent A compound obtained by the reaction of an alcohol with an acid anhydride is more preferable. Further, a polycarboxylic acid in which the acid anhydride is a saturated aliphatic cyclic acid anhydride is preferable.

The polyhydric alcohols having 2 to 6 functional groups are not particularly limited as long as they are compounds having an alcoholic hydroxyl group, and examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2- butanediol, Diols such as 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecanedimethanol, Triols such as glycerin, trimethylol ethane, trimethylol propane, trimethylol butane and 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol and dimethylol propane, and hexaols such as dipentaerythritol And the like.

Particularly preferred alcohols are alcohols having 5 or more carbon atoms, and particularly preferred are alcohols having 1 to 6 carbon atoms such as 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, Diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecanedimethanol and norbornenediol are preferable, and 2-ethyl- Alcohols having a branched chain structure or cyclic structure such as 1,3-propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol and norbornenediol, desirable.

Examples of the acid anhydride include methyl tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic acid anhydride, bicyclo [2,2,1] 3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4- Among them, methylhexahydrophthalic anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride are preferable.

The conditions for the addition reaction are not particularly specified, but one of the specific reaction conditions is a method in which the acid anhydride and the polyhydric alcohol are reacted at 40 to 150 캜 under the conditions of a non-catalytic and solvent-free conditions and heated. However, the reaction conditions are not limited thereto.

Specific preferred acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, anhydrous acid, hexahydrophthalic anhydride, Butane tetracarboxylic acid anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid Acid anhydrides such as acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, and the like.

In particular, it is preferable to use methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic acid anhydride, bicyclo [2,2,1] heptane- Methyl bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride are preferable .

Particularly preferred are methylhexahydrophthalic anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride.

Further, the use of a cyanatoester compound as the other component is preferable. In addition to the curing reaction by itself, the cyanate ester compound has a higher crosslink density due to the reaction with the epoxy resin, and a heat-resistant cured product can be obtained. Examples of the cyanate ester resin include 2,2-bis (4-cyanate phenyl) propane, bis (3,5-dimethyl- Ethane, derivatives thereof, and aromatic cyanate ester compounds. Further, it can also be synthesized by, for example, reacting various phenol resins as described in the above-mentioned curing agent with cyanide or a salt thereof.

In the present invention, those having a structure in which a methylene structure at the benzyl position is not contained in a molecule, such as 2,2-bis (4-cyanate phenyl) propane or its derivatives (partial polymerizers and the like) Or two or more of them may be used in combination.

The epoxy resin composition of the present invention may contain a phosphorus-containing compound as a flame retardancy-imparting component. The phosphorus-containing compound may be of reaction type or of addition type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylallylenyl phosphate, cresyldiphenyl phosphate, cresyl-2,6-dicyclylenyl phosphate, Dicyclylenylenylphosphate), 1,4-phenylenebis (dicyclylenylenylphosphate), and 4,4'-biphenyl (dicyclylenylenylphosphate); 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H- ; Phosphorus-containing epoxy compounds obtained by reacting an epoxy resin with active hydrogens of the above-mentioned phosphates, and red phosphorus. Of these, phosphoric acid esters, phosphates or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylene bis Silylenyl phosphate), 1,4-phenylenebis (dicyclylenylenylphosphate), 4,4'-biphenyl (dicyclylenylphosphate) or phosphorus-containing epoxy compounds are particularly preferable. The content of the phosphorus-containing compound is preferably 0.1 to 0.6 (weight ratio) of phosphorus-containing compound / total epoxy resin. When the ratio is less than 0.1, the flame retardancy may decrease. When the ratio is more than 0.6, the hygroscopicity and dielectric properties of the cured product may be adversely affected.

The epoxy resin composition of the present invention may optionally contain a binder resin. As the binder resin, a butyral resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, an NBR-phenol resin, an epoxy-NBR resin, a polyamide resin, a polyimide resin, . The blending amount of the binder resin is preferably within 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 by weight based on 100 parts by weight of the total amount of the epoxy resin and the curing agent do.

An inorganic filler may be added to the epoxy resin composition of the present invention if necessary. Examples of the inorganic filler include powders of crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, stearate, spinel, titania and talg, Beads, and the like. However, the present invention is not limited thereto. These fillers may be used singly or in combination of two or more kinds. The content of these inorganic fillers in the epoxy resin composition of the present invention is 0 to 95% by weight. The epoxy resin composition of the present invention may further contain various additives such as silane coupling agent, stearic acid, palmitic acid, zinc stearate, release agents such as calcium stearate, pigments, and various thermosetting resins.

When the epoxy resin composition of the present invention is used as an optical material, it is possible to supplement mechanical strength and the like without impairing transparency by using a filler having a nano-order level as the particle size of the inorganic filler to be used. It is preferable from the viewpoint of transparency to use a filler having an average particle diameter of 500 nm or less, particularly an average particle diameter of 200 nm or less as a reference as a nano-order level.

When the epoxy resin composition of the present invention is used for an optical material, particularly a photo-semiconductor encapsulant, a phosphor may be added as needed. The phosphor has a function of absorbing a part of blue light emitted from the blue LED element and forming white light by emitting wavelength-converted yellow light, for example. The phosphor is previously dispersed in the epoxy resin composition, and then the optical semiconductor is sealed. The phosphor is not particularly limited and conventionally known phosphors can be used. Examples of the phosphor include aluminates, thiogalates, and orthosilicates of rare earth elements. More specifically, a fluorescent material such as a YAG fluorescent material, a TAG fluorescent material, an orthosilicate fluorescent material, a thiogallate fluorescent material, a sulfide fluorescent material, or the like can be given, and YAlO ₃ : Ce, Y ₃ Al ₅ O ₁₂ : Ce, Y ₄ Al ₂ O ₉ : Ce, Y ₂ O ₂ S: Eu, Sr ₅ (PO ₄ ) ₃ Cl: Eu and (SrEu) O.Al ₂ O ₃ . As the particle diameter of such a fluorescent substance, those having a particle diameter known in this field are used, but the average particle diameter is preferably 1 to 250 탆, particularly 2 to 50 탆. When these phosphors are used, the amount thereof is preferably 1 to 80 parts by weight, more preferably 5 to 60 parts by weight, per 100 parts by weight of the resin component.

When the epoxy resin composition of the present invention is used for an optical material, particularly a photo-semiconductor encapsulant, a thixotropic property-imparting agent including a fine silica powder (also referred to as an aerosol or an aerosol) is added for the purpose of preventing settling during curing of various phosphors can do. Examples of such fine silica 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 R812, Aerosil R812S, Aerosil R805, RY200, and RX200 (manufactured by NIPPON AEROSIL CO., LTD.).

When the epoxy resin composition of the present invention is used in an optical material, in particular, in an optical semiconductor sealing material, a phosphorus compound or a phenol compound as an antioxidant or an amine compound as a light stabilizer may be contained for the purpose of preventing coloring.

Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, tetrakis , 6,6-tetramethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6, A mixed ester of 6-pentamethyl-4-piperidino and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane , Decane diacid bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin- Tetramethyl-4-piperidyl methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis , 2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1- [2- [3- Ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] Propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis (1,2,2,6,6- (2,6-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, decane diacid bis N ', N' ', N' '' - N, N ', N'-tetramethyl-1 (octyloxy) Tetrakis- (4,6-bis- (N - methyl- 2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin- -Diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl- A polycondensation product of 6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, a poly [6- (1,1,3,3-tetramethylbutyl) Amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [ - tetramethyl-4-piperidyl) , A polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol, 2,2,4,4-tetramethyl-20- (β-lauryl Oxycarbonyl) ethyl-7-oxa-3,20-diazabicyclo [5.1.11.2] heneic acid-21-one, beta -alanine, N, - (2,2,6,6- Acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine -2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispyro [5,1,11,2] heneic acid-21- 4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11,2] -henate acid-20-propanoate dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 2,2,6,6-tetramethyl- N, N'-bis (2,2,6,6-tetramethyl-4-piperazin-1-yl) 2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-yl) - (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimide- , 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5- chlorobenzotriazole, 2- The reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate with polyethylene glycol, 2- (2H-benzotriazol- Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and the like; Based compounds such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5 - [(hexyl) oxy] phenol and the like, Is a hindered amine compound to be.

