JP5517237B2 - Method for producing epoxy compound, epoxy compound, curable resin composition and cured product thereof - Google Patents

Description

  The present invention relates to a high-purity epoxy compound having a small amount of chlorine, a curable resin composition containing the epoxy compound, and a cured product thereof.

Epoxy resins are generally cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., adhesives, paints, laminates, moldings It is used in a wide range of fields such as materials, casting materials and resists. In recent years, especially in the field of semiconductor-related materials, electronic devices such as mobile phones with cameras, ultra-thin liquid crystals, plasma TVs, and light-weight notebook computers have become key to light, thin, short, and small. Very high characteristics have been demanded for packaging materials represented by resins. In particular, the structure of the tip package is complicated, and there are an increasing number of things that are difficult to seal without liquid sealing. For example, a cavity down type structure such as Enhanced BGA needs to be partially sealed and cannot be handled by transfer molding. For these reasons, the development of highly functional liquid epoxy resins has been demanded.
In recent years, RTM has been used as a composite material, a car body or a ship structural material because of its simplicity of manufacturing method. In such a composition, a low-viscosity epoxy resin is desired because it is easily impregnated into carbon fiber or the like.

  In addition, in the field of optoelectronics, especially in recent years, advanced information technology, in order to smoothly transmit and process a huge amount of information, technology that utilizes optical signals will be developed instead of conventional signal transmission using electrical wiring. In particular, in the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, development of resins having excellent transparency is desired. In response to these requirements, alicyclic epoxy resins have attracted attention. Specifically, it is an epoxy resin group having an epoxycyclohexane skeleton.

Conventionally, such an epoxy resin is generally produced by using an organic peroxide. However, in this production method, there is a risk of runaway, etc., and the product has a high molecular weight. Further, an adduct of an organic oxide, particularly a carboxylic acid adduct, is produced in the product, and these are electric and electronic materials. There is a problem that carboxylate ions are eluted in a severe environment.
For these reasons, in recent years, epoxidation using hydrogen peroxide has been studied. For example, many combinations of heteropolyacids and quaternary ammonium salts have been reported. The quaternary ammonium salt used in these is generally a quaternary ammonium halide. Although the quaternary ammonium halide is excellent in the reactivity, there arises a problem that hydrogen halide is added to the epoxy ring generated during the reaction. These halides are not preferable, particularly when they are used in electrical and electronic materials, which causes a decrease in electrical reliability. Further, when a quaternary ammonium halide is used, although the reactivity is good in the reaction, there is a problem that a large amount of hydrolysis products are generated, and there is a problem in terms of productivity.

JP 2002-69079 A Japanese Patent Laid-Open No. 2001-17863 JP 2005-169363 A JP 2004-115455 A JP-A-5-213919

  The present invention provides a method for producing an epoxy compound using hydrogen peroxide, and provides an epoxy compound having a low halogen content, and a curable resin composition suitable for optical applications using the epoxy compound.

  As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.

That is, the present invention provides (1)
A method for producing an epoxy compound, comprising oxidizing a compound having a carbon-carbon double bond in the presence of hydrogen peroxide, tungstic acids and a quaternary ammonium carboxylate;
(2)
The method for producing an epoxy compound according to item (1), wherein the tungstic acid is at least one acid selected from tungstic acid, phosphotungstic acid or silicotungstic acid, or a salt thereof;
(3)
The method for producing an epoxy compound according to item (1), wherein the counter cation of tungstic acid is any one of proton, sodium ion, potassium ion, calcium ion, and ammonium ion,
(4)
Two or more types of tungstic acids are used, the method for producing an epoxy compound according to the above item (1),
(5)
Two or more types of tungstic acids are a combination of an acidic substance and a basic substance, The method for producing an epoxy compound as described in (4) above,
(6)
The method for producing an epoxy compound according to item (1), wherein the quaternary ammonium carboxylate is an acetate salt;
(7)
The ratio of the usage amount of tungstic acid and quaternary ammonium carboxylate is 1.1 to 10 times equivalent to the valence number of tungstic acid used, and the quaternary ammonium carboxylate is used as described above ( 1) to a method for producing an epoxy compound according to (6),
(8)
The ratio of the amount of the tungstic acid to the quaternary ammonium carboxylate used is a quaternary ammonium carboxylate equivalent to 0.1 to 0.8 times the valence of the tungstic acid. 1) to a method for producing an epoxy compound according to (6),
(9)
It is a polyvalent epoxy compound produced by an epoxidation process using hydrogen peroxide for a compound having a carbon-carbon double bond, and its total chlorine content is 1 ppm or more and 100 ppm or less. An epoxy compound characterized in that the amount of the carboxylic acid adduct of formula 1 to 5 is 0.5% or less (gas chromatography area%),
(10)
A curable resin composition containing the epoxy compound obtained by the production method according to any one of (1) to (8) or the epoxy compound according to (9),
(11)
A curable resin composition comprising the epoxy compound obtained by the production method according to any one of (1) to (8) or the epoxy compound according to (9) and a phosphorus-containing antioxidant;
(12)
The curable resin composition according to the above item (10) or (11), which contains a curing agent and / or a curing catalyst,
(13)
The curable resin composition according to item (12), wherein the curing agent has an acid anhydride structure and / or a carboxylic acid structure,
(14)
The curable resin composition according to item (12), wherein the curing catalyst is a sulfonium salt or an iodonium salt,
(15)
Hardened | cured material formed by hardening | curing curable resin composition as described in any one of said item | term (12)-(14),
About.

  In the present invention, an epoxy compound having a low halogen content and a hydrolyzate can be obtained by using a specific quaternary ammonium salt. The epoxy compound obtained by the present invention is excellent in thermal stability, and the curable fat composition of the present invention including the epoxy compound includes electrical / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, resists, etc. It is very useful for optical materials because of its wide range of applications, especially low colorability.

The present invention is characterized in that tungstic acids and a quaternary ammonium carboxylate are used in an oxidation reaction of a carbon-carbon double bond using hydrogen peroxide.

The compound having a carbon-carbon double bond is not particularly limited as long as it is a compound having a carbon-carbon double bond in the molecule, but in the present invention, it is particularly preferable that the double bond is in a cyclo ring. In particular, those having a cyclohexene structure and further a cyclohexene carboxyester structure in the molecule are preferred. Specific compounds include esterification reaction of cyclohexene carboxylic acid and alcohol or esterification reaction of cyclohexene methanol and carboxylic acid (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), etc.) Described), or Tyschenko reaction of cyclohexene aldehyde (method described in JP-A-2003-170059, JP-A-2004-262871, etc.), and further transesterification of cyclohexene carboxylic acid ester (JP-A-2006-052187). And the like, which are obtained by oxidizing a compound that can be produced by the method described in Japanese Patent Publication No.
The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentane. Diols, diols such as 1,6-hexanediol and cyclohexanedimethanol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, pentaerythritol, etc. And tetraols. Examples of carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.

