JPWO2009123276A1 - Epoxy compound having protecting group and curable resin composition containing the same - Google Patents

Abstract

The polyfunctional epoxy compound (A) includes a compound (B) having at least one hydroxyl group and a carboxyl group in one molecule, a polybasic acid anhydride (C), and a vinyl ether compound represented by the specific formula (1) ( A modified polyfunctional epoxy compound having at least one epoxy group and a partial structure represented by the specific formula (3) in one molecule obtained by reacting D).

Description

  The present invention relates to an epoxy compound that can be cured by heat and a curable composition containing the same. More specifically, the present invention relates to a polyfunctional epoxy compound having an epoxy group and a modified carboxyl group, and a curable composition containing the epoxy compound and a thermosetting agent or a cationic polymerization initiator.

Conventionally, a resin composition utilizing the cationic polymerizability of a resin having a cyclic ether group typified by an epoxy resin is known as one of the combinations used for a curable composition, and the resin composition is cured. The cured product obtained in this way is excellent in terms of chemical performance, physical performance, and weather resistance. For these reasons, epoxy resin compositions are widely used in fields such as paints, inks, adhesives, and plastic molded articles. In addition, as a compound having both an epoxy group and a carboxyl group in one molecule, a compound obtained by reacting both a compound having a hydroxyl group and a carboxyl group, and a polybasic acid anhydride with a polyfunctional epoxy compound Is known (Patent Document 1). However, since the carboxyl group itself is a reactive functional group capable of forming a chemical bond with an epoxy group by heating it, a self-crosslinking compound having both an epoxy group and a carboxyl group in one molecule is The problem is that the viscosity tends to increase during storage and the pot life is short.
In Patent Document 2, thermosetting containing a self-crosslinking compound having a functional group obtained by reaction of a carboxyl group and vinyl ether in one molecule and a reactive functional group capable of forming a chemical bond with the carboxyl group. It is described that the resin composition is excellent in storage stability. However, the compound described in Patent Document 2 is limited to a compound having an aliphatic skeleton, and is not satisfactory in heat resistance and adhesion as a coating material and lithography characteristics as a photoresist.

Japanese Patent No. 3698499 Japanese Patent No. 2682256

  It is an object of the present invention to obtain a modified polyfunctional epoxy compound (resin) that can be used as a raw material for paints and resist compositions and is excellent in storage stability, cured product adhesion, and lithography properties.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a modified epoxy compound obtained by protecting the carboxyl group of an epoxy compound having a carboxyl group in the molecule with a specific vinyl ether compound, which has excellent storage stability. The present invention has been completed by finding that the cured product has excellent adhesion and lithographic properties and excellent adhesion.

That is, the present invention relates to (1) polyfunctional epoxy compound (A), compound (B) having at least one hydroxyl group and carboxyl group in one molecule, polybasic acid anhydride (C) and the following formula (1): )

In (Equation _{(1), R 1, R} 2 and R ₃ are each independently a hydrogen atom, an alkyl group or an aryl group having 1 to 18 carbon atoms, the alkyl and aryl groups have a substituent R ₄ represents an aliphatic hydrocarbon residue having 1 to 18 carbon atoms containing or not containing 1 to 17 oxygen atoms, or an aryl group, and these groups may have a substituent. N is the formula (2) bonded to any carbon atom of R ₄

(In Formula (2), R < ₁ > -R < ₃ > represents the same meaning as in Formula (1).) Represents the number of substituents represented by any one of 1-4. )
And at least one epoxy group in one molecule obtained by reacting the vinyl ether compound (D) represented by formula (3)

(In formula (3), R _{1 to} R ₃ represent the same meaning as in formula (1).)
A modified polyfunctional epoxy compound having a partial structure represented by
(2) The polyfunctional epoxy compound (A) has a softening point of 50 to 100 ° C. and 100 to 900 g / eq. The modified polyfunctional epoxy compound according to (1), which has an epoxy equivalent of
(3) The modified multifunctional epoxy compound according to (1) or (2), wherein the multifunctional epoxy compound (A) is obtained by epoxidizing a multifunctional phenol.
(4) The polyfunctional epoxy compound (A) has the formula (4)

(In Formula (4), R _{11 to} R ₁₆ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. N is an average representing the number of repeating units represented by the structure in parentheses. Value and represents 1 to 8.)
The modified polyfunctional epoxy compound according to (3), represented by:
(5) The modified polyfunctional epoxy compound according to (4), wherein the polyfunctional epoxy compound (A) is an o-cresol novolac type epoxy compound,
(6) The polyfunctional epoxy compound (A) has the formula (5)

(In formula (5), n is an average value representing the number of repeating units represented by the structure in parentheses and represents 0 to 8.)
The modified polyfunctional epoxy compound according to (3), represented by:
(7) The polyfunctional epoxy compound (A) has the formula (6)

(In Formula (6), R _{21 to} R ₂₈ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Q is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In the case where a plurality of X are present in one molecule, each X may be the same or different, and n is an average value representing the number of repeating units represented by the structure in parentheses and represents 0-8. )
The modified polyfunctional epoxy compound according to (3), represented by:
(8) The polyfunctional epoxy compound (A) has the formula (7)

(In formula (7), R _{31 to} R ₃₄ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. N is an average value representing the number of repeating units represented by the structure in parentheses. And represents 1-4.)
The modified polyfunctional epoxy compound according to (3), represented by:
(9) The modified polyfunctional epoxy compound according to (1) or (2), wherein the polyfunctional epoxy compound (A) has a cyclic structure composed of an aliphatic hydrocarbon in the structure,
(10) The above (1), wherein the compound (B) having at least one hydroxyl group and carboxyl group in one molecule is at least one selected from the group consisting of dimethylolpropionic acid, dimethylolbutanoic acid and dimethylolacetic acid. Thru | or the modified polyfunctional epoxy compound in any one of (9),
(11) A curable composition containing the modified polyfunctional epoxy compound according to any one of (1) to (10) and a thermosetting agent or a cationic polymerization initiator,
(12) A curable composition containing the modified polyfunctional epoxy compound according to any one of (1) to (10), a cationic polymerization initiator, and a dissociation catalyst,
(13) The modified polyfunctional epoxy compound according to any one of (1) to (10), or the cured product of the curable composition according to (11) or (12),
About.

  The modified polyfunctional epoxy compound of the present invention has excellent storage stability and lithographic properties, and its cured product is excellent in adhesion, so that it is suitably used as a raw material for paints and alkali-developable resist compositions.

