TW201809875A - Epoxy carboxylate compound, polycarboxylic acid-based compound, energy beam curable resin composition containing the same and its cured product - Google Patents

Abstract

The purpose of the present invention is to provide an activating energy beam curable resin composition which is cured by active energy rays such as ultraviolet rays, it has excellent photosensitivity and good developing properties, the obtained cured product is excellent in various properties such as sufficient curability and dielectric properties, it also has excellent electrical reliability under high temperature and high humidity conditions. The reactive epoxy carboxylate compound (A) of the present invention is obtained by reacting epoxy resin (a) represented by the following general formula (1) with a compound (b) having both ethylenically unsaturated groups and carboxy groups polymerizable in one molecule and/or a compound (c) having both a hydroxyl group and a carboxy group in one molecule. wherein, R1, R2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, a represents 1 to 3, respectively. N is the repeat count number and is 1 to 10.

Description

An epoxy carboxylic acid ester compound, a polyvalent carboxylic acid compound, an energy ray-curable resin composition containing the same, and a cured product of the resin composition

The present invention relates to an epoxy carboxylic acid ester compound (A), an acid modified polycarboxylic acid compound (B), an active energy ray-curable resin composition containing the same, and a cured product of the resin composition, wherein The epoxy carboxylic acid ester compound (A) is an epoxy resin (a) having a polycyclic hydrocarbon group, a compound (b) having a polymerizable ethylenically unsaturated group and a carboxyl group in a molecule, and/or It is obtained by reacting a compound (c) having both a hydroxyl group and a carboxyl group in a molecule.

In order to improve the size, weight, and communication speed of the portable device, the printed wiring board is required to have high precision and high density. Accordingly, the requirements for the solder resist of the circuit itself covering the wiring board are gradually increasing. Increasingly, it is required to have superior heat resistance, thermal stability, low dielectric properties, high reliability, and excellent electrical characteristics particularly under high temperature and high humidity.

As a solder resist material (material for film formation), Patent Document 1 discloses a material in which a carboxylate compound is low in acid value and excellent in developability. It is further disclosed that the compound has a resist inkability. The acid-modified epoxy acrylate described in Patent Document 2 exhibits high toughness after curing, and is studied as a solder resist.

It has been revealed that the conventional acid-modified epoxy acrylates, particularly the acid-modified epoxy acrylates having a biphenyl skeleton, exhibit relatively good dispersibility (Patent Document 3).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 06-324490

[Patent Document 2] Japanese Patent Laid-Open Publication No. H11-140144

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-055814

However, the curable resin composition containing an epoxy resin having a biphenyl skeleton described in Patent Document 3 can be used for a material such as an electronic device that requires extremely high reliability, although a relatively high-reliability cured product can be obtained. The words are not yet sufficient.

In particular, in recent years, the active energy ray-curable resin composition is required to have higher reliability against temperature, humidity, and the like. For example, it is required to have not only electrical characteristics, driving under severe conditions, and excellent punching resistance, but also fine workability. In this case, it is necessary to have the same performance as the conventional article, such as sensitivity, developability, and hardenability.

In order to solve the above problems, the present inventors have found that a reactive epoxy carboxylic acid ester (A) obtained by using an epoxy resin having a specific biphenyl structure is used, and further, the use of the aforementioned reactive epoxy carboxylic acid ester (A) is used. The resin composition of the obtained reactive carboxylic acid compound (B) has excellent properties.

That is, the present invention relates to a reactive epoxy carboxylate compound (A) which is an epoxy resin (a) represented by the following formula (1) and which is polymerizable in the molecule. The compound (b) having an unsaturated group and a carboxyl group and/or the compound (c) having both a hydroxyl group and a carboxyl group in the molecule are reacted.

(wherein R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and a represents 1 to 3, respectively. The number of n-type repeats is 1 to 10)

Further, a reactive polycarboxylic acid compound (B) obtained by reacting the above reactive epoxy carboxylate compound (A) with a polyprotic acid anhydride (d).

Further, the active energy ray-curable resin composition containing the reactive epoxy carboxylate compound (A) and/or the reactive polycarboxylic acid compound (B) described above.

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

Further, the above active energy ray-curable resin composition containing a photopolymerization initiator is used.

Further, the aforementioned active energy ray-curable resin composition containing a coloring pigment.

Further, the active energy ray-curable resin composition belonging to the molding material is further described.

Further, the active energy ray-curable resin composition which is a material for forming a film is used.

Further, the active energy ray-curable resin composition belonging to the composition of the resist material is further described.

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

Further, the article coated with the cured product of the active energy ray-curable resin composition described above.

By using the epoxy carboxylic acid ester (A) and/or the polyvalent carboxylic acid compound (B) of the present invention, an active energy ray-curable resin composition having the following characteristics can be obtained: excellent light sensitivity and good developability. The cured product obtained from the resin composition is excellent in various properties such as curability and dielectric properties, and further has excellent electrical reliability under high temperature and high humidity. Therefore, the resin composition of the present invention is suitable for a material for molding, a material for forming a film, and a material for a resist. Especially in terms of reliability under high temperature and high humidity, it can be used It is used for solder resists for printed wiring boards, interlayer insulating materials for multilayer printed wiring boards, solder resists for flexible printed wiring boards, plating resists, and photosensitive optical waveguides.

The reactive epoxy carboxylate compound (A) of the present invention is an epoxy resin (a) represented by the following formula (1) and a compound having a polymerizable ethylenically unsaturated group and a carboxyl group in the molecule. (b) and, if necessary, a compound (c) having both a hydroxyl group and a carboxyl group in one molecule.

In other words, the ethylenically unsaturated group and the hydroxyl group are introduced into the molecular chain of the epoxy carboxylic acid ester compound at an arbitrary ratio to exhibit the characteristics of the present invention.

(wherein R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and a represents 1 to 3, respectively. The number of n-type repeats is 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 formula (1).

The hydrocarbon group having 1 to 3 carbon atoms in the formula may, for example, be a methyl group, an ethyl group, a propyl group or an isopropyl group.

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

The softening point (ring and ball method) of the epoxy resin (a) used is preferably from 50 to 150 ° C, more preferably from 52 to 100 ° C, and particularly preferably from 52 to 95 ° C. When the temperature is below 50 ° C, the adhesion is severe, the operation is difficult, and there is a problem in productivity. Moreover, when it is 150 ° C or more, it is not close to the molding temperature, and fluidity at the time of molding cannot be ensured, which is not preferable.

Moreover, the melting viscosity of the epoxy resin (a) at 150 ° C is 0.05 to 5 Pa. s is better, especially good for 0.05 to 2.0Pa. s. When the viscosity is high, there is a problem in fluidity, and there is a problem in fluidity or embedding at the time of pressing. Less than 0.05Pa. When s, the molecular weight is too small, so there is a lack of heat resistance.

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

The epoxy carboxylic acid ester compound (A) and the polyvalent carboxylic acid compound (B) using the epoxy resin (a) have a total chlorine content of 50% or less, so that electrical properties under high temperature and high humidity can be greatly improved. Metal corrosion.

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 a method of oxidizing with a peracid such as peracetic acid, a method of oxidizing with hydrogen peroxide water, a method of oxidizing with air (oxygen), or a method of oxidizing with a peroxycarboxylic acid, but the like. Not limited to this.

The method of epoxidation by peracid is specifically exemplified by, for example, Japan. The method described in JP-A-2006-52187 and the like.

In the epoxidation method by the hydrogen peroxide water, various methods can be applied, but in particular, for example, JP-A-59-108793, JP-A-62-234550, and JP-A-5 Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. 2011-079794, Japanese Laid-Open Patent Publication No. 2011-084558, JP-A-2010-083836, and JP-A-2010-095521.

(wherein R ₁ and R ₂ each independently represent a hydrogen atom and a hydrocarbon group having 1 to 3 carbon atoms, and a represents 1 to 3, respectively. n represents an average of the number of repetitions of 1 to 10)

The allyl ether resin can be produced by a known production method, but is not particularly limited. For example, the corresponding phenol resin and the allyl halide or the methallyl halide are in a solvent, and the alkali is used. It exists in the presence of a reaction.

a compound (b) having more than one polymerizable ethylenically unsaturated group and one or more carboxyl groups in the molecule used in the present invention It is used to impart reactivity to the active energy ray. Such a compound may, for example, be a monocarboxylic acid compound or a polyvalent carboxylic acid compound.

The monocarboxylic acid compound may, for example, be a reaction product of (meth)acrylic acid or crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a saturated or unsaturated diprotonic acid and a monoglycidyl compound containing an unsaturated group. . The above-mentioned acrylic acid may, for example, be (meth)acrylic acid, β-styrylacrylic acid, β-furan methacrylic acid, (meth)acrylic acid dimer, saturated or unsaturated diprotonic anhydride, and in one molecule. Mohr reaction of a half ester of a molar reactant, a saturated or unsaturated diprotonic acid, and a monoglycidyl (meth)acrylate derivative having a hydroxyl group (meth) acrylate derivative Semi-esters of the substance.

The polycarboxylic acid compound may, for example, be a half ester of a molar reactant, a saturated or unsaturated diprotonic acid, and a plurality of epoxys with a (meth) acrylate derivative having a plurality of hydroxyl groups in one molecule. A half ester of a molar reaction of a glycidyl (meth)acrylate derivative or the like.

Among these, the point of sensitivity of the active energy ray-curable resin composition is, for example, a reaction product of (meth)acrylic acid, (meth)acrylic acid, and ε-caprolactone, or Cinnamon acid. The compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule is preferably one having no hydroxyl group in the compound.

The compound (c) having one or more hydroxyl groups and one or more carboxyl groups in one molecule used in the present invention is intended for the purpose of introducing a hydroxyl group into a carboxylate compound. These are: in one molecule A compound having both a hydroxyl group and a carboxyl group, a compound having two or more hydroxyl groups and one carboxyl group in one molecule, and a compound having one or more hydroxyl groups and two or more carboxyl groups in one molecule.

The compound (c) having both a hydroxyl group and a carboxyl group in one molecule may, for example, be hydroxypropionic acid, hydroxybutyric acid or hydroxystearic acid. The compound (c) having two or more hydroxyl groups and one carboxyl group in one molecule may, for example, be dimethylol acetic acid, dimethylolpropionic acid or dimethylolbutanoic acid. A compound having one or more hydroxyl groups and two or more carboxyl groups in one molecule may, for example, be hydroxydecanoic acid.

Among these, in view of the effects of the present invention, it is preferred that the hydroxy group contain two or more members in one molecule. Further, in consideration of the stability of the carboxylic acid esterification reaction, it is preferred that the carboxyl group be one in one molecule. The best one has two hydroxyl groups and one carboxyl group in one molecule. Dimethylolpropionic acid and dimethylolbutanoic acid are particularly suitable for the consideration of raw materials. The compound (c) having one or more hydroxyl groups and one or more carboxyl groups in one molecule is preferably one which does not have a polymerizable ethylenically unsaturated group in the compound.

Among these, in consideration of the reaction stability of the epoxy resin (a) and the compound (b) and/or the compound (c), the compound (b) and/or the carboxyl group of the compound (c) Preferably, one is preferred, and a monocarboxylic acid is preferred. When a monocarboxylic acid and a polycarboxylic acid are used together, the total mole amount of the monocarboxylic acid/the total molar amount of the polycarboxylic acid is 15 or more. good.

The loading ratio of the epoxy resin (a) in the reaction to the carboxylic acid of the above compound (b) and/or the aforementioned compound (c) may be used according to the use. And change it as appropriate. When the epoxy group of all the epoxy groups of the epoxy resin (a) is carboxylated, since the unreacted epoxy group does not remain, the storage stability of the reactive carboxylate compound (A) is high. When there is no unreacted epoxy group, the reactivity of the reactive carboxylate compound (A) depends on the introduced double bond.

On the other hand, the reaction of the introduced double bond can be carried out by reducing the amount of the carboxylic acid compound of the compound (b) and/or the compound (c), and leaving the unreacted residual epoxy group. The reactivity of the unreacted epoxy group and the unreacted epoxy group are utilized in combination, for example, by a polymerization reaction or a thermal polymerization reaction by a photocationic catalyst (complex hardening). However, in this case, it is necessary to pay attention to the study on the preservation and production conditions of the reactive carboxylic acid ester compound (A).

When the reactive carboxylic acid ester compound (A) having no unreacted epoxy group is produced, the compound (b) or the compound (b) and the compound (b) which are sufficiently reacted with the epoxy group of the epoxy resin (a) are used. The above compound (c) may be used. In the present invention, the total amount of the above compound (b) and/or the aforementioned compound (c) is preferably from 90 to 120 equivalent% based on 1 equivalent of the epoxy resin (a). If it is this range, it can be manufactured under relatively stable conditions. On the other hand, when the loading amount of the carboxylic acid compound is large, there is a possibility that the excess carboxylic acid compound (b) or (b) and (c) remain, which is not preferable.

Further, when the reactive carboxylic acid ester compound (A) having an unreacted epoxy group is produced, the compound (b) or the compound (b) and the aforementioned compound (b) having the epoxy group residual amount of the epