KR20180011001A - Reactive epoxy carboxylate compound, reactive polycarboxylic acid compound, active energy ray curable resin composition containing them and cured product thereof, and article - Google Patents

Abstract

The present invention is to provide an active energy ray-curable resin composition which is cured by an active energy ray such as ultraviolet rays and the like, has excellent light sensitivity, and has good developing properties, wherein an obtained cured product has all excellent properties such as sufficient curing and dielectric properties, etc., and which has excellent electrical reliability under high temperature and high humidity. According to the present invention, a reactive epoxycarboxylate compound (A) is obtained by allowing a reaction of an epoxy resin (a) represented by formula (1) with a compound (b) having a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule and/or a compound (c) having a hydroxyl group and a carboxyl group in one molecule. In the formula (1), R_1 and R_2 independently represent a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and a represents 1 to 3. Also, n is a repetition number, and is 1 to 10.

Description

TECHNICAL FIELD [0001] The present invention relates to a reactive epoxy resin composition, a reactive epoxy carboxylate compound, a reactive polycarboxylic acid compound, an active energy ray-curable resin composition containing the same, a cured product thereof, THEREOF, AND ARTICLE}

(B) having both an ethylenic unsaturated group capable of polymerizing in one molecule and a carboxy group and / or a compound (c) having a hydroxyl group and a carboxy group together in one molecule, in an epoxy resin (a) having a polycyclic hydrocarbon group, (A), a reactive polycarboxylic acid compound (B) as an acid-modified product thereof, an active energy ray-curable resin composition containing the same, and a cured product thereof.

The printed wiring board is required to have high accuracy and high densification in order to reduce the size and weight of the portable device and to improve the communication speed and accordingly the demand for the solder resist for covering the circuit itself of the wiring board becomes higher and higher, Heat resistance and thermal stability as well as excellent electrical properties under low temperature and high humidity conditions.

As a solder resist material (film forming material), Patent Document 1 discloses a carboxylate compound as a material having a low acid value and excellent developability. It is also disclosed that this compound has resist ink suitability. The acid-modified epoxy acrylate described in Patent Document 2 exhibits high toughness after curing and has been studied as a solder resist.

Conventional acid-modified epoxy acrylates, particularly acid-modified epoxy acrylates having a biphenyl skeleton, have been disclosed to exhibit relatively good dispersibility (Patent Document 3).

JP-A-06-324490 Japanese Patent Application Laid-Open No. 11-140144 Japanese Patent Application Laid-Open No. 2005-055814

However, the curable resin composition containing an epoxy resin having a biphenyl skeleton described in Patent Document 3 can obtain a cured product having relatively high reliability, but it is still insufficient for use in materials for electronic devices and the like that require very high reliability .

In particular, recent active energy ray-curable resin compositions are required to have higher reliability with respect to temperature, humidity, etc., for example, excellent electrical properties, driving under extreme conditions, and impact resistance, and also require fine workability. At this time, it is necessary that the sensitivity, developability, curability, and the like have performance equal to or higher than that of the conventional product.

In order to solve the above-mentioned problems, the present inventors have found that a reactive epoxy resin composition comprising a reactive epoxy carboxylate compound (A) obtained by using an epoxy resin having a specific biphenyl structure and a reactive epoxy resin (A) obtained by using the reactive epoxy carboxylate compound It has been found that the resin composition using the carboxylic acid compound (B) has excellent properties.

That is, the present invention relates to an epoxy resin composition comprising (a) an epoxy resin (a) represented by the following general formula (1), a compound (b) having both an ethylenically unsaturated group capable of polymerizing in one molecule and a carboxy group and / And a reactive epoxy carboxylate compound (A) obtained by reacting the compound (c).

(Wherein R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group of 1 to 3 carbon atoms, and a represents 1 to 3, and n is a repeating number of 1 to 10.)

Further, the present invention relates to a reactive polycarboxylic acid compound (B) obtained by reacting the reactive epoxy carboxylate compound (A) with a polybasic acid anhydride (d).

Further, the present invention relates to an active energy ray-curable resin composition comprising the reactive epoxy carboxylate compound (A) and / or the reactive polycarboxylic acid compound (B).

Further, the present invention relates to the active energy ray-curable resin composition containing the reactive compound (C).

Further, the present invention relates to an active energy ray-curable resin composition comprising a photopolymerization initiator.

Further, the present invention relates to an active energy ray-curable resin composition comprising a coloring pigment.

Further, the present invention relates to the active energy ray-curable resin composition as a molding material.

Further, the present invention relates to the active energy ray-curable resin composition as a film-forming material.

Further, the present invention relates to the active energy ray-curable resin composition as a resist material composition.

Further, the present invention relates to a cured product of the active energy ray-curable resin composition.

Further, the present invention relates to an article overcoated with a cured product of the active energy ray-curable resin composition.

By using the reactive epoxy carboxylate compound (A) and / or the reactive polycarboxylic acid compound (B) of the present invention, it is possible to obtain a cured product having excellent light sensitivity and good developing property, It is possible to obtain an active energy ray curable resin composition having excellent properties and excellent electrical reliability under high temperature and high humidity. Therefore, the resin composition of the present invention is suitable for a molding material, a film forming material, and a resist material. In particular, it is used for a solder resist for a printed wiring board, an interlayer insulating material for a multilayer printed wiring board, a solder resist for a flexible printed wiring board, a plating resist, and a photosensitive optical waveguide from the reliability under high temperature and high humidity.

(Mode for carrying out the invention)

The reactive epoxy carboxylate compound (A) of the present invention is obtained by reacting the epoxy resin (a) represented by the following formula (1) with a compound (b) having both an ethylenically unsaturated group capable of polymerizing in one molecule and a carboxy group, (C) having both a hydroxyl group and a carboxy group in the molecule.

That is, the characteristics of the present invention are exhibited by introducing the ethylenic unsaturated group and the hydroxyl group simultaneously into the molecular chain of the epoxy carboxylate compound at an arbitrary ratio.