The modified polyfunctional epoxy compound of the present invention comprises a polyfunctional epoxy compound (A), a compound (B) having at least one hydroxyl group and one carboxyl group in one molecule, and a polybasic acid anhydride (C). And a vinyl ether compound (D).
Here, each of the polyfunctional epoxy compound (A), a compound (B) having at least one hydroxyl group and one carboxyl group in one molecule, a polybasic acid anhydride (C), and a vinyl ether compound (D) The compound will be described in detail.

  Specific examples of the polyfunctional epoxy compound (A) that can be used in the present invention include phenols (phenol, alkyl-substituted phenol, halogenated phenol, naphthol, alkyl-substituted naphthol, halogenated naphthol, dihydroxybenzene, dihydroxynaphthalene, and bisphenols. Etc.) and aldehydes (formaldehyde, acetaldehyde, benzaldehyde, etc.) and bisphenols, phenols novolaks or bisphenols novolaks obtained by epoxidizing bisphenols, phenols novolaks or bisphenols novolacs , Aralkyl-type epoxy compounds of phenols (as described above), epoxy compounds having a cyclic structure consisting of aliphatic hydrocarbons in the structure, olefins They include epoxy compounds and the like obtained by the oxidation reaction of compounds with, but can be used without particular limitation as long as the epoxy compound having a plurality of epoxy groups in one molecule. Of these epoxy compounds, the softening point is preferably 50 to 100 ° C., and the epoxy equivalent is 100 to 900 g / eq. Multifunctional epoxy compound having physical properties of, more preferably, a softening point of 55 to 80 ° C., an epoxy equivalent of 170 to 350 g / eq. A polyfunctional epoxy compound having the following physical properties is used. When the softening point of the polyfunctional epoxy compound (A) is too low, the softening point of the modified polyfunctional epoxy compound of the present invention obtained by the reaction is inevitably low. As a result, the modified polyfunctional epoxy compound is used. It may be difficult to form a uniform film on the substrate with the used photoresist, or the dried photoresist may become sticky. Moreover, when the softening point of a polyfunctional epoxy compound (A) is too high, the solubility with respect to the solvent of the modified polyfunctional epoxy compound of this invention obtained by reaction falls, and manufacture of the modified polyfunctional epoxy compound of this invention is carried out. There is a risk that it may become difficult, or the actual property of the photoresist with respect to the solvent or alkali may be reduced. In addition, the softening point of the polyfunctional epoxy compound (A) mentioned here is a value measured according to JIS K7234.

Further, when the epoxy equivalent of the polyfunctional epoxy compound (A) is too low, the modified polyfunctional epoxy compound of the present invention obtained by the reaction often becomes crystalline or liquid, and the modified polyfunctional epoxy compound is used. It may be difficult to form a uniform film on the substrate with the used photoresist, or the dried photoresist may become sticky. On the other hand, when the epoxy equivalent of the polyfunctional epoxy compound (A) is too high, the compound having at least one hydroxyl group and one carboxyl group in one molecule introduced as a reactive group into the modified polyfunctional epoxy compound (B) Furthermore, the number of polybasic acid anhydrides (C) is decreased, and there is a possibility that adhesion, cured physical properties, and alkali developability of the photoresist using the modified polyfunctional epoxy compound to the substrate may be lowered. In addition, the epoxy equivalent of a polyfunctional epoxy compound (A) said here is the value measured based on JISK7236.
Preferred skeletons of the polyfunctional epoxy compound (A) include phenol novolak type epoxy compounds, bisphenol A novolak type epoxy compounds, bisphenol F type epoxy compounds, phenol aralkyl type epoxy compounds, polyfunctional alicyclic epoxy compounds, and bisphenol A type. An epoxy compound etc. are mentioned. Of these polyfunctional epoxy compounds (A), preferred skeletons from the viewpoint of storage stability of the modified polyfunctional epoxy compounds include phenol novolac epoxy compounds, bisphenol F epoxy compounds, phenol aralkyl epoxy compounds, Functional alicyclic epoxy compounds, bisphenol A type epoxy compounds, and the like, and more preferable skeletons include phenol novolac type epoxy compounds, bisphenol F type epoxy compounds, phenol aralkyl type epoxy compounds, bisphenol A type epoxy compounds, and the like. More preferable skeletons include phenol novolac type epoxy compounds and bisphenol A type epoxy compounds.
Softening point 50-100 ° C. and epoxy equivalent 100-900 g / eq. Examples of a commercially available product of a polyfunctional epoxy compound (A) having a preferable skeleton having the following physical properties include EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-4400H, EPPN-201, BREN-S ( All are trade names, phenolic novolak type epoxy compounds manufactured by Nippon Kayaku Co., Ltd.), Epicoat 157S70 (trade names, bisphenol A novolac type epoxy compounds manufactured by Japan Epoxy Resin Co., Ltd.), Epicoat 1001, Epicoat 1002 (all products Name, Japan Epoxy Resin Co., Ltd. bisphenol A type epoxy compound), Epicoat 4004P (trade name, Japan Epoxy Resin Co., Ltd. bisphenol F type epoxy compound), NER-7604 (trade name, Nippon Kayaku Co., Ltd.) Bisphenol F type epoxy compound), NC-3000H (trade name, phenol aralkyl type epoxy compound manufactured by Nippon Kayaku Co., Ltd.), EHPE3150 (trade name, polyfunctional alicyclic epoxy compound manufactured by Daicel Chemical Industries, Ltd.) Etc.
Among these, a particularly preferable skeleton is a phenol novolak type epoxy compound, and an o-cresol novolak type epoxy compound is particularly preferable. Examples of commercially available o-cresol novolac epoxy compounds include EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-4400H, and the like.

  The compound (B) having at least one hydroxyl group and carboxyl group in one molecule that can be used in the present invention (hereinafter simply referred to as “compound (B)”) is at least one compound in one molecule. Although it will not specifically limit if it is a compound which has a hydroxyl group and a carboxyl group, As a specific example of a preferable compound (B), dimethylol propionic acid, dimethylol butanoic acid, dimethylol acetic acid, dimethylol butyric acid, dimethylol valeric acid, Examples thereof include polyhydroxy-containing monocarboxylic acids such as dimethylol caproic acid, and monohydroxymonocarboxylic acids such as hydroxypivalic acid and p-hydroxybenzoic acid. Among these carboxylic acids, more preferred are polyhydroxy-containing monocarboxylic acids such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, and dimethylolcaproic acid. Of these, dimethylolpropionic acid, dimethylolbutanoic acid, and dimethylolacetic acid are particularly preferred because they are inexpensive and easily available from the market.

  The polybasic acid anhydride (C) that can be used in the present invention is not particularly limited as long as it is a polybasic acid anhydride. Specific examples of preferable polybasic acid anhydrides (C) include, for example, Succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, trimellitic acid, pyromellitic acid and the like. Of these acid anhydrides, more preferred are succinic anhydride and tetrahydrophthalic anhydride.

The vinyl ether compound (D) that can be used in the present invention has a structure represented by the formula (1).
Examples of the alkyl group having 1 to 18 carbon atoms represented by R _{1 to} R _{3 in} Formula (1) include a linear or branched alkyl group having 1 to 18 carbon atoms, and the aryl group includes a phenyl group. And a naphthyl group. In addition, the substituent which the alkyl group and aryl group which R < ₁ > -R < ₃ > represents may have is not specifically limited.
The aliphatic hydrocarbon residue having 1 to 18 carbon atoms represented by R _{4 in the} formula (1) is a saturated or unsaturated linear or branched aliphatic hydrocarbon having 1 to 18 carbon atoms. It is a substituent excluding one hydrogen atom, and is usually a saturated hydrocarbon residue having 1 to 18 carbon atoms. The saturated hydrocarbon residue having 1 to 18 carbon atoms may contain 1 to 17 oxygen atoms in the structure. As used herein, the saturated hydrocarbon residue containing an oxygen atom in the structure is, for example, a saturated hydrocarbon residue containing no oxygen atom in the structure having 2 carbon atoms is —CH ₂ CH ₃ . A saturated hydrocarbon residue containing one oxygen atom in the structure having 2 carbon atoms means —CH ₂ OCH _3, and part or all of the C—C bonds in the saturated hydrocarbon are C—O—C bonds. It has been replaced with.
Examples of the aryl group represented by R ₄ in the formula (1) include the same aryl groups represented by R _{1 to} R _{3 in} the formula (1). Incidentally, the substituent which may be possessed by the aliphatic hydrocarbon residue or an aryl group R ₄ represents is not particularly limited.
N in Formula (1) represents the number of substituents represented by Formula (2) bonded to an arbitrary carbon atom of R ₄ , and is any one of 1 to 4.
The vinyl ether compound (D) that can be used in the present invention is not particularly limited as long as it is a compound represented by the formula (1), but all of R _{1 to} R ₃ in the formula (1) are hydrogen. Vinyl ether compounds that are atoms and vinyl thioether compounds corresponding to these are preferred. Specific examples of the preferred vinyl ether compound (D) include methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, Allyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 9-hydroxynonyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, cyclohexanedimethanol monovinyl ether, triethylene glycol monovinyl ether, 1,4-butanediol divinyl ether, nonanediol divinyl ether, cyclohexane Geo Distearate vinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether and pentaerythritol tetravinyl ether, and aliphatic vinyl thioether compounds corresponding to the vinyl ether compounds. Of these compounds, more preferred are isopropyl vinyl ether and t-butyl vinyl ether.

  In the present invention, the method of reacting the polyfunctional epoxy compound (A) with the compound (B), polybasic acid anhydride (C) and vinyl ether compound (D) can take various forms, but the molecular weight can be controlled. Since it is easy, the polybasic acid anhydride (C) is first reacted with the reactant (M-1) obtained by reacting the polyfunctional epoxy compound (A) with the compound (B), and then obtained. A method of reacting the vinyl ether compound (D) with the reactant (M-2) is preferred. Here, you may use a polyfunctional epoxy compound (A), a compound (B), a polybasic acid anhydride (C), and a vinyl ether compound (D) individually or in mixture of 2 or more types, respectively.

First, a method for obtaining a reactant (M-1) by reacting a polyfunctional epoxy compound (A) with a compound (B) will be described.
Reaction of the said polyfunctional epoxy compound (A) and a compound (B) is 0.01-0.5 in conversion of a carboxyl group in the compound (B) with respect to 1 equivalent of epoxy groups of a polyfunctional epoxy compound (A). It is preferable to carry out an equivalent reaction, particularly preferably 0.1 to 0.3 equivalent.

  A solvent may be used in the reaction between the polyfunctional epoxy compound (A) and the compound (B). Solvents that can be used include ketones such as ethyl methyl ketone, cyclohexanone, and cyclopentanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, and glycol ethers such as dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether. , Organic esters such as esters, ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, aliphatic hydrocarbons such as octane, decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, and other petroleum solvents And solvents. When a solvent is used, it can be used as it is in the subsequent steps without removing the solvent from the solution of the reactant (M-1). In order to promote the reaction, it is preferable to use a catalyst (for example, triphenylphosphine, benzyldimethylamine, methyltriethylammonium chloride, triphenylstibine, chromium octoate, etc.). It is more preferable that the catalytic activity of the catalyst used is substantially inactivated by oxidation using an organic peroxide or the like after completion of the reaction. The amount of the catalyst used is preferably 5% by mass or less based on the total amount of the polyfunctional epoxy compound (A) and the compound (B) used in the reaction. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, hydroquinone, methylhydroquinone, p-methoxyphenol, catechol, pyrogallol, etc.), and the amount used thereof is a polyfunctional epoxy compound ( Preferably it is 1 mass% or less with respect to the total amount of A) and a compound (B). The reaction temperature is usually 60 to 150 ° C., and the reaction time is usually 5 to 30 hours. The end point of the reaction can be confirmed by acid value measurement (based on JIS K5601-2-1: 1999) by titrating the reaction solution with a potassium hydroxide standard solution. The time when the acid value is 0 to 5.0 mgKOH / g can be used as a measure of the end point of the reaction. In this way, the reactant (M-1) can be obtained.

Next, a method for obtaining the reactant (M-2) by reacting the reactant (M-1) with the polybasic acid anhydride (C) will be described.
The reaction of the reaction product (M-1) obtained by the above-described method with the polybasic acid anhydride (C) is performed using a polybasic acid anhydride (1 equivalent) with respect to 1 equivalent of the hydroxyl group in the reaction product (M-1). C) is preferably reacted in an amount of 0.1 to 1.0 equivalent. The reaction temperature is usually 60 to 150 ° C., and the reaction time is usually 1 to 10 hours. Thus, the reaction product (M-2) of the reaction product (M-1) and the polybasic acid anhydride (C) can be obtained. The end point of the reaction can be confirmed by acid value measurement (based on JIS K5601-2-1: 1999) by titrating the reaction solution with a potassium hydroxide standard solution. The time when the acid value becomes the theoretical value ± 1.0 mgKOH / g calculated from the charged amount can be used as a measure of the end point of the reaction.

Next, a method for obtaining the modified polyfunctional epoxy compound of the present invention by reacting the reactant (M-2) with the vinyl ether compound (D) will be described.
The reaction of the reaction product (M-2) obtained by the above-described method with the vinyl ether compound (D) is performed by adding 0.1% of the vinyl ether compound (D) to 1 equivalent of the carboxyl group in the reaction product (M-2). It is preferable to make it react 5-10 equivalent, and 1.0-3.0 equivalent is especially preferable. The reaction temperature is usually 0 to 100 ° C, preferably 10 to 60 ° C. The reaction time depends on the reaction temperature and the equivalent of the vinyl ether compound used in the reaction, but is usually about 10 minutes to 60 hours. For the purpose of suppressing by-products and shortening the reaction time, an acid catalyst can be used in the reaction. However, when an acid catalyst is used, it is washed with water or adsorbent (for example, a synthetic hydrotalcite system) after completion of the reaction. It is necessary to remove by adsorption using an adsorbent exemplified by an adsorbent and the like. Specific examples of the acid catalyst include monooctyl phosphate, bis (2-ethylhexyl) phosphate, butyl acetate and the like. The end point of the reaction can be confirmed by acid value measurement (based on JIS K5601-2-1: 1999) by titrating the reaction solution with a potassium hydroxide standard solution. The time when the acid value is 0 to 3.0 mgKOH / g can be used as a measure of the end point of the reaction.
Incidentally, the vinyl ether compound (D) remaining in the modified polyfunctional epoxy compound after the completion of the reaction without participating in the above-described synthesis reaction may deteriorate various physical properties of the cured product. It is preferable to remove from the functional epoxy compound by a technique such as vacuum distillation.

  The modified polyfunctional epoxy compound of the present invention thus obtained has an acid value, an epoxy equivalent (based on JIS K-7236), a proton NMR measurement using a deuterated chloroform solvent, an LC- It can also be confirmed by MS or the like.

Next, the manufacturing method of the modified polyfunctional epoxy compound of the present invention is specifically shown by the following schematic diagram using exemplary compounds.
That is, first, dimethylolpropionic acid (compound (B)) represented by the formula (9) is added to an o-cresol novolac type epoxy compound represented by the formula (8) (polyfunctional epoxy compound (A)) in a solvent, The reaction is performed in the presence of a catalyst to obtain a compound represented by the formula (10) (corresponding to the reactant (M-1)). Next, the compound represented by the formula (10) is reacted with tetrahydrophthalic anhydride (polybasic acid anhydride (C)) represented by the formula (11) to give the compound represented by the formula (12) (the above-mentioned reactant (M- Equivalent to 2). Next, the modified polyfunctional epoxy compound of the present invention represented by the formula (14) is obtained by reacting the compound represented by the formula (12) with the isopropyl vinyl ether represented by the formula (13) (vinyl ether compound (D)). In addition, although the following schematic diagram is an illustration when one epoxy group in the polyfunctional epoxy compound (A) is modified by the compounds (B) to (D), the number of modified epoxy groups is one. It is not limited to.

  The modified polyfunctional epoxy compound of the present invention is a self-crosslinking polyfunctional epoxy compound having an epoxy group and a carboxyl group in one molecule by dissociating the vinyl ether compound by heating. Pigments, dyes, glass flakes, aluminum flakes, mica flakes and other colorants, fillers, diluents, curing catalysts, flow regulators, UV absorbers, leveling agents, antioxidants, etc., paints, inks, It can be used for adhesives and molded products.

  When the modified polyfunctional epoxy compound of the present invention is used as a coating material, for example, a pigment paste in which the pigment and additives are sufficiently kneaded using an apparatus such as a mixing mixer and a ball mill and uniformly dispersed is prepared. The pigment paste and the modified polyfunctional epoxy compound of the present invention previously dissolved in a diluent are further kneaded and dispersed using the above apparatus, and then adjusted to a desired concentration using the diluent, whereby the paint is prepared. Can be obtained. Cured by applying heat treatment at 50 to 250 ° C. for 2 to 30 minutes on the coating obtained by applying the paint by a method such as roll coating, spraying, brushing, spatula, bar coater, dip coating or electrodeposition coating. It can be a thing.

Next, the curable composition of this invention is demonstrated.
Although the modified polyfunctional epoxy compound of the present invention can be cured by heating alone as described above, the curable composition of the present invention is intended to shorten the curing time and increase the crosslinking density of the modified polyfunctional epoxy compound of the present invention. And a combination of a thermosetting agent or a cationic polymerization initiator.

First, the curable composition of the present invention containing a thermosetting agent will be described.
As the thermosetting agent, a conventionally known curing accelerator for epoxy compounds can be used as the thermosetting agent. Specific examples of the thermosetting agent include imidazoles such as 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5,4,0) undecene. And tertiary amines such as -7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. The usage-amount of these thermosetting agents in the curable composition of this invention is 0.1-5.0 mass parts normally with respect to 100 mass parts of modified polyfunctional epoxy compounds of this invention.

The curable composition of the present invention containing a thermosetting agent is a conventionally known method such as a kneader, a roll, etc. for the modified polyfunctional epoxy compound of the present invention, a thermosetting agent, and if necessary an inorganic filler or other compounding agent. It is obtained by mixing using. Inorganic fillers and other compounding agents may be selected according to the specific use of the curable composition of the present invention, and the type of the filler is within the range that does not impair the properties required for the intended use. There is no limit to the amount of addition.
Although there is no restriction | limiting in particular also in the usage method of the curable composition of this invention obtained in this way, For example, it shape | molds by a casting method or using a transfer molding machine etc., and 2-10 at 80-200 degreeC. The cured product can be obtained by heating for a period of time.

Next, the curable composition of the present invention containing a cationic polymerization initiator will be described.
As the cationic polymerization initiator, a conventionally known cationic polymerization initiator that generates an acid by light irradiation or heating can be used, and among them, a photocationic polymerization initiator is preferable. Examples of the cationic photopolymerization initiator include aromatic iodonium salts and aromatic sulfonium salts.
Of these, specific examples of the aromatic iodonium salt include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and the like. Can be mentioned.

Specific examples of the aromatic sulfonium salt include CPI-101A (trade name, thiophenyldiphenylsulfonium hexafluoroantimonate manufactured by San Apro Co., Ltd.), SP-172 (trade name, Asahi Denka Kogyo ( 4- {4- (2-chlorobenzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate) and UVI-6974 (trade name, aromatic sulfonium hexa In the present invention, it is preferable to use an aromatic sulfonium salt as described above because it is thermally stable. These cationic photopolymerization initiators may be used alone or in combination of two or more.
The usage-amount of these cationic polymerization initiators in the curable composition of this invention is 0.5-20 mass parts normally with respect to 100 mass parts of modified polyfunctional epoxy compounds of this invention.

Next, the curable composition of the present invention containing a dissociation catalyst will be described.
As described above, the modified polyfunctional epoxy compound of the present invention can be cured by heating alone. However, the curable composition of the present invention can have alkali developability by regenerating the carboxyl group, A cationic polymerization initiator and a dissociation catalyst can be used in combination for the purpose of improving the adhesion.
As the dissociation catalyst, a Lewis acid, a proton acid, or an acid generator that generates an acid by light irradiation or heating can be used, and the pKa of the acid or the generated acid is preferably 3.0 or less. When pKa is large, the reaction rate of vinyl ether elimination is slow, which is not preferable. Specific examples of acids having a pKa of 3.0 or less include sulfuric acid, sulfurous acid, hydrochloric acid, p-toluenesulfonic acid, chlorosulfonic acid, phosphoric acid, dichloroacetic acid, trichloroacetic acid, benzenesulfonic acid, o-nitrobenzoic acid, m -Nitrobenzoic acid, bis (2-ethylhexyl) phosphate, etc. are mentioned.

The curable composition of the present invention containing the modified polyfunctional epoxy compound of the present invention, a cationic polymerization initiator, and optionally a solvent, a dissociation catalyst, etc. is used as a solvent-developable photoresist and the modified polyfunctional epoxy of the present invention. The curable composition of the present invention containing a compound, a cationic polymerization initiator, a dissociation catalyst, and if necessary a solvent, can be used as an alkali development type photoresist, in which a thick film of 50 μm or more can be formed. It can be used as a resist. When used as a solvent development type photoresist, the substrate containing the modified polyfunctional epoxy compound of the present invention and a cationic polymerization initiator is spin-coated on a substrate and prebaked at 40 to 150 ° C or at 40 to 150 ° C. By the post-exposure baking, the adhesiveness with the substrate can be further improved by dissociating part or all of the vinyl ether. When used as an alkali development type photoresist, after spin-coating on the substrate in the same manner as the solvent development type photoresist, pre-baking at 40 to 150 ° C. or post-exposure baking at 40 to 150 ° C. The solubility in an alkali developer can be regenerated by dissociating part or all of it. Further, the exposure and post-exposure baking can cause the epoxy group to undergo a crosslinking reaction only in the exposed portion. As a result, the exposed portion becomes insoluble in an organic solvent or an alkaline developer and can be patterned.
Although the above-mentioned method relates to a negative photoresist, the curable composition of the present invention can be a positive photoresist.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, these Examples are only the illustrations for demonstrating this invention suitably, and do not limit this invention at all. In Examples and Comparative Examples, unless otherwise specified, “part” means “mass part” and “%” means “mass%”. The physical property values were measured by the following methods.
Epoxy equivalent: Conforms to JIS K7236 Acid value: Conforms to JIS K5601-2-1 Nonvolatile content: Conforms to JIS K7235 Viscosity: Viscosity measured at 25 ° C. with an E-type viscometer (Toki Sangyo Co., Ltd., TV-20)

Example 1
A bisphenol A novolak-type epoxy compound represented by the following formula (15) as a polyfunctional epoxy compound (A) while performing nitrogen purging on a flask equipped with a stirrer, a reflux condenser, and a stirring device (trade name: Epicoat 157S70, Japan Epoxy Resin Co., Ltd., softening point: 70 ° C., epoxy equivalent: 210 g / eq.) 116 parts,

  Add 10.6 parts of dimethylolpropionic acid as compound (B), 0.5 part of triphenylphosphine as catalyst and 60 parts of cyclopentanone as solvent, dissolve under stirring, warm to 98 ° C. and stir for 4 hours did. The reaction solution was cooled to room temperature, and the acid value of the reaction solution was measured and found to be 1 mgKOH / g or less. Next, 13.3 parts of tetrahydrophthalic anhydride as a polybasic acid anhydride (C) was added to the reaction solution, dissolved under stirring, heated to 80 ° C., and stirred for 2 hours. The reaction solution was cooled to room temperature and the acid value of the reaction solution was measured and found to be 35 mgKOH / g. Subsequently, 22.5 parts of isopropyl vinyl ether as a vinyl ether compound (D) and 0.56 part of bis (2-ethylhexyl) phosphate as an acid catalyst were added to the reaction liquid, and the mixture was stirred at room temperature for 5 hours. The acid value of the reaction solution was measured and found to be 1 mgKOH / g or less. 28 parts of Kyoward 500 (trade name, synthetic hydrotalcite-based adsorbent manufactured by Kyowa Chemical Industry Co., Ltd.) as an adsorbent was added to the reaction solution, and the mixture was stirred at room temperature for 24 hours. After removing the adsorbent with a 10 μm membrane filter, unreacted isopropyl vinyl ether was distilled off with a rotary evaporator to obtain 192 parts of a cyclopentanone solution (E-1) of the modified polyfunctional epoxy compound of the present invention. The acid value of the obtained solution was 0.5 mgKOH / g or less, the viscosity was 6.14 Pa · s, and the nonvolatile content was 69%.

Example 2
An o-cresol novolak-type epoxy compound represented by the following formula (16) as a polyfunctional epoxy compound (A) while performing nitrogen purging on a flask equipped with a stirrer, a reflux condenser, and a stirring device (trade name EOCN-1020, Nippon Kayaku Co., Ltd., softening point: 60 ° C., epoxy equivalent: 195 g / eq.) 190 parts,

  20 parts of dimethylolpropionic acid as compound (B), 0.9 part of triphenylphosphine as a catalyst, and 90 parts of cyclopentanone as a solvent were added, dissolved under stirring, heated to 98 ° C. and stirred for 4 hours. The reaction solution was cooled to room temperature, and the acid value of the reaction solution was measured and found to be 1 mgKOH / g or less. Next, 45 parts of tetrahydrophthalic anhydride as a polybasic acid anhydride (C) and 20 parts of cyclopentanone as a solvent were added to the reaction solution, dissolved under stirring, heated to 98 ° C., and stirred for 3 hours. It was 45 mgKOH / g when the reaction liquid was cooled to room temperature and the acid value of the reaction liquid was measured. Subsequently, 30 parts of isopropyl vinyl ether as a vinyl ether compound (D) and 1.5 parts of bis (2-ethylhexyl) phosphate as an acid catalyst were added and stirred at room temperature for 5 hours. The acid value of the reaction solution was measured and found to be 1 mgKOH / g or less. 75 parts of the above-mentioned Kyoward 500 as an adsorbent was added to the reaction solution and stirred at room temperature for 24 hours. After removing the adsorbent with a 10 μm membrane filter, unreacted isopropyl vinyl ether was distilled off with a rotary evaporator to obtain 300 parts of a cyclopentanone solution (E-2) of the modified polyfunctional epoxy compound of the present invention. The obtained solution had an acid value of 0.5 mgKOH / g or less, a viscosity of 5.60 Pa · s, and a nonvolatile content of 71%.

Example 3
A bisphenol F-type epoxy compound represented by the following formula (17) as a polyfunctional epoxy compound (A) with a nitrogen purge in a flask equipped with a stirrer, a reflux condenser, and a stirring device (trade name: NER-7604, Nippon Kayaku) Manufactured by Yakuhin Co., Ltd., softening point: 70 ° C., epoxy equivalent: 325 g / eq.) 119 parts,

  Add 7.3 parts of dimethylolpropionic acid as compound (B), 0.5 part of triphenylphosphine as catalyst and 60 parts of cyclopentanone as solvent, dissolve under stirring, warm to 98 ° C. and stir for 4 hours did. The reaction solution was cooled to room temperature, and the acid value of the reaction solution was measured and found to be 1 mgKOH / g or less. Next, 13.3 parts of tetrahydrophthalic anhydride as a polybasic acid anhydride (C) was added to the reaction solution, dissolved under stirring, heated to 80 ° C., and stirred for 2 hours. It was 43.8 mgKOH / g when the reaction liquid was cooled to room temperature and the acid value of the reaction liquid was measured. Subsequently, 22.5 parts of isopropyl vinyl ether as a vinyl ether compound (D) and 0.56 part of bis (2-ethylhexyl) phosphate as an acid catalyst were added to the reaction liquid, and the mixture was stirred at room temperature for 5 hours. The acid value of the reaction solution was measured and found to be 1 mgKOH / g or less. 28 parts of Kyoward 500 as an adsorbent was added to the reaction solution and stirred at room temperature for 24 hours. After removing the adsorbent with a 10 μm membrane filter, unreacted isopropyl vinyl ether was distilled off with a rotary evaporator to obtain 183 parts of a cyclopentanone solution (E-3) of the modified polyfunctional epoxy compound of the present invention. The acid value of the obtained solution was 0.5 mgKOH / g or less, the viscosity was 5.31 Pa · s, and the nonvolatile content was 70.5%.

Example 4
A phenol aralkyl-type epoxy compound represented by the following formula (18) as a polyfunctional epoxy compound (A) while purging nitrogen in a flask equipped with a stirrer, a reflux condenser, and a stirring device (trade name NC-3000H, Nippon Kayaku) Manufactured by Yakuhin Co., Ltd., softening point: 70 ° C., epoxy equivalent: 290 g / eq.) 178 parts,

  Add 12.3 parts of dimethylolpropionic acid as compound (B), 0.9 part of triphenylphosphine as catalyst and 90 parts of cyclopentanone as solvent, dissolve under stirring, warm to 98 ° C. and stir for 4 hours did. The reaction solution was cooled to room temperature, and the acid value of the reaction solution was measured and found to be 1 mgKOH / g or less. Next, 20 parts of tetrahydrophthalic anhydride as a polybasic acid anhydride (C) was added to the reaction solution, dissolved under stirring, heated to 98 ° C. and stirred for 2 hours. It was 28.4 mgKOH / g when the reaction liquid was cooled to room temperature and the acid value of the reaction liquid was measured. Subsequently, 30 parts of isopropyl vinyl ether as a vinyl ether compound (D) and 1.0 part of bis (2-ethylhexyl) phosphate as an acid catalyst were added to the reaction solution, and the mixture was stirred at room temperature for 5 hours. The acid value of the reaction solution was measured and found to be 1 mgKOH / g or less. 50 parts of the above-mentioned Kyoward 500 was added to the reaction solution as an adsorbent and stirred at room temperature for 24 hours. After removing the adsorbent with a 10 μm membrane filter, unreacted isopropyl vinyl ether was distilled off with a rotary evaporator to obtain 250 parts of a cyclopentanone solution (E-4) of the modified polyfunctional epoxy compound of the present invention. The obtained solution had an acid value of 0.5 mgKOH / g or less, a viscosity of 0.8 Pa · s, and a nonvolatile content of 69%.

  An alicyclic epoxy compound represented by the following formula (19) as a polyfunctional epoxy compound (A) while performing a nitrogen purge on a flask equipped with a stirrer, a reflux condenser, and a stirrer (trade name: EHPE3150, Daicel Chemical Industries Ltd.) Made by company, softening point: 77 ° C., epoxy equivalent: 180 g / eq.) 114 parts,

  Add 12.7 parts of dimethylolpropionic acid as compound (B), 0.6 part of triphenylphosphine as catalyst, and 60 parts of cyclopentanone as solvent, dissolve under stirring, warm to 98 ° C. and stir for 4 hours did. The reaction solution was cooled to room temperature, and the acid value of the reaction solution was measured and found to be 1 mgKOH / g or less. Next, 20 parts of tetrahydrophthalic anhydride as a polybasic acid anhydride (C) was added to the reaction solution, dissolved under stirring, heated to 98 ° C. and stirred for 2 hours. It was 26.1 mgKOH / g when the reaction liquid was cooled to room temperature and the acid value of the reaction liquid was measured. Subsequently, 25 parts of isopropyl vinyl ether as a vinyl ether compound (D) and 0.8 part of bis (2-ethylhexyl) phosphate as an acid catalyst were added to the reaction solution, followed by stirring at room temperature for 5 hours. The acid value of the reaction solution was measured and found to be 1 mgKOH / g or less. 50 parts of the above-mentioned Kyoward 500 was added to the reaction solution as an adsorbent and stirred at room temperature for 24 hours. After removing the adsorbent with a 10 μm membrane filter, unreacted isopropyl vinyl ether was distilled off with a rotary evaporator to obtain 175 parts of a cyclopentanone solution (E-5) of the modified polyfunctional epoxy compound of the present invention. The obtained solution had an acid value of 0.5 mgKOH / g or less, a viscosity of 1.0 Pa · s, and a nonvolatile content of 70%.

Example 6
A bisphenol A-type epoxy compound represented by the following formula (20) as a polyfunctional epoxy compound (A) while performing a nitrogen purge on a flask equipped with a stirrer, a reflux condenser, and a stirring device (trade name: Epicoat 828, Japan Epoxy Resin) Manufactured by Co., Ltd., softening point: 20 ° C. or less, epoxy equivalent: 190 g / eq.) 114 parts,

  Add 12.1 parts of dimethylolpropionic acid as compound (B), 0.55 parts of triphenylphosphine as catalyst, and 60 parts of cyclopentanone as solvent, dissolve under stirring, warm to 98 ° C. and stir for 4 hours did. The reaction solution was cooled to room temperature, and the acid value of the reaction solution was measured and found to be 1 mgKOH / g or less. Next, 20 parts of tetrahydrophthalic anhydride as a polybasic acid anhydride (C) was added to the reaction solution, dissolved under stirring, heated to 98 ° C. and stirred for 2 hours. It was 40 mgKOH / g when the reaction liquid was cooled to room temperature and the acid value of the reaction liquid was measured. Subsequently, 25 parts of isopropyl vinyl ether as a vinyl ether compound (D) and 0.8 part of bis (2-ethylhexyl) phosphate as an acid catalyst were added to the reaction solution, followed by stirring at room temperature for 5 hours. The acid value of the reaction solution was measured and found to be 1 mgKOH / g or less. 50 parts of the above-mentioned Kyoward 500 was added to the reaction solution as an adsorbent and stirred at room temperature for 24 hours. After removing the adsorbent with a 10 μm membrane filter, unreacted isopropyl vinyl ether was distilled off with a rotary evaporator to obtain 178 parts of a cyclopentanone solution (E-6) of the modified polyfunctional epoxy compound of the present invention. The obtained solution had an acid value of 0.5 mgKOH / g or less, a viscosity of 1.0 Pa · s, and a nonvolatile content of 70%.

Example 7
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 190 parts of the same o-cresol novolac-type epoxy compound used in Example 2 as the polyfunctional epoxy compound (A) while performing a nitrogen purge, compound (B ) 20 parts of dimethylolpropionic acid, 0.9 part of triphenylphosphine as a catalyst, 90 parts of cyclopentanone as a solvent, dissolved under stirring, heated to 98 ° C. and stirred for 4 hours. The reaction solution was cooled to room temperature, and the acid value of the reaction solution was measured and found to be 1 mgKOH / g or less. Next, 45 parts of tetrahydrophthalic anhydride as a polybasic acid anhydride (C) and 20 parts of cyclopentanone as a solvent were added to the reaction solution, dissolved under stirring, heated to 98 ° C., and stirred for 3 hours. It was 45 mgKOH / g when the reaction liquid was cooled to room temperature and the acid value of the reaction liquid was measured. Subsequently, 30 parts of isopropyl vinyl ether as a vinyl ether compound (D) was added to the reaction solution and stirred at room temperature for 72 hours. The acid value of the reaction solution was measured and found to be 1 mgKOH / g or less. Unreacted isopropyl vinyl ether was distilled off with a rotary evaporator to obtain 300 parts of a cyclopentanone solution (E-7) of the modified polyfunctional epoxy compound of the present invention. The obtained solution had an acid value of 0.5 mgKOH / g or less, a viscosity of 5.39 Pa · s, and a nonvolatile content of 71%.

Comparative Example 1
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 190 parts of the same o-cresol novolac-type epoxy compound used in Example 2 as the polyfunctional epoxy compound (A) while performing a nitrogen purge, compound (B ) 20 parts of dimethylolpropionic acid, 0.9 part of triphenylphosphine as a catalyst, 90 parts of cyclopentanone as a solvent, dissolved under stirring, heated to 98 ° C. and stirred for 4 hours. The reaction solution was cooled to room temperature, and the acid value of the reaction solution was measured and found to be 1 mgKOH / g or less. Next, 45 parts of tetrahydrophthalic anhydride as a polybasic acid anhydride (C) and 20 parts of cyclopentanone as a solvent were added to the reaction solution, dissolved under stirring, heated to 98 ° C., and stirred for 3 hours. It was 45 mgKOH / g when the reaction liquid was cooled to room temperature and the acid value of the reaction liquid was measured. The reaction solution was filtered through a 10 μm membrane filter to obtain 350 parts of a comparative modified polyfunctional epoxy compound cyclopentanone solution (R-1) having a carboxyl group. The epoxy equivalent of the obtained solution was 489 g / eq. The acid value was 45 mgKOH / g, the viscosity was 19.6 Pa · s, and the nonvolatile content was 70%.

Characteristic Evaluation The temporal stability of the modified polyfunctional epoxy compound of the present invention obtained in Examples 1 to 7 and the epoxy compound for Comparative Example obtained in Comparative Example 1 was evaluated. That is, the viscosity at 25 ° C of the cyclopentanone solution of the modified polyfunctional epoxy compound obtained in each of the above Examples and Comparative Examples was measured at the initial stage (immediately after production) and after storage at 23 ° C and 40 ° C for 28 days. The increase rate of the viscosity after storage with respect to the initial viscosity (= viscosity after storage / initial viscosity) was calculated. The results are shown in Table 1. In addition, what the viscosity exceeded the measurement limit due to the change with time was described as “impossible to measure”.

  From the results of Table 1, the modified polyfunctional epoxy compounds (E-1 to E-7) of the present invention are modified polyfunctional epoxy compounds (R-1) in which the carboxyl groups obtained in the comparative examples are not protected with vinyl ether. It is clear that the stability over time is superior to that.

Application example 1
In a flask equipped with a stirrer, a reflux condenser and a stirrer, 100 parts by mass of the cyclopentanone solution (E-1) of the modified polyfunctional epoxy compound of the present invention obtained in Example 1 was added to C.I. I. 1 part by weight of Pigment Blue 60 was added and dispersed by stirring to obtain a paint. The obtained coating material was applied to a glass substrate using a bar coater, dried and cured at 200 ° C. for 30 minutes to obtain a cured coating film.

Examples 8 to 10 (curable composition)
According to the blending amount shown in Table 2 (unit is part by mass), the polyfunctional epoxy compound, the photocationic polymerization initiator, and other components were mixed for 1 hour at 40 ° C. in a separable flask equipped with stirring blades. The obtained composition was filtered using a 10 μm membrane filter to obtain the curable composition of the present invention.

  The curable compositions of Examples 8 and 9 were applied to a silicon wafer in a thickness of 50 μm, dried at 95 ° C. for 20 minutes using a hot plate, and then contacted with a negative mask to form an i-line exposure apparatus (mask aligner: USHIO) Pattern exposure (soft contact, i-line) was performed. Next, post-exposure baking (PEB) is performed at 95 ° C. for 6 minutes using a hot plate, and immersion development is performed at 23 ° C. for 6 minutes using propylene glycol monomethyl ether acetate to obtain a resin pattern cured on the substrate. It was.

  The curable composition of Example 10 was applied to a silicon wafer with a thickness of 50 μm, dried at 95 ° C. for 20 minutes using a hot plate, and then contacted with a negative mask, and an i-line exposure apparatus (mask aligner: manufactured by USHIO INC.) ) Was used for pattern exposure (soft contact, i-line). Next, post-exposure baking (PEB) is performed at 95 ° C. for 6 minutes on a hot plate, and immersion development is performed at 23 ° C. for 6 minutes using a 2.38% tetramethylammonium hydroxide aqueous solution (TMAH). A resin pattern cured on top was obtained.

The following evaluation was performed about the resin pattern of the curable composition of Examples 8-10 obtained above. The results are shown in Table 2 below.
Optimum exposure amount: Exposure amount with the best mask transfer accuracy Aspect ratio: Film thickness / The finest pattern width in close contact among the formed resist patterns

注：
カチオン重合開始剤（商品名 ＵＶＩ−６９７４、ダウケミカル社製５０％炭酸プロピレン溶液）
フッ素系レベリング剤（商品名 メガファックＦ−４７０、ＤＩＣ社製）

note:
Cationic polymerization initiator (trade name UVI-6974, 50% propylene carbonate solution manufactured by Dow Chemical Company)
Fluorine leveling agent (Brand name MegaFuck F-470, manufactured by DIC)

  From the results in Table 2, it is clear that the curable composition using the modified polyfunctional epoxy compound of the present invention has sufficient characteristics as a thick film resist.

  The modified polyfunctional epoxy compound of the present invention and the curable composition containing the same can be suitably used as a raw material for paints and resist compositions.

Claims (13)

In the polyfunctional epoxy compound (A), a compound (B) having at least one hydroxyl group and a carboxyl group in one molecule, a polybasic acid anhydride (C) and the following formula (1)

In (Equation _{(1), R 1, R} 2 and R ₃ are each independently a hydrogen atom, an alkyl group or an aryl group having 1 to 18 carbon atoms, the alkyl and aryl groups have a substituent R ₄ represents an aliphatic hydrocarbon residue having 1 to 18 carbon atoms containing or not containing 1 to 17 oxygen atoms, or an aryl group, and these groups may have a substituent. N is the formula (2) bonded to any carbon atom of R ₄

(In formula (2), R _{1 to} R ₃ represent the same meaning as in formula (1).)
It represents the number of substituents represented by any one of 1-4. )
And at least one epoxy group in one molecule obtained by reacting the vinyl ether compound (D) represented by formula (3)

(In formula (3), R _{1 to} R ₃ represent the same meaning as in formula (1).)
The modified polyfunctional epoxy compound which has the partial structure shown by these.   The polyfunctional epoxy compound (A) has a softening point of 50 to 100 ° C. and 100 to 900 g / eq. The modified polyfunctional epoxy compound according to claim 1, having an epoxy equivalent of   The modified multifunctional epoxy compound according to claim 1 or 2, wherein the multifunctional epoxy compound (A) is obtained by epoxidizing a multifunctional phenol. The polyfunctional epoxy compound (A) has the formula (4)

(In Formula (4), R _{11 to} R ₁₆ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. N is an average representing the number of repeating units represented by the structure in parentheses. Value and represents 1 to 8.)
The modified polyfunctional epoxy compound of Claim 3 represented by these.   The modified polyfunctional epoxy compound according to claim 4, wherein the polyfunctional epoxy compound (A) is an o-cresol novolac type epoxy compound. The polyfunctional epoxy compound (A) has the formula (5)

(In formula (5), n is an average value representing the number of repeating units represented by the structure in parentheses and represents 0 to 8.)
The modified polyfunctional epoxy compound of Claim 3 represented by these. The polyfunctional epoxy compound (A) has the formula (6)

(In Formula (6), R _{21 to} R ₂₈ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Q is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In the case where a plurality of X are present in one molecule, each X may be the same or different, and n is an average value representing the number of repeating units represented by the structure in parentheses and represents 0-8. )
The modified polyfunctional epoxy compound of Claim 3 represented by these. The polyfunctional epoxy compound (A) has the formula (7)

(In formula (7), R _{31 to} R ₃₄ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. N is an average value representing the number of repeating units represented by the structure in parentheses. And represents 1-4.)
The modified polyfunctional epoxy compound of Claim 3 represented by these.   The modified polyfunctional epoxy compound according to claim 1 or 2, wherein the polyfunctional epoxy compound (A) has a cyclic structure composed of an aliphatic hydrocarbon in the structure.   The compound (B) having at least one hydroxyl group and carboxyl group in one molecule is at least one selected from the group consisting of dimethylolpropionic acid, dimethylolbutanoic acid and dimethylolacetic acid. The modified polyfunctional epoxy compound according to any one of the above.   A curable composition containing the modified polyfunctional epoxy compound according to any one of claims 1 to 10, and a thermosetting agent or a cationic polymerization initiator.   A curable composition comprising the modified polyfunctional epoxy compound according to any one of claims 1 to 10, a cationic polymerization initiator, and a dissociation catalyst.   The modified polyfunctional epoxy compound according to any one of claims 1 to 10, or a cured product of the curable composition according to claim 11 or 12.