TWI317355B - Process for production of high purity epoxy resin, and epoxy resin composition - Google Patents

Description

1317355 Mei, invention description: [Technical field of the invention]: Yuming provides an epoxy resin combination which can easily manufacture high-purity epoxy compound 1 and reliability using the high-purity epoxy compound Things. Inter-, electronic components [Prior Art] Epoxy resins are widely used in various fields such as electrical, plastic, construction, civil engineering, and the like due to their excellent properties. It is widely used as an electrical seal material due to its excellent electrical insulation properties or heat resistance. In recent years, due to the high integration of semiconductor elements, thinning, and improvement in mounting efficiency, etc., it is required to improve the reliability of these types of oxygen. / There are two main ways to improve the reliability of epoxy resin compositions. As the first method, a decrease in the dentate-containing group in which the 'eight-d (d) is slightly present in the epoxy resin is exemplified. Epoxy 榭 匕 匕 ', ν 礼 曰 之 之 之 含有 含有 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知 众所周知A situation that causes adverse effects. Further, as a second method, the households are prepared to have a low stress and low moisture absorption of the hardened material. Previously, it has been widely used as an epoxy resin composition for a semiconductor sealing material, which is a phenol-based resin.

The hardener is composed of ruthenium dioxide or the like as A 乍. However, the phenolic phenolic epoxy resin has insufficient heat resistance to the cured product, and has a disadvantage that the sputum is liable to cause cracks. In the low- and humidification of the epoxy resin composition, it is preferred to use a large amount of uranium sulphate, such as yttrium, which is less hygroscopic, such as a so-called filler-high filling. In the case of the phenolic phenolic resin, the viscosity of the epoxy composition and the adhesion of the enamel resin are increased, so that the fine electrons of the seal are damaged by the molding. The month b can be found in the problem of the beta piece. In order to solve such a weak subject a ^, there are various schemes. Regarding the method for the reliable use of the oxy-resin composition, the dentate present in a trace amount in the epoxy oxime contains a reduction method from the muon group, for example, Japanese Patent Laid-Open No. π 61 In the publication No. 13 of the No. 13 365, there is no method for adding an alkali metal hydroxide read epoxy resin in the presence of a solvent containing isobutanol or a second alcohol. Further, Japanese Laid-Open Patent Publication No. SHO 62-648A discloses a method of reacting an epoxy resin at a temperature of 20 to 50 t in the presence of an alcohol, a metal hydroxide, and a related mobile catalyst. The use of isobutanol or the second and alcohols in the reaction to cause the reaction of the alcohol with the epoxy group in the reaction results in an increase in the epoxy equivalent weight, which is not preferable. Further, although the above-mentioned Japanese Patent Laid-Open No. 62-64817 has a relatively low temperature reaction, it is easy to cause a reaction between an alcohol and an epoxy group by using a related mobile catalyst mJ, and it is necessary to use a higher-priced catalyst, which is disadvantageous for industrial production. . Further, in Japanese Laid-Open Patent Publication No. SHO-62-256821, it is disclosed that a bisphenol substituted by an ortho position of a benzene hydroxy group is treated under conditions in which a caustic alkali is used in a specific amount or less. A method of reducing the halogen content in an epoxy resin by using a crude epoxy resin produced by an alcohol. Further, in Japanese Patent Laid-Open Publication No. SHO63-268723, it is disclosed that a crude epoxy resin produced from polyvalent benzene and epi-alcohol is added with a base 92657.doc 1317355 metal hydroxide water-soluble pan·&gt ;, and! Aqueous solvent, which makes the hydrophobicity boil, extracts water out of the system, f is co-suspended with water, and further performs a closed-loop reaction, a method of hydrolyzing dentate content. b reduction plus the above-mentioned Japanese Patent Laid-Open No. 62-2 is also disclosed in the specification, which discloses an epoxy resin which is substituted by benzene powdery oxy group: substituted bis(tetra) and epirubic (tetra) alcohol. In addition to the specific structure of the resin, there is a case where the seam is clean + # θ to achieve a poor reaction of 600 ppm or less, that is, 6 (10) Ppm or less, and the epoxy ring is opened, and the thermal method is called A method common in industry. Further, in the first stage of the reaction, since the water content in the system is high, the epoxy group and the water in the system react with the alkali metal hydroxide as a catalyst to cause ring opening of the epoxy group. Therefore, it is possible to generate α-diol, resulting in a decrease in the epoxy group content. Further, the produced diol contains a highly reactive mercapto alcoholic hydroxyl group. Therefore, (4) in the case of an epoxy resin having a very low total gas content, 'the hydroxyl group of the produced diol reacts with the epoxy group, so that it is liable to cause poor polymerization or gel formation. Disadvantages. In the second method for improving the reliability of the epoxy resin composition, that is, the low stress and the low moisture absorption of the hardened Epoxy resin, a two-functional one having two ethoxylates per molecule is used. The case of a low molecular weight epoxy resin composition based on this has been found to be effective since its inception. Since the bifunctional epoxy resin has a low crosslinking density, the cured product is low-stressed, and a low molecular weight epoxy resin is used, thereby solving the problem of poor formation or damage of the epoxy resin composition filled with a large amount of filler. The problem of microelectronic components. However, the use of the epoxy resin composition of the above-mentioned bifunctional epoxy resin of 92657.doc 1317355 is compared with the use of the polyoxygen oxy-oxygen resin of the polyoxygen enamel, which has a lowering of the crosslink density. The disadvantage of reduced heat resistance. In order to solve such a problem, Ψ 1 , it is known that there is a reaction between an alcoholic hydroxyl group present in a bifunctional US epoxy resin and an epoxidized propylene gas to cause glycidol to turn into a molecule. The method of polyfunctionalization of a divergent structure is disclosed in Japanese Laid-Open Patent Publication No. Hei 04-3535-17, which discloses an alcoholic oxime of an epoxy resin having a glycidyl group containing three or more benzenes in the i molecule. A method in which hydrogen is reacted with chlorinated propane, and glycidyl ether is etherified to improve heat resistance and water resistance. However, these methods are effective for increasing the f: the raw water is effective, but the polyfunctional grouping which is formed by introducing an epoxy group having a shorter molecular chain such as epoxidized propane causes an increase in the modulus of elasticity, so that it is considered There is still a problem with the view of low stress. ^ It's more than four steps in recent years, such as the high integration of semiconductor components, the small layering of the package, or the improvement of the mounting efficiency, and the use of the ring-shaped milk tree in these applications is even more demanding. ^ ^ The progress of the life - step by step, seeking to satisfy both the presence of the hardened material in the epoxy resin. # _ A Τ 面面素3 has a base reduction, low stress and low thirst with epoxy resin There are such methods presented. .,, '(10) Miscellaneous, but not yet [invention] It satisfies a small amount at the same time; and the epoxy resin is hardened. Therefore, the present invention provides a low stress of the epoxy resin in the epoxy resin in the epoxy resin. And low moisture absorption. The inventors conducted an active discussion to solve the problem of Shangcheng _, and found that the total chlorine contained in the ruin of the 92657.doc 1317355 contains a ring with a specific divergence structure; the content of the temple is below, and the final is completed. invention. a new matter that can solve these problems. Therefore, the present invention provides a method for manufacturing a high-strength % 虱 compound which is set to be less than 500 ppm, and is characterized by: General