(Wherein R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group of 1 to 3 carbon atoms, and a represents 1 to 3, and n is a repeating number of 1 to 10.)

The epoxy resin (a) used in the present invention is an epoxy resin having a polycyclic hydrocarbon group represented by the above general formula (1).

Examples of the hydrocarbon group having 1 to 3 carbon atoms in the formula include a methyl group, an ethyl group, a propyl group and an isopropyl group.

n is preferably from 1 to 10, more preferably from 2 to 8, and particularly preferably from 2 to 4.

The softening point (ring method) of the epoxy resin (a) to be used is preferably 50 to 150 占 폚, more preferably 52 to 100 占 폚, particularly preferably 52 to 95 占 폚. When the temperature is lower than 50 캜, there is a great deal of sticking, which makes handling difficult and causes problems in productivity. If it is more than 150 ° C, the temperature is close to the molding temperature, and fluidity at the time of molding can not be secured.

The epoxy resin (a) has a melt viscosity at 150 캜 of preferably 0.05 to 5 Pa · s, particularly preferably 0.05 to 2.0 Pa · s. If the viscosity is high, there is a problem in fluidity, which may cause problems in the flow property and the filling property at the time of pressing. If it is less than 0.05 Pa · s, the molecular weight is too small, which may result in insufficient heat resistance.

The total amount of chlorine remaining in the epoxy resin (a) is preferably 1000 ppm or less, more preferably 600 ppm or less, particularly preferably 300 ppm or less. The sulfate ion extracted by hot water extraction is preferably 1000 ppm or less, more preferably 600 ppm or less.

The reactive epoxycarboxylate compound (A) and the reactive polycarboxylic acid compound (B) using the epoxy resin (a) have an overall chlorine content of 50% or less in the prior art, and therefore the electrical properties and metal corrosion resistance under high temperature and high humidity .

The epoxy resin (a) can be obtained by oxidizing a substituted or unsubstituted allyl ether resin represented by the following formula (2). Examples of the oxidation method include, but are not limited to, a method of oxidizing with peracid such as peracetic acid, a method of oxidizing with hydrogen peroxide, a method of oxidizing with air (oxygen), a method of oxidizing with carbonic acid peroxide, and the like.

As the method of epoxidation by peroxide, specifically, the method described in JP-A-2006-52187 can be mentioned.

In the method of epoxidation by hydrogen peroxide water, various methods can be adopted. Specifically, JP-A-59-108793, JP-A-62-234550, JP-A-5-213919 Japanese Unexamined Patent Application Publication No. 11-349579, Japanese Unexamined Patent Publication No. 1-33471, Japanese Unexamined Patent Application Publication No. 2001-17864, Japanese Unexamined Patent Publication No. 3-57102, Japanese Unexamined Patent Publication No. 2011-225654, Japanese Patent Laid-Open Publication No. 2011-079794, Japanese Laid-Open Patent Publication No. 2011-084558, Japanese Laid-Open Patent Publication No. 2010-083836, Japanese Laid-Open Patent Publication No. 2010-095521, and the like.

(Wherein R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group of 1 to 3 carbon atoms, a represents 1 to 3, and n represents an average value of the number of repeating units of 1 to 10.)

The allyl ether resin can be produced by a known production method but is not particularly limited. For example, by reacting a corresponding phenol resin with an allyl halide or a metal halide in the presence of a base in a solvent Can be obtained.

The compound (b) having at least one polymerizable ethylenic unsaturated group and at least one carboxy group in the molecule used in the present invention is used for imparting reactivity to an active energy ray. Such a compound includes a monocarbonic acid compound and a polycarboxylic acid compound.

Examples of the monocarbonic acid compound include (meth) acrylic acid, crotonic acid,? -Cyanosinic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound. Examples of the (meth) acrylic acids in the above include (meth) acrylic acid,? -Styryl acrylic acid,? -Furfuryl acrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride, (Meth) acrylate derivatives having a hydroxyl group and half esters, which are sugar mole reactants, half ester esters, which are sugar mole reactants of saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives, and the like have.

Examples of the polycarboxylic acid compound include (meth) acrylate derivatives having a plurality of hydroxyl groups in one molecule, half esters such as sugar-molar reactant, glycidyl (meth) acrylate derivatives having a saturated or unsaturated dibasic acid and a plurality of epoxy groups And the half-esters, which are sugar-molar reactants.

Of these, the reaction product of (meth) acrylic acid, (meth) acrylic acid and epsilon -caprolactone, or cinnamic acid is preferable from the viewpoint of sensitivity when the active energy ray-curable resin composition is used. As the compound (b) having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in one molecule, it is preferable that the compound does not have a hydroxyl group in the compound.

The compound (c) having at least one hydroxyl group and at least one carboxy group in a molecule used in the present invention is used for the purpose of introducing a hydroxyl group into the carboxylate compound. These include a compound having one hydroxyl group and one carboxy group in one molecule, a compound having at least two hydroxyl groups and one carboxy group in one molecule, a compound having at least one hydroxyl group and at least two carboxy groups in one molecule .

Examples of the compound (c) having one hydroxyl group and one carboxy group in one molecule include hydroxypropionic acid, hydroxybutanoic acid, and hydroxystearic acid. Examples of the compound (c) having two or more hydroxyl groups and one carboxy group in one molecule include dimethylolacetic acid, dimethylolpropionic acid, and dimethylolbutanoic acid. Examples of the compound having at least one hydroxyl group and at least two carboxyl groups in one molecule include hydroxyphthalic acid and the like.

Among them, it is preferable that two or more hydroxyl groups are contained in one molecule in consideration of the effect of the present invention. The carboxy group is preferably one in one molecule in view of the stability of the carboxylation reaction. Most preferably, it has two hydroxyl groups and one carboxy group in one molecule. Considering the availability of the raw materials, dimethylol propionic acid and dimethylol butanoic acid are particularly suitable. As the compound (c) having at least one hydroxyl group and at least one carboxy group in one molecule, it is preferable that the compound (c) does not have a polymerizable ethylenic unsaturated group in the compound.