  Furthermore, the acetal compound by the acetal reaction of a cyclohexene aldehyde derivative and an alcohol form is mentioned. As a reaction method, it can be produced by applying a general acetalization reaction. For example, a method of carrying out the reaction while azeotropic dehydration using a solvent such as toluene or xylene as a reaction medium (US Pat. No. 2,945,008), concentrated hydrochloric acid A method in which polyhydric alcohol is dissolved in the mixture and then the reaction is carried out while gradually adding aldehydes (Japanese Patent Laid-Open No. 48-96590), a method using water as a reaction medium (US Pat. No. 3,092,640), A method using an organic solvent (Japanese Patent Laid-Open No. 7-215979), a method using a solid acid catalyst (Japanese Patent Laid-Open No. 2007-230992), and the like are disclosed. A cyclic acetal structure is preferable from the viewpoint of structural stability.

  As a specific epoxidation technique, a raw material compound having a carbon-carbon double bond, tungstic acid, and quaternary ammonium salt are reacted in an emulsion of an organic substance and hydrogen peroxide solution.

Examples of the tungstic acid include tungstic acid; phosphotungstic acid such as 12-tungstophosphoric acid, 12-tungstoboric acid or 18-tungstophosphoric acid; silicotungstic acid such as 12-tungstosilicic acid and salts thereof.
Examples of the counter cation of these salts include quaternary ammonium ions, alkaline earth metal ions, and alkali metal ions.

Specifically, tetramethylammonium ion, benzyltriethylammonium ion, tridecanylmethylammonium ion, dilauryldimethylammonium ion, trioctylmethylammonium ion, trialkylmethyl (mixed type of octyl group and decanyl group) ammonium ion, Quaternary ammonium ions such as hexadecylmethylammonium ion, trimethylstearylammonium ion, tetrapentylammonium ion, cetyltrimethylammonium ion, benzyltributylammonium ion, tricaprylmethylammonium ion, dicetyldimethylammonium ion, calcium ion magnesium ion, etc. Alkaline earth metal ions, sodium, potassium, cesium and other alkalis Although such genera ions include, but are not limited to.
Particularly preferred counter cations are sodium ion, potassium ion, calcium ion and ammonium ion.
The amount used is 0.5 to 20 mmol, preferably 1.0 to 20 mmol, and more preferably 2.5 to 15 mmol in terms of tungsten element with respect to 1 mol of the raw material.
Tungstic acids are preferably used in combination of two or more. For example, a combination of acidic tungstic acids and basic tungstic acids is preferred, and tungstic acid, 12-tungstophosphoric acid, 12-tungstoboric acid, 18- One or more selected from tungstophosphoric acid and 12-tungstosilicic acid, alkali or alkaline earth metal salt of tungstic acid, alkali or alkaline earth metal salt of tungstophosphoric acid, alkali or alkaline earth of 12-tungstoboric acid One or more kinds of combinations selected from alkali metal salts, alkali or alkaline earth metal salts of 18-tungstophosphoric acid, and alkali or alkaline earth metal salts of 12-tungstosilicate, particularly tungstic acid, 12-tungstri Acid, 12 and one or more selected from tungstosilicic acid, alkali or alkaline earth metal salts of tungstic acid, one or more combinations selected from the group consisting of an alkali or alkaline earth metal salt of 12-tungstophosphoric acid.

As the quaternary ammonium salt, a quaternary ammonium salt having a total carbon number of 10 or more, preferably 25 to 100, more preferably 25 to 55 can be preferably used, and in particular, the alkyl chain is preferably an aliphatic chain. .
Specifically, tridecanylmethylammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl (a mixed type of a compound in which the alkyl group is an octyl group and a compound in which the decanyl group is a compound) ammonium salt, trihexa Examples include decylmethylammonium salt, trimethylstearylammonium salt, tetrapentylammonium salt, cetyltrimethylammonium salt, benzyltributylammonium salt, dicetyldimethylammonium salt, tricetylmethylammonium salt, and di-cured tallow alkyldimethylammonium salt. It is not limited to.
The anion species of these salts use carboxylate ions. As the carboxylate ion, acetate ion, carbonate ion and formate ion are preferable, and acetate ion is particularly preferable. When a halogen ion is used as a counter ion, there is a problem that the halogen ion remains by reacting with an epoxy group generated by the halogen. Furthermore, it is not preferable to use sulfate ions such as sulfate ions and methyl sulfate ions as counter ions because hydrolysis of the ester structure is observed.
When the number of carbon atoms exceeds 100, the hydrophobicity becomes too strong, and the solubility of the quaternary ammonium salt in the organic layer may deteriorate. If the number of carbon atoms is 10 or less, the hydrophilicity becomes strong, and the compatibility of the quaternary ammonium salt with the organic layer may also deteriorate.

In general, halogen remains in the quaternary ammonium salt. In the present invention, it is particularly preferable to use a quaternary ammonium salt of 1% by weight or less, more preferably 1000 ppm or less, and still more preferably 700 ppm or less. When the total halogen content exceeds 1% by weight, a large amount of halogen remains in the product, which is not preferable.
The amount of tungstic acid and quaternary ammonium carboxylate used is preferably 0.01 to 0.8 times equivalent, or 1.1 to 10 times equivalent to the valence of the tungstic acid used. More preferably, it is 0.05 to 0.7 times equivalent, or 1.2 to 6.0 times equivalent, and more preferably 0.05 to 0.5 times equivalent, or 1.3 to 4.5 times equivalent. is there.

For example, since tungstic acid is divalent with H ₂ WO ₄ , the quaternary ammonium carboxylate is 0.02 to 1.6 mol, or 2.2 to 20 mol per mol of tungstic acid. A range is preferred. In addition, since it is trivalent in the case of tungstophosphoric acid, it is similarly 0.03 to 2.4 mol, or 3.3 to 20 mol, and in the case of silicotungstic acid, it is tetravalent, so 0.04 to 3.2. Mole or 4.4 to 40 mol is preferred.
When the amount of the quaternary ammonium carboxylate is lower than 1.1 times equivalent of the valence of tungstic acids, the epoxidation reaction is difficult to proceed (in some cases, the reaction proceeds faster), and a by-product is produced. The problem is that things are easy to make. When the amount is more than 10 times the equivalent, not only is the treatment of the excess quaternary ammonium carboxylate difficult, but it also serves to suppress the reaction, which is not preferable.