As the amine compound as the light stabilizer, the following commercially available products can be used.

Examples of commercially available amine compounds include, but are not limited to, THINUVIN 765, THINUVIN 770DF, THINUVIN 144, THINUVIN 123, THINUVIN 622LD, THINUVIN 152, CHIMASSORB 944 as products of Ciba Specialty Chemicals, LA- -57, LA-62, LA-63P, LA-77Y, LA-81, LA-82 and LA-87.

The phosphorus compound is not particularly limited and examples thereof include 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-tert-butylphenyl) butane, distearylpentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenyl bisphenol A, pentaerythritol diphosphite, dicyclohexyl Tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert- butylphenyl) phosphite, (2,6-di-tert-butylphenyl) phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphite, Butylphenyl) phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2-tert- butyl-4-methylphenyl) Fate, 2,2'-methylene Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-ethylidenebis (4-methyl- (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,4-di-tert- butylphenyl) Phenyl) -4,3'-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylene diphosphonite, tetrakis butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylene diphosphonite, tetrakis Bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4- Butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylene diphosphonite, tributylphosphate, trimethylphosphate, tricresylphosphate, triphenylphosphate, Triphenylphosphate, triethylphosphate, diphenylcresylphosphate, diphenylmonoctalkenylphosphate, tributoxyethylphosphate, dibutylphosphate, dioctylphosphate, diisopropylphosphate, and the like.

Commercially available products of the phosphorus compound may be used. Examples of commercially available phosphoryl compounds include, but are not limited to, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, ADK STAB TPP.

The phenol compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3- (3,5- ) Propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,4- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythrityl-tetrakis [ (3-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis- [2- [3- Methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol-bis [3- (3- Methyl-4-hydroxyphenyl) propionate], 2,2'-butylidenebis (4,6-di-tert-butyl Butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'- Butylphenol acrylate, methylene bis (4-ethyl-6-tert-butylphenol), 2-tert- butyl-6- (3- (4-tert-butylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,4'-thiobis (3-methyl- tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) Butylphenol, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis Phenol), bis- [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) -butanooic acid] -glycol ester, 2,4-di- Di-tert-pentylphenol, 2- [1- (2-hydroxy-3,5-di-tert- pentylphenyl) ethyl] , 3-bis- (4'-hydroxy-3'-tert-butylphenyl) -butanoic acid] glycine Esters and the like.

Commercially available products of the phenolic compound may be used. Examples of commercially available phenol compounds include, but are not limited to, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, ADEKA CORPORATION manufactures ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO- 90, ADK STAB AO-330, Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP and the like available from Sumitomo Chemical Co.,

In addition, commercially available additives can be used as the coloring preventing agent for the resin. For example, THINUVIN 328, THINUVIN 234, THINUVIN 326, THINUVIN 120, THINUVIN 477, THINUVIN 479, CHIMASSORB 2020FDL, CHIMASSORB 119FL and the like can be cited as products of Ciba Specialty Chemicals.

The phosphorus compound, the amine compound, and the phenol compound, and the amount thereof is not particularly limited, but it is preferably in the range of 0.005 to 5.0% by weight based on the epoxy resin composition of the present invention .

The epoxy resin composition of the present invention is obtained by uniformly mixing each component. The epoxy resin composition of the present invention can be easily made into a cured product by the same method as a conventionally known method. For example, the epoxy resin component, the curing agent component and, if necessary, the curing accelerator, the phosphorus-containing compound, the binder resin, the inorganic filler and the compounding agent are uniformly made using an extruder, a kneader, a roll or a planetary mixer To obtain an epoxy resin composition. When the obtained epoxy resin composition is a liquid, the composition is impregnated into a substrate by potting or casting, or poured into a mold to form a mold and cured by heating. When the obtained epoxy resin composition is solid, it is molded by using a mold or a transfer molding machine after melting, and further cured by heating. The curing temperature and time are preferably 80 to 200 占 폚 for 2 to 10 hours. As the curing method, it is possible to cure at a high temperature in a short time, but it is preferable to raise the temperature with the stepwise to proceed the curing reaction. Concretely, initial curing is performed at 80 to 150 ° C, and post curing is performed at 100 to 200 ° C. As the curing step, the temperature is preferably divided into 2 to 8 steps, more preferably 2 to 4 steps.

The epoxy resin composition of the present invention may be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl formamide, dimethylacetamide, N-methylpyrrolidone, And then impregnated with a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper or the like, followed by heating and drying, to obtain a cured product of the epoxy resin composition of the present invention . The amount of the solvent used in the mixture of the epoxy resin composition of the present invention and the solvent is usually 10 to 70% by weight, preferably 15 to 70% by weight. In addition, an epoxy resin cured product containing carbon fibers may be obtained by RTM as the liquid composition.

 Further, the epoxy resin composition of the present invention may be used as a film-like sealing composition. In the case of obtaining such a film-like resin composition, the epoxy resin composition of the present invention is coated on the release film with the varnish, the solvent is removed under heating, and B-staging is carried out to obtain a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multi-layer substrate or the like, as a batch film sealing of optical semiconductors.

Next, the case of using the epoxy resin composition of the present invention as a sealing material or a die bond material of optical semiconductor will be described in detail.

When the epoxy resin composition of the present invention is used as a sealing material for optical semiconductors such as a high-brightness white LED, or as a die bonding material, additives such as epoxy resin, curing agent, coupling agent, antioxidant and light stabilizer are sufficiently mixed to prepare an epoxy resin composition And is used as a sealing material or on both the die bonding material and the sealing material. As the mixing method, mixing is carried out at room temperature or by using a kneader, three rolls, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill or the like.

BACKGROUND ART An optical semiconductor device such as a high-brightness white LED generally has a semiconductor chip such as GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN, etc. stacked on a substrate of sapphire, spinel, SiC, Is bonded to the lead frame, the heat sink, and the package using an adhesive (die bond material). There is also a type in which a wire such as a gold wire is connected to allow current to flow. The semiconductor chip is sealed with a sealing material such as epoxy resin in order to protect the semiconductor chip from heat or moisture and also to serve as a lens function. The epoxy resin composition of the present invention can be used as the sealing material or die bond material. From the viewpoint of the process, it is preferable to use the epoxy resin composition of the present invention for both the die bond material and the sealing material.

As a method of bonding the semiconductor chip to the substrate using the epoxy resin composition of the present invention, the epoxy resin composition of the present invention is applied by dispenser, potting, or screen printing, and then the semiconductor chip is heated to cure the semiconductor chip . Heating can be carried out using a hot air circulation type, an infrared ray or a high frequency wave.

The heating conditions are preferably, for example, 80 to 230 DEG C for about 1 minute to 24 hours. Cured at a temperature of 120 to 180 DEG C for 30 minutes to 10 hours after pre-curing for 30 minutes to 5 hours, for example, at 80 to 120 DEG C for the purpose of reducing the internal stress generated upon heat curing.

As a molding method of the sealing material, there is a molding method in which a sealing material is injected into a mold in which a substrate having the semiconductor chip fixed thereon as described above is injected, followed by heat curing and molding, a sealing material is preliminarily injected onto the mold, A compression molding method in which a semiconductor chip is dipped into a die after heat curing is used.

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

Heating can be carried out using a hot air circulation type, an infrared ray or a high frequency wave. The heating conditions are preferably, for example, 80 to 230 DEG C for 1 minute to 24 hours. Cured at a temperature of 120 to 180 DEG C for 30 minutes to 10 hours after pre-curing for 30 minutes to 5 hours, for example, at 80 to 120 DEG C for the purpose of reducing the internal stress generated upon heat curing.

Further, general applications in which a curable resin such as an epoxy resin is used can be enumerated. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP and the like), insulating materials (printed boards, , A sealing material, a sealing material, a cyanate resin composition for a substrate, an acrylic ester resin as a curing agent for a resist, and an additive to other resins.

Examples of the adhesive include adhesives for civil engineering, construction, automobile, general office and medical use, and adhesives for electronic materials. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, adhesives for semiconductors such as die bonding agents and underfill, underfill for BGA reinforcement, anisotropic conductive films (ACF), anisotropic conductive pastes For example, can be cited.

Potting, dipping, transfer mold sealing for ICs, LSIs, etc .; potting sealing for COB, COF, TAB, etc. for ICs and LSIs; underfill for use in flip chips, etc. for encapsulants, transistors, diodes, light emitting diodes, And sealing (including underfill for reinforcement) when mounting IC packages such as QFP, BGA, and CSP.

The cured product obtained in the present invention can be used for various uses including optical component materials. The optical material is a general material used for passing light such as visible light, infrared light, ultraviolet light, X-ray, and laser through the material. More specifically, other sealing materials for LEDs such as a lamp type, an SMD type, and the like are listed below. A liquid crystal film such as a substrate material in a liquid crystal display field, a light guide plate, a prism sheet, a deflection plate, a retardation plate, a viewing angle correcting film, an adhesive, and a polarizer protective film. In addition, the LEDs used in the color PDP (plasma display) sealant, antireflection film, optical compensation film, housing material, protective film for the front glass, substitute material for the front glass, adhesive, A light guide plate, a prism sheet, a deflecting plate, a retardation plate, a viewing angle correcting film, an adhesive, and a substrate for a plasma addressed liquid crystal display (PALC) A protective film for a front glass in an organic EL (electroluminescence) display, an alternative material for a front glass, an adhesive, various film substrates in a field emission display (FED), a front glass Protective film, glass replacement material, and adhesive. In the field of optical recording, a disk substrate material for a VD (video disk), a CD / CD-ROM, a CD-R / RW, a DVD-R / DVD-RAM, a MO / MD, a PD A lens, a protective film, a sealing material, and an adhesive.

In the field of optical instruments, it is a lens material for a still camera, a finder prism, a target prism, a finder cover, and a light receiving sensor part. It is also a photographing lens and a finder of a video camera. Further, projection lenses, protective films, sealing materials, and adhesives of projection televisions and the like are used. Materials for lenses of optical sensing devices, sealing materials, adhesives, and films. In the field of optical components, fiber materials, lenses, waveguides, sealing materials of devices, adhesives, etc. around optical switches in optical communication systems. An optical fiber material around the optical connector, a ferrule, a sealing material, and an adhesive. Optical passive components, optical circuit components, lenses, waveguides, LED sealing materials, CCD sealing materials, and adhesives. A substrate material, a fiber material, a sealing material of an element, and an adhesive in the vicinity of an optoelectronic integrated circuit (OEIC). In the field of optical fiber, it is an optical fiber for connection to digital devices such as sensors for industrial use, illumination / light guide for decorative display, display / mark, communication infrastructure, and home digital devices. In the semiconductor integrated circuit peripheral material, it is a resist material for microlithography for LSI and super LSI materials. In the field of automobiles and transportation vehicles, it is used in automobile lamp reflector, bearing retainer, gear part, corrosion coat, switch part, head lamp, engine parts, electric parts, various internal and external parts, drive engine, brake oil tank, , Interior materials, wire nets for protection and bonding, fuel hoses, automobile lamps, and glass substitutes. Further, it is a multilayer glass for a railway car. Also, the toughness-imparting agent of the structural material of the aircraft, the members around the engine, the wire ness for protection and binding, and the corrosion-resistant coat. In the construction sector, it is used for interior and working materials, electric covers, sheets, glass interlayers, glass substitutes, and solar cell materials. For agricultural use, it is a house film. As a next-generation optoelectronic functional organic material, it is possible to use an organic EL device peripheral material, an organic photorefractive element, an optical amplifier as a photo-optical conversion device, an optical computing element, a substrate material around organic solar cells, Adhesives and the like.

Examples of encapsulants include potting, dipping, transfer mold sealing for potentiometers, transistors, diodes, light emitting diodes, ICs and LSIs, potting seals for COB, COF and TAB in IC and LSI, underfill for BGA, CSP And sealing (reinforcing underfill) at the time of mounting the IC package and the like.

Other applications of the optical material include general applications in which an epoxy resin composition is used, such as adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials Coatings, etc.), sealants, additives to other resins, and the like. Examples of the adhesive include adhesives for civil engineering, construction, automobile, general office, medical adhesive, and electronic materials. Among these, adhesives for electronic materials include interlayer adhesives for multilayer boards such as build-up substrates, adhesives for semiconductors such as die bonding agents and underfill, underfill for BGA reinforcement, anisotropic conductive films (ACF), anisotropic conductive pastes (ACP) , And the like.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples. The present invention is not limited to these Synthesis Examples and Examples. The physical properties in Examples were measured by the following methods.

(1) Molecular weight: The weight average molecular weight in terms of polystyrene measured by the GPC method under the following conditions was calculated.

Various conditions of GPC

Manufacturer: Shimadzu Corporation

Column: Guard column SHODEX GPC LF-G LF-804 (3 pieces)

Flow rate: 1.0 ml / min.

Column temperature: 40 ° C

Solvents used: THF (tetrahydrofuran)

Detector: RI (differential refraction detector)

(2) Epoxy equivalent: measured by the method described in JIS K-7236.

(3) Viscosity: TOKI SANGYO CO., LTD. Production Measurement at 25 ° C using an E-type viscometer (TV-20).

Example 1

The flask equipped with a stirrer, a reflux condenser, and a stirrer was evacuated once and purged with nitrogen, and a phenol compound (TPA1) (TrisP-PA HONSHU CHEMICAL , 370 parts of epichlorohydrin, 37 parts of methyl glycidyl ether and 37 parts of methanol, and the water bath was heated to 75 占 폚. As a result of the internal temperature exceeding 65 캜, 42 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then further reacted at 70 캜 for 1 hour. After completion of the reaction, the reaction mixture was washed with water, and a solvent such as excess epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 占 폚 using a rotary evaporator. 400 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 占 폚. After 8 hours of 30% by weight aqueous sodium hydroxide solution was added under stirring, the reaction was carried out for 1 hour, followed by washing with water until the wash water became neutral. The obtained solution was treated with methyl isobutyl Ketone and the like were distilled off to obtain 182 parts of an epoxy resin (EP1). The obtained epoxy resin had an epoxy equivalent of 222 g / eq., A softening point of 59.6 ° C, an ICI melt viscosity of 0.10 Pa · s (150 ° C) and a color of 0.2 or less (Gardner 40% methyl ethyl ketone (MEK) solution). Mn was 582, Mw was 695, and Mw / Mn was 1.19 (in terms of polystyrene). Total chlorine was 960 ppm. As a result of GPC measurement, it was found that 69.8 area% of the compound of the formula (2), 14.7 area% of the alcohol adduct of the formula (3) and 13.4 area% of the other multimers.

