TW201006859A - Epoxy compound having protection group and curable resin composition containing the same - Google Patents

Abstract

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

Description

201006859 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an epoxy compound which can be hardened by heat and a curable composition containing the same. More specifically, it 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 heat curing agent or a cationic polymerization initiator. Φ [Prior Art] Conventionally, a cationically polymerizable resin composition having a resin having a cyclic ether group represented by an epoxy resin is known as a component in a curable composition, and such a component is known. The cured product obtained by curing the resin composition is excellent in chemical properties, physical properties, and further weather resistance. For these reasons, the epoxy resin composition is widely used in fields such as paints, inks, adhesives, plastic molded articles and the like. Further, a compound having both an epoxy group and a carboxyl group in one molecule is known as a compound obtained by reacting a polyfunctional epoxidized φ compound with a compound having a hydroxyl group and a carboxyl group and a polybasic acid anhydride (Patent Document 1) . However, the carboxyl group itself is a reactive functional group which is heated to form a chemical bond with the epoxy group, so that a self-crosslinking type compound having an epoxy group and a carboxyl group at the same time causes an increase in viscosity during storage, so storage Short lifespan is a problem. Patent Document 2 discloses a thermosetting resin composition containing a self-crosslinking type compound having a functional group obtained by reacting a carboxyl group in one molecule with a vinyl ether and a reactive functional group capable of forming a chemical bond with a carboxyl group. Excellent storage stability. However, the skeleton described in Patent Document 2 is limited to the aliphatic compound of -5 to 201006859, and it is not satisfactory as the heat resistance or adhesion of the coating material and the lithographic etching property as a photoresist. [Patent Document 1: Japanese Patent No. 3 69 8499] Patent Document 2: Japanese Patent No. 2 6 822 56 [Disclosure of the Invention] [Problems to be Solved by the Invention] The present invention aims to obtain usable as a paint and light. A modified polyfunctional epoxy compound (resin) which is excellent in raw material, storage stability, hardenability and lithographic etching property of the composition. [Means for Solving the Problem] As a result of active investigation by the present inventors to solve the above problems, it has been found that a modified epoxy compound obtained by protecting a carboxyl group of an epoxy compound having a carboxyl group in a molecule by a specific vinyl ether compound The present invention has been completed by having excellent storage stability and lithographic etching characteristics while having excellent adhesion of a cured product. That is, the present invention relates to: (1) A modified polyfunctional epoxy compound characterized by having at least one epoxy group in one molecule and a partial structure represented by the formula (3): 201006859 】

(In the formula (3), R!, R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group, and the alkyl group and the aryl group may have a substituent); On the functional epoxy compound (A), a compound (B) having at least one or more hydroxyl groups and carboxyl groups in one molecule, a polybasic acid anhydride (C), and a vinyl ether compound (D) represented by the following formula (1) are reacted. And, [Chemical 1]

(In the formula (1), 'Ri, R2 and R3 each independently represent a hydrogen atom, an alkyl group or an aryl group having 1 to 18 carbon atoms, and the alkyl group and the aryl group may have a substituent; and R4 represents 1 to 17; An oxygen atom or an aliphatic hydrocarbon group residue having an carbon number i-18, or an aryl group, wherein the group may have a substituent; η represents a formula (2) bonded to any carbon atom of R4. ) indicates the number of substituents, and is any one of 1 to 4: [Chemical 2]

Ri R2

(in the formula (2), 'is the same as in the formula (1)) 201006859 (2) The modified polyfunctional epoxy compound as described in the above (1) wherein the polyfunctional epoxy compound (A) has 50~ The softening point of 100 ° C and the epoxy equivalent of 100 to 900 g / eq. (3) The modified polyfunctional epoxy compound according to the above (1) or (2) wherein the polyfunctional epoxy compound (A) is obtained by epoxidizing a polyfunctional phenol. (4) The modified polyfunctional epoxy compound as described in the above (3) wherein the polyfunctional epoxy compound (A) is represented by the formula (4), [Chemical 4]

(In the formula (4), Ru to R16 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and η represents an average 値 of the number of repeating units represented by a structure in parentheses, and represents 1 to 8 ). (5) The modified polyfunctional epoxy compound according to the above (4), wherein the polyfunctional epoxy compound (fluorene) is an o-cresol novolac type epoxy compound. (6) The modified polyfunctional epoxy compound according to the above (3), wherein the polyfunctional epoxy compound (Α) is represented by the formula (5): -8- 201006859

❹ (In the formula (5), η represents the average 値 of the number of repeating units represented by the structure in parentheses, and represents 0 to 8). (7) A modified polyfunctional epoxy compound as described in the above (3)

(In the formula (6), R21 to R·28 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms; and Q each independently represents a hydrogen atom or a carbon number of 1 to 4; X is plural When present in one molecule, each X may be the same or different; η represents the average 値' of the number of repeating units represented by the structure in parentheses and represents 〇~8). (8) The modified polyfunctional epoxy compound according to the above (3), wherein the polyfunctional epoxy compound (Α) is represented by the formula (7): -9 - 201006859

(In the formula (7), R3i to R34 each independently represent a hydrogen atom, a halogen atom or a carbon number; and η represents an average 値 of the number of repeating units represented by the structure in parentheses, and represents 1 to 4) ° (9) The modified polyfunctional epoxy compound according to (1) or (2) above, wherein the structure of the polyfunctional epoxy compound has a cyclic structure composed of a fatty acid aliphatic hydrocarbon. (10) The modified polyfunctional epoxy compound according to any one of (1) to (9) above, wherein the compound (Β) having at least one of a trans group and a carboxyl group in one molecule is selected from the group consisting of At least one of a group consisting of propyl propionic acid, dimethylol butyric acid, and dimethylol acetic acid. (11) A curable composition comprising the modified polyfunctional epoxy compound according to any one of the above (1) to (10), a thermosetting agent or a cationic polymerization initiator. (12) A curable composition comprising the modified polyfunctional epoxy compound, the cationic polymerization initiator, and the dissociation catalyst according to any one of the above (1) to (10). (13) A cured polyfunctional compound according to any one of the above (1) to (1), wherein the curable composition according to (11) or (12) Hardened matter. [Effect of the Invention] -10-201006859 The modified polyfunctional epoxy compound of the present invention has stability and lithographic etching properties, and the adhesion of the cured product is used as a coating material and an alkali developing resist composition. [Embodiment] The modified polyfunctional epoxy compound of the present invention is obtained by reacting a compound (B) having at least one or more groups in one molecule, a polybasic acid anhydride (C) and a vinyl group in a plurality of substances (A). .