  A commercially available product may be used as the quaternary ammonium salt having a carboxylate ion as an anion. For example, the raw material quaternary ammonium salt is treated with a metal hydroxide or an ion exchange resin to be converted into a quaternary ammonium hydroxide. Further, it may be produced by a method of reacting with various carboxylic acids. Examples of the raw material quaternary ammonium salt include quaternary ammonium halides and various metal salts. If there is a suitable quaternary ammonium hydroxide, it may be used.

A buffer solution is preferably used for the oxidation reaction in the present invention.
Any buffer can be used, but it is preferable to use an aqueous phosphate solution in this reaction. The pH is preferably adjusted between pH 4 and 10, more preferably pH 5-9. When the pH is 4 or less, the hydrolysis reaction and polymerization reaction of the epoxy group easily proceed. On the other hand, when the pH is 10 or more, the reaction becomes extremely slow and the reaction time is too long.
In particular, in the present invention, it is preferable to adjust the pH to be between 6 and 8 when the tungstic acid as a catalyst is dissolved.
For example, in the case of a phosphoric acid-phosphate aqueous solution which is a preferable buffer solution, the buffer solution is used in an amount of 0.1 to 10 mol% equivalent of phosphoric acid (or sodium dihydrogen phosphate, etc.) with respect to hydrogen peroxide. And a method of adjusting pH with a basic compound (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, etc.). It is also possible to adjust using sodium dihydrogen phosphate, disodium hydrogen phosphate, or the like. The preferred phosphate concentration is 0.1 to 60% by weight, preferably 1 to 45% by weight.
In this reaction, a buffer solution is not used, but disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, sodium tripolyphosphate, etc. (or hydrates thereof) can be converted to phosphate without adjusting pH. May be added directly. In the sense of simplifying the process, there is no troublesome pH adjustment, and direct addition is particularly preferable. The amount of phosphate used in this case is usually 0.1 to 5 mol% equivalent, preferably 0.2 to 4 mol% equivalent, more preferably 0.3 to 3 mol% equivalent to hydrogen peroxide. It is. At this time, if the amount exceeds 5 mol% equivalent to hydrogen peroxide, pH adjustment is required, and if it is less than 0.1 mol% equivalent, the resulting hydrolyzate of the epoxy compound is likely to proceed or the reaction is slow. The harmful effect of becoming.

  This reaction is epoxidized using hydrogen peroxide. As the hydrogen peroxide used in this reaction, an aqueous solution having a hydrogen peroxide concentration of 10 to 40% by weight is preferable because of easy handling. When the concentration exceeds 40% by weight, handling becomes difficult and the decomposition reaction of the produced epoxy compound also tends to proceed.

  This reaction uses an organic solvent. The amount of the organic solvent to be used is 0.3 to 10 by weight, preferably 0.3 to 5, and more preferably 0.8 to the compound 1 having a carbon-carbon double bond as a reaction substrate. 5 to 2.5. When the weight ratio exceeds 10, the progress of the reaction is extremely slow, which is not preferable. Specific examples of usable organic solvents include alkanes such as hexane, cyclohexane and heptane, aromatic hydrocarbon compounds such as toluene and xylene, and alcohols such as methanol, ethanol, isopropanol, butanol, hexanol and cyclohexanol. it can. In some cases, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and anone; ethers such as diethyl ether, tetrahydrofuran, and dioxane; ester compounds such as ethyl acetate, butyl acetate, and methyl formate; A tolyl compound can also be used. Particularly preferred solvents are alkanes such as hexane, cyclohexane and heptane, and aromatic hydrocarbon compounds such as toluene and xylene.

  As a specific reaction operation method, for example, when the reaction is performed in a batch-type reaction kettle, a compound having a carbon-carbon double bond, hydrogen peroxide (aqueous solution), tungstic acid, buffer solution (or phosphates) Add quaternary ammonium salt and organic solvent and stir in two layers. There is no specific designation for the stirring speed. Since heat is often generated when hydrogen peroxide is added, a method of gradually adding hydrogen peroxide after each component may be added.

At this time, a buffer solution (or water and phosphoric acid or phosphate) and tungstic acid are added to adjust the pH, and then a quaternary ammonium salt, an organic solvent, and a compound having a carbon-carbon double bond are added. A technique of dropping hydrogen peroxide is used when stirring in layers.
Alternatively, while stirring water, organic solvent, and a compound having a carbon-carbon double bond, tungstic acid and phosphoric acid (or phosphates) are added, pH is adjusted, and quaternary ammonium salt is added. However, it is possible to use a method of dropping hydrogen peroxide when stirring in two layers.

  Although reaction temperature is not specifically limited, 0-90 degreeC is preferable, More preferably, it is 0-75 degreeC, Furthermore, the range of 15-60 degreeC, Especially 30-55 degreeC is preferable. When the reaction temperature is too high, there arises a problem that the hydrolysis reaction easily proceeds, and further the product is easily colored. Further, when the reaction temperature is low, the reaction rate becomes extremely slow.

  Although the reaction time depends on the reaction temperature, the amount of catalyst, etc., from the viewpoint of industrial production, a long-time reaction is not preferable because it consumes a large amount of energy. A preferable range is 1 to 48 hours, preferably 3 to 36 hours, and more preferably 4 to 24 hours.

After completion of the reaction, quenching of excess hydrogen peroxide is performed. The quenching treatment is preferably performed using a basic compound. By quenching with a basic compound, the residual amount of heteropolyacid (salts) as a catalyst can be greatly reduced. It is also preferable to use a reducing agent and a basic compound in combination.
As a preferred treatment method, after adjusting the pH to 6 to 10 with a basic compound, the remaining hydrogen peroxide is quenched using a reducing agent. When the pH is 6 or less, there is a large exotherm when reducing excess hydrogen peroxide, and the produced epoxy compound may be partially hydrolyzed. Further, when the pH is 10 or more, hydrolysis of the epoxy compound and further hydrolysis of the ester bond may be caused.

Examples of the reducing agent include sodium sulfite, sodium thiosulfate, hydrazine, oxalic acid, ascorbic acid, glucose and the like. As the amount of the reducing agent used, excess hydrogen peroxide is usually 0.01 to 20 times mol, more preferably 0.05 to 10 times mol, still more preferably 0.05 to 3 times mol, based on the number of moles. is there.
These are preferably added as an aqueous solution, and the concentration is 0.5 to 30% by weight.