Among them, in consideration of the stability of the reaction between the epoxy resin (a) and the compound (b) and / or the compound (c), the compound (b) and / or the compound (c) Is preferably a monocarbonic acid, and even when a monocarboxylic acid and a polycarboxylic acid are used in combination, it is preferable that the value represented by the total molar amount of the monocarboxylic acid / the total molar amount of the polycarboxylic acid is 15 or more.

The charging ratio of the epoxy resin (a) and the total amount of the carbonic acid of the compound (b) and / or the compound (c) in this reaction may be appropriately changed depending on the application. When all the epoxy groups of the epoxy resin (a) are carboxylated, unreacted epoxy groups do not remain, so that the storage stability of the reactive epoxy carboxylate compound (A) is high. When there is no unreacted epoxy group, the reactivity of the reactive epoxy carboxylate compound (A) depends on the double bond introduced.

On the other hand, by reducing the amount of the compound (b) and / or the carboxylic acid compound of the compound (c) to reduce the residual unreacted epoxy group, the reactivity of the introduced double bond and the reactivity of the unreacted epoxy group, (Complex curing) by using a polymerization reaction by a photo cationic catalyst or a thermal polymerization reaction in combination. However, in this case, attention should be paid to examination of the conditions for preservation and production of the reactive epoxy carboxylate compound (A).

When the reactive epoxy carboxylate compound (A) having no unreacted epoxy group is produced, the compound (b) or the compound (b) and the compound (c) in an amount sufficient for the epoxy group of the epoxy resin (a) . In the present invention, the total amount of the compound (b) and / or the compound (c) is preferably 90 to 120 equivalent% based on 1 equivalent of the epoxy resin (a). Within this range, production under relatively stable conditions is possible. If the amount of the carbonic acid compound to be added is larger than this, the excess of the carboxylic acid compound (b) or (b) and (c) may remain, which is not preferable.

When the reactive epoxy carboxylate compound (A) having an unreacted epoxy group is produced, the compound (b) or the compound (b) and the compound (c) in an amount that the epoxy group of the epoxy resin It is good to use. In the present invention, the total amount of the compound (b) or (b) and (c) is preferably 20 to 90 equivalent% based on 1 equivalent of the epoxy resin (a). When the amount of the carbonic acid compound to be added is too small, the efficiency of complex curing is lowered. In this case, it is necessary to pay attention to the gelation during the reaction and the stability with time of the reactive epoxy carboxylate compound (A).

In the case of producing the reactive epoxy carboxylate compound (A), a compound (b) having at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in one molecule and at least one hydroxyl group and at least one carboxyl group (B): (c) is preferably in the range of 9: 1 to 1: 9 and more preferably in the range of 4: 6 to 8: 2 in terms of the molar ratio of the compound (c) Within this range, it is possible to prevent the lowering of the sensitivity when the amount of the compound (b) is too small, and to prevent the effect (c) of the case where the amount of the compound (c) is too small. There is no particular limitation on the order of introduction of (b) and (c) in the carboxylation reaction (hereinafter referred to as "main carboxylation reaction") in the present invention.

In the present carboxylation reaction, a solvent is not necessarily required, but may be reacted by diluting with a solvent. The solvent usable here may be the same as the solvent used for the synthesis of the epoxy resin (a), and is not particularly limited as long as it is a solvent which does not react with the present carboxylation reaction. The amount of the solvent to be used is appropriately adjusted depending on the viscosity and application of the resin to be obtained, but is preferably 30 to 90% by weight, and preferably 50 to 80% by weight, of the total amount of the reactants.

Examples of usable solvents include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane and decane; and mixtures thereof, such as petroleum ether, white gasoline, Naphtha, and the like. Examples of the ester solvents include alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate, cyclic esters such as? -Butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol Mono or polyalkylene glycol monoalkyl ethers such as glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate and butylene glycol monomethyl ether acetate; Polycarboxylic acid alkyl esters such as ether monoacetates, dialkyl glutarates, dialkyl succinates and dialkyl adipates. Examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether, alicyclic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, Glycol ethers such as triethylene glycol diethyl ether, and cyclic ethers such as tetrahydrofuran. Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

In addition, it can be carried out alone or in a mixed organic solvent such as a reactive epoxy carboxylate compound (A) and a reactive compound (C) other than the reactive polycarboxylic acid compound (B). In this case, when used as a curable resin composition, it is preferable because it can be directly used as a composition.

In the reaction, it is preferable to use a catalyst in order to accelerate the reaction, and the amount of the catalyst to be used is preferably such that the amount of the reaction product, that is, the epoxy resin (a), the compound (b) and / Based on the total amount of the reactants plus the solvent and others. The reaction temperature at that time is 60 to 150 占 폚, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, Boron, chromium octanoate, zirconium octanoate and the like, and the like.

As the thermal polymerization inhibitor, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenyl picrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4-hydroxytoluene and the like are used .

This reaction is defined as the end point when the acid value of the sample becomes 5 mgKOH / g or less, preferably 2 mgKOH / g or less, while appropriately sampling.

The preferred range of the molecular weight of the reactive epoxy carboxylate compound (A) of the present invention thus obtained is 1,000 to 30,000, more preferably 1,500 to 20,000 in terms of polystyrene reduced weight average molecular weight (Gw) in the GPC measurement.

If the molecular weight is smaller than the molecular weight, the hardness of the cured product is not sufficiently exhibited. If the molecular weight is too large, the viscosity becomes high and the coating becomes difficult.

The reactive epoxy carboxylate compound (A) of the present invention is considered to include the structure represented by the following formula (3), but is not limited thereto.

(Wherein, R _1, which is the same as R ₂ or A is a formula (1) of R _1, R ₂ or a)

Next, the reactive polycarboxylic acid compound (B) of the present invention will be explained.

The reactive polycarboxylic acid compound (B) of the present invention is obtained by reacting the reactive epoxy carboxylate compound (A) with a polybasic acid anhydride (d).

