KR20150031232A - Epoxy resin, epoxy resin composition and cured product - Google Patents

Abstract

(식 중, 복수 존재하는 R은 각각 독립해서 존재하고, 수소원자, 탄소수 1∼6의 알킬기, 또는 탄소수 1∼6의 알콕시기를 나타낸다.)The curable epoxy resin composition may contain an epoxy resin containing the compound represented by the following formula (1) as a main component in an amount of 70 to 95% (gel permeation chromatography area%) and containing the epoxy resin and a curing agent or a curing catalyst have.

(Wherein the plural Rs present independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms)

Description

EPOXY RESIN, EPOXY RESIN COMPOSITION AND CURED PRODUCT < RTI ID = 0.0 >

TECHNICAL FIELD The present invention relates to an epoxy resin, an epoxy resin composition, and a cured product thereof suitable for use in electric and electronic materials requiring heat resistance.

BACKGROUND ART Epoxy resin compositions are widely used in fields such as electric and electronic parts, structural materials, adhesives, paints and the like due to workability and excellent electrical properties, heat resistance, adhesiveness, moisture resistance (water resistance)

In recent years, however, in the field of electric and electronic fields, in accordance with the development of the resin composition, the viscosity of the resin composition has been increased, and the viscosity, adhesiveness, dielectric properties, low viscosity for high filling of the filler (inorganic or organic filler) The improvement of various characteristics such as the upsizing of the semiconductor device is required more. In addition, as a structural material, there is a demand for materials that are light in weight and excellent in mechanical properties for use in aerospace materials, leisure sports equipment, and the like. Particularly, in the field of semiconductor encapsulation and the substrate (substrate itself or peripheral materials), it is required to have a very high level of heat resistance and high fluidity required characteristics such as thinning, stacking, systemization, and three- do. Particularly, in accordance with the expansion of the plastic package to the in-vehicle use, the demand for improvement of the heat resistance becomes more strict, and it is a resin having a high Tg and a low linear expansion rate, naturally it is required to respond to solder reflow, , Or maintenance is required.

 JEITA Semiconductor Technology Roadmap Expert Committee, [2012] JEITA Semiconductor Technology Roadmap Expert Committee, 2008, STRJ Report, Report on Semiconductor Roadmap Expert Committee, 2008, Chapter 8, p1-1, [online] May 30 search], <http://strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm>  Takayuki Nobuyuki, Matsushita Denko Kibo Tea Device technology High-temperature operation IC for vehicle, No. 74, Japan, May 31, 2001, pp. 35-40

Heat resistance is one of the characteristics that is particularly required for high performance. Heat resistance has conventionally been regarded as important, but in general, when the heat resistance is increased, problems such as deterioration of absorption characteristics and deterioration of flame retardancy occur at the same time, making it difficult to achieve compatibility.

Therefore, development of an epoxy resin capable of achieving both characteristics that are inferior to heat resistance has been expected.

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) An epoxy resin containing 70 to 95% (gel permeation chromatography area%) of a compound represented by the following formula (1) as a main component.

(Wherein the plural Rs present independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms)

(2) The epoxy resin according to (1) above, wherein the epoxy equivalent is 1.02 to 1: 1 based on the theoretical epoxy equivalent.

(3) The epoxy resin according to (1) above, wherein the total chlorine content is 5,000 ppm or less.

(4) An epoxy resin composition comprising the epoxy resin according to any one of (1) to (3) and a curing agent as essential components.

(5) An epoxy resin composition comprising an epoxy resin according to any one of (1) to (3) and a curing catalyst as essential components.

(6) A cured product obtained by curing the epoxy resin composition according to any one of (4) to (5).

.

(Effects of the Invention)

Since the cured product of the present invention has excellent heat resistance, absorption characteristics and flame retardancy, it can be used as an insulating material for electrical and electronic parts, a laminated board (printed wiring board, build-up substrate, etc.), various composite materials including CFRP, .

The epoxy resin of the present invention relates to an epoxy resin having a phenolphthalein skeletal derivative structure. The basic skeleton of the epoxy resin of the present invention is disclosed in British Patent No. 1158606 (Patent Document 1). According to Patent Document 1, the epoxy equivalents per kg is 3.4 (294 g / eq in terms of the current epoxy equivalent), the color is Gardner 8 (40% in methyl glycol), the softening point is 66 ° C. (kolfer heater) An epoxy resin having a phenolphthalein skeletal derivative structure of 2.2% is disclosed. In addition, physical properties of curing with DDS (diaminodiphenylsulfone) are disclosed.

This resin from the present data has a very large amount of chlorine, which is not suitable for use in electronic materials, and since it is highly colored, it is suggested that it is difficult to use in applications where color beauty is required. The epoxy equivalent of 294 g / eq., Which is larger than the theoretical value (252.7 g / eq.), Suggests that the epihalohydrin structure is retained without closure of the epoxy due to the chlorine content. If the structure is such that the epoxy ring is not completed in spite of the fact that the epoxy ring is not completely formed, crosslinking does not proceed well, and when curing with a phenol resin, anion polymerization with a basic catalyst such as imidazole, or cation polymerization with an onium salt, There are many problems in characteristics such as characteristics and absorbency. Particularly, in the use of electronic materials, not only these curing but also curing of the amine system is expected to cause corrosion of the wiring caused by the glass of the chlorine at the time of curing, which is a factor to deteriorate the electrical reliability.

In recent years, there have been many cases in which copper wires are used for joining semiconductor chips and substrates, and the problem of such electric corrosion becomes more important and becomes a problem to be solved.

The epoxy resin of the present invention is represented by the following formula (1)

(Wherein the plurality of R's present independently exist and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms) in an amount of 70 to 95% (gel permeation chromatography %), And more preferably 70 to 93%. Here, when synthesizing a compound having a purity of more than 95% in the content of the compound represented by the above formula (1), it is industrially undesirable because it has enormous energy, and when the purity is excessively high, However, there is a possibility that the toughness deteriorates. If it is less than 70%, the ring of the epoxy is not completely ring-closed and a compound having no functional group is contained in a large amount, which is not preferable. Most of these compounds which are not completely ring-closed contain chlorine in many cases. As for the use of electronic materials, it is not preferable because the glass of chlorine ions under high temperature and high humidity conditions and the corrosion of the wiring due to this are concerned.

If the epoxy resin having a phenolphthalein structure remains in the present epoxy resin, the epoxy resin having a phenolphthalein structure is not preferable, and preferably 2% or less, particularly preferably 2% or less, Is less than 1%. The epoxy resin having the phenolphthalein structure is largely influenced by impurities derived from the raw material. If it exceeds 2%, coloring becomes particularly strong, which is not preferable.

Most preferred for R is a hydrogen atom. Examples of the alkyl group having 1 to 6 carbon atoms represented by R include straight, branched or cyclic alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group. Here, R is preferably a methyl group or an ethyl group, and a methyl group is particularly preferable.

Examples of the alkoxy group having 1 to 6 carbon atoms represented by R include a straight chain, branched chain or cyclic alkoxy group such as methoxy group, ethoxy group, propoxy group and butoxy group. Here, R is preferably a methoxy group, an ethoxy group or a propoxy group, and a methoxy group is particularly preferable.

The epoxy resin equivalent of the epoxy resin containing the compound represented by the above formula (1) is preferably 1.02 to 1.13 times the theoretical epoxy equivalent. More preferably, it is 1.03 to 1.10 times. If it is less than 1.02 times, the synthesis and refining of epoxy may require a great deal of cost, and if it exceeds 1.11 times, there may be a problem due to the above-described amount of chlorine.

The total chlorine remaining in the epoxy resin obtained by the reaction is preferably 5,000 ppm or less, more preferably 3,000 ppm or less, particularly preferably 2,000 ppm or less. The adverse effects due to the chlorine amount are the same as described above. Further, it is preferably not more than 5 ppm, more preferably not more than 3 ppm, for chlorine ion and sodium ion, respectively. Chlorine ions are described above, and needless to say, cationic ions such as sodium ions are also a very important factor in power device applications, and are one cause of the failure mode when a high voltage is applied.

Here, the theoretical epoxy equivalent represents the epoxy equivalence calculated when the phenolic hydroxyl group of the phenol compound represented by the following formula (P) is glycidylated without excess.

(Wherein R has the same meaning as defined above).

The specific epoxy equivalent is preferably 257.8 g / eq. To 285.6 g / eq., And more preferably 260.3 g / eq. To 278.0 g / eq., When all R are hydrogen atoms. When the epoxy equivalent is within the above range, an epoxy resin excellent in heat resistance and electrical reliability of the cured product can be obtained.

The epoxy resin of the present invention has a resin-like shape having a softening point. Here, the softening point is preferably 70 to 130 占 폚, more preferably 80 to 120 占 폚. When the substituent R is a hydrogen atom, it is particularly preferably 70 to 120 캜, more preferably 80 to 110 캜. If the softening point is too low, blocking at the time of storage becomes a problem, and there are many problems such as handling at low temperatures. On the other hand, when the softening point is excessively high, there is a case where the handling becomes poor at the time of kneading with another resin. Further, the melt viscosity is preferably 1 Pas 占 (ICI melt viscosity 150 占 폚 cone plate method) or less. When a mixture of an inorganic material (such as a filler) is used, the fluidity is poor, and the glass cloth or the like becomes finer and the impregnability is lowered.

The epoxy resin of the present invention is excellent in transparency (color). It is preferably 2 or less and more preferably 1.5 or less in Gardner colorimetric method [visual 40% MEK (methyl ethyl ketone) solution]. Particularly, in general PCB substrates and the like as well as development in optical materials, it is required to have little coloring because it affects the color of the substrate.

Further, the epoxy resin of the present invention has a high refractive index. Preferably 1.61 or more, more preferably 1.62 or more, and particularly preferably 1.62 to 1.65. Particularly, in the field where the refractive index is required to be adjusted, the higher the refractive index, the lower the directional turnover of the composition to be used and contribute to the improvement of the light resistance characteristic. Further, in applications such as lenses, it is preferable to use a lens having a smaller refractive index as the refractive index becomes higher.

Hereinafter, a method for producing an epoxy resin of the present invention will be described.

The epoxy resin of the present invention containing the compound represented by the above formula (1) can be produced by reacting an epoxy resin represented by the formula (P) synthesized from a phenolphthalein derivative and an aminobenzene derivative (for example, JP 2005-290378 A ) Can be obtained by the reaction of a phenolic compound (DPPI) with epihalohydrin. A specific example of the production method of the epoxy resin of the present invention is shown below.

It is known that phenolphthalein derivatives can be synthesized with phthalic acid and various phenols. When the phenol used is phenol, phenolphthalein is obtained, and when cresol is used, cresol phthalein is obtained.

Examples of the various phenols include phenol, cresol, ethyl phenol, propyl phenol, xylenol and methyl butyl phenol.

The phenolphthalein derivative obtained by the above synthesis includes, for example, a structure represented by the following formula (2).

(Wherein R has the same meaning as defined above, and n represents an integer of 1 to 2.)

Examples of the aminobenzene derivative include those represented by the following formula (3).

(Wherein R represents the same meaning as described above, and m represents an integer of 1 to 2.)

The amount of the residual phenolphthalein derivative in the phenol compound (DPPI) is preferably not more than 2%, more preferably not more than 1%, further preferably not more than 0.5%, particularly preferably not more than 0.1% (by high performance liquid chromatography Measure). When this phenolphthalein derivative remains, the coloration tends to increase during the reaction. The same applies to aminobenzene derivatives. The amount of residual iron (ICP emission analysis) is also one of the factors due to the coloring. The residual iron content is preferably 100 ppm or less, more preferably 50 ppm or less, particularly preferably 10 ppm or less. The main phenolic compound (DPPI) is required to have a purity of 98% or more.

The amount of residual phenolphthalein derivative can be adjusted by purification (cleaning, recrystallization, re-precipitation, etc.) of DPPI.

In the reaction for obtaining the epoxy resin of the present invention, epihalohydrin is preferably epichlorohydrin which is industrially readily available. The amount of the epihalohydrin to be used is generally 3.0 to 15 mol, preferably 3.0 to 10 mol, more preferably 3.5 to 8.5 mol, particularly preferably 5.5 to 8.5 mol per mol of the hydroxyl group of the phenol compound (DPPI) It is mall.

When the amount is less than 3.0 moles, the epoxy equivalence may become large, and the workability of the produced epoxy resin may be deteriorated. If it exceeds 15 moles, the amount of the solvent becomes large.

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 matter or an aqueous solution thereof may be used. In the present invention, Is preferred.

The amount of the alkali metal hydroxide to be used is generally 0.90 to 1.5 moles, preferably 0.95 to 1.25 moles, more preferably 0.99 to 1.15 moles, per 1 mole of the hydroxyl group of the raw material phenol mixture.

A quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride may be added as a catalyst in order to promote 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 starting phenol mixture.

In the present reaction, it is preferable to use a nonpolar proton solvent (dimethylsulfoxide, dioxane, dimethylimidazolidinone, etc.) or an alcohol having 1 to 5 carbon atoms in addition to the epihalohydrin. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol and isopropyl alcohol. The amount of the nonpolar proton solvent or the alcohol having 1 to 5 carbon atoms is usually 2 to 50% by weight, preferably 4 to 25% by weight based on the amount of epihalohydrin used. In addition, the exocytosis may be carried out while controlling moisture in the system by a method such as azeotropic dehydration.

When the water content in the system is large, the electrical reliability of the obtained epoxy resin may be deteriorated, and it is preferable to control the water content to 5% or less. In addition, when an epoxy resin is obtained by using a nonpolar proton solvent, an epoxy resin having excellent electrical reliability can be obtained, so that a nonpolar proton solvent can be suitably used.

The reaction temperature is usually from 30 to 90 캜, preferably from 35 to 80 캜. Particularly, in the present invention, the reaction temperature is preferably 60 DEG C or higher for a higher purity of the epoxidation, and the reaction under the condition close to the reflux condition is particularly preferable. 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 does not proceed to the end, and if the reaction time is prolonged, by-products are generated, which is not preferable.

Epihalohydrin, a solvent, and the like are removed from the reaction product of these epoxidation reactions after washing with water or without heating and under reduced pressure. In order to make the hydrolyzable halogen less epoxy resin, the recovered epoxy resin is mixed with 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 usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 mol of the hydroxyl group of the starting phenol mixture used for the epoxidation. The reaction temperature is usually from 50 to 120 캜, and the reaction time is usually from 0.5 to 2 hours.

Further, in the reaction with epihalohydrin, it is preferable that the inert gas is substituted with an inert gas such as nitrogen from the beginning of the reaction, and the oxygen concentration in the syngas is preferably 10% or less. Residual oxygen affects the coloring. As a method, an inert gas such as nitrogen may be blown (in a gas or a liquid) before the introduction of a phenol compound (DPPI), or a step of evacuating by a reduced pressure and then substituting with an inert gas. If there is no substitution with an inert gas, the resultant resin may be colored. When the inert gas is blown in, the amount thereof varies depending on the volume of the reaction vessel, but it is preferable to blow the inert gas in an amount capable of displacing 1 to 3 times the volume of the reaction vessel in 0.5 to 10 hours Do.

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 composition of the present invention contains the epoxy resin and curing catalyst of the present invention as essential components. It is also preferable that other epoxy resins or curing agents are contained as optional components.

The epoxy resin composition of the present invention may contain an epoxy resin in addition to 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 that 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'-tetramethyl - [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (Phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene and the like) with formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o- Hydroxybenzophenone, dicycloheptene dihydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (Methoxymethyl) -1,1'-biphenyl, 1,4-bis (chloromethyl) benzene or 1,4-bis (methoxymethyl) benzene and their modifications, tetrabromobisphenol Halogenated bisphenols such as A Alicyclic epoxy resins, glycidylamine epoxy resins, glycidyl ester epoxy resins, silsesquioxane epoxy resins (chain, cyclic, ladder, or their derivatives) derived from alcohols, alicyclic epoxy resins, Or an epoxy resin having a glycidyl group and / or an epoxy cyclohexane structure in a siloxane structure having at least two or more mixed structures), and the like. However, the present invention is not limited thereto.

In particular, when the epoxy resin composition of the present invention is used for optical purposes, 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 cyclohexenecarboxylic acid with alcohols or an esterification reaction of cyclohexene methanol with carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980) (Described in JP-A-2003-170059, JP-A-2004-262871, etc.) of cyclohexene aldehyde and transesterification reaction of cyclohexenecarboxylic acid ester A method described in, for example, Japanese Patent Application Laid-Open No. 2006-052187).

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 such as hexane diol and cyclohexane dimethanol, triols such as glycerin, trimethylol ethane, trimethylol propane, trimethylol butane and 2-hydroxymethyl-1,4-butanediol, 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.

Examples of the compound having a cyclohexene structure other than the above include an acetal compound obtained by an acetal reaction between a cyclohexene aldehyde derivative and an alcohol. As a reaction method, it can be prepared by applying a general acetalization reaction. For example, there can be used a method in which a reaction is carried out while azeotropically dehydrating a reaction medium with a solvent such as toluene or xylene (U.S. Patent No. 2945008) (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 reacting an organic solvent (Japanese Patent Application Laid-Open No. 7-215979), a method using a solid acid catalyst (Japanese Patent Application Laid-Open No. 2007-230992), and the like. From the stability of the structure, a cyclic acetal structure is preferable.

Specific examples of these epoxy resins include ERL-4221, UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical), Celloxide 2021P, Epolide GT401, EHPE3150 and EHPE3150CE And dicyclopentadiene epoxide. However, the present invention is not limited to these examples (Reference: General Synthetic Epoxy Resin Foundation I p76-85).

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

Specific examples of the curing catalyst 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- But are not limited to, imidazole, imidazole, triazole, tetrazole 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, Benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-benzyl- 2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-s-triazine, 2,4- (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2'-ethyl, 4-methylimidazole Azine, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole Phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl- , And 5-dicyanoethoxymethylimidazole, and heterocyclic compounds such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid , Salts of polyvalent carboxylic acids such as oxalic acid, amides such as dicyandiamide, diaza compounds such as 1,8-diazabicyclo (5.4.0) undecene-7, and their tetraphenylborates, phenols Novolaks, salts with polycarboxylic acids or phosphines, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethyl Ammonium hydroxide, trimethylpropylammonium hydroxide, trimethylene Ammonium salts such as butyl ammonium hydroxide, trimethyl cetyl ammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate and trioctylmethylammonium acetate , Phosphines such as triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide and tetraphenylphosphonium tetraphenylborate, phosphonium compounds such as 2,4,6-trisaminomethylphenol and the like, Amine salts such as zinc salts, tin salts, and zirconium salts of carboxylic acid metal salts (2-ethylhexanoic acid, stearic acid, behenic acid and mystric acid), phosphate ester metal salts (such as octylphosphoric acid, ), Alkoxy metal salts (tributyl aluminum, tetrapropyl zirconium and the like), acetylacetone salts (acetylacetone zirconium chelate, Etc.) and the like can be mentioned. In the present invention, phosphonium salts, ammonium salts, and metal compounds are particularly preferable in terms of coloration upon curing and changes thereof. Also, when quaternary salt is used, a salt with a halogen may leave a halogen in the cured product.

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 thereof include amine compounds, acid anhydride compounds, amide compounds, phenol resins, and carboxylic acid compounds. Specific examples of the curing agent that can be used include polyamides synthesized from dimers of diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, dianododiphenylsulfone, isophoronediamine, dicyandiamide, linoleic acid and ethylenediamine Nitrogen-containing compounds such as resins (amines, amide compounds); Examples thereof include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, anhydrous nadic acid, 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 Acid anhydrides such as 1,3,4-tricarboxylic acid-3,4-anhydride; A carboxylic acid resin obtained by an addition reaction of various alcohols, carbinol-modified silicon and the above-mentioned acid anhydride; 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, 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 A phenol resin such as a condensate; An imidazole, a trifluoroborane-amine complex, and a compound of a guanidine derivative, but the present invention is not limited thereto. These may be used alone or in combination of two or more.

In the present invention, the above-mentioned phenol resin is particularly preferable for use in electronic materials applications.

The amount of the curing agent to be used in the curable 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, the curing is incomplete in all cases and good cured properties may not be obtained.

In addition, the use of a cyanate ester compound as the other component is preferable. In addition to the curing reaction of the cyanate ester compound alone, the cyanate ester compound can be made into a heat-resistant cured product having a higher crosslink density by the reaction with the epoxy resin. 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 be synthesized by reacting various phenol resins with cyanide or their salts, for example, as described in the above-mentioned hardening material. In the present invention, particularly preferred are those having a structure in which no methylene structure of the benzyl position is present in the molecule, such as 2,2-bis (4-cyanate phenyl) propane or its derivatives (partial polymerizers and the like) These may be used alone or in combination of two or more.

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, tricilylenyl phosphate, cresyldiphenyl phosphate, cresyl-2,6-dicylenyl phosphate, Phosphoric acid esters such as 1,4-phenylenebis (dicylenylphosphate) and 4,4'-biphenyl (dicylenylphosphate); 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H- ; Phosphorus-containing epoxy compounds obtained by reacting an epoxy resin with the active hydrogen of the above-mentioned phosphates, and red phosphorus. Of these, phosphoric acid esters, phosphates or phosphorus-containing epoxy compounds are preferable, and 1,3- Phenylenebis (dicylenylphosphate), 4,4'-biphenyl (dicylenylphosphate) or phosphorus-containing epoxy compounds are particularly preferred. The content of the phosphorus-containing compound is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (weight ratio). If it is less than 0.1, flame retardancy is insufficient, and if it is more than 0.6, hygroscopicity and dielectric properties of the cured product may be adversely affected.

In the epoxy resin composition of the present invention, a binder resin may be blended if necessary. 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, But the present invention is not limited thereto. 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, talc, Beads, and the like. However, the present invention is not limited to these. 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 antioxidants, light stabilizers, silane coupling agents, stearic acid, palmitic acid, zinc stearate, release agents such as calcium stearate, pigments, and various thermosetting resins have. Particularly, for the coupling agent, it is preferable to add a coupling agent having an epoxy group or a coupling agent having a thiol.

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 a method similar to a conventionally known method. For example, when 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 uniformized using an extruder, a kneader, a roll, a planetary mixer or the like To obtain an epoxy resin composition. When the obtained epoxy resin composition is in a liquid phase, the composition is impregnated into a substrate by potting or casting, or is poured into a mold to be molded, and then cured by heating. When the obtained epoxy resin composition is solid, it is molded after molding by use of a mold, a transfer molding machine or the like, and is cured by heating. The curing temperature and time are 80 to 200 캜 and 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 that the temperature is raised by a stepwise and the curing reaction proceeds. Concretely, initial curing is performed at 80 to 150 캜, and post-curing is performed at 100 to 200 캜. 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 or N-methylpyrrolidone to prepare a curable resin composition varnish, A prepreg obtained by impregnating a substrate such as a glass fiber, a carbon fiber, a polyester fiber, a polyamide fiber, an alumina fiber, or paper by heating and drying is hot-pressed to obtain a cured product of the epoxy resin composition of the present invention. The amount of the solvent used is usually from 10 to 70% by weight, preferably from 15 to 70% by weight, in the mixture of the epoxy resin composition of the present invention and the solvent.

The epoxy resin composition of the present invention may also be used as a film-like sealing composition. In the case of obtaining such a film-like resin composition, the curable resin composition of the present invention is coated with the varnish on a release film, the solvent is removed under heating, and B staging is performed 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, and as a batch film sealing of optical semiconductors.

Specific examples of applications of these compositions include adhesives, paints, coatings, molding materials (including sheets, films, FRP and the like), insulating materials (sealing materials including printed boards and wire coatings, sealing materials, cyanate resin compositions ), An acrylic acid ester-based resin as a curing agent for a resist, and additives to other resins. In the present invention, it is particularly preferable to use an insulating material for electronic materials (a sealing material including a printed substrate, a wire coating, etc., a sealing material, and a cyanate resin composition for a substrate).

Examples of the adhesive include adhesives for electronic materials, as well as adhesives for civil engineering, construction, automobile, general office, and medical applications. Examples of the adhesive for electronic materials include adhesives for semiconductors such as die-bonding agents and underfill, adhesives for BGA reinforcement, anisotropic conductive films (ACF), anisotropic conductive pastes (ACP), etc. And an adhesive for mounting of the adhesive layer.

Potting, dipping, transfer mold sealing for IC, LSI, and other potting seals such as COB, COF, TAB for flip chip, etc. for encapsulants, substrates, capacitors, transistors, diodes, light emitting diodes Sealing (including reinforcing solder) and package substrates for mounting IC packages such as adhesive, QFP, BGA, and CSP. It is also suitable for use as a network board or a board requiring functionality such as a module board.

Example

EXAMPLES The present invention will be described in more detail with reference to the following examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples.

Various analytical methods used in the examples are described below.

Epoxy equivalent: according to JIS K 7236 (ISO 3001)

ICI Melt Viscosity: According to JIS K 7117-2 (ISO 3219)

Softening point: according to JIS K 7234

Total chlorine: According to JIS K 7243-3 (ISO 21672-3)

Chloride ion: According to JIS K 7243-1 (ISO 21672-1)

Sodium ion: Determined by ion chromatography

Iron: ICP emission spectrometric analysis

Refractive index: according to ISO 5661

Gardner Color: According to ISO 4630-1

GPC: Column (Shodex KF-603, KF-602x2, KF-601x2)

The connecting eluent was tetrahydrofuran

The flow rate is 0.5 ml / min.

The column temperature was 40 [

Detection: RI (differential refraction detector)

Example 1

(DPPI1) [prepared by dissolving the phenol compound (DPPI1) in a nitrogen atmosphere (oxygen concentration: 4.9%) and nitrogen purge (2 L / hr) under vacuum once in a 1 L four-necked flask equipped with a stirrer, a reflux condenser and an agitator 256 parts of residual phenolphthalein having a purity of 99% or higher and a content of iron powder of <5 ppm, 842 parts of epichlorohydrin and 180 parts of methanol were added in the compound (P) in which all substituents R were hydrogen atoms, and the water bath was heated to 75 ° C did. When the internal temperature exceeded 65 캜, 21 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further performed 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. 600 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 캜. 26 parts of an aqueous solution of 30% by weight of sodium hydroxide was added under stirring, and the reaction was carried out for 1 hour. Thereafter, the mixture was washed with water until the washing water became neutral, and the obtained solution was treated with methyl isobutyl ketone And the like were distilled off to obtain 305 parts of an epoxy resin (EP1). The obtained epoxy resin had an epoxy equivalent of 266 g / eq., A softening point of 89 占 폚, an ICI melting point of 0.42 Pa 占 퐏 (150 占 폚), a total chlorine content of 1600 ppm, a hydrolyzable chlorine of 1540 ppm, a chlorine ion of 2 ppm, (Gardner 40% MEK (methyl ethyl ketone) solution). The structure of the above formula (1) was 93 area% (GPC).

Example 2

A 1 L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen (oxygen concentration: 5.3%) once under vacuum, and subjected to nitrogen purge (2 L / hr) A compound SABIC PPPBP having a purity of not less than 99% and 200 ppm of residual phenolphthalein, 500 ppm of phenolphthalein in addition to iron powder of not more than 5 ppm] was used in the formula (P). The resulting epoxy resin (EP2) had an epoxy equivalent of 266 g / eq., A softening point of 90 占 폚, an ICI melting point of 0.44 占 퐏 (150 占 폚), a total chlorine content of 2000 ppm, a hydrolyzable chlorine of 1950 ppm, a chlorine ion of 1 ppm, Color 0.2 [Gardner 40% MEK solution]. The structure of the above formula (1) was 93 area% (GPC).

Example 3

(DPPI1) [2] was introduced into a 1 L four-necked flask equipped with a stirrer, a reflux condenser and a stirrer under nitrogen purge for 30 minutes at 4 L / h (oxygen concentration 6.5% 256 parts of residual phenolphthalein having a purity of not less than 99% and a sulfur content of not more than 5 ppm, 661 parts of epichlorohydrin and 165 parts of methanol were added in the above compound (P) in which all substituent groups R were hydrogen atoms, and the water bath was heated to 75 DEG C It has warmed up. When the internal temperature exceeded 65 캜, 57 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then the reaction was further performed 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. 600 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 占 폚. And 5 parts of an aqueous solution of 30% by weight of sodium hydroxide were added thereto under stirring. After the reaction was carried out for 1 hour, washing was carried out until washing water became neutral, and the obtained solution was treated with methyl isobutyl ketone And the like were distilled off to obtain 297 parts of an epoxy resin (EP3). The resulting epoxy resin had an epoxy equivalent of 277 g / eq., A softening point of 96 占 폚, an ICI melting point of 0.62 Pa 占 퐏 (150 占 폚), a total chlorine content of 2230 ppm, a hydrolyzable chlorine of 2100 ppm, a chlorine ion of 0.5 ppm, Or less [Gardner 40% MEK solution]. The structure of the above formula (1) was 82 area% (GPC).

Example 4

(DPPI1) [wherein, in the formula (1), a 1-L four-necked flask equipped with a stirrer, a reflux condenser and an agitator was once evacuated and purged with nitrogen (oxygen concentration 5.2% , 256 parts of residual phenolphthalein having a purity of not less than 99% and an iron content of not more than 5 ppm, 661 parts of epichlorohydrin and 200 parts of dimethyl sulfoxide were added, and the water bath was heated to 45 DEG C It has warmed up. When the internal temperature exceeded 40 캜, 57 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further performed 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. 600 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 占 폚. 16 parts of a 30% by weight aqueous solution of sodium hydroxide was added under stirring, and the reaction was carried out for 1 hour. Thereafter, the mixture was washed with water until the washing water became neutral, and the obtained solution was treated with methyl isobutyl ketone And the like were distilled off to obtain 300 parts of an epoxy resin (EP4). The obtained epoxy resin had an epoxy equivalent of 270 g / eq., A softening point of 92 占 폚, an ICI melting point of 0.48 占 퐏 (150 占 폚), a total chlorine content of 1050 ppm, a hydrolyzable chlorine of 960 ppm, a chlorine ion of 0.3 ppm, [Gardner 40% MEK solution]. The structure of the above formula (1) was 90 area% (GPC).

Example 5

A flask equipped with a stirrer, a reflux condenser, and a stirrer was evacuated once, purged with nitrogen and subjected to nitrogen purge (2 L / hr) to obtain a phenol compound (DPPI3) Atomic phosphorus compound SABIC PPPBP Purity not less than 99% Residual phenolphthalein 210 ppm, iron content <5 ppm, phenolphthalein 1% added] The reaction was carried out in the same manner as in Example 1. The obtained epoxy resin (EP5) had an epoxy equivalent of 262 g / eq., A softening point of 89 占 폚, an ICI melting point of 0.42 Pa 占 퐏 (150 占 폚), a total chlorine content of 3200 ppm, a hydrolyzable chlorine content of 2700 ppm, a chlorine ion content of 5 ppm, Color 3 (Gardner 40% MEK solution). The structure of the above formula (1) was 90 area% (GPC).

Comparative Example 1

In a flask equipped with a stirrer, a reflux condenser and a stirrer, phenol compound (DPPI1) [compound SABIC PPPBP in which all substituent groups R are hydrogen atoms in the formula (P): 99% or more purity 200 ppm of residual phenolphthalein, iron content < 842 parts of epichlorohydrin and 3 parts of benzyltrimethylammonium chloride were added, and the water bath was heated to 70 ° C. 100 parts of a 49% sodium hydroxide aqueous solution was added dropwise thereto over 90 minutes, and then the reaction was further performed at 70 DEG C for 4 hours. After completion of the reaction, the reaction mixture was washed with water, and excess epichlorohydrin and other solvents were distilled off from the oil layer using a rotary evaporator at 140 DEG C under reduced pressure to obtain 290 parts of an epoxy resin (EP6). The obtained epoxy resin had an epoxy equivalent of 297 g / eq., A softening point of 95 캜, an ICI melting point of 0.70 Pa s (150 캜), a total chlorine content of 10450 ppm, a hydrolyzable chlorine content of 9700 ppm, a chlorine ion content of 0.5 ppm, (Gardner 40% MEK solution). The structure of the above formula (1) was 65 area% (GPC).

Example 6 and Comparative Example 2

(EP7 (trisphenol methane type epoxy resin, EPPN-502H manufactured by Nippon Kayaku K.K.), phenol aralkyl resin (manufactured by Mitsui Chemicals, Inc.) as a curing agent, and an epoxy resin (Hereinafter referred to as "MILLEX XLC-3L", hereinafter referred to as "PN1") were mixed in the proportions (parts by weight) shown in Table 1 and uniformly mixed and kneaded using a mixing roll to obtain a sealing epoxy resin composition. This epoxy resin composition was pulverized with a mixer, and tabletted by a tablet machine. The tableted epoxy resin composition was transferred (175 DEG C for 60 seconds), and after the demolding, test pieces for curing and evaluation were obtained under the conditions of 160 DEG C x 2 hours + 180 DEG C x 6 hours.

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

TMA (TM-7000 manufactured by Shin-Kori Co., Ltd., temperature rising rate: 2 占 폚 / min)

From this result, it was confirmed that the heat-resistant resin (Tg) was higher than the general trisphenol-methane-type epoxy resin as the high heat-resistant resin.

Example 7, Example 8 and Comparative Example 3

(EP5) for comparison with the epoxy resin (EP1, EP3) obtained above and phenol novolac (H-1, hereinafter referred to as PN2, manufactured by Meiwa Kasei Kogyo K.K.) as a curing agent were used, (Parts by weight), and they were uniformly mixed and kneaded using a mixing roll to obtain a sealing epoxy resin composition. This epoxy resin composition was pulverized with a mixer, and tabletted by a tablet machine. The tableted epoxy resin composition was transferred (175 DEG C for 60 seconds), and after the demolding, test pieces for curing and evaluation were obtained under the conditions of 160 DEG C x 2 hours + 180 DEG C x 6 hours.

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

TMA (TM-7000 manufactured by Shin-Kori Co., Ltd., temperature rising rate: 2 占 폚 / min)

From the above results, it was confirmed that the epoxy resin of the present invention can give a cured product having high heat resistance as compared with the epoxy resin of the comparative example.

Examples 9 to 12 and Comparative Example 4, Comparative Example 5

(EP8, manufactured by Nippon Kayaku Co., Ltd., orthocresol novolak type epoxy resin EOCN-1020-65), a phenol aralkyl resin (available from Mitsui Chemicals, Inc.) as a curing agent, MSR-2212 manufactured by Tatsumori KK) as an inorganic filler, triphenylphosphine (trade name: TPP, manufactured by Hokko Kagaku Kogyo Co., Ltd.) as a curing accelerator, (Trade name: KBM-403, Shin-Etsu Chemical Co., Ltd.) as an additive were blended in a ratio (parts by weight) shown in Table 3, And the mixture was homogeneously mixed and kneaded using a roll to obtain an epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer, and tabletted by a tablet machine. The tableted epoxy resin composition was transferred (175 DEG C for 60 seconds), and after the demolding, test pieces for curing and evaluation were obtained under the conditions of 160 DEG C x 2 hours + 180 DEG C x 6 hours.

DMA measurement conditions

Dynamic viscoelasticity measuring instrument: TA-instruments, DMA-2980

Measuring temperature range: -30 ℃ ~ 280 ℃

On rate: 2 ℃ / min

Specimen size: 5 mm × 50 mm cut out (thickness about 800 μm) was used.

Interpretation condition

Tg: The peak point (tan? MAX) of Tan? In the DMA measurement is Tg.