Here, the polyfunctional epoxy compound (A), the compound (B) having one or more hydroxyl groups and one carboxyl group, and the compound of the vinyl ether compound (D) can be used as the polyfunctional ring which can be used in the present invention. The oxygen compound (for example, by using a phenol (phenol, an alkyl-substituted naphthol, an alkyl-substituted naphthol, a halogenated naphthol, a dihydroxy group, a bisphenol, etc.) and an aldehyde (formaldehyde, acetaldehyde, a bisphenol of benzaldehyde; a bisphenol type obtained by clearing a phenol novolak or a bisphenol novolak, a phenolic novolac type or a bisphenol phenol compound; and an aralkyl type ring structure of a phenol (same as above) The cyclic structure composed of an aliphatic hydrocarbon is obtained by subjecting a compound having an olefin to an oxidation reaction, but the epoxy compound is used as long as it is a ring having a plurality of epoxy groups in one molecule. Preferably, it has an excellent storage property of 50 to 1 〇〇 ° C and an epoxy equivalent of 100 to 900 g/eq, so that it can be suitably used. A functional epoxidized hydroxyl group and a carboxy B ether compound (in the molecule D) With a polybasic acid anhydride (C f fine description. A ) Specific examples, halogenated phenol, benzene, dihydroxynaphthalene, etc.) condensed varnish aldehyde varnish type epoxy oxide compound; in epoxy compound; epoxy compound and other oxygen compounds may have softening point polyfunctionality Epoxy•11 - 201006859 The compound is more preferably a polyfunctional epoxy compound having a softening point of 55 to 80 ° C and an epoxy equivalent of 17 〇 to 350 g / eq. Softening of the polyfunctional epoxy compound (A) When the point is too low, the softening point of the modified polyfunctional epoxy compound of the present invention obtained by the reaction is inevitably low, and as a result, it becomes difficult to form a photoresist on the substrate by using the modified polyfunctional epoxy compound. Forming a uniform film, there is a fear of sticking in the dried photoresist. When the softening point of the polyfunctional epoxy compound is too high, the modified polyfunctional epoxy compound of the present invention obtained by the reaction is solvent. The solubility becomes low and it becomes difficult to produce the modified polyfunctional epoxy compound of the present invention, and the photosensitivity of the photoresist to the solvent or the base is lowered. Here, the softening of the polyfunctional epoxy compound (A) is also referred to herein. Points are based on JI 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 may be crystallized or liquid. It is difficult to form a uniform film on the substrate by using the modified polyfunctional epoxy compound photoresist, and the photoresist is dried after drying. On the other hand, the polyfunctional epoxy compound (A) When the epoxy equivalent is too high, a compound having at least one hydroxyl group and one mercapto group (B) and a polybasic acid anhydride (C) are introduced as a reactive group in the modified polyfunctional epoxy compound, and the amount of the polybasic acid anhydride (C) is small. The photoresist of the modified polyfunctional epoxy compound has a decrease in adhesion, hardenability, and 鹸 developability of the substrate. Further, the epoxy equivalent of the polyfunctional epoxy compound (A) herein is based on The enthalpy determined by JIS K7236. Preferred examples of the polyfunctional epoxy resin (A) include a phenolic awake varnish type epoxy compound, a bisphenol A novolac type epoxy compound, a bis-12-201006859 phenol F type epoxy compound, and a phenol aralkyl compound. A base epoxy compound, a polyfunctional alicyclic epoxy compound, a bisphenol A type epoxy compound, or the like. Further, in the polyfunctional epoxy compound (A), a phenol novolak type epoxy compound or a bisphenol F type ring is exemplified as a preferred skeleton in terms of storage stability of the modified polyfunctional epoxy compound. Oxygen compounds, phenol aralkyl type epoxy compounds, polyfunctional alicyclic epoxy compounds, bisphenol A type epoxy compounds, etc. 'Better skeletons are phenol novolac type epoxy compounds, diacid F type epoxy Compound, phenol aralkyl type epoxy compound, bisphenol A type epoxy compound

W and the like; and preferred skeletons are phenol novolak type epoxy compounds, bisphenol A type epoxy compounds, and the like. It has a softening point of 50 to 100. (: An example of a commercially available product of a polyfunctional epoxy compound (A) having a preferred skeleton of an epoxy equivalent of 1 〇〇 to 9 〇 0 g/eq. Examples are EOCN-102S, EOCN-103S, EOCN- 104S, EOCN-1020, EOCN-4400H, EPPN-201, BREN-S (each is a phenolic novolac type epoxy compound manufactured by Sakamoto Chemical Co., Ltd.), φ EPICOTE157S70 (trade name, Japanese ring) Epoxy Resin Co., Ltd. bisphenol A novolac type epoxy compound), EPIC OTE 1001, EPICOTE 1 002 (each is a trade name, bisphenol A epoxy compound manufactured by Nippon Epoxy Co., Ltd.), EPICOTE 40 04P (trade name, bisphenol F epoxy compound manufactured by Sakamoto Epoxy Co., Ltd.), NER-7604 (trade name, bisphenol F epoxy compound manufactured by Nippon Kayaku Co., Ltd.), NC -3000H (trade name, phenolic aralkyl type epoxy compound manufactured by Nippon Kayaku Co., Ltd.), EHPE 3 150 (trade name, polyfunctional alicyclic epoxy-13 manufactured by DAICELL Chemical Industry Co., Ltd. - 201006859 Compound), etc. Among these, the best skeleton is phenolic phenol A varnish type epoxy compound, particularly preferably an o-cresol novolak type epoxy compound. Examples of commercially available products of o-cresol novolak type epoxy compounds are exemplified by EOCN-102S, EOCN-103S, EOCN- 104S, EOCN-1 020, EOCN-4400H, etc. In the present invention, a compound (B) having at least one hydroxyl group and a carboxyl group in one molecule (hereinafter referred to as "compound (B)") may be used as long as it is one molecule The compound of at least one of the hydroxyl group and the carboxyl group is not particularly limited, but specific examples of the preferred compound (B) include dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolacetic acid, and dimethylol. a monocarboxylic acid containing a polyhydroxy group such as butyric acid, dimethylol valeric acid or dihydroxymethylhexanoic acid; a monohydroxymonocarboxylic acid such as hydroxytrimethylacetic acid or p-hydroxybenzoic acid; and the like. More preferably, it is dimethylolpropionic acid, dimethylolbutanoic acid, dimethylol acetic acid, dimethylolbutanoic acid, dimethylolvaleric acid, dimethylolhexanoic acid, etc. a monocarboxylic acid of a hydroxy group. Among these, it is cheap and easy to obtain from the market. Preferably, it is dimethylolpropionic acid, dimethylolbutanoic acid, or dimethylol acetic acid. The polybasic acid anhydride (C) which can be used in the present invention is not particularly limited as long as it is a polybasic acid anhydride, but is preferably a polybasic acid anhydride. Specific examples of (C) can be exemplified by, for example, succinic anhydride, maleic anhydride, fumaric anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl endochethylene. Tetrahydrophthalic anhydride, benzotricarboxylic acid, pyromellitic acid, and the like. Among these acid anhydrides, the most preferred ones are succinic anhydride, tetrahydrophthalic anhydride and the like. -14- 201006859 The vinyl ether compound (D) which can be used in the present invention has a structure represented by the above formula (1). The alkyl group having 1 to 18 carbon atoms represented by Rrh of the formula (1) is exemplified by a linear or branched chain alkyl group having 1 to 18 carbon atoms, and examples of the aryl group include a phenyl group or a naphthyl group. Further, the alkyl group and the aryl group which may be represented have a substituent which is not particularly limited. The aliphatic hydrocarbon residue having a carbon number of 1 to 18 represented by R4 in the formula (1) means a linear or branched aliphatic hydrocarbon group which is saturated or unsaturated from 1 to 18 carbon atoms. The substituent after a hydrogen atom is usually a saturated hydrocarbon group having 1 to 18 carbon atoms. Further, the saturated hydrocarbon residue having 1 to 18 carbon atoms may have 1 to 17 oxygen atoms in the structure. Here, the saturated hydrocarbon residue containing an oxygen atom in the structure means that the structure having a carbon number of 2 contains 1 oxygen with respect to a saturated hydrocarbon residue having no oxygen atom in the structure of carbon number 2, for example, -CH2CH3. The saturated hydrocarbon residue of the atom is -CH2OCH3, which is a part or all of the CC bond in the saturated hydrocarbon replaced by a C-0-C bond. The aryl group represented by R4 in the formula (1) is exemplified by the same as the aryl group represented by R] to R3 in the formula (1). Further, the aliphatic hydrocarbon residue represented by R4 and the substituent which the aryl group may have are not particularly limited. In the formula (1), η represents any one of the substituents represented by the above formula (2) bonded to any carbon atom of R4, and is any one of 1 to 4. The vinyl ether compound (D) which can be used in the invention is not particularly limited as long as it is a compound represented by the above formula (1), but is preferably a vinyl ether compound in which all of Ri to R3 in the formula (1) are hydrogen atoms and correspond to These ethylene sulfide compounds. Specific examples of the preferred vinyl ether compound (D), for example, -15-201006859 are methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl B. Dilute ether, tert-butyl acetyl alcohol, 2_ethylhexyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, allyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 9_ By mercapto vinyl ether, 4-hydroxycyclohexyl vinyl ether, cycloheximide dimethanol monoethyl ether, triethylene glycol monovinyl ether, hydrazine, 4 · butanediol divinyl ether, decanediol II Vinyl ether, cyclohexanediol divinyl ether, cycloheximide dimethanol dihexyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether and pentaerythritol tetravinyl ether Compounds, etc. Among these compounds, more preferred are isopropyl vinyl ether, t-butyl vinyl ether and the like. In the present invention, the method of reacting the polyfunctional epoxy compound (A) with the compound (B), the polybasic acid anhydride (C) and the vinyl ether compound (D) can take various forms, but in terms of easy control of molecular weight' A preferred method is to first react a polyfunctional epoxy compound (A) with a compound to obtain a reactant (M-1), and react the reactant (M-1) with a polybasic acid anhydride (C) to obtain a reactant (M). 2) 'Reacting the reactant (M·2) with the ethyl ether ether compound (D). Here, the polyfunctional epoxy compound (A), the compound (B), the polybasic acid anhydride (C), and the vinyl ether compound (D) may be used singly or in combination of two or more. First, a method of reacting a polyfunctional epoxy compound (A) with a compound (B) to obtain a reactant (?