Hereinafter, the acid addition process will be described in detail. The acid addition step is carried out for the purpose of introducing a carboxyl group into the reactive epoxy carboxylate compound (A) obtained in the previous step, if necessary, to obtain a reactive polycarboxylic acid compound (B). The reason for introducing a carboxy group is that it has a purpose of imparting solubility to alkaline water to the active energy ray unexamined portion and imparting adhesion to a metal or an inorganic material in applications where resist patterning or the like is required . Concretely, a carboxyl group is introduced through an ester bond by addition reaction of a polybasic acid anhydride (d) to a hydroxyl group generated by the carboxylation reaction.

The reaction of adding the polybasic acid anhydride (d) can be carried out by adding a polybasic acid anhydride (d) to the carboxylation reaction solution. The amount added may be appropriately changed depending on the application.

As the polybasic acid anhydride (d) that can be used, any compound having an acid anhydride structure in a molecule can be used. However, it is preferable to use a polyfunctional acid anhydride such as anhydrous succinic anhydride, phthalic anhydride, Particularly preferred are phthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride.

When the reactive polycarboxylic acid compound (B) of the present invention is used as an alkali developing type resist, the solid acid value of the reactive polycarboxylic acid compound (B) finally obtained from the polybasic acid anhydride (d) (JIS K5601-2-1: 1999 Is in the range of 30 to 120 mg · KOH / g, and more preferably 40 to 105 mg · KOH / g. When the acid value of the solid at this time is in this range, the developability of the aqueous alkali solution of the active energy ray-curable resin composition of the present invention is satisfactory. That is, the good developability of the aqueous alkali solution means that the good patterning performance and the management of the phenomenon are wide, and the excess acid anhydride remains.

In the reaction, it is preferable to use a catalyst in order to accelerate the reaction. The amount of the catalyst to be used is preferably in the range of 1 to 50 parts by weight per 100 parts by weight of the epoxy compound (a), the compound (b) and / or the reactive epoxy Is 0.1 to 10% by weight based on the total amount of the reaction product of the carboxylate compound (A) and the polybasic acid anhydride (d), and optionally the solvent and others. The reaction temperature at that time is 60 to 150 占 폚, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, Boron, chromium octanoate, zirconium octanoate, and the like.

The acid addition reaction may be carried out by reacting with a solvent or by diluting with a solvent. The solvent usable here may be the same as the solvent used for the synthesis of the epoxy resin (a) and the carboxylation reaction, and is not particularly limited as long as it is a solvent which does not react with the acid addition reaction. Further, in the case where a solvent is used in the carboxylation reaction as the previous step, the solvent is directly added to the acid addition reaction, which is the next step, without removing the solvent, provided that the reaction does not show a reaction to the both reactions. .

The amount of the solvent to be used is appropriately adjusted depending on the viscosity and the purpose of the resin to be obtained, but is preferably 90 to 30% by weight, more preferably 80 to 50% by weight, based on the total amount of the reactants.

Examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylmethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane and decane; and mixtures thereof, such as petroleum ether, white gasoline, Naphtha, and the like.

Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate, cyclic esters such as? -Butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol Mono or polyalkylene glycol monoalkyl ethers such as glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate and butylene glycol monomethyl ether acetate; Polycarboxylic acid alkyl esters such as ether monoacetates, dialkyl glutarates, dialkyl succinates and dialkyl adipates.

Examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether, alicyclic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, Glycol ethers such as triethylene glycol diethyl ether, and cyclic ethers such as tetrahydrofuran.

Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

In addition, it can be carried out in a single or mixed organic solvent such as the later-described reactive compound (C). In this case, when the composition is used as a curable composition, it is preferable because it can be directly used as a composition.

The thermal polymerization inhibitor and the like are preferably the same as those exemplified in the above carboxylation reaction.

In this reaction, while sampling appropriately, the acid value of the reactant is set to the end point with a point of plus or minus 10% of the set acid value.

The reactive polycarboxylic acid compound (B) of the present invention is considered to include a compound represented by the following formula (4) as an example of the structure, but is not limited thereto.

(Wherein R ₁ , R ₂ Or a is a group represented by R ₁ and R ₂ in the formula (1) Same as a)

Next, the active energy ray-curable resin composition of the present invention will be described.

The active energy ray-curable resin composition of the present invention contains the reactive epoxy carboxylate compound (A) and / or the reactive polycarboxylic acid compound (B).

The active energy ray-curable resin composition of the present invention contains 5 to 97% by weight, preferably 10 to 87% by weight, of the reactive epoxy carboxylate compound (A) and / or the reactive polycarboxylic acid compound (B) in the composition.

The active energy ray-curable resin composition of the present invention may further contain a reactive compound (C). Further, other components may be appropriately added depending on the application.

When the reactive compound (C) other than the compounds (A) and (B) is contained, the amount thereof is 3 to 95% by weight, preferably 3 to 90% by weight. Other components may be contained in an upper limit of about 70% by weight, if necessary.

As the reactive compound (C) usable in the present invention, those other than the reactive epoxy carboxylate compound (A) and the reactive polycarboxylic acid compound (B) are preferable. Specific examples include so-called reactive oligomers such as radical reaction type acrylates, cationic reaction type other epoxy compounds, and vinyl compounds which are responsive to both of them.

Examples of the acrylates include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, other epoxy acrylates, polyester acrylates and urethane acrylates.

Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (Meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc .; .

Examples of the polyfunctional (meth) acrylates include butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, ) Acrylate, diethylenedi (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, adipic acid epoxy Di (meth) acrylate of ε-caprolactone adduct of di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogenated bisphenol ethylene oxide (meth) acrylate, bisphenol di (Meth) acrylate, dipentaerythritol and ε-caprolactone, dipentaerythritol poly (meth) acrylate, trimethylene (Meth) acrylate, ethylene oxide adduct thereof, pentaerythritol tri (meth) acrylate and its ethylene oxide adduct, pentaerythritol tetra (metha) acrylate, ) Acrylate, dipentaerythritol hexa (meth) acrylate, and ethylene oxide adduct thereof.

Examples of vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds. Examples of the vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of the styrene include styrene, methylstyrene, and ethylstyrene. Other examples of the vinyl compound include triallyl isocyanurate and trimethallyl isocyanurate.

As the so-called reactive oligomers, urethane acrylate having a functional group capable of reacting with an active energy ray and a urethane bond in the same molecule, a polyester acrylate having a functional group capable of reacting with an active energy ray and an ester bond in the same molecule , Epoxy acrylates derived from an epoxy resin and having a functional group capable of forming an active energy ray in the same molecule, and reactive oligomers in which these bonds are used in combination.

The cationic reaction type monomer is not particularly limited as long as it is a compound having an epoxy group in general. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl- 4-epoxycyclohexanecarboxylate (manufactured by Union Carbide Co., Ltd., "Sylucker UVR-6110" and the like), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide ELR-4206 " manufactured by Kubaido Co., Ltd.), limonene dioxide ("Celloxide 3000" manufactured by Daicel Chemical Industries, Ltd.), allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl- (3,4-epoxycyclohexyl) -5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate Quot; UVR-6128 "), bis (3,4-epoxycyclohexylmethyl) adi Bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane, and the like.

Of these, the reactive compound (C) is most preferably a radical-curing acrylate. In the case of the cationic type, since the carbonic acid reacts with the epoxy, it is necessary to prepare a two-liquid mixture type.

The active energy ray-curable resin composition of the present invention contains 5 to 97% by weight, preferably 10 to 87% by weight, of the reactive epoxy carboxylate compound (A) and / or the reactive polycarboxylic acid compound (B) ) And (B) contain 3 to 95% by weight, more preferably 3 to 90% by weight, of the reactive compound (C). If necessary, other components may be contained in an upper limit of about 70% by weight.

The reactive epoxy carboxylate compound (A) and / or the reactive polycarboxylic acid compound (B) of the present invention can be appropriately used depending on the use of the active energy ray-curable resin composition of the present invention. For example, in the case of a solvent developing type in which a pattern is formed by a printing method or an unreacted portion is caused to flow out depending on a solvent, the reactive epoxy carboxylate compound (A ) Is used, and when developing with alkaline water, the reactive polycarboxylic acid compound (B) is used. Generally, since the alkaline water developing type easily forms a fine pattern, the reactive polycarboxylic acid compound (B) is often used in this application. Of course, any combination of (A) and (B) may be used depending on the required use and performance.

The active energy ray-curable resin composition of the present invention is easily cured by an active energy ray. Specific examples of the active energy ray include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays and laser beams, particle beams such as alpha rays, beta rays and electron beams. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferable in view of the suitable use of the present invention.

The coloring pigment usable in the present invention is used to make the active energy ray-curable resin composition of the present invention as a coloring material. Since the reactive epoxy carboxylate compound (A) and the reactive polycarboxylic acid compound (B) of the present invention have affinity to an excellent pigment, that is, dispersibility, the dispersion progresses well and the pigment concentration can be made thick. In addition, in the composition requiring development, since the dispersion is in a more suitable state, good patterning characteristics are exhibited, and the development residue in the development dissolution portion is also small.

Examples of the coloring pigments include organic pigments such as phthalocyanine pigments, azo pigments and quinacridone pigments, and inorganic pigments such as carbon black and titanium oxide. Among these, the dispersibility of carbon black is high, and thus it is more preferable.

In the present invention, the molding material refers to a material obtained by molding an uncured composition into a mold or by molding an object by pressing the mold, followed by molding by causing a curing reaction with an active energy ray, For example, by irradiating focal light such as a laser to a curing reaction.

Specific examples of the use include a sheet formed into a flat shape, a sealing material for protecting the element, a nanoimprint material which is pressed by pressing a " mold " finely processed with a non-cured composition, A peripheral encapsulating material such as a light emitting diode, a photoelectric conversion element, or the like, which is strict, can be used as a suitable application.

In the present invention, the film-forming material is used for the purpose of covering the substrate surface. Specific applications include ink materials such as gravure ink, flexo ink, silk screen ink and offset ink, coating materials such as hard coating, top coating, overprint varnish and clear coating, various adhesives for laminating, , A resist material such as a solder resist, an etching resist, and a resist for a micromachine. The so-called dry film coating film-forming material, which temporarily forms a film-forming material on a peelable base material to form a film, and then adheres to a base material for the original purpose to form a film.

The carboxyl group of the reactive polycarboxylic acid compound (B) enhances adhesion to the substrate. In view of the fact that the reactive polycarboxylic acid compound (B) is soluble in an aqueous alkali solution, the composition of the present invention comprising the reactive polycarboxylic acid compound (B) can be used for a plastic substrate or an alkaline water- It is also preferable to use a composition.

The resist composition used in the present invention means a composition in which a coating layer of the composition is formed on a substrate and then an active energy ray such as ultraviolet rays is partially irradiated to obtain an active region Energy ray-sensitive composition. Specifically, it is a composition used for the purpose of removing the irradiating unit or the non-irradiating unit by any method, for example, dissolving them with a solvent or an alkali solution or the like, and drawing.

The active energy ray-curable resin composition for resists of the present invention can be applied to various materials capable of patterning, and is useful, for example, in an interlayer insulating material for a solder resist material or a build-up method, A wiring board, an optical electronic board, an optical board, and the like.

Particularly suitable applications are color resists such as printing inks and color filters, in particular black matrix resists, taking advantage of the properties of obtaining a hardened cured product, making use of permanent resists such as solder resists, and good pigment dispersibility .

The active energy ray-curable resin composition of the present invention is also used in dry film applications requiring mechanical strength before curing reaction by energy rays. That is, since the balance of the hydroxyl group and the epoxy group of the epoxy resin (a) used in the present invention is within a specific range, the reactive epoxy carboxylate compound (A) of the present invention has a relatively high molecular weight, I will exert.