Basic compounds include metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, phosphorus such as sodium phosphate and sodium hydrogen phosphate. Examples thereof include basic solids such as acid salts, ion exchange resins, and alumina.
These may be added in solid form or as an aqueous solution, but metal hydroxide, metal carbonate and the like are particularly preferably added as an aqueous solution, and the concentration thereof is 0.5 to 30% by weight.
The amount used is water or organic solvents (for example, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl isobutyl ketone and methyl ethyl ketone, hydrocarbons such as cyclohexane, heptane and octane, methanol, ethanol, isopropyl alcohol, etc. And other alcohols such as alcohols) is usually 0.01 to 20 times mol, more preferably 0.05 to 10 times mol, and still more preferably, relative to the number of moles of excess hydrogen peroxide. Is 0.05 to 3 moles.
When a solid base that does not dissolve in water or an organic solvent is used, it is preferable to use an amount of 1 to 1000 times by weight with respect to the amount of hydrogen peroxide remaining in the system. More preferably, it is 10-500 times, More preferably, it is 10-300 times. In the case of using a solid base that does not dissolve in water or an organic solvent, the treatment may be carried out after separation of an aqueous layer and an organic layer described later.

After hydrogen peroxide quench (or before quenching), the organic and aqueous layers are separated. At this time, when the organic layer and the aqueous layer are not separated, or the organic solvent is not used, the operation is performed by adding the above-mentioned organic solvent, and the reaction product is extracted from the aqueous layer. The organic solvent used in this case is 0.5 to 10 times, preferably 0.5 to 5 times in weight ratio with respect to the compound having a raw material carbon-carbon double bond to be obtained. This operation is repeated several times as necessary, and the separated organic layer is purified by washing with water as necessary.
The obtained organic layer may be an ion exchange resin, a metal oxide (especially, silica gel, alumina, etc. are preferred), activated carbon (especially, preferably a chemical activated carbon), a composite metal salt (especially a basic composite metal salt). Are preferably removed), a mineral with a viscosity (especially a layered viscosity mineral such as montmorillonite is preferred) and the like, and after washing with water and filtration, the solvent is distilled off to obtain the desired epoxy compound.

The epoxy compound thus obtained contains, as impurities, a hydrolyzate resulting from a reaction between an epoxy group and water, a product in which a halogen such as chlorine is introduced, a carboxylic acid adduct such as acetic acid, and the like. Further, polymerized high molecular weight polymer of epoxy groups and other side reaction products are generated depending on the reaction conditions.
The epoxy compound obtained in the present invention is particularly characterized in that the amount of carboxylic acid adducts such as halogen amount and acetic acid adduct is reduced. Introducing halogens and acetic acid adducts are regarded as a problem particularly in electronic materials because they may significantly reduce electrical properties.
The amount of halogen contained in the epoxy compound obtained in the present invention is 1 to 1000 ppm, more preferably 1 to 500 ppm, and particularly preferably 1 to 100 ppm (measured by a combustion method and can be replaced by a hydrolysis method).
Further, the amount of carboxylic acid adduct is preferably 1% or less, particularly 0.5% or less, more preferably 0.3% or less (measured by gas chromatography).

The obtained epoxy compound can be used as various resin raw materials such as epoxy acrylate and derivatives thereof, oxazolidone compounds, and cyclic carbonate compounds.

Hereinafter, the curable resin composition (referred to as the curable resin composition of the present invention) containing the epoxy compound (referred to as the epoxy compound of the present invention) obtained as described above will be described.
The curable resin composition of the present invention contains the epoxy compound of the present invention. In the curable resin composition of the present invention, two methods of heat curing with a curing agent (curable resin composition A) and cationic curing with an acid as a curing catalyst (curable resin composition B) can be applied.

In the curable resin composition A and the curable resin composition B, the epoxy compound of the present invention can be used alone or in combination with other epoxy resins. When used in combination, the proportion of the epoxy compound of the present invention in all epoxy resins (the epoxy compound of the present invention and other epoxy resins; the same shall apply hereinafter) is preferably 30% by weight or more, particularly preferably 40% by weight or more. However, when using the epoxy compound of this invention as a modifier of curable resin composition, it adds in the ratio of 1 to 30 weight%.

Examples of other epoxy resins that can be used in combination with the epoxy compound of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins, and the like. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetaldehyde Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, etc. and their modified products, halogenated bisphenols such as tetrabromobisphenol A, or alcohols Glycidyl etherified product of alicyclic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain, cyclic, ladder, or a mixture of at least two of them) Siloxane structure with glycidyl group and / or epoxycyclohexa Include solid or liquid epoxy resin having an epoxy resin) having the structure, but not limited thereto.

When using especially the curable resin composition of this invention for an optical use, combined use with an alicyclic epoxy resin or an epoxy resin of a silsesquioxane structure is preferable. In particular, in the case of an alicyclic epoxy resin, a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is preferable.
These epoxy resins include esterification reaction of cyclohexene carboxylic acid and alcohols or esterification reaction of cyclohexene methanol and carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), etc.) Described), or Tyschenko reaction of cyclohexene aldehyde (method described in JP-A-2003-170059, JP-A-2004-262871, etc.), and further transesterification of cyclohexene carboxylic acid ester (JP-A-2006-052187). And the like, which are obtained by oxidizing a compound that can be produced by the method described in Japanese Patent Publication No.
The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentane. Diols, diols such as 1,6-hexanediol and cyclohexanedimethanol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, pentaerythritol, etc. And tetraols. Examples of carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.

Furthermore, the acetal compound by the acetal reaction of a cyclohexene aldehyde derivative and an alcohol form is mentioned. As a reaction method, it can be produced by applying a general acetalization reaction. For example, a method of carrying out a reaction while azeotropically dehydrating using a solvent such as toluene or xylene as a reaction medium (US Pat. No. 2,945,008), concentrated hydrochloric acid A method in which polyhydric alcohol is dissolved in the mixture and then the reaction is carried out while gradually adding aldehydes (Japanese Patent Laid-Open No. 48-96590), a method using water as a reaction medium (US Pat. No. 3,092,640), A method using an organic solvent (Japanese Patent Laid-Open No. 7-215979), a method using a solid acid catalyst (Japanese Patent Laid-Open No. 2007-230992), and the like are disclosed. A cyclic acetal structure is preferable from the viewpoint of structural stability.
Specific examples of these epoxy resins include ERL-4221, UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical), Celoxide 2021P, Eporide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel). Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited to these (Reference: Review Epoxy Resin Basic Edition I p76-85).
These may be used alone or in combination of two or more.

Hereinafter, each curable resin composition will be described.
Thermal curing with a curing agent (curable resin composition A)
Examples of the curing agent contained in the curable resin composition A of the present invention include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and nitrogen-containing compounds such as polyamide resins synthesized from linolenic acid and ethylenediamine (amine, Amide compounds); phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydro Phthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, Cyclohe Acid anhydrides such as sun-1,3,4-tricarboxylic acid-3,4-anhydride; carboxylic acid resins obtained by addition reaction of various alcohols, carbinol-modified silicones and the above-mentioned acid anhydrides; phenol Resin, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1' -Biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, Alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, Hydroxynaphthalene and the like) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1, Heavy weight with 1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4′-bis (chloromethyl) benzene, 1,4′-bis (methoxymethyl) benzene, etc. Condensates and modified products thereof, polyphenols such as halogenated bisphenols such as tetrabromobisphenol A, terpene and phenol condensates; compounds such as imidazole, trifluoroborane-amine complexes, and guanidine derivatives, these It is not limited to. These may be used alone or in combination of two or more.
In the present invention, a compound having an acid anhydride structure and / or a carboxylic acid structure represented by the aforementioned acid anhydride and carboxylic acid resin is particularly preferable.