-1) will be described. The reaction of the above polyfunctional epoxy compound (A) with the compound (B) is preferably in the form of a carboxyl group with respect to 1 equivalent of the epoxy group of the polyfunctional epoxy compound (A). 1 to 0.5 equivalents of the reaction 'best-16-201006859 is 0.1 to 0.3 equivalents. A solvent can also be used in the reaction of the polyfunctional epoxy compound (A) with the compound (B). Examples of the solvent that can be used include ketones such as ethyl methyl ketone, cyclohexanone, and cyclopentanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; dipropylene glycol dimethyl ether and dipropylene glycol. a glycol ether such as diethyl ether; an ester of ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate; an aliphatic hydrocarbon such as octane or decane; petroleum ether and petroleum An organic solvent such as a petroleum solvent such as brain, φ hydrogenated petroleum brain or solvent oil (solvent naphtha). When a solvent is used, the solvent may not be removed from the solution of the reactant (M-1) and used in the subsequent step. Further, it is preferred to use a catalyst for promoting the reaction (for example, triphenylphosphine, benzyldimethylamine, methyltriethylammonium chloride, triphenyl stibine, chromium octoate, etc.), In the case of a catalyst, it is more preferable to carry out an oxidation treatment using an organic peroxide or the like after completion of the reaction, so that the catalytic activity of the catalyst to be used becomes substantially inactive. 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. It is preferred to use a polymerization inhibitor (for example, hydroquinone, methylhydroquinone, p-methoxyphenol, catechol, pyrogallol, etc.) for preventing polymerization in the reaction, and the amount thereof is used in comparison with the reaction. The total amount of the polyfunctional epoxy compound (A) and the compound (B) is preferably 1% by mass or less. 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 titrating the reaction solution with potassium hydroxide standard and measuring by acid value (according to JIS K5 60 1 -2-l: 1 999 ). When the acid value becomes 0 to 5 mg KOH/g, it can be used as a standard for the reaction end point. The reactant (M-1) was thus obtained. -17- 201006859 Next, a method of reacting a reactant (Μ-1) with a polybasic acid anhydride (C) to obtain a reactant (M-2) will be described. The reaction of the reactant (M-1) obtained by the above method with the polybasic acid anhydride (C) is preferably one equivalent of the hydroxyl group in the reactant (M-1) to make the polyanhydride of 〇·1~1·〇 equivalent (C). )reaction. The reaction temperature is usually 60 to 150 ° C. The reaction time is usually 1 to 1 hour. The reactant (M-2) of the reactant (M_1) and the polybasic acid anhydride (C) can thus be obtained. The end point of the reaction can be confirmed by titrating the reaction solution with potassium hydroxide standard and measuring by acid value (according to 181 560 560 1 2-1 : 1 999 ). The acid value becomes the standard of the reaction end point when it is 1.0 mg KOH/g of theoretical alumina calculated from the amount added. Next, a method of reacting the reactant (M-2) with a vinyl ether compound (D) to obtain a modified polyfunctional epoxy compound of the present invention will be described. The reaction of the reactant (M-2) obtained by the above method with the vinyl ether compound (D) is preferably carried out by reacting 0.5 to 10 equivalents of the vinyl ether compound (D) with respect to 1 equivalent of the carboxyl group in the reactant (M-2). Preferably, it is 1.0 to 3. 0 equivalents. The reaction temperature is usually from 〇 to 100 ° C, preferably from 10 to 60 ° C. The reaction time is related to the reaction temperature or the equivalent weight of the vinyl ether compound used in the reaction, but it is usually from about 1 minute to about 60 hours. For the purpose of suppressing by-products or shortening the reaction time, an acid catalyst may be used in the reaction. However, when an acid catalyst is used, it is necessary to use a water washing or an adsorbent after completion of the reaction (for example, a synthetic hydrotalcite-based adsorbent or the like). The adsorbent) is adsorbed and removed. Specific examples of the acid catalyst include monooctyl phosphate, bis(2-ethylhexyl) phosphate, and butyl acetate. The end point of the reaction can be confirmed by acid value determination (according to JIS K5 60 1 -2- 1: 1 999) by using potassium hydroxide standard droplets to determine the reaction liquid. When the acid value becomes 0 to 3.0 mg KOH/g, it can be used as a standard for the reaction end point. Further, the vinyl ether compound (D) which does not participate in the above-mentioned synthesis reaction and remains in the modified polyfunctional epoxy compound after the completion of the reaction has a tendency to lower the physical properties of the cured product, so it is preferable to change from the present invention. The polyfunctional epoxy compound is removed by distillation or the like. The modified polyfunctional epoxy compound of the present invention thus obtained may be measured by an epoxy equivalent (according to JIS K-7236), a proton NMR using a deuterated chloroform solvent, or LC- except for the acid value φ. MS, etc. will confirm. Next, the method for producing the modified polyfunctional epoxy compound of the present invention is specifically shown by the following pattern using an exemplary compound. That is, the o-cresol novolac type epoxy compound (polyfunctional epoxy compound (A)) represented by the formula (8) is first introduced in the presence of a solvent and a catalyst, and is represented by the formula (9). The dimethylolpropionic acid (compound (B)) is subjected to a reaction to obtain a compound represented by the formula (10) (corresponding to the aforementioned reaction φ (M-1)). Next, a compound represented by the formula (1〇) is reacted with a tetrahydrophthalic anhydride (polybasic acid anhydride (C)) represented by the formula (11) to obtain a compound represented by the formula (12) (corresponding to the aforementioned reactant (Μ) ·2 )). Next, 'the compound represented by the formula (12) is reacted with an propyl vinyl ether (vinyl ether compound (D)) represented by the formula (13) to obtain a modified polyfunctional epoxy compound of the present invention represented by the formula (14). . Further, in the following schematic diagram, the epoxy group of the polyfunctional epoxy compound (A) is modified by the compounds (B) to (D), but the number of modified epoxy groups is not limited to one. -19- 201006859 【化8】