Examples 1-2

Synthesis was carried out in the same manner as in Example 1 except that no methyl glycidyl ether was added.

The obtained epoxy resin (EP2) had an epoxy equivalent of 209 g / eq., A softening point of 60.0 占 폚, an ICI melt viscosity of 0.09 Pa 占 퐏 (150 占 폚) and a color of 0.2 or less (Gardner 40% MEK solution). Mn was 571, Mw was 673, Mw / Mn was 1.18 (in terms of polystyrene), and total chlorine was 1020 ppm. Further, as a result of GPC measurement, 80.3% by area of the compound of the formula (2), 2.2% by area of the alcohol adduct of the formula (3) and 14.1% by area of the other multimers.

Example 2 and Comparative Example 1

Epoxy resin (EP3 manufactured by Nippon Kayaku Co., Ltd., NC-6000, epoxy equivalent: 208 g / eq., Softening point: 60.2 占 폚, GPC result: (GPC) Mn 574 Mw 677 (in terms of polystyrene), Gardner color 1), as a curing agent, 87.1% by area, 87.1% by area, an alcohol adduct of formula (Manufactured by MEIWA PLASTIC INDUSTRIES, LTD., Manufactured by Phenol novolac H-1, hereinafter referred to as PN1) was used in a ratio (parts by weight) shown in the following Table 1, and mixed and kneaded uniformly using a mixing roll, To obtain an epoxy resin composition. This epoxy resin composition was pulverized with a mixer and tabulated with a tablet machine. This tabletted epoxy resin composition was transferred (175 DEG C for 60 seconds) and further demolded and cured under the conditions of 160 DEG C x 2 hours + 180 DEG C x 6 hours to obtain evaluation test pieces.

The physical properties of the cured product were measured in the following manner.

<Bending strength>

Measured according to JIS K-6911

<IZOD impact test conditions>

Measured according to JIS K-6911

From the results, it can be seen that the epoxy resin of the present invention is effective in improving the drift.

Although the present invention has been described in detail with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

The present application is based on Japanese patent application (Japanese Patent Application No. 2013-005317) filed on Jan. 16, 2013, which is incorporated by reference in its entirety. In addition, all references cited herein are taken as a whole.

The epoxy resin composition containing the epoxy resin of the present invention can be applied to optical members requiring high optical properties.

Claims (9)

(1) and epihalohydrin, and wherein, in the measurement by GPC (Gel Permeation Chromatography), glycidyl of 1% by area to 20% by area of the triglycidyl ether compound Wherein the epoxy group is an alcohol moiety represented by the following formula (A).

[In the above formula (A), each R independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and * bonds to an oxygen atom. And two R's do not together form a hydrogen atom or an alkyl group having 1 to 5 carbon atoms] The method according to claim 1,
Wherein the reaction of the compound of formula (1) with epihalohydrin is carried out in a mixed solution of epihalohydrin and an alcohol having 1 to 5 carbon atoms. 3. The method according to claim 1 or 2,
Wherein after the completion of the reaction of the compound of the formula (1) and epihalohydrin, a solution of toluene or a ketone compound having 4 to 7 carbon atoms in carbon number is obtained and the solution is post-treated with a metal hydroxide aqueous solution. An epoxy resin composition comprising the epoxy resin according to any one of claims 1 to 3 as an essential component. 5. The method of claim 4,
Wherein the epoxy resin composition contains a transition metal salt. 5. The method of claim 4,
A quaternary ammonium salt, and a quaternary phosphonium salt. 5. The method of claim 4,
An epoxy resin composition comprising a non-halogen quaternary ammonium salt. 8. The method according to any one of claims 4 to 7,
An epoxy resin composition comprising at least one of an acid anhydride and a polycarboxylic acid as a curing agent. A cured product obtained by curing the epoxy resin composition according to any one of claims 4 to 8.