Flammability

Determination of flame retardancy: It was conducted in accordance with UL94. However, the sample size was 12.5 mm wide × 150 mm long, and the thickness was 0.8 mm.

· Residual salt time: the sum of the time of the decontamination after 10 times of application to the sample of 5 sets

Example 13

A 1 L four-necked flask equipped with a stirrer, a reflux condenser and an agitator was charged with a phenol compound (DPPI1) [compound SABIC BPPPP in which all substituent groups R were hydrogen atoms in the formula (P): 99 ppm or more, 200 ppm of residual phenolphthalein, 5 ppm], 694 parts of epichlorohydrin and 173 parts of dimethyl sulfoxide were added, and the water bath was heated to 50 캜. When the internal temperature exceeded 45 캜, 66 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 캜 for 2 hours and 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. 760 parts of methyl isobutyl ketone was dissolved in the residue, the sodium chloride and the like produced by washing with water were removed, and the organic layer was heated to 70 ° C. 30 parts by weight of 30% by weight aqueous sodium hydroxide solution was added with stirring, After rinsing, the water was washed until the washing water became neutral, and methyl isobutyl ketone or the like was distilled off at 180 DEG C under reduced pressure using a rotary evaporator to obtain 355 parts of an epoxy resin (EP10). The obtained epoxy resin had an epoxy equivalent of 268 g / eq., A softening point of 99 占 폚, an ICI melt viscosity of 1.03 Pa 占 퐏 (150 占 폚), a total chlorine content of 305 ppm, a hydrolyzable chlorine content of 270 ppm, a chlorine ion content of 0.1 ppm, (Gardner 40% THF solution). The structure of the above formula (1) was 85.2 area% (GPC).

Example 14

A 1 L four-necked flask equipped with a stirrer, a reflux condenser and an agitator was charged with a phenol compound (DPPI1) [compound SABIC BPPPP in which all substituent groups R were hydrogen atoms in the formula (P): 99 ppm or more, 200 ppm of residual phenolphthalein, 5 ppm], 971 parts of epichlorohydrin and 165 parts of dimethyl sulfoxide were added, and the water bath was heated to 45 캜. When the internal temperature exceeded 40 캜, 66 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further conducted at 45 캜 for 2 hours and 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. To the residue was added 760 parts of methyl isobutyl ketone to dissolve. After removal of sodium chloride produced by washing with water, the organic layer was heated to 70 ° C, 30 parts by weight of 30% by weight aqueous sodium hydroxide solution was added under stirring, and the mixture was reacted for 1 hour Thereafter, washing was carried out until the washing water became neutral, and methyl isobutyl ketone or the like was distilled off at 180 캜 using a rotary evaporator under reduced pressure to obtain 353 parts of an epoxy resin (EP11). The obtained epoxy resin had an epoxy equivalent of 267 g / eq., A softening point of 99 占 폚, an ICI melting point of 0.91 Pa 占 퐏 (150 占 폚), a total chlorine content of 540 ppm, a hydrolyzable chlorine of 430 ppm, a chlorine ion of 0.1 ppm, (Gardner 40% THF solution). The structure of the above formula (1) was 87.1 area% (GPC).

Example 15

(Trade name: SEJ-01R manufactured by Nippon Kayaku) as an epoxy resin to be used in combination with an epoxy resin (EP10) obtained in the above, and a cationic catalyst (trade name: SI-150 manufactured by SANSHIN KAGAKU KOGYO KK) 50: 2 (parts by weight) to obtain an epoxy resin composition. The epoxy resin composition was molded into a mold, and a test piece for curing and evaluation was obtained under the conditions of 150 占 폚 for 3 hours. As a result of DMA measurement using the obtained test piece, the Tg was 184 DEG C. (Measurement conditions were as described above)

Example 16

Evaluation was carried out in the same manner as in Example 15 except that the epoxy resin (EP10) was changed to epoxy resin (EP11). As a result of measurement of DMA, Tg was 189 DEG C. (Measurement conditions were as described above)

From the above results, it became clear that the epoxy resin of the present invention can achieve both high heat resistance and flame retardancy.

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. 2012-129407) filed on June 7, 2012, which is incorporated by reference in its entirety. All references cited here are also accepted as a whole.

(Industrial availability)

The epoxy resin of the present invention can be used as an epoxy resin composition together with a curing agent to form an epoxy resin composition which can be used as an adhesive agent, a coating material, a coating agent, a molding material (including a sheet, a film, an FRP, A cyanate resin composition for a substrate), an acrylic ester resin as a curing agent for a resist, and an additive to other resins and the like.

Claims (6)

An epoxy resin characterized by containing 70 to 95% (gel permeation chromatography area%) of a compound represented by the following formula (1) as a main component.

Wherein the plurality of R present are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. The method according to claim 1,
Wherein the epoxy equivalent is 1.02 to 1.1 times the theoretical epoxy equivalent. The method according to claim 1,
Wherein the total chlorine content is 5,000 ppm or less. An epoxy resin composition comprising the epoxy resin according to any one of claims 1 to 3 and a curing agent as essential components. An epoxy resin composition comprising the epoxy resin according to any one of claims 1 to 3 and a curing catalyst as essential components. A cured product obtained by curing the epoxy resin composition according to claim 4 or 5.