(wherein, R represents a residue of a divalent phenol compound and/or a residue of a divalent alcohol compound, and η represents an epoxy compound represented by an average value of more than 〇 and less than 1 )), that is, η is 〇 When the component ratio is more than 7〇% and is not 'high 1〇〇/°, the reaction is carried out at a temperature of 95 ° C to 15 CTC in the presence of an alkali metal hydroxide to generate the following general formula (π): Ο- Η

CH X-?CH [ [wherein R represents a residue of a divalent phenol compound and/or a residue of a divalent alcohol compound; η represents a value whose average value is greater than 〇 and less than 1 ;; and, an X-based hydrogen atom or By the following general formula (III): Η2Η Η2 η2 Η -ccco~Rocc-ch2 OH Ο (wherein R has the above meaning) 92657.doc -10- 1317355 No epoxy compound, and/or By the following general formula (v):

[in the formula

Ri, R2, R5 and r6 represent a hydrogen atom, an alkyl group, an allylphenyl group or a halogen atom, which may be the same or different; and 11 is an epoxy compound having an average value of more than 0 and less than 1 Å. Further, the present invention provides a high-purity epoxy resin composition containing a high-purity epoxidized quinone obtained from the above production method and an epoxy resin hardener as an essential component, and a cured product thereof. Further, the present invention provides a southern purity epoxy resin composition for an electronic component sealing material comprising the high-purity coating oxygen compound obtained by the above production method and an epoxy resin curing agent as an essential component, and a cured product thereof. [Embodiment] The epoxy resin of the present invention comprises the following general formula (I):

(wherein R represents a divalent phenol compound residue and/or a divalent alcohol compound residue ' and η represents a bifunctional epoxy compound whose average value is larger than 〇 and less than 1 )), and By the following general formula (Π): 92657.doc >12-

X 1317355

€H C’, (T H2 h2

I O 0,

O^CH Hn [wherein, R represents a residue of a divalent phenol compound and/or a residue of a divalent alcohol compound, and η represents a value whose average value is larger than 〇 and less than 1 ;; and, an X-based hydrogen atom or by The following general formula (III): Η2 η η2 η?η c~9-c-0-R_0 a c-c, -ch2 OH 〇 / (wherein 'R has the meaning indicated above) A trifunctional epoxy compound which is not a pure chlorine content and has a purity of 5 jaws T and an oxygen compound. Here, the total gas content is a gas amount measured by the method of the 爪-7246 method. Usually, the gas-containing group formed in all forms of the epoxy resin produced by the epichlorohydrin is used. Specifically, 'as a chlorine containing right soil' is known by the following formula (VI): Η2 η . —〇_C~C~CH, I I * OHCl is given by the following formula (VII): No. 1, 2 — Epigas alcohol h2c-ci

-O-CH H2C-OH shows 1,3 -gas alcohol and is represented by the following formula (VIII): 92657.doc -13. I3l7355 ϊ·ΐ 2 0*-C- Η Η, -Cc——c ]

H

o

I 〇 — C II — The chloranil matrix represented. Therefore, the gas-containing group containing 1,2-epichlorohydrin as a main component is also called easy-to-handle cleavage chlorine, which is relatively easy to reduce, but it is not necessary to reduce it to ensure higher reliability. The epichlorohydrin is a hydrolyzable gas which is a main component, and it is necessary to lower the oxime represented by the formula (VII), the 3-epichlorohydrin, and the chloromethyl group represented by the formula (VIII). In particular, when the total content of ruthenium or the like in the epoxy resin is not more than 500 ppm, it is an epoxy resin excellent in reliability. A better total chlorine content is (10) (four) or less. The η of the general formula _2 functional epoxy compound used in the invention of the present application is η. The composition of bismuth is more than qing, and the number of components less than (10) is less than 1 due to an increase in viscosity. The component having a n of 0 is preferably 75% to 99%, and ^aa 3 is preferably 8% to 99%. Further, the content of the component of _ 〇 is analyzed by the gel permeation π color method of the refractive index as the detector, and the content thereof is a value obtained from the obtained chromatographic area %. The high-purity epoxy compound of the present invention contains a plurality of general formula (II):

</ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; 〇 the following values; and, the X-type hydrogen atom or the group represented by the following general formula (III) η2 Η Η2 Η2 η -CCCOROcC-CHi OH, 0 - (wherein, R has the above meaning) A polyfunctional epoxy compound is shown. The polyfunctional epoxy compound represented by the above general formula (II) contains a ruthenium having three or more epoxy groups in a work molecule and having a specific divergence k of polymorphism. Specifically, it is a compound in which a bifunctional epoxy resin is added to a hydroxyl group in a molecule of an epoxy compound. This compound is different from the compound in which the epoxy group is added to the hydroxyl group in the molecule of the epoxy compound, and the molecular chain of the divergent portion of the side lock is long. The cross-linking point distance becomes larger. Therefore, it has a feature of maintaining heat resistance, but is less likely to cause an increase in the modulus of elasticity. Further, the polyfunctional epoxy compound represented by the general formula (5) preferably has a content of i to hop in the high-purity emulsified compound. If it is less than 1%, it is not preferable from the viewpoint of heat resistance. If it exceeds (10), the rate of bombing may increase, which is not good from the viewpoint of low stress. Better contain: two ~:,. Particularly preferably, 2 to I, these compounds are obtained by high-speed liquid chromatography of the detector for measurement, and the concentration is determined by measuring the wavelength, and the content is determined from the obtained chromatographic area %. . Wrong by the shell! The analytical instrument is used as a high-speed liquid chromatography method for detectors. 92657.doc -15 - 1317355. The method for producing a high-purity epoxy compound of the present invention is based on a 2-functional epoxy compound in which the component content of n = 0 disclosed in the general formula (1) is 70% or more and less than 1% by weight, per 1 kg. The bifunctional epoxy compound is added with 5 to 1 g of potassium oxynitride, and the reaction is carried out under the conditions of a temperature of 95 to 150 ° C and a potassium hydroxide aqueous solution concentration of 8 Torr / Torr or more. As a preferable specific example of the bifunctional epoxy compound disclosed by the general formula (I), there are bisphenol A, bisphenol F, bisphenol C, bisphenol kappa bis bisphenol z, bipans s, tetramethyl A reaction product of a bisphenol A such as bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol s or tetramethyl bisphenol z with an epihalohydrin, that is, an epoxy resin of a bisphenol. A bisphenol type epoxy resin which is a reaction between a bisphenol and a phenanthrenol such as a bisphenol or a tetradecyl bisphenol. As for the light-based diphenyl sulfides, diterpene diphenyl sulfide, 4,4,-thiobis(3_methyl_6_tri-butylphenol), and the like can be exemplified. The reactant is dihydroxy diphenyl sulfide type epoxy resin, catechol, m-diphenol, methyl resorcinol, hydroquinone, monomethyl hydroquinone, dimethyl p-benzene. The reaction of diphenol, tridecyl-p-diphenol, mono-t-butyl hydroquinone, di-tert-butyl-p-diphenol and other dihydroxybenzenes with epi-alcohol A known epoxy compound such as a dihydroxynaphthalene type epoxy resin which is a reaction product of a type of epoxy resin, dihydroxynaphthalene, dimethylol naphthalene or dimethylol naphthalene with an ifi alcohol. The repeating unit η of the epoxy compound which is preferably used in the rutting is preferably an average of (7) two times (but not including 0), more preferably 5 or less, and particularly preferably 3 or less. The average η can be obtained from a number average molecular weight measured by, for example, GPC or the like, or a measured value of the end of the ruthenium equivalent of 92657.doc -16 - 1317355. Further, condensates of phenols and/or naphthols and acetaldehydes, benzophenones and/or condensates of naphthols and benzenedimethyl glycol, phenols and/or naphthols may be exemplified. a phenol compound such as a condensate of isopropenyl acetophenone, a reaction product of a phenol and/or a naphthol and a monopentadiene, a condensate of a phenol and/or a naphthol and a biphenyl condensate d An epoxy resin or the like obtained by reacting with a reaction product of an epidentic alcohol. Examples of the phenols include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol, phenylphenol, and the like, and naphthols. Listed are 丨 naphthol, 2-naphthol and the like. Further, examples of the aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, benzaldehyde, gas aldehyde, aldehyde, glyoxal, malondialdehyde, dibutyl pentoxide, and pentane , two awake, g, m, propylene, crotonaldehyde, salicylaldehyde, o-phthalaldehyde, hydroxybenzaldehyde and so on. The condensing agent of the hydrazine system may, for example, be bis(f-based)biphenyl, bis(ethoxymethyl)biphenyl, bis(ethoxymethyl)biphenyl, bis(chloromethyl)biphenyl, or the like. . Further, as for the other examples of the bifunctional epoxy compound disclosed by the general formula (1), there are as a double-disc A, a double-president, a double-c, a double-kappa, a double-z, a double-desir, a tetra-methyl group. Double-sided a, tetramethyl double F, tetramethyl double s, tetramethyl double Z, etc. Ethylene bromide and / or epoxy propylene compound additions The epoxy resin of the reactant, and an epoxy resin which is a reaction product of an ethylene bromide and/or epoxidized adduct of diphenyl expectorate, tetramethyl bisbenzene, etc., with an epidentate alcohol. As for the dihydroxybiphenyl sulfide, it can be exemplified as dihydroxybiphenyl sulfide, 92657.doc • 17-1317355 120~140 °C. The reaction can be carried out under any conditions of reduced pressure, under normal pressure and under pressure, but it is preferred to react at a low pressure under normal pressure in a manufacturing facility. The reaction time is preferably from 10 minutes to 1 hour, but usually from 3 minutes to 5 hours. Further, it is necessary to carry out the reaction under the conditions that the concentration of the aqueous alkali metal hydroxide solution in the reaction system is 80% or more. If the amount of water in the reaction system is large, the reaction of the water with the epoxy group leads to an increase in the epoxy equivalent, which is not preferable. Therefore, in the case where water is present in the reaction system, it is necessary to perform a pre-dehydration treatment so that the concentration of the aqueous solution becomes 8% or more at the time of adding potassium hydroxide. The dehydration treatment may be, for example, a method of dehydrating by heating under normal pressure or reduced pressure, or a method of using a dehydrating agent such as anhydrous sodium sulfate or molecular sieve. The 4 4 reaction can be carried out in the presence of an organic gluten. The organic solvent may, for example, be a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, a hydrocarbon solvent such as toluene or xylene, or an alcohol solvent such as methanol or ethanol, or a methyl bath. a cellosolve solvent such as a fiber or a ethyl cellosolve; an ether such as dioxane or diethoxyethane; a guanamine solvent such as dimercaptoamine; A non-protic polar solvent, etc. Particularly good is decyl isobutyl hydrazine and a smile. 7. A related catalyst such as a fourth ammonium salt or a fourth scale salt may also be used. Further, as a form of potassium hydroxide used in the reaction, it is preferably a solid helium gas having a purity of 90% or more. By using solid potassium hydroxide, it is not necessary to control the moisture in the system to a minimum. Particularly preferred is a purity of 95% or more. ^^# is a condensate of an alcohol in the reaction of an epoxy compound with potassium hydroxide at 39281.doc-19-1317355; a phenol and/or a naphthol a condensate with isopropenylethyl benzene; a phenolic compound and/or a reaction product of a naphthol and a dicyclopentadiene; a phenol compound such as a condensate of a phenol and/or a naphthol and a biphenyl condensing agent; Wait. Examples of the above phenols include phenol, indophenol, dinonylphenol, butylphenol, amylphenol, nonylphenol, butylnonylphenol, tridecylphenol, and phenylphenol. Examples thereof include naphthol and 2-naphthol. As the aldehyde, there may be exemplified a furfural, an acetaldehyde, a propionaldehyde, a butyraldehyde, a valeraldehyde, a hexane, a scorpion, a gas, a bromine, a ethane, a propylene, a dibutyl sulphate, a glutaraldehyde. , adipaldehyde, p-glyoxal, sebacaldehyde, acrolein 'crotonaldehyde, o- each of the road, phthalate, benzoyl chain and so on. The condensing agent of the genus is exemplified by (fluorenyl)biphenyl, bis(methoxyindenyl)biphenyl, bis(ethoxymethyl)biphenyl, bis(chloroindenyl)biphenyl, and the like. As other known curing agents, examples include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, phthalic anhydride, trimellitic anhydride, methyl decanoic acid, and the like. Anhydrides, di-ethyltriamine, ethylhexylamine, m-diphenyldiamine, isophorhedimide, diaminobiphenylmethane, diaminobiphenyl fluorene, diamine linkage An condensate of an acid such as phenyl ether, dicyanoguanamine or a dimer acid and a polyamine, that is, an amine compound such as polyamine. Further, as the curing agent which causes the epoxy group to be polymerized and hardened, examples thereof include a phosphine compound such as triphenylphosphine, a scaly salt such as tetraphenyl bromine scale, 2-methylimidazole, 2-phenylimidazole, and 2 -imidazoles such as ethyl-4-f-imidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, and the like, and the phenylhydrazine 92657.doc -21 - 1317355 acid, The salts of cyanuric acid, boron, etc., are the amines of the ginseng (dimethylaminomethyl), such as abbreviated earth; bauxite, 2,4,6-salt, diazabicyclo(4)/ Ammonium-based quaternary phenols such as ammonium quaternary esters such as ammonium-reducing phenols, phenolic phenolic aromas: (4) False compounds such as butterflies and amines, screaming compounds, etc., or sulphate. These hardenings are used in combination. It can also be used alone, or it can be used in the epoxy resin combination of the present invention. The ratio of each of the equivalents of the latex resin hardener is 1% of the oxygen, and the hardener is preferably U~U. The ratio of equivalents. Further, the base is G·5 Μ Μ equivalent, and the hardened hardener is added to the polymerization of the oxy-oxyl group to make it (u~ίο parts by weight, and more preferably 10 parts by weight of the epoxy resin is lyophilized, more preferably 〇 2 to 5 parts by weight. : In the oxygen resin composition, a hardening accelerator can be used as needed, and examples thereof include a phosphine, a azole, a third-grade amine, a trifluorochemical collar, and the like. The third type of the hardening-promoting type is used as the m-heart (4) force. It can also be used alone or in combination with the weight ratio of the epoxy resin composition. (10) parts by weight is G·1~ 1 g parts by weight, more preferably 0.2 to 5 in the epoxy resin composition of the present invention, can be #栌# i #ra filler. As for Yiyi, according to the south, the use of inorganic filling _ ▼, ''', For example, there may be exemplified, for example, molten cerium oxide, emulsified emulsifier #, glazed powder, oxidized odor, carbon (four), etc. The (4) machine is filled: it may be used alone or in combination of two or more types. And 3G to 98% by weight of the total amount of the material I, preferably 5G to 95% by weight. In the epoxy resin composition of the fuel, the moon can be added as needed, and the fiber can be added as needed. Chemicals, pigments, plasticizers, etc. 92657.doc -22- 1317355 Further, as the bifunctional epoxy compound used in the present invention, it is preferred to use the general formula (IV) and/or the general formula (V). The epoxy compound shown by the general formula (IV) may, for example, be bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, or the like. The reaction of bisphenols such as mercapto bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol S, tetradecyl bisphenol Z, etc. with epihalohydrin is