There are no particular restrictions on the method of forming the film, but it is possible to use various methods such as a concave printing method such as a gravure printing method, a convex printing method such as flexo printing, a plate printing method such as a silk screen, a flat printing method such as an offset printing method, a roll coater, Various coating methods such as a coater, a curtain coater, and a spin coater can be arbitrarily adopted.

The cured product of the active energy ray-curable resin composition of the present invention means that the active energy ray-curable resin composition of the present invention is irradiated with active energy rays and cured.

In addition, for the purpose of satisfying the active energy ray-curable resin composition of the present invention for various uses, other components may be added to the resin composition at an upper limit of 70 mass%. Other components include a photopolymerization initiator, other additives, a coloring material, and a volatile solvent added for adjusting the viscosity for the purpose of imparting a coating property or the like. Other components that can be used are illustrated below.

Examples of the radical type photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2- Hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4 2-methyl anthraquinone, 2-chloro anthraquinone, 2-amylanthraquinone, 2-aminopyranone, And the like; anthraquinones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; ketalates such as acetophenone dimethylketal and benzyldimethylketal; Benzophenones such as phenol, 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine Oxides, and phosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; and the like.

Examples of the cationic photopolymerization initiator include diazonium salts of Lewis acids, iodonium salts of Lewis acids, sulfonium salts of Lewis acids, phosphonium salts of Lewis acids, other halides, triazine initiators, And other photo acid generators.

Examples of the diazonium salt of Lewis acid include p-methoxyphenyldiazonium fluorophosphonate, N, N-diethylaminophenyldiazonium hexafluorophosphonate (SANEIDA SI-60L / SI-80L / SI-100L, etc.). Examples of the iodonium salt of Lewis acid include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and the like. (Cyracure UVI-6990 manufactured by Union Carbide Co., Ltd.), triphenylsulfonium hexafluoroantimonate (Cyracure UVI-6974 manufactured by Union Carbide Co., Ltd.) as the sulfonium salt of Lewis acid, triphenylsulfonium hexafluorophosphate Etc.), and the phosphonium salt of Lewis acid includes triphenylphosphonium hexafluoroantimonate and the like.

Examples of other halides include 2,2,2-trichloro- [1-4 '- (dimethylethyl) phenyl] ethanone (Trigonal PI manufactured by AKZO), 2.2- ), Ethanone (such as Sandray 1000 manufactured by Sandoz), and alpha, alpha, alpha -tribromomethylphenyl sulfone (BMPS manufactured by Seitetsu Kagaku Co., Ltd.). Examples of the triazine initiator include 2,4,6-tris (trichloromethyl) -triazine, 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine (Triazine A, (2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine (Triazine PMS manufactured by Panchim Co., (Triazine B manufactured by Panchim Corp.), 2,4-trichloromethyl- (4'-methoxynaphthyl) -6-triazine (manufactured by Panchim Corp.), 2 [ (Trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd.), 2 (2'-furylethylidene) -4,6-bis (trichloromethyl) and s-triazine (manufactured by Sanwa Chemical Co., Ltd.).

Examples of the photoacid generators include 9-phenyl acridine, 2,2 ' -bis (o-chlorophenyl) naphthoquinone, -4,4 ', 5,5'-tetraphenyl-1,2-biimidazole (biimidazole manufactured by Guro Gainesha), 2,2-azobis (2-amino-propane) dihydrochloride (V50 manufactured by Wako Pure Chemical Industries, Ltd.), 2,2-azobis [2- (imidazoline-2-yl) propane] dihydrochloride (VA044 manufactured by Wako Pure Chemical Industries, Pentadecyl) (1,2,3,4,5,6,? - (methylethyl) -benzene] iron (II) hexafluorophosphonate (Irgacure 261 manufactured by Ciba Geigy), bis (Pentadienyl) bis [2,6-difluoro-3- (1H-pyryl-1-yl) phenyl] titanium (CGI-784 manufactured by Ciba Geigy).

In addition, an azo-based initiator such as azobisisobutyronitrile and a peroxide-based radical-type initiator that responds to heat such as benzoyl peroxide may be used together. Both radical initiators and cationic initiators may be used together. The initiator may be used alone or in combination of two or more.

Examples of other additives include thermosetting catalysts such as melamine and the like, thixotropic agents such as aerosol, polymerization inhibitors such as silicone type and fluorine leveling agents and defoaming agents, hydroquinone and hydroquinone monomethyl ether, stabilizers, antioxidants Etc. may be used.

As other pigment materials, for example, those not intended for coloring, so-called extender pigments may be used. Examples thereof include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, and clay.

(So-called inner polymer), for example, other epoxy resin, phenol resin, urethane resin, polyester resin, ketone formaldehyde resin, cresol resin, xylene resin, di Allyl phthalate resins, styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof. These are preferably used in the range of up to 40 mass% in the resin composition.

Especially when the above-mentioned reactive polycarboxylic acid compound (B) is to be used for the solder resist, it is preferable to use a known general epoxy resin as a resin which does not show reactivity with an active energy ray. As a result, the carboxyl group derived from the reactive polycarboxylic acid compound (B) remains after the reaction and curing by the active energy ray, and as a result, the cured product thereof is inferior in water resistance and hydrolytic ability. By using an epoxy resin, the residual carboxy group is further carboxylated to form a stronger crosslinked structure.

A volatile solvent may be added to the resin composition in a range of up to 50% by mass, more preferably up to 35% by mass, depending on the purpose of use.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise stated in the examples, parts represent parts by weight.

The softening point, the epoxy equivalent, the acid value and the total chlorine content were measured under the following conditions.

1) Epoxy equivalent: Measured by the method according to JIS K 7236: 2001.

2) Softening point: Measured according to JIS K 7234: 1986

3) Acid value: Measured according to JIS K 0070: 1992

4) The measurement conditions of GPC are as follows.

Model: TOSOHHLC-8220GPC

Column: TSKGEL Super HZM-N

Eluent: THF (tetrahydrofuran); 0.35 ml per minute. 40 ℃

Detector: differential refractometer

Molecular weight standard: Polystyrene

5) Total chlorine amount: The resin was burned and adsorbed to pure water of gas, and then measured by ion chromatography (instrument, measuring conditions).