  In the curable resin composition A of the present invention, the amount of the curing agent used is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy groups of all epoxy resins. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

In the curable resin composition A of the present invention, a curing accelerator may be used in combination with the curing agent. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza- Tertiary amines such as bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, etc. Quaternary ammonium salts, triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, quaternary phosphonium salts such as tetrabutylphosphonium salts, and the like can be given. (The counter ion of the quaternary salt is not particularly specified, such as halogen, organic acid ion, hydroxide ion, etc., but organic acid ion and hydroxide ion are particularly preferable), metal compounds such as tin octylate, etc. It is done. When using a hardening accelerator, 0.01-5.0 weight part is used as needed with respect to 100 weight part of epoxy resins.

The curable resin composition A of the present invention may contain a phosphorus-containing compound as a flame retardant imparting component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric acid esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes A phosphorus-containing product obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned, and phosphoric esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The phosphorus-containing compound content is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (weight ratio). If it is 0.1 or less, the flame retardancy is insufficient, and if it is 0.6 or more, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.

Furthermore, you may add antioxidant to the curable resin composition A of this invention as needed. Antioxidants that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. Antioxidants can be used alone or in combination of two or more. The usage-amount of antioxidant is 0.008-1 weight part normally with respect to 100 weight part with respect to the resin component in the curable resin composition of this invention, Preferably it is 0.01-0.5 weight part. It is.

Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant. Specific examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate and the like; 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl- 6-t-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1 , 1-Dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspir B Bisphenols such as [5,5] undecane; 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6 -Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, Bis [3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-t-butyl- High molecular phenols such as 4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione and tocophenol are exemplified.

Specific examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like. .

Specific examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4 -Di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc. 9,10-dihydro 9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxaphosphaphenanthrene oxides such as 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are exemplified.

These antioxidants can be used alone, but two or more of them may be used in combination. In the present invention, a phosphorus-based antioxidant is particularly preferable.

Furthermore, you may add a light stabilizer to the curable resin composition A of this invention as needed.
As the light stabilizer, hindered amine-based light stabilizers, particularly HALS and the like are suitable. HALS is not particularly limited, but representative examples include dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4- A polycondensate of piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{6- (1,1,3,3-tetramethyl Butyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetra Methyl-4-piperidyl) imino}], bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] Methyl] butyl malonate, bis (2,2 6,6-tetramethyl-4-piperidyl) .HALS which sebacate and the like are may be used only one kind or two or more of them may be used in combination.

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

An inorganic filler can be added to the curable resin composition A of the present invention as necessary. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the curable resin composition A of the present invention. Furthermore, the curable resin composition of the present invention includes various agents such as silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers. A compounding agent and various thermosetting resins can be added.

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

The curable resin composition A of the present invention is obtained by uniformly mixing each component. The curable resin composition A of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the epoxy compound of the present invention, a curing agent and, if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent are sufficient until uniform using an extruder, kneader, roll, etc. as necessary. To obtain a curable resin composition, potting the curable resin composition, after melting (without melting in the case of a liquid, casting), or molding using a transfer molding machine, and further 80-200 The cured product of the present invention can be obtained by heating at a temperature of 2 to 10 hours.

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

  Moreover, the curable resin composition A of this invention can be used also as a modifier of a film type composition. Specifically, it can be used to improve the flexibility of the B-stage. When obtaining such a film-type resin composition, such a film-type resin composition is applied onto the release film using the curable resin composition A of the present invention as the curable resin composition varnish, After removing the solvent under heating, it is obtained as a sheet-like adhesive by performing B-stage. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

Furthermore, the curable resin composition A of the present invention can be used in general applications in which a thermosetting resin such as an epoxy resin is used. For example, adhesives, paints, coating agents, molding materials (sheets, films) , FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.), sealing materials, sealing materials, cyanate resin compositions for substrates, and acrylic ester resins as resist curing agents, etc. And additives to other resins.

Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, underfill for QFP, BGA, CSP, etc., and sealing (including reinforcing underfill) can be used.

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

As the acidic curing catalyst, a cationic polymerization initiator is preferable, and a photocationic polymerization initiator is particularly preferable. Examples of the cationic polymerization initiator include those having an onium salt such as an iodonium salt, a sulfonium salt, or a diazonium salt, and these can be used alone or in combination of two or more.
Examples of active energy ray cationic polymerization initiators include metal fluoroboron complex salts and boron trifluoride complex compounds (US Pat. No. 3,379,653), bis (perfluoroalkylsulfonyl) methane metal salts (US Pat. No. 3,586,616), aryldiazonium Compound (US Pat. No. 3,708,296), aromatic onium salt of group VIa element (US Pat. No. 4,058,400), aromatic onium salt of group Va element (US Pat. No. 4069055), dicarbonyl chelate of group IIIa to Va element (US Pat. No. 4068091), thiopyrylium salts (US Pat. No. 4,139,655), group VIb elements in the form of MF ₆ -anions (US Pat. No. 4,161,478; M is selected from phosphorus, antimony and arsenic). Arylsulfonium complex salt (US Pat. No. 4,231,951) , Aromatic iodonium and aromatic sulfonium complexes (US Pat. No. 4,256,828), and bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluorometal salts (Journal of Polymer Science, Polymer Chemistry, Volume 2) 1789 (1984)). In addition, mixed ligand metal salts of iron compounds and silanol-aluminum complexes can also be used.
As specific examples, “Adekaoptomer SP150”, “Adekaoptomer SP170” (all manufactured by Asahi Denka Kogyo Co., Ltd.), “UVE-1014” (manufactured by General Electronics Co., Ltd.), “CD-1012” (Sartomer Company) Product), “RP-2074” (manufactured by Rhodia), and the like.
The amount of the cationic polymerization initiator used is preferably 0.01 to 50 parts by weight and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin component.

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

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

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

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

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

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

The cured product obtained by curing the curable resin composition A and the curable resin composition B of the present invention can be used for various applications including optical component materials. The optical material refers to general materials used for applications that allow light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material. More specifically, in addition to LED sealing materials such as lamp type and SMD type, the following may be mentioned. It is a peripheral material for liquid crystal display devices such as a substrate material, a light guide plate, a prism sheet, a polarizing plate, a retardation plate, a viewing angle correction film, an adhesive, and a film for a liquid crystal such as a polarizer protective film in the liquid crystal display field. In addition, color PDP (plasma display) sealing materials, antireflection films, optical correction films, housing materials, front glass protective films, front glass replacement materials, adhesives, and LED displays that are expected as next-generation flat panel displays LED molding materials, LED sealing materials, front glass protective films, front glass substitute materials, adhesives, and substrate materials for plasma addressed liquid crystal (PALC) displays, light guide plates, prism sheets, deflection plates , Phase difference plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass substitute material, adhesive, and various in field emission display (FED) Film substrate Front glass protective films, front glass substitute material, an adhesive. In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Pickup lenses, protective films, sealing materials, adhesives and the like.

In the optical equipment field, they are still camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor sections. It is also a photographic lens and viewfinder for video cameras. Projection lenses for projection televisions, protective films, sealing materials, adhesives, and the like. These include lens materials, sealing materials, adhesives, and films for optical sensing devices. In the field of optical components, they are fiber materials, lenses, waveguides, element sealing materials, adhesives and the like around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. For optical passive components and optical circuit components, there are lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, and the like. These are substrate materials, fiber materials, device sealing materials, adhesives, etc. around an optoelectronic integrated circuit (OEIC). In the field of optical fiber, it is an optical fiber for lighting, light guides for decorative displays, sensors for industrial use, displays / signs, etc., and for communication infrastructure and home digital equipment connection. As the semiconductor integrated circuit peripheral material, it is a resist material for microlithography for LSI and VLSI material. In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Rusted steel plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, glass replacements. In addition, it is a multilayer glass for railway vehicles. Further, they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wireness, and corrosion-resistant coatings. In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film. Next-generation optical / electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.

Other uses of the optical material include general uses in which the curable resin composition A is used. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), In addition to insulating materials (including printed circuit boards and wire coatings), sealants, additives to other resins and the like can be mentioned.

Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, underfill for sealing, and sealing (reinforcing underfill) when mounting IC packages such as BGA and CSP.

The curable resin composition A and the curable resin composition B of the present invention can also be applied to an optical semiconductor device. Such an optical semiconductor device can be manufactured by sealing an optical semiconductor element (optical semiconductor chip) with the curable resin composition of the present invention. As the sealing method, a method of molding (casting and curing) a sealing resin for sealing the optical semiconductor element by a method such as casting, potting or printing can be employed. The molding conditions can be adopted as they are as the molding conditions in the sealing molding of a semiconductor element with a curable resin composition that has been conventionally performed, and if appropriately set according to the composition of the curable resin composition for optical semiconductor encapsulation, etc. Good.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, “parts” is parts by weight unless otherwise specified. The present invention is not limited to these examples. In the examples, the epoxy equivalent was measured using JIS K-7236, and the viscosity was measured using an E-type viscometer at 25 ° C.

Example 1
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 30 parts of a 10% by weight sodium dihydrogen phosphate aqueous solution and 1.9 parts of 12-tungstophosphoric acid while purging with nitrogen, and 10% by weight hydrogen phosphate. The pH was adjusted to 5.0 with a disodium aqueous solution. Furthermore, after adding 6 parts of trioctylmethylammonium acetate (TOMAA-50 Lion Akzo concentration 50% by weight xylene solution) and purifying the tungstic acid catalyst, 150 parts of toluene was added and dissolved to form a two-layer solution. Stir at room temperature for 1 hour.
Here, the formula (1)

After adding 110 parts of the compound represented by formula (1), the temperature of the solution was raised to 50 ° C., while stirring, 106 parts of 35 wt% aqueous hydrogen peroxide was added, and the mixture was further stirred at 50 ° C. for 10 hours. After cooling to room temperature, the pH was adjusted to 7.5 with 100 parts of a 1% by weight aqueous sodium hydroxide solution, the aqueous layer was discarded, and 50 parts of a 20% by weight aqueous sodium thiosulfate solution was added and stirred for 1 hour, and then allowed to stand. did. Thereafter, the organic layer separated into two layers was taken out.
To the obtained organic layer, 30 parts of silica gel and 30 parts of activated carbon (CAP SUPER made by NORIT) were added and stirred at room temperature for 2 hours, followed by filtration under reduced pressure. The residue after filtration was further washed with 100 parts of toluene. Mixed with liquid. The obtained solution was washed with 100 parts of water three times, and the organic solvent was distilled off using a rotary evaporator to obtain 110 parts of the target epoxy compound (EP1). The resulting epoxy compound was light yellow and the epoxy equivalent was 130 g / eq. The viscosity was 227 mPa · s. The total chlorine content was 110 ppm.

Comparative Example 1
In Example 1, the same operation was performed except that trioctylmethylammonium chloride (manufactured by Lion Akzo, isopropyl alcohol solution having a concentration of 75% by weight) was used instead of trioctylmethylammonium acetate.
The obtained epoxy compound (EP2) was a pale yellow liquid, and the epoxy equivalent was 132 g / eq. The viscosity was 233 mPa · s. The total chlorine content was 2510 ppm, and the acetyl content was 0.1% (GC (gas chromatography; hereinafter the same) area%) or less.

Example 2
In Example 1, the same operation was performed except that di-tallow alkyldimethylammonium acetate (a hexane solution or slurry having a concentration of 50% by weight made by Lion Akzo) was used instead of trioctylmethylammonium acetate.
The obtained epoxy compound (EP3) was a pale yellow liquid, and the epoxy equivalent was 130 g / eq. The viscosity was 230 mPa · s. The total chlorine content was 79 ppm, and the acetyl content was 0.1% (GC area%) or less.

Comparative Example 2
In Example 1, the same operation was performed except that di-tallow alkyldimethylammonium chloride (manufactured by Lion Akzo, isopropyl alcohol-containing flakes having a concentration of 90% by weight) was used instead of trioctylmethylammonium acetate.
The obtained epoxy compound (EP4) was a pale yellow liquid, and the epoxy equivalent was 132 g / eq. The viscosity was 230 mPa · s. The total chlorine content was 1790 ppm, and the acetyl content was 0.1% (GC area%) or less.

The physical properties of the epoxy compounds obtained in Examples 1-2 and Comparative Examples 1-2 are shown in the following table. In the table, GC data is the result of gas chromatography measurement under the following conditions.
Column: HP-5MS 15m-0.25mm-0.25μm
Carrier gas: Helium 1.0mL / min. (Constant flow mode)
Oven: 100 ° C-15 ° C / min.-300 ° C (15min. Hold)
Injection: 1μL, split ratio 50: 1, 300 ℃
Ionization method: EI (EI ion source)
Measurement sample: Take a 0.2mL sample from the emulsion solution of the organic and aqueous layers and dilute with 5mL of acetone.
The total amount of chlorine is precisely weighed about 0.1 g of the sample, burned with a combustion device, and then the gas is absorbed in an absorption liquid (absorption liquid: 20 mL of 0.1% hydrogen peroxide solution). It is the result of measuring.

It has been confirmed that the production method of the present invention can produce an epoxy compound with a small total amount of chlorine. Therefore, it turns out that the epoxy compound obtained by this invention is useful for an electrical and electronic material use.

Example 3
26 parts of EP1 obtained in Example 1, a 1: 1 mixture of H-TMAn (an acid anhydride made by Mitsubishi Gas Chemical Co., Inc.) and MH-700G (an acid anhydride made by Shin Nippon Chemical Co., Ltd.) as a curing agent 18.3 parts Were uniformly mixed and cured at 120 ° C. for 1 hour and 150 ° C. for 3 hours.
(Hardened product C-1)

Comparative Example 3
In Example 3, it was cured in the same manner except that 26 parts of EP1 was changed to 26.2 parts of EP2.
(Curing product; C-2)

Example 4 and Comparative Example 4
The cured products (C-1) and (C-2) obtained in Example 3 and Comparative Example 3 were confirmed to have YI (based on Yellow Index JIS K7105-6.3) when heated at 150 ° C. for 96 hours. . The results are shown in Table 2 below.

Table 2
Cured product Before heating After heating Tg (DMA)
(YI) (YI) (° C)
Example 4 C-1 2.5 2.9 274
Comparative Example 4 C-2 2.3 6.8 272

From this result, it is clear that the curable resin composition obtained by using the epoxy compound of the present invention gives a cured product excellent in heat-resistant coloring.

Example 5
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, while purging with nitrogen, 20 parts of water, 150 parts of toluene, and a dispersion of the compound of the above formula (1) were mixed with sodium tungstate dihydrate 1.0. Part, 1.9 parts of 12-tungstophosphoric acid, 1.6 parts of sodium dihydrogen phosphate dihydrate were added, and the pH of the aqueous layer was adjusted to 6.5. Further, 6 parts of trioctylmethylammonium acetate (TOMAA-50, Lion, Akzo, concentration 50% xylene solution) was added, the temperature was raised to 48 ° C., and with stirring, 106 parts of 35% by weight hydrogen peroxide water was added, followed by post reaction. The mixture was further stirred at 48 ° C for 6 hours. After cooling to 30 ° C., the pH was adjusted to 8.5 with a 5% aqueous sodium hydroxide solution, and further 100 parts of a 10% by weight aqueous sodium thiosulfate solution were added and stirred for 1 hour, and then allowed to stand. Thereafter, the organic layer separated into two layers was taken out.
30 parts of the obtained organic layer Wengel SH (Hojoon bentonite) and 30 parts of activated carbon (CP2 made by Ajinomoto Fine Techno) were added and stirred at room temperature for 4 hours, followed by filtration under reduced pressure. Wash and mix with the previous filtrate. The obtained solution was washed with 100 parts of water three times, and the organic solvent was distilled off using a rotary evaporator to obtain 108 parts of the target epoxy compound (EP5). The obtained epoxy compound was colorless and the epoxy equivalent was 130 g / eq. This was a liquid epoxy compound. The total chlorine content was 25 ppm, and the acetyl content was 0.1% (GC area%) or less.

Example 6
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 20 parts of water, 1.0 part of sodium tungstate dihydrate and 1.9 parts of 12-tungstophosphoric acid while purging with nitrogen. Sodium dihydrogen acid dihydrate (1.0 part) was added to adjust the pH of the aqueous layer to 6.0. Further, 6 parts of trioctylmethylammonium acetate (TOMAA-50, manufactured by Lion Akzo, 50% concentration xylene solution), 150 parts of toluene and 110 parts of the compound of formula (1) were added, and the temperature was raised to 48 ° C. While stirring this, 106 parts of 35% by weight hydrogen peroxide water was added, and the mixture was further stirred at 48 ° C. for 6 hours as a post reaction. After cooling to 30 ° C., the pH was adjusted to 8.5 with a 5% aqueous sodium hydroxide solution, and after liquid separation, 100 parts of a 10% by weight aqueous sodium thiosulfate solution was added to the obtained organic layer, and the mixture was stirred for 1 hour. Liquid separation was performed, and the organic layer was taken out.
30 parts of the obtained organic layer Wengel SH (Bonnite manufactured by Hojun) and 30 parts of activated carbon (ZN2 manufactured by Ajinomoto Fine-Techno) were added and stirred at room temperature for 4 hours, followed by filtration under reduced pressure. Wash and mix with the previous filtrate. The obtained solution was washed with 100 parts of water three times, and the organic solvent was distilled off using a rotary evaporator to obtain 108 parts of the target epoxy compound (EP6). The obtained epoxy compound was colorless, and the epoxy equivalent was 131 g / eq. This was a liquid epoxy compound. The total chlorine content was 18 ppm, and the acetyl content was 0.1% (GC area%) or less.

Example 7
In Example 5, the formula (1) was 110 parts, and the following formula (2) was produced by the method described in JP-A-7-17917.

に示される構造のオレフィン樹脂を１２０部に変えた以外は同様に合成を行い、本発明のエポキシ化合物（ＥＰ７）を１１９部得た。エポキシ当量は１４２ｇ／ｅｑの液状のエポキシ化合物であった。また全塩素１８ｐｐｍ、アセチル体は０．１％（ＧＣ 面積％）以下であった。

Synthesis was carried out in the same manner except that the olefin resin having the structure shown in FIG. 1 was changed to 120 parts, and 119 parts of the epoxy compound (EP7) of the present invention was obtained. The epoxy equivalent was 142 g / eq of a liquid epoxy compound. The total chlorine content was 18 ppm, and the acetyl content was 0.1% (GC area%) or less.

Example 8
In Example 5, 110 parts of the formula (1) were synthesized by dehydration esterification of 1,4-cyclohexanedimethanol and 3-cyclohexenecarboxylic acid.

に示される構造のオレフィン樹脂を１８０部、トルエンを１８０部、反応時間を１４時間に変えた以外は同様に合成を行い、本発明のエポキシ化合物（ＥＰ８）を１６９部得た。エポキシ当量は２０７ｇ／ｅｑ．の液状のエポキシ化合物であった。また全塩素２１ｐｐｍ、アセチル体は０．１％（ＧＣ 面積％）以下であった。

Synthesis was carried out in the same manner except that 180 parts of the olefin resin having the structure shown in the above, 180 parts of toluene, and 14 hours of reaction time were changed to obtain 169 parts of the epoxy compound (EP8) of the present invention. Epoxy equivalent is 207 g / eq. This was a liquid epoxy compound. The total chlorine was 21 ppm, and the acetyl content was 0.1% (GC area%) or less.

Example 9
In Example 5, 110 parts of the formula (1) were synthesized by dehydration esterification of 1,4-cyclohexanedicarboxylic acid and 3-cyclohexenemethanol.

に示される構造のオレフィン樹脂を１８０部、トルエンを１８０部、反応時間を１３時間に変えた以外は同様に合成を行い、本発明のエポキシ化合物（ＥＰ９）を１７５部得た。エポキシ当量は２０４ｇ／ｅｑ．の半晶状（部分的に結晶が出ている）のエポキシ化合物であった。また全塩素２０ｐｐｍ、アセチル体は０．１％（ＧＣ 面積％）以下であった。

Synthesis was carried out in the same manner except that 180 parts of the olefin resin having the structure shown in the above, 180 parts of toluene and 13 hours of reaction time were changed to 175 parts of the epoxy compound (EP9) of the present invention. Epoxy equivalent is 204 g / eq. This was a semi-crystalline epoxy compound (partially crystallized). The total chlorine content was 20 ppm, and the acetyl content was 0.1% (GC area%) or less.

Example 10
In Example 5, 110 parts of the formula (1) were synthesized by dehydration esterification of trimethylolpropane and 3-cyclohexenecarboxylic acid, and the following formula (5)

に示される構造のオレフィン樹脂を１５３部、トルエンを１６０部、反応時間を８時間に変えた以外は同様に合成を行い、本発明のエポキシ化合物（ＥＰ１０）を１４６部得た。エポキシ当量は１７２ｇ／ｅｑ．の液状のエポキシ化合物であった。また全塩素１７ｐｐｍ、アセチル体は０．１％（ＧＣ 面積％）以下であった。

The synthesis was carried out in the same manner except that 153 parts of the olefin resin having the structure shown in the above, 160 parts of toluene and 160 hours of reaction time were changed to 8 hours to obtain 146 parts of the epoxy compound (EP10) of the present invention. Epoxy equivalent was 172 g / eq. This was a liquid epoxy compound. The total chlorine content was 17 ppm, and the acetyl content was 0.1% (GC area%) or less.

Example 11
In Example 5, 110 parts of the formula (1) were synthesized by dehydration condensation of 1,2-cyclohexanedicarboxylic acid and cyclohexenemethanol.

に示される構造のオレフィン樹脂を１８０部、トルエンを１８０部、反応時間を１０時間に変えた以外は同様に合成を行い、本発明のエポキシ化合物（ＥＰ１１）を１７０部得た。エポキシ当量は２０２ｇ／ｅｑの液状のエポキシ化合物であった。また全塩素１０ｐｐｍ、アセチル体は０．１％（ＧＣ 面積％）以下であった。

Synthesis was carried out in the same manner except that 180 parts of the olefin resin having the structure shown in the above, 180 parts of toluene and 10 hours of reaction time were changed to obtain 170 parts of the epoxy compound (EP11) of the present invention. The epoxy equivalent was 202 g / eq of a liquid epoxy compound. Further, the total chlorine was 10 ppm, and the acetyl content was 0.1% (GC area%) or less.

Example 12
In Example 5, 110 parts of the formula (1) were synthesized by dehydration condensation of adipic acid and cyclohexene methanol.

に示される構造のオレフィン樹脂を１６７部に変えた以外は同様に合成を行い、本発明のエポキシ化合物（ＥＰ１２）を１６１部得た。エポキシ当量は１７２ｇ／ｅｑの液状のエポキシ化合物であった。また全塩素１５ｐｐｍ、アセチル体は０．１％（ＧＣ 面積％）以下であった。

Synthesis was carried out in the same manner except that the olefin resin having the structure shown in FIG. 1 was changed to 167 parts, and 161 parts of the epoxy compound (EP12) of the present invention was obtained. The epoxy equivalent was a liquid epoxy compound having a concentration of 172 g / eq. The total chlorine content was 15 ppm, and the acetyl content was 0.1% (GC area%) or less.

Examples 13 and 14 and Comparative Example 5
As an example, the epoxy compounds EP5 and EP6 of the present invention obtained in Examples 5 and 6 and a commercially available epoxy compound EP13 (same structure as ERL-4221 EP5 and EP6 manufactured by Dow Chemical) as a comparative example were used, and a curing agent was used. H-TMAn (an acid anhydride made by Mitsubishi Gas Chemical Co., Ltd.), MH-700G (an acid anhydride made by Shin Nippon Chemical Co., Ltd.), 1: 1 mixture, tetraphenylphosphonium bromide as a curing catalyst, uniformly mixed, 120 Curing was performed for 1 hour at 150C and 3 hours at 150C. The obtained cured product was subjected to an electrical conductivity test.
Table 3 shows the resin characteristics of the epoxy compound used, and Table 4 shows the results of measurement of the composition and electrical conductivity. In addition, the following electrical conductivity is a measurement result of the electrical conductivity of the extraction water by a pressure cooker test (121 degreeC 20 hours).

From the above results, it is clear that the epoxy compound of the present invention having almost no acetic acid adduct is excellent in electrical characteristics.

Claims (8)

A method for producing a polyvalent epoxy compound comprising oxidizing a compound having a carbon-carbon double bond in the presence of hydrogen peroxide, tungstic acids and a quaternary ammonium carboxylate, A method for producing a polyvalent epoxy compound, comprising using 0.5 to 20 mmol of tungstic acid in terms of tungsten element per 1 mol of a raw material of a compound having a heavy bond. The method for producing an epoxy compound according to claim 1, wherein the tungstic acid is at least one acid selected from tungstic acid, phosphotungstic acid or silicotungstic acid, or a salt thereof. The method for producing an epoxy compound according to claim 1, wherein the counter cation of the tungstic acid is any one of proton, sodium ion, potassium ion, calcium ion, and ammonium ion. The method for producing an epoxy compound according to claim 1, wherein two or more types of tungstic acids are used. The method for producing an epoxy compound according to claim 1, wherein the two or more types of tungstic acids are a combination of an acidic substance and a basic substance. The method for producing an epoxy compound according to claim 1, wherein the quaternary ammonium carboxylate is an acetate. The ratio of the amount of tungstic acid to quaternary ammonium carboxylate used is a quaternary ammonium carboxylate equivalent to 1.1 to 10 times the valence of tungstic acid. The manufacturing method of the epoxy compound as described in any one of 6. The ratio of the amount of the tungstic acid to the quaternary ammonium carboxylate is 0.1 to 0.8 times the quaternary ammonium carboxylate equivalent to the valence of the tungstic acid used per mole of tungstic acid. It uses, The manufacturing method of the epoxy compound as described in any one of Claims 1-6 characterized by the above-mentioned.