a double epoxy resin. Examples of the phenols include a bisphenol type epoxy resin which is a reaction product of a bisphenol and an epihalohydrin such as bisphenol or tetramethylbisphenol. Examples of the dihydroxydiphenyl sulfides include dihydroxy groups. A reaction product of a benzene sulfide or a 4,4'-thiobis(3-methyl-6-tri-butylphenol) with an epihalohydrin, that is, a dihydroxydiphenyl sulfide type epoxy resin. Examples of the epoxy resin represented by the general formula (V) include catechol, resorcin, methyl resorcin, hydroquinone, monodecyl hydroquinone, and dinonyl. Benzene a reaction of dihydroxybenzenes such as phenol, tridecyl hydroquinone, mono-tert-butyl hydroquinone, di-tertiary-tert-butyl hydroquinone, and epidentate alcohol, i.e., dihydroxybenzene The present invention will be described in more detail by way of examples and comparative examples. However, the present invention is not limited to the examples, and the "parts" disclosed in the following examples, Unless otherwise specified, it means "parts by weight." In the following description, the epoxy equivalent, the total gas content, the n=0 component measured by GPC, and the measurement by HPLC have the present invention. The polyfunctional epoxy compound of a specific divergence structure was separately determined by the following method: Epoxy equivalent 92657.doc -23 - 1317355 The sample was dissolved in a dioxane ring, and a dioxane ring of 0.,1 N-hydrochloric acid was added. The solution was reacted at room temperature for 30 minutes. The cresol red was used as an indicator to titrate in a 0.1 N-sodium hydroxide solution, and the difference from the titer of the blank test was determined. The value of the sample to be removed was determined as the epoxy equivalent (g/eq). The total gas content is the total gas content (ppm) based on the value measured in accordance with JIS K-7246. (n = 0 component measured by GPC) Using a GPC analyzer HLC-8020 manufactured by Toyo Co., Ltd., a differential refractometer was used as a detector. The GPC column used was separated by a G2000HXL manufactured by Toyo Co., Ltd. and a G1000HXL column system to separate the n=0 component. The content of the component of n = 0 is the content (%) by dividing the peak area of the n = 0 component obtained by the obtained GPC chromatography by the area % of the peak area of the whole component. The polyfunctional epoxy compound having the specific divergence configuration of the present invention as determined by HPLC was analyzed using an ultraviolet visual detector at a measurement wavelength of 285 nm using an HPLC analyzer series 1100 manufactured by Agilent Technologies. The HPLC column used was a Gadenza CD-C18 manufactured by Intact Co., Ltd., and the column size was 10 mm × X 4.6 mm in length, and a polyfunctional epoxy compound having a specific divergent structure of the present invention was isolated. The content of the polyfunctional epoxy compound having the specific divergence structure of the present invention is obtained by dividing the peak area of the polyfunctional epoxy compound having a specific divergence structure obtained by the obtained HPLC chromatography by the area % of the peak area of the whole component. Content (%). Examples 1 to 2 and Comparative Examples 1 to 2 92657.doc -24 - 1317355 Example 1. 177 g/eq of % oxygen s was placed in an i 1 separable flask equipped with a stirrer, a thermometer, and a condenser. Gas content 丨200 ppm 'n = 0 component determined by GpC is 89%' and analysis by HPLC does not include ruthenium, a polyfunctional epoxy compound having a specific divergent structure of the present invention, 4_2_third 15 parts of bisbutyl-2,5-dihydroxy-benzene diglycidyl ether and 47 parts of toluene were heated until 80 ° C to dissolve the resin. 6_2 parts of solid potassium hydroxide having a concentration of 97% was added at the same temperature, and the temperature was raised to n5t under stirring, and the reaction was carried out at the same temperature for 1 hour. After completion of the reaction, the mixture was cooled to 8 Torr, and 50 parts of water was added to dissolve the salt, and the mixture was allowed to stand to separate and remove the aqueous phase of the lower layer and the gelatin of the by-product. The resin solution was washed with phosphoric acid/guar solution until the neutralized water washing solution was neutral, and the mixture was subjected to hydrazine. The target resin (epoxy resin A) was obtained by removing toluene at 1.3 3 KPa and 150 °C. The reaction conditions and the like of the examples are shown in Table, and the obtained resin properties, yields and the like are shown in Table 2. Example 2. The same operation as in Example i was carried out except that 9.3 parts of a 97% solid potassium hydroxide addition amount and a water 0.7 injury were reacted at 1 〇〇C for 3 hours. B). The reaction conditions and the like of the examples are shown in Table, and the obtained resin properties, yields and the like are shown in Table 2. Comparative Example 1. 92657.doc -25 - 1317355 Table 2 Property Unit Example 1 Example 2 Comparative Example 1 Comparative Example 2 Name of Resin Epoxy Resin B Epoxy Resin C Epoxy Resin D Epoxy Equivalent. g/eq 183 181 180 173 Total gas content ppm 240 460 610 310 Polyfunctional epoxy compound of the invention analyzed by HPLC % 3.8 2.5 1.2 0.0 n=0 component content % analyzed by GPC 82 84 82 93 Yield g 139 145 122 128 Yield % 93 97 81 85 Examples 3 to 4 and Comparative Examples 3 to 4 Example 3. Epoxy was placed in a 1 L separable flask equipped with a stirrer, a thermometer, and a condenser The equivalent of 1 86 g / eq, the total chlorine content of 1 00 ppm, the n = 0 component determined by GPC is 90%, and the analysis by HPLC does not include the polyfunctional epoxy compound having the specific divergent structure of the present invention. 150 parts of diglycidyl ether of 4,4'-dihydroxy-3,3',5,5, tetramethylbiphenyl, and 470 parts of methyl isobutyl ketone were heated until 80 ° C to dissolve the resin. 8.5 parts of a solid potassium hydroxide having a concentration of 95% was added thereto at the same temperature, and the mixture was heated to 100 ° C with stirring, and reacted at the same temperature for 1 hour. After completion of the reaction, the mixture was cooled to 80 ° C, and 50 parts of water was added to dissolve the salt, and the mixture was allowed to stand to separate and remove the aqueous phase of the lower layer and the gel of the by-product. The resin solution was washed with a phosphoric acid solution until the neutralized water washing solution was neutral, and filtered. The methyl isobutyl ketone was removed at 1.3 3 KPa and 1 50 ° C to obtain the intended resin (epoxy resin E). The reaction conditions and the like of the examples are shown in Table 3. The obtained resin properties, yield 92657.doc -27 - 1317355 Table 5 Manufacturing conditions Unit Example 5 Example 6 Comparative Example 5 Types of alkali metal hydroxides Potassium hydroxide Potassium hydroxide sodium hydroxide test metal hydroxide form solid solid liquid test metal hydroxide concentration % 95 95 48 per 1 kg epoxy resin test metal hydroxide addition amount g 53 40 40 reaction temperature ° C 100 115 90 Concentration of metal hydroxide in reaction % 95 95 48 Table 6 Properties Unit Example 5 Example 6 Comparative Example 5 Name of resin Epoxy resin K Epoxy resin L Epoxy resin 环氧 Epoxy equivalent g /eq 184 180 179 Total gas content ppm 110 280 600 % of the polyfunctional epoxy compound of the present invention analyzed by HPLC 4.2 3.8 1.9 n = 0 component content % analyzed by GPC 88 87 82 Yield g 132 140 118% yield 88 93 77 Comparative Production Example 1. Epoxy resin E was mixed with 100 parts of 1,4-di-tert-butyl-2 in a 1 L separable flask equipped with a stirrer 'thermometer and condenser. , 5-dihydroxy-benzene 2.2 parts, two 5 parts of benzene was heated until 130 ° C. 0.5 part of triphenylphosphine was added at the same temperature, and reacted at 160 ° C for 5 hours. After the completion of the reaction, diphenylbenzene was distilled off at 160 ° C and 1.33 KPa to obtain an epoxy equivalent of 183 g/eq, a total chlorine content of 290 ppm, an n=0 component of 83% as measured by GPC, and a borrowing. The analysis by HPLC did not include the oxirane resin (polyoxyl resin N) having the polyfunctional epoxy compound of the specific divergent structure of the present invention. Examples 7 to 8 and Comparative Examples 6 to 7. 92657.doc -31 - 1317355 In order to make the effects of the epoxy resin A to the brain shown in Table 2 more clear, μ_月曰C~D and the present hair are for Epoxy resin is more than 87% by weight of the epoxy tree coating resin and epoxy resin hardener produced in Production Example 1, and is used as a combination of a emulsified enamel powder. Epoxy hard soil is used as a hardening accelerator, using a Brazilian enamel release agent, using epoxy decane as a decane coupling:;: Fossil eve powder inorganic filling (four) 丨, Wei epoxy (four) composition milk /, people to 1QQ~ Each of the formulations was kneaded at 12QC, and each g/f of each material obtained by cooling and pulverizing was shown in Table 7. Each test piece was obtained by using a low-pressure forming machine under the conditions of a mold/wareness of 170 C, a pressure of 64 kg/cm 2 and a forming time of 12 sec. The test pieces were allowed to stand at 18 (rc temperature for 6 hours), and the obtained test piece was subjected to bending strength and modulus at room temperature, bending strength and modulus of elasticity at 2501, glass transition temperature, and temperature of 85 ° C. , humidity 85% 'water absorption rate at 72 hours, freeze-pulverized test piece and classified into 100~15〇mesh, and 10 g of these pulverized test pieces and 4〇g of pure water in a pressure-resistant Teflon container at 180 The electrical conductivity of pure water at 30 hours of hydrazine extraction and the amount of chloride ions extracted per resin composition are shown in Table 8. Table 7 Mixing ratio unit Example 7 Example 8 Comparative Example 6 Comparative Example 7 Comparative Manufacturing Example 1 Type of epoxy resin epoxy resin λ epoxy resin 环氧树脂 epoxy resin C epoxy resin D epoxy resin 环氧树脂 epoxy resin 100 100 100 100 100 epoxy resin hardener * 1 part 95.5 96.6 94.1 101 95.5 inorganic charge 4 doses*2 parts 1308 1316 1299 1345 1308 Hardening accelerator *3 parts 2.3 2.3 2.3 2.3 2.3 Release agent parts 1.9 1.9 1.9 1.9 1,9 decane coupling ' *4 parts 9 9 9 9 9 parts 1 1 1 1 1 92657 .doc •32- 1317355 *1: Minghe Chemical Company produces benzene Aralkyl resin MEH-7800S Hydroxyl equivalent = 175 g/eq *2 : Electrochemical industrial manufacturing is carried out by mixing spherical molten silica powder in the following ratio: FB-60 20% by weight average particle size 25 μιη FB -35 50% by weight average particle diameter 10 SO-C3 30% by weight average particle diameter 0.7 μιη *3 : Triphenylphosphine*4: Epoxydecane ΚΒΜ-403 manufactured by Shin-Etsu Chemical Co., Ltd. Table 8 Characteristic value unit Example 7 Example 8 Comparative Example 6 Comparative Example 7 Comparative Production Example 1 Type of epoxy resin Epoxy resin B Epoxy resin B Epoxy resin D Epoxy resin N Bending strength at room temperature kg/mm2 11.85 11.87 11.82 12.08 11.21 Flexural modulus at room temperature kg/mm2 1460 1480 1480 1560 1405 Bending strength when heated kg/mm2 0.88 0.90 .0.82 0.91 0.72 Flexural modulus at heat kg/mm2 45.2 46.5 45.8 55.3 45.3 Glass transfer temperature °c 114 115 107 1Π 110 Water absorption % 0.175 0.178 0.182 0.186 0.188 Electrical conductivity / xs / cm 48 90 125 88 105 Gas ion ppm 13 23 62 20 42 Industrial Applicability The high-purity epoxy resin of the present invention has heat resistance, low Moist, excellent mechanical properties. Further, the elution of the ionic impurities is also small, and the use of the epoxy resin of the present invention as the epoxy resin composition is preferably used as a sealing material in the electric and electronic fields. Further, the method for producing a high-purity epoxy resin of the present invention can produce the high-purity epoxy resin of the present invention easily and in high yield, and can be utilized in industrial production. 92657.doc -33 -

Claims (1)

Patent Application No. 3110159, Replacing the Patent Scope (September 95) Picking up, Patent Application Range: A method for producing a high-purity epoxy compound having a total chlorine content of less than 500 ppm, which is characterized by the following general formula (I): (wherein, R represents a divalent phenol compound residue and/or a divalent alcohol compound residue; and η represents an average value thereof is greater than 〇 and a value of 3 or less.) For more than and less than 100%, in the presence of alkali metal hydroxide, at 95. (: ~15〇1 temperature makes its reaction' generated by the following general formula (π): CH, ,〇 1 'Clb Wherein 'R represents a divalent phenolic compound residue and/or a divalent alcohol compound residue' η means that the average value thereof is greater than 〇 and the value below 3 is a hydrogen atom or by the following general formula (III): Further, a mixture of epoxy compounds which is not a group of X (wherein R has the above-mentioned meaning) is a component of the group represented by the general formula (ΠΙ). 2. The manufacturer of the high-purity epoxy compound according to the first paragraph of the patent application of the patent application 92657-950908.doc 1317355 The epoxy compound produced by the invention contains 9% by weight or more and less than _. An epoxy compound represented by the general formula (I), and an epoxy compound represented by the general formula (II) in a ratio of more than 〇% and less than 1% by weight. 3. The manufacturer of the high-purity epoxy compound according to claim 1 or 2, wherein the hydroxide is metal hydroxide. 4·H. Manufacture of high-purity epoxy compound of the third item of the patent range: In the above formula, the emulsified potassium compound of 5 parts per lkg of the epoxy compound represented by the general formula (1) is used as a concentration of 8〇% or more. The aqueous solution is dehydrated by hydrogenation to cause a reaction 5. The high purity epoxidation method of claim </ RTI> of the invention is carried out in the presence of a third alcohol. General (IV) 6 [Formula 6. The method for producing a high-purity epoxy compound according to the invention of claim i, wherein the epoxy compound represented by the above formula (1) is represented by the following one Η 2 Ri R8 represents a hydrogen atom, An alkyl group, an allyl group, a phenyl group or a halogen atom, which may be the same or different; a Y-type chemical bond, or an alkyl group having a carbon number of a heart, an allyl group, a phenyl group, an aromatic group I aryl group, an oxygen atom , sulfur atom, contiguous group or several groups; and 11 series whose average value is greater than 0 and less than 1〇] 92657-950908.doc 1317355 Us〇άί \ R, k ,...0丄~ % ' ηϊ ! S:CH, ch2 ～2 fTl is shown as τ' and, in the following formula, [R丨, R2, r5, and r矣_ &amp; base, awkward, non-oxygen atom, alkyl, propylene or # atom It may be the same or different, and D is an epoxy compound whose average value is larger than 〇 and less than 1 〕. Second application: The high-purity epoxidized product of the sixth item of the range = general formula Μ) is an epoxy compound tetramethyl bis: 8. 1 epoxy resin or tetramethylbiphenyl type epoxy resin. _: A high-purity epoxy resin composition comprising, as an essential component, a homogenous ring rolling compound and an epoxy resin hardening agent according to the manufacturing method of the sixth item. Epoxy tree 9. A high-purity epoxy resin composition for electronic component sealing materials, which is obtained by the high purity = oxygen compound and epoxy resin hardener material obtained by the manufacturing method of the scope of claim 6 ingredient. a:: more: obtained by hardening the epoxy resin composition as claimed in claim 8 or 9. 92657-950908.doc