(Synthesis Example 1)

25 parts by mass of water, 500 parts by mass of dimethylsulfoxide, 500 parts by mass of a phenol resin (phenol-biphenylene-type hydroxyl equivalent of 200 g / eq, softening point of 65 占 폚) were added to a flask equipped with a stirrer, a reflux condenser, And the temperature was raised to 45 캜 and dissolved. Next, the mixture was cooled to 38 to 40 DEG C, and 130.0 parts (1.3 molar equivalents based on 1 molar equivalent of the hydroxyl group of the phenol resin) of the flaky caustic soda (99% pure by Toso) was added over 60 minutes. Thereafter, 294.3 parts by mass (1.3 mol equivalent based on 1 molar equivalent of the hydroxyl group of the phenol resin) of methallyl chloride (purity: 99%, manufactured by TOKYO CASEY KOGYO KK) was added dropwise over 60 minutes, For 1 hour at 60 to 65 ° C.

After completion of the reaction, water and dimethylsulfoxide were distilled off under heating and decompression at 125 DEG C or lower using a rotary evaporator. Then, 740 parts by mass of methyl isobutyl ketone was added, and water washing was repeated to confirm that the aqueous layer became neutral. Thereafter, the solvent was distilled off from the oil layer using a rotary evaporator under reduced pressure and nitrogen bubbling to obtain a methallyl ether resin (hereinafter referred to as "MEP") of the formula (2) with n = 2.0 Quot;).

(Synthesis Example 2)

1000 parts by mass of an ethyl acetate solution containing MEP obtained in Synthesis Example 1 (concentration of MEP: 50% by mass) was added to a flask equipped with a stirrer, a reflux condenser and an agitator while nitrogen purge was carried out. 0.04 parts by mol of potassium tungstate as a tungstic acid compound, 0.06 parts by mol of potassium phosphate as a phosphoric acid compound, and 60.0 parts by mass of acetic acid as an organic carbonic acid per 100 parts by mass of MEP were added per 1 molar portion, and the mixture was heated to 50 캜 . After the temperature was elevated, a 35% hydrogen peroxide aqueous solution was added over a period of 20 minutes to an amount equivalent to 2 molar equivalents of hydrogen peroxide to 1 molar equivalent of the metallyl group in MEP, while stirring. After completion of the addition, the mixture was directly stirred at 50 占 폚 for 24 hours.

Next, the liquid separation treatment was carried out, and the aqueous phase was separated to obtain a solution containing the epoxy resin (a1). The obtained epoxy resin (a1) had an epoxy equivalent of 274 g / eq., An ICI melt viscosity of 0.07 Pa · s at a softening point of 59 ° C and a temperature of 150 ° C, and a total chlorine content of 10 ppm or less.

(Example 1): Synthesis of reactive epoxy carboxylate compound (A)

274 g of the epoxy resin (a1) obtained in Synthesis Example 2 as an epoxy resin (a), 274 g of acrylic acid (abbreviated as AA) as the above-mentioned compound (b) was added to a flask equipped with a stirrer, a reflux condenser and a stirrer, (DMPA, Mw = 134) as the compound (c) shown in Table 1, 3 g of triphenylphosphine as a catalyst, 3 g of propylene glycol monomethyl ether as a solvent Monoacetate was added so that the solid content became 80% by weight, and the reaction was carried out at 100 DEG C for 24 hours to obtain a solution of the reactive epoxy carboxylate compound (A1) of the present invention. The total chlorine content of the obtained reactive epoxycarboxylate compound (A1) solution was 10 ppm or less. The weight average molecular weight was 1150.

The reaction end point was determined by the solid acid value (AV) and the measured values are shown in Table 1. The acid value measurement was carried out by measuring the reaction solution and calculating the acid value as a solid content.

(Comparative Example 1): Synthesis of reactive epoxy carboxylate compound

A phenol biphenyl novolak type epoxy resin (NC-3000H, manufactured by Nippon Kayaku Co., Ltd.) was used as the epoxy resin (a) while a nitrogen purge was performed, to a flask equipped with a stirrer, a reflux condenser and an agitator Acrylic acid (abbreviated AA, Mw = 72) as the compound (b) and dimethanolpropionic acid (abbreviated as DMPA, Mw = 134) as the compound (c) 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so as to have a solid content of 80% by weight and reacted at 100 占 폚 for 24 hours to obtain a comparative carboxylate compound ( A2). The weight average molecular weight was 1,400.

The reaction end point was determined by the solid acid value (AV), and the measured values are shown in Table 1. The acid value measurement was carried out in the reaction solution and converted to an acid value as a solid content.

(Example 2): Synthesis of reactive polycarboxylic acid compound (B)

Tetrahydrophthalic anhydride (abbreviated as THPA) as the polybasic acid anhydride (d) was added to 434 g of the reactive epoxy carboxylate compound (A1) solution obtained in Example 1 in the amount described in Table 2, and the amount of propylene Glycol monomethyl ether monoacetate was added and heated at 100 占 폚 for acid addition reaction to obtain a solution of the reactive polycarboxylic acid compound (B1) of the present invention. The total chlorine content of the obtained reactive polycarboxylic acid compound (B1) solution was 10 ppm or less.

(Comparative Example 2): Synthesis of reactive polycarboxylic acid compound

(Abbreviated as THPA) serving as the polybasic acid anhydride (d) was added to 452 g of the carboxylate compound (A2) solution obtained in Comparative Example 1 in the amount of the base in Table 2 and propylene glycol mono Methyl ether monoacetate was added, and the mixture was heated to 100 占 폚 for acid addition reaction to obtain a reactive polycarboxylic acid compound solution (B2). The total chlorine content of the obtained reactive polycarboxylic acid compound solution was 300 ppm.

(Example 3, Comparative Example 3): Preparation of resin composition

56.73 g of the reactive polycarboxylic acid compound (B1, B2) obtained in Example 2 and Comparative Example 2, and DPCA-60 (trade name: polyfunctional acrylate monomer manufactured by Nippon Kayaku Co., Ltd.) as the reactive compound (C) (Manufactured by Nippon Kayaku Co., Ltd.) as a curing component, and 2.8 g of Irgacure 907 (manufactured by BASF) as a photopolymerization initiator and 0.58 g of Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) , 0.73 g of melamine as a thermosetting catalyst, and 5.67 g of propylene glycol monomethyl ether monoacetate as a concentration adjusting solvent were added and kneaded with a bead mill to uniformly disperse the mixture to obtain a resin composition.

(Example 4 and Comparative Example 4)

The resin composition obtained in Example 3 and Comparative Example 3 was uniformly applied to a polyethylene terephthalate film as a support film using a wire bar coater # 20 and passed through a hot-air drying furnace at a temperature of 70 占 폚, After forming a paper layer, a polyethylene film serving as a protective film was adhered to the resin layer to obtain a dry film. The obtained dry film was adhered to the entire surface of the substrate while peeling the protective film to a polyimide printed substrate (copper circuit thickness: 12 탆, polyimide film thickness: 25 탆) using a heating roll at 80 캜 .

Next, a mask on which a circuit pattern was drawn using an ultraviolet ray exposure apparatus (model HMW-680GW, manufactured by Oak Seisakusho Co., Ltd.) and a mask of 500 mJ / cm < 2 > Of ultraviolet rays. Thereafter, the film on the dry film was peeled off to confirm the peeling state. Thereafter, spraying was performed with a 1% aqueous solution of sodium carbonate to remove the resin from the unexposed portion. After washing with water and drying, the printed board was heated and cured by a hot air dryer at 150 ° C for 60 minutes to obtain a cured film. Sensitivity, developability, curability, dielectric constant and dielectric tangent were measured for the obtained cured film (water) based on the following measurement conditions. The results are shown in Table 3.

Sensitivity evaluation: It was judged that the sensitivities remained at the time of development at the exposure part passing through the step tablet, until the concentration part at the several stages. The greater the number (the value), the higher the sensitivity of the tablet (the unit).

Evaluation of developability: Developability was evaluated in terms of developability (unit: second) with the time until the pattern portion was completely developed, that is, the break time, at the time of developing the exposed portion through the pattern mask.

Curability evaluation: The curability evaluation showed a pencil hardness of the cured film after completion of heating at 150 캜. The evaluation method was in accordance with JIS K5600-5-4: 1999.

Evaluation of dielectric constant: dielectric loss tangent evaluation: A 1 GHz cavity resonator manufactured by Kanto Denshi Co., Ltd. was used for testing by a cavity resonator perturbation method. However, the sample size was 1.7 mm in width × 100 mm in length and 1.7 mm in thickness (dielectric constant unit:%).

From the above results, it can be seen that although the resist composition of the present invention does not show a difference in superiority, it is cured by actinic energy rays such as ultraviolet rays and has excellent light sensitivity and good developing property. It was confirmed that all of the characteristics such as sufficient curability and dielectric properties were excellent.

(Example 5, Comparative Example 5)

The electrical properties under high temperature and high humidity were evaluated as a reliability evaluation for temperature and humidity. The evaluation base (cured film) obtained in Example 4 and Comparative Example 4 was exposed to a bias voltage of DC 100 V in a high-temperature and high-humidity bath at 120 ° C and 85% RH, and after 100 hours and 150 hours after the migration, .

From the above results, it was found that the cured product using the resin composition of the present invention had excellent results in the evaluation of the properties under high temperature and high humidity, with respect to the cured product using the comparative resin composition.

In the evaluation of electrical reliability under high temperature and high humidity, it is required that the bias voltage of DC 100 V is kept slightly changed over 150 hours under an environment of 120 ° C and 85% RH. In this respect, the reactive epoxy carboxylate compound of the present invention using the epoxy resin (a) represented by the formula (1) has the same sensitivity, developability and curability as the case of using the reactive epoxy carboxylate compound for comparison And further has excellent electrical reliability under high temperature and high humidity.

Claims (11)

(B) a compound (b) having both an ethylenically unsaturated group capable of polymerizing in one molecule and a carboxy group, and a compound (c) having both a hydroxyl group and a carboxy group in one molecule in the epoxy resin (a) represented by the following general formula (A) obtained by reacting both or both of the reactive epoxy carboxylate compound

(Wherein R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group of 1 to 3 carbon atoms, a represents 1 to 3, and n represents a repeating number of 1 to 10). A reactive polycarboxylic acid compound (B) obtained by reacting the reactive epoxy carboxylate compound (A) according to claim 1 with a polybasic acid anhydride (d). (B) a compound (b) having both an ethylenically unsaturated group capable of polymerizing in one molecule and a carboxy group, and a compound (c) having a hydroxyl group and a carboxy group together in one molecule in the epoxy resin (a) represented by the following general formula (A) obtained by reacting a reactive epoxy compound
The reactive polycarboxylic acid compound (B) obtained by reacting the reactive epoxy carboxylate compound (A) with a polybasic acid anhydride (d)
Wherein the active energy ray-curable resin composition comprises:

(Wherein R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group of 1 to 3 carbon atoms, a represents 1 to 3, and n represents a repeating number of 1 to 10). The method of claim 3,
Further, the active energy ray-curable resin composition comprising the reactive compound (C). The method of claim 3,
Further, an active energy ray-curable resin composition comprising a photopolymerization initiator. The method of claim 3,
Further, an active energy ray-curable resin composition comprising a coloring pigment. 7. The method according to any one of claims 3 to 6,
Wherein the active energy ray-curable resin composition is a molding material. 7. The method according to any one of claims 3 to 6,
An active energy ray-curable resin composition which is a film-forming material. 7. The method according to any one of claims 3 to 6,
An active energy ray curable resin composition which is a resist material composition. A cured product of the active energy ray-curable resin composition according to any one of claims 3 to 6. An article overcoated with a cured product of the active energy ray-curable resin composition according to claim 10.