CH2—CH—CH2 V .β] hm ch2 >CH2-CH—CH2 , ch3 0 (im=2 严 OH h3c— i—COOH ch2oh (9) ▼ o-ch2-ch—ch2 o—ch2—ch—ch2 〇/ ϊ π V , CH〇一〇ch2ohII I ch2—o—c—c-ch3 1 ch2oh •ch2

Do)

O-CHg-CH-CH: , CH:

c=o

iso-C^H? (13) /0 0H2C—C-CHK H3C-CH c=〇

Ch~ch3

iso-CgHv -20- (14) 201006859 The modified polyfunctional epoxy compound of the present invention is a self-crosslinking type polyfunctional ring having an epoxy group and a carboxyl group in one molecule by releasing a vinyl ether compound by heating. Oxygen compounds, so if necessary, add commonly used pigments, dyes, glass flakes, aluminum flakes, mica flakes, etc., coloring agents, thinners, hardening catalysts, flow regulators, UV absorbers, uniform Chemical agents, antioxidants, etc., used in coatings, inks, adhesives, molded articles, and the like. Φ When the modified polyfunctional epoxy compound of the present invention is used as a coating material, for example, a pigment and an additive are mixed, and a device such as a kneader or a ball mill is sufficiently kneaded to prepare a uniformly dispersed pigment paste. 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 a diluent to obtain a coating material. The coating film obtained by coating the coating by roll coating, spraying, bristles, doctor blade 'bar coating' dip coating, electroplating coating, etc., can be hardened by heat treatment at 50 to 250 ° C for 2 to 30 minutes. Things. φ Next, the curable composition of the present invention will be described. The modified polyfunctional epoxy compound of the present invention is cured by heat alone as described above, but the curable composition of the present invention can also be used in the modified polyfunctional epoxy compound of the present invention to shorten the hardening time or to improve crosslinking. Density thermal hardener or cationic polymerization initiator. First, the curable composition of the present invention containing a thermosetting agent will be described. 〇 As the thermosetting agent, a hardening accelerator for a conventionally known epoxy compound can be used as the curing agent. Specific examples of the heat hardener are exemplified by 2-imidazole-21 - 201006859, 2-ethyl-4-methylimidazole, etc.; 2-(dimethylaminomethyl)phenol, 1,8-diaza A heterobicyclic ring (5.4.0) a tertiary amine such as undecene-7 or a phosphine such as triphenylphosphine; a metal compound such as tin octylate or the like. The amount of the heat curing agent used in the curable composition of the present invention is usually 0.1 to 5.0 parts by mass based on 1 part by mass of the modified polyfunctional epoxy compound of the present invention. The curable composition of the present invention containing a thermosetting agent can be mixed with a modified polyfunctional epoxy compound of the present invention, a thermal hardener, and an inorganic chelating agent or other additives as needed, using a conventionally known method such as a kneader or a roll. And get. Further, the base-free sputum-filling agent or other additives may be selected according to the specific use of the curable composition of the present invention, and the type or amount of the sclerosing agent may be selected as long as it does not impair the necessary characteristics of the intended use. Any restrictions. The method of using the curable composition of the present invention thus obtained is not particularly limited. For example, it can be molded by an injection molding method or using a rotary molding machine or the like, and heated at 80 to 200 ° C for 2 to 10 hours to obtain a cured product. . Next, the curable composition of the present invention containing a cationic polymerization initiator will be described. As the cationic initiator, a conventionally known cationic polymerization initiator which generates an acid by light irradiation or heating can be used, and among them, a photocationic polymerization initiator is preferred. As an example of the photocationic polymerization initiator, an aromatic iodine salt and an aromatic onium salt can be exemplified. Specific examples of the aromatic iodine salt are, for example, diphenyl iodine tetrakis(pentafluorophenyl) borate, diphenyl iodine hexafluorophosphate, diphenyl iodonium hexafluoroantimonate. , bis(4-mercaptophenyl) iodine hexafluorophosphate-22-201006859 and the like. Further, as a specific example of the aromatic onium salt, for example, CPI-101 A (trade name, thiophenyldiphenylphosphonium hexafluoroantimonate manufactured by SAN-APRO Co., Ltd.), SP-172 (commercial product) Name, 4-{4-(2-chlorobenzhydryl)phenylthio}phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, manufactured by Asahi Kasei Co., Ltd., and UVI-6974 ( The product name, a mixture of aromatic hexafluoroantimonate (manufactured by Dow Chemical Co., Ltd.), etc., in order to achieve heat stability in the present invention, it is preferred to use the above-mentioned aromatic sulfonium salt. These photocationic polymerization initiators may be used singly or in combination of two or more. The amount of the cationic polymerization initiator to be used in the curable composition of the present invention is usually from 0.5 to 20 parts by mass based on 100 parts by mass of the modified polyfunctional epoxy compound of the present invention. Next, the curable composition of the present invention containing the dissociation catalyst will be described. The modified polyfunctional epoxy compound of the present invention can be separately heated and φ-hardened as described above, but the curable composition of the present invention can also be used to regenerate the carboxyl group. A cationic polymerization initiator and a dissociation catalyst which have an alkali developability and improve adhesion to a substrate. As the dissociation catalyst, a Lewis acid, a protic acid or an acid generator which generates an acid by irradiation or heating may be used, and the acid or the acid to be produced preferably has a pKa of 3.0 or less. If the pKa is large, the reaction rate of the vinyl ether from the reaction is slowed down. Specific examples of the acid 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, and the like. m-Nitrobenzene-23- 201006859 Formic acid, bis(2-ethylhexyl) phosphate, and the like. The curable composition of the present invention containing the modified polyfunctional epoxy compound of the present invention, a cationic polymerization initiator, and a solvent, a dissociation catalyst or the like as needed may be used as a solvent development type photoresist and the present invention. The curable composition of the present invention, which is a modified polyfunctional epoxy compound, a cationic polymerization initiator, a dissociation catalyst, and a solvent according to necessity, can be used as an alkali-developing photoresist, and each of them can be formed at least 50 μm or more. The film thickness is used as a photoresist. When used as a solvent developing type photoresist, an additive 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 Baking or baking after exposure at 40 to 150 ° C to partially or completely dissociate one of the vinyl ethers can further improve the adhesion to the substrate. When used as an alkali-developing type photoresist, the solvent-developing photoresist is spin-coated on a substrate in the same manner, and then pre-baked at 40 to 150 ° C or at 40 to 15 (TC). After exposure and baking, one or all of the vinyl ether is dissociated, and the solubility in the alkali developing solution can be regenerated. Further, by exposure and post-exposure baking, only the epoxy group of the exposed portion undergoes a crosslinking reaction, and as a result, the result is obtained. The exposure portion is patterned by insolubilizing the organic solvent or the alkali developing solution. The above method is for a negative photoresist, but the curable composition of the present invention may be a positive photoresist. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but these examples are merely intended to illustrate the preferred embodiments of the present invention, and the present invention is not limited to those of the present invention. In the examples and comparative examples, 'if it is not particularly limited, the parts mean parts by mass, and % means % by mass. Further, the physical properties are determined by the following methods. Epoxy equivalent: according to JIS K7236 Acid value: according to JIS K560 1 -2 -1 Non-volatile: According to JIS K723 5 Viscosity: Borrow E-type viscometer (made by Toki Sangyo Co., Ltd., TV-20) ^ The viscosity at 25 ° C was measured. Example 1 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, nitrogen gas was added while blowing. 116 parts of a bisphenol A novolak type epoxy compound represented by the following formula (15) as a polyfunctional epoxy compound (A) (trade name EPICOTE 157S70, manufactured by Nippon Epoxy Resin Co., Ltd., softening point: 70 ° C , epoxy equivalent: 210g/eq): [Chemical 9]

n=2 10.6 parts of dimethylolpropionic acid as compound (B), 0.5 part of triphenylphosphine as a catalyst of -25-201006859, and 60 parts of cyclopentanone as a solvent, dissolved under stirring, and heated to 983⁄4 stirring 4 hours. The reaction solution was cooled to room temperature, and the acid value of the reaction liquid was measured and found to be 1 mg KOH/g or less. Then, 13.3 parts of tetrahydrophthalic anhydride as the polybasic acid anhydride (C) was added to the reaction liquid, and the mixture was dissolved under stirring, and the mixture was heated to 80 ° C and stirred for 2 hours. The reaction solution was cooled to room temperature, and the acid value of the reaction liquid after cooling was determined to be 35 mg KOH / g. Then, 22.5 parts of isopropyl vinyl ether as the vinyl ether compound (D) and 0.56 parts of bis(2-ethylhexyl phosphate) as an acid catalyst were added to the reaction mixture, followed by stirring at room temperature for 5 hours. The acid value of the reaction liquid was measured to be 1 mg KOH/g or less. To the reaction liquid, 28 parts of KUEWORD 500 (trade name, synthetic hydrotalcite-based adsorbent manufactured by Kyowa Chemical Co., Ltd.) as an adsorbent was added and stirred at room temperature for 24 hours. After removing the adsorbent by a membrane filter of 10 μm, the unreacted isopropyl vinyl ether was distilled off by 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 〇.5 mg KOH/g or less, the viscosity was 6.14 Pa·s, and the nonvolatile content was 69%. Example 2 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 190 parts of an o-cresol novolac represented by the following formula (16) was added as a polyfunctional epoxy compound (A) while applying a nitrogen purge. Type epoxy compound (trade name: EOCN-1 020, manufactured by Nippon Kayaku Co., Ltd., softening point: 60 ° C, epoxy equivalent: 195 g/eq): -26- 201006859 [Chemical 1 〇]

20 parts of dimethylolpropionic acid as a compound (Β), 0.9 part of triphenylphosphine as a catalyst, and 90 parts of cyclopentanone as a solvent were dissolved under stirring, and the mixture was heated to 98 ° C and stirred for 4 hours. The reaction solution was cooled to room temperature, and after measuring the acid value of the reaction solution, it was 1 mg KOH/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 mixture, and the mixture was dissolved under stirring, and the mixture was heated to 98 ° C for 3 hours. The reaction solution was cooled to room temperature, and the acid value of the reaction liquid after cooling was determined to be 45 mg KOH/g. Then, 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 to the reaction liquid, and the mixture was stirred at room temperature for 5 hours. The acid value of the reaction liquid was measured to be 1 mg KOH/g or less. To the reaction mixture, 75 parts of the above φ KUEWORD 500 as an adsorbent was added and stirred at room temperature for 24 hours. After removing the adsorbent by a membrane filter of 10 μm, the unreacted isopropyl vinyl ether was distilled off by 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 mg KOH/g or less, a viscosity of 5.60 Pa·s, and a nonvolatile content of 71%. Example 3

In the flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 119 parts of a bisphenol F-type ring represented by the following formula (17) was added as a polyfunctional epoxy compound (A -27-201006859) while nitrogen gas blowing was applied. Oxygen compound (trade name NER-7604, manufactured by Nippon Kayaku Co., Ltd.) Softening point: 7 ° C, epoxy equivalent: 325 g / eq [Chemical 1 1] C^2-/CH-CH2 〇-CH2-gH一Ο—CHu-CH—CH: CHg Ο * /η (17) :Η or a CH2-CH—CH2,〇/ n=6

7.3 parts of dimethylolpropionic acid as the compound (B), 0.5 part of triphenylphosphine as a catalyst, and 60 parts of cyclopentanone as a solvent were dissolved under stirring, and the mixture was heated to 98 ° C and stirred for 4 hours. The reaction solution was cooled to room temperature, and the acid value of the reaction liquid was measured and found to be 1 mg KOH/g or less. Then, 13.3 parts of tetrahydrophthalic anhydride as the polybasic acid anhydride (C) was added to the reaction liquid, and the mixture was dissolved under stirring, and the mixture was heated to 80 ° C and stirred for 2 hours. The reaction solution was cooled to room temperature, and the acid value of the reaction liquid after cooling was determined to be 43.8 mg KOH / g. Next, 22.5 parts of isopropyl vinyl ether as a vinyl ether compound (D) and 56 parts of bis(2-ethylhexyl phosphate) as an acid catalyst were added to the reaction mixture, followed by stirring at room temperature for 5 hours. The acid value of the reaction liquid was measured to be 1 mg KOH/g or less. To the reaction liquid, 28 parts of the above KUEWORD 500 as an adsorbent was added and stirred at room temperature for 24 hours. After removing the adsorbent by a membrane filter of 1 μm, the unreacted isopropyl vinyl ether was distilled off by a rotary evaporator to obtain 183 parts of a cyclopentanone solution (E-3) of the modified polyfunctional epoxy compound of the present invention. ). The obtained solution had an acid value of 0.5 mg KOH/g or less, a viscosity of 5.31 Pa·s, and a nonvolatile content of 7 0.5%. -28-201006859 Example 4 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 178 parts of a phenol aryl group represented by the following formula (18) was added as a polyfunctional epoxy compound (A) while nitrogen gas blowing was applied thereto. Alkyl epoxy compound (trade name NC-3 000H, manufactured by Nippon Kayaku Co., Ltd., softening point: 70 ° C, epoxy equivalent: 290 g / eq):

• 【化12】

12_3 parts of dimethylolpropionic acid as the compound (B), 〇9 parts of triphenylphosphine as a catalyst, and 90 parts of cyclopentanone as a solvent were dissolved under stirring, and the mixture was heated to 981 and stirred for 4 hours. The reaction solution was cooled to room temperature, and the acid value of the reaction liquid was measured and found to be 1 mg KOH/g or less. Next, 20 parts of φ as a polybasic acid anhydride (C) tetrahydrophthalic anhydride was added to the reaction liquid, and the mixture was dissolved under stirring, and the mixture was heated to 98 ° C and stirred for 2 hours. The reaction solution was cooled to room temperature, and the acid value of the reaction liquid after cooling was measured to be 28.4 mg KOH / g. Then, 30 parts of isopropyl vinyl ether as a vinyl ether compound (D) and 1 part by weight of bis(2-ethylhexyl phosphate) as an acid catalyst were added to the reaction mixture, and the mixture was stirred at room temperature for 5 hours. The acid value of the reaction liquid was measured to be 1 mg KOH/g or less. 50 parts of the above KUEWORD 500 as an adsorbent was added to the reaction mixture and stirred at room temperature for 24 hours. After removing the adsorbent by a 10 μm membrane filter, the unreacted isopropyl vinyl ether was distilled off by a rotary evaporator to obtain 250 parts of the cyclopentanone solution of the modified -29-201006859 polyfunctional epoxy compound of the present invention ( Ed). The obtained solution had an acid value of 0.5 mg KOH/g or less, a viscosity of 〇·8 Pa·s, and a nonvolatile content of 6 9%. Example 5

To a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 114 parts of an alicyclic epoxy compound (trade name) represented by the following formula (19) was added as a polyfunctional epoxy compound (A) while nitrogen gas blowing was applied thereto. EHPE3150, manufactured by DAICEL Chemical Industry Co., Ltd., softening point: 77 ° C, epoxy equivalent: I80 g / eq): [Chem. 1 3]

V_/^CH—CH2 V. ft CH—CH, (/ Η Η (19) °-±

H CH—CH〇

O l-HmH-n=24 12.7 parts of dihydroxymethylpropionic acid as compound (B), 0.6 parts of triphenyl scale as a catalyst, and 60 parts of cyclopentanone as a solvent, dissolved under stirring, and heated to 98 Stir at °C for 4 hours. The reaction solution was cooled to room temperature, and the acid value of the reaction liquid was measured and found to be 1 mg KOH/g or less. Next, 20 parts of tetrahydrophthalic anhydride as a polybasic acid anhydride (C) was added to the reaction liquid, and the mixture was dissolved with stirring, and the mixture was heated to 98 ° C and stirred for 2 hours. The reaction solution was cooled to room temperature, and the acid value of the reaction liquid after cooling was determined to be 26.1 mg KOH / g. Next, add -30-201006859 to the reaction solution, add 25 parts of isopropyl vinyl ether as the vinyl ether compound (D), and 8 parts of bis(2-ethylhexyl phosphate) as an acid catalyst. Stir for 5 hours. The acid value of the reaction liquid was measured to be 1 mg KOH/g or less. 50 parts of the reaction solution was added to the above-mentioned KUEWORD 500 as an adsorbent and stirred at room temperature for 24 hours. After removing the adsorbent by a membrane filter of 1 μm, the unreacted isopropyl vinyl ether was distilled off by a rotary evaporator to obtain 175 parts of a cyclopentanone solution of the modified polyfunctional epoxy compound of the present invention (E-5). ). The obtained solution had an acid φ value of 0.5 mg KOH/g or less, a viscosity of 1.0 Pa·s, and a nonvolatile content of 70%. Example 6 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 114 parts of a bisphenol A type epoxy represented by the following formula (20) was added as a polyfunctional epoxy compound (A) while applying a nitrogen purge. Compound (trade name)

EPICOTE 828, manufactured by Nippon Epoxy Co., Ltd., softening point: below 20C 'epoxy equivalent: I90g/eq): 【化1 4 ch2«-ch—ch2—〇0~CH2—CH—CH2—Ο-ϊ —* h (20) I w —...f 0H3 oh 'ch2-ch-ch2 ch3 0 n=0.14 12.1 part of dimethylolpropionic acid as compound (b), 0.55 part of triphenylphosphine as catalyst, 60 The cyclopentanone as a solvent was dissolved under stirring and heated to 98 ° C for 4 hours. The reaction solution was cooled to room temperature, and the acid value of the reaction -31 - 201006859 liquid was measured and found to be 1 mg KOH/g or less. Then, 20 parts of tetrahydrophthalic anhydride as the polybasic acid anhydride (C) was added to the reaction liquid, and the mixture was dissolved under stirring, and the mixture was heated to 98 ° C and stirred for 2 hours. The reaction solution was cooled to room temperature, and the acid value of the reaction liquid after cooling was determined to be 40 mg KOH / g. Then, 25 parts of isopropyl vinyl ether as the vinyl ether compound (D) and 0.8 parts 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 liquid was measured to be 1 mg KOH/g or less. 50 parts of the above KUEWORD 500 as an adsorbent was added to the reaction mixture and stirred at room temperature for 24 hours. After removing the adsorbent by a membrane filter of 10 μm, the unreacted isopropyl vinyl ether was distilled off by 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 mg KOH/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 cooling tube, and a stirring device, 190 parts of the ortho-cresol novolac which is the same as the user of Example 2 was added as a polyfunctional epoxy compound (A) while nitrogen gas blowing was applied. a varnish-type epoxy compound, 20 parts of dimethylolpropionic acid as the compound (B), 0,9 parts of triphenyl scale as a catalyst, and 90 parts of cyclopentanone as a solvent, dissolved under stirring, and heated to 98 Stir at °C for 4 hours. The reaction solution was cooled to room temperature, and the acid value of the reaction solution was measured to be 1 mg KOH/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 mixture, and the mixture was dissolved under stirring, and the mixture was heated to 98 ° C and stirred for 3 hours 201006859. The reaction solution was cooled to room temperature, and the acid value of the reaction liquid after cooling was determined to be 45 mg KOH/g. Next, 30 parts of isopropyl vinyl ether as the vinyl ether compound (D) was added to the reaction liquid, and the mixture was stirred at room temperature for 72 hours. The acid value of the reaction liquid was measured to be 1 mg KOH/g or less. Unreacted isopropyl vinyl ether was distilled off by a rotary evaporator to obtain 300 parts of a cyclopentanone solution (E-7) of the modified polyfunctional epoxide of the present invention. The acid value of the obtained solution was 〇. 5 mg KOH/g or less, the viscosity was 5.39 Pa·s, and the nonvolatile content was 71%. Comparative Example 1 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 190 parts of the ortho-cresol novolac which is the same as the user of Example 2 was added as a polyfunctional epoxy compound (A) while applying nitrogen gas. a varnish-type epoxy compound, 20 parts of dimethylolpropionic acid as the compound (B), 0.9 part of triphenylphosphine as a catalyst, and 90 parts of cyclopentanone as a solvent, dissolved under stirring, and heated to 98 ° C Stir for 4 hours. The reaction solution was cooled to room temperature, and the acid value of the anti-φ solution was measured to be 1 mg KOH/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 liquid, and the mixture was dissolved under stirring, and the mixture was heated to 98 ° C and stirred for 3 hours. The reaction solution was cooled to room temperature, and the acid value of the reaction liquid after cooling was determined to be 45 mg KOH/g. The reaction solution was filtered through a 10 μm membrane filter to obtain 350 parts of a cyclopentanone solution (R-1) having a modified polyfunctional epoxy compound having a carboxyl group. The obtained solution had an epoxy equivalent of 489 g/eq, an acid value of 45 mg KOH/g, a viscosity of 19.6 Pa·s, and a nonvolatile content of 70%. -33-201006859 Evaluation of Characteristics The time-dependent stability of the modified polyfunctional epoxy compound of the present invention obtained in Examples 1 to 7 and the comparative epoxy compound obtained in Comparative Example 1 was evaluated. That is, 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 (just after the production) and after storage at 23 t and 40 ° C for 28 days at 25 ° C. Viscosity, the increase rate of the viscosity after storage relative to the initial viscosity (= post-storage viscosity/initial viscosity) was calculated. The results are shown in Table 1. Also, due to changes in viscosity over time, the viscosity exceeds the limit of measurement. "Table 1. Viscosity after storage versus initial (after manufacturing) viscosity increase rate of polyfunctional epoxy compound storage temperature 2 3〇C 4 0 °C E -1 1.8 Unable to measure E-2 E-3 1.0 1.6 1 .1 5.6 E-4 1.2 4.1 E-5 1.4 12.3 E-6 1.2 1.6 E-7 1.0 1 .1 R-1 Cannot be measured

From the results of Table 1, the modified polyfunctional epoxy compound (E-1 to E-7) of the present invention and the modified polyfunctional epoxy compound protected by the carboxyl group obtained by the comparative example without vinyl ether (R·1) can be understood. It is superior to its 'time stability. -34-201006859 Application Example 1 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 100 parts by mass of the modified polyfunctional epoxy compound cyclopentanone solution of the present invention obtained in Example 1 (E-1) 1 part by mass of CI Pigment Blue 60 was added and stirred to obtain a coating. The obtained coating material was coated on a release substrate using a bar coater, and dried at 200 ° C for 30 minutes to obtain a hardened coating cured film. • Examples 8 to 10 (curable composition) According to the addition amount (unit: mass parts) described in Table 2, the polyfunctional epoxy compound, the photocationic polymerization initiator, and other components can be separated by a stirring blade. The flask was mixed at 40 ° C for 1 hour, and the resulting composition was filtered using a 10 μm membrane filter to obtain a curable composition of the present invention. The hardenable compositions of Examples 8 and 9 were coated on a ruthenium wafer at a thickness of 50 μm, and were exposed to a negative mask after drying at 95 ° C for 20 minutes using a hot plate, using an i-line exposure apparatus (mask aligner) (mask aligner): φ USHIO Motor Co., Ltd.) performs pattern exposure (soft contact, i line). Subsequently, the film was subjected to post-exposure baking (PEB) at 95 ° C for 6 minutes, and immersed for 6 minutes at 23 ° C using propylene glycol monomethyl ether acetate to obtain a hardened resin pattern on the substrate. type. The sclerosing composition of Example 10 was coated on a ruthenium wafer at a thickness of 50 μm, and dried at 95 ° C for 20 minutes using a hot plate to contact the negative mask, using an i-line exposure apparatus (mask aligner: USHIO Motor Co., Ltd.) Performs pattern exposure (soft contact, i-line). Next, the film was exposed to post-bake (PEB) at 95 ° C for 6 minutes using a hot plate, and immersed for 6 minutes at 23 ° C for 2 minutes using a 2.38 % KOH-35-201006859 'tetramethylammonium aqueous solution (TM AH ). Processing, obtaining a hardened resin pattern on the substrate. The resin patterns of the hardenable compositions of Examples 8 to 10 obtained above were evaluated as follows. The results are shown in Table 2. Optimum exposure: The amount of exposure when the mask transfer accuracy is optimal. Aspect ratio: Film thickness / the finest pattern width of the formed photoresist pattern. Table 2 Evaluation of characteristics of hardenable composition Addition of sinus Example 8 9 10 Modified polyfunctional epoxy compound (E-2) obtained in Example 2 100 100 100 Cationic polymerization initiator UVI-6974 5 5 5 Dissociation Di(2-ethylhexyl) mordyl 10 10 Solvent cyclopentanone 10 10 10 Homogenizer F-470 0.06 0.06 0.06 Optimum exposure (mJ/cm3) 2500 2400 2400 Aspect ratio 5 5 5 Note: Cationic polymerization Starting agent (trade name: UVI-6974, 50% propylene carbonate solution manufactured by The Dow Chemical Company) Fluorine leveling agent (trade name: MEGAFAC F-470, manufactured by DIC Corporation) From the results of Table 2, the use of the present invention is known. The curable composition of the modified polyfunctional epoxy compound has sufficient characteristics as a thick film photoresist. -36-201006859 [Industrial Applicability] The modified polyfunctional epoxy compound of the present invention and a curable composition containing the same can be suitably used as a raw material of a coating material and a photoresist composition.

-37-

Claims (1)

201006859 VII. Patent application scope: 1. A modified polyfunctional epoxy compound characterized by having at least one epoxy group in one molecule and a partial structure represented by formula (3): ° CH—R2 Ri (In the formula (3), R, R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group, and the alkyl group and the aryl group may have a substituent); On the functional epoxy compound (A), a compound (B) having at least one or more hydroxyl groups and carboxyl groups in one molecule, a polybasic acid anhydride (C), and a vinyl ether compound (D) represented by the following formula (1) are reacted. And, [Chemical 1] (In the formula (1), Ri, R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group, and the alkyl group and the aryl group may have a substituent; and R4 represents 1 to 17; An oxygen atom or an aliphatic hydrocarbon group having 1 to 18 carbon atoms or an aryl group which does not contain an oxygen atom, and the group may have a substituent; η represents a formula (2) bonded to any carbon atom of R4. ) indicates the number of substituents, and is any one of 1 to 4: -38- (2) 201006859 [Chemical 2] (In the formula (2), H3 represents the same meaning as in the formula (1)) ❹ 2. The modified polyfunctional epoxy compound according to the first aspect of the patent application, wherein the polyfunctional epoxy compound (A) has 50 a softening point of ~100 ° C and an epoxy equivalent of 100 to 900 g / eq. 3. The polyfunctional epoxy compound modified according to claim 1 or 2, wherein the polyfunctional epoxy compound (A) is obtained by epoxidizing a polyfunctional powder. 4. A modified polyfunctional epoxide as claimed in claim 3, wherein the polyfunctional epoxy compound (A) is represented by the formula (4). 【化4】 (4) In the formula (4), Rii to Ri6 each independently represent a hydrogen atom, a crypto atom or an alkyl group having 1 to 4 carbon atoms, and η represents an average 値 of the number of repeating units represented by a structure in parentheses, and Indicates 1 to 8). 5. A modified polyfunctional epoxide as claimed in claim 4, wherein the polyfunctional epoxy compound (Α) is an o-cresol novolac type epoxy compound. 6. The modified polyfunctional epoxide-39-201006859 as claimed in claim 3, wherein the polyfunctional epoxy compound (A) is represented by the formula (5): (In the formula (5), η represents the average 値' of the number of repeating units represented by the structure in parentheses and represents 0 to 8). 7. A modified polyfunctional epoxide as claimed in claim 3, wherein the polyfunctional epoxy compound (Α) is represented by the formula (6): (In the formula (6), R21 to R28 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms; and Q each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and X is present in plural plural In one molecule, each X may be the same or different; η represents the average 値' of the number of repeating units represented by the structure in parentheses and represents 0 to 8). 8. A modified polyfunctional epoxide as claimed in claim 3, wherein the polyfunctional epoxy compound (Α) is represented by the formula (7): -40- 201006859 (In the formula (7), 'R3 and -113 4 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms; η represents an average 値 of the number of repeating units represented by a structure in parentheses, and represents 1 ~4). 9. The modified polyfunctional epoxy compound according to claim 1 or 2, wherein the polyfunctional epoxy compound has a cyclic structure composed of aliphatic hydrocarbons. 10. The modified polyfunctional epoxy compound according to any one of claims 1 to 9, wherein the compound (Β) having at least one or more of a hydroxyl group and a carboxyl group in one molecule is selected from the group consisting of dimethylol At least one of a group consisting of acid, dimethylolbutanoic acid and dimethylol acetic acid. 1 1 A curable composition characterized by comprising a 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 characterized by comprising a modified polyfunctional epoxy compound, a cationic polymerization initiator, and a dissociation catalyst according to any one of claims 1 to 10. 13. A cured product characterized by the modification of the polyfunctional epoxy compound according to any one of claims 1 to 1 or the hardening of the hardening composition of claim 1 or 1 Things. -41 - 201006859 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: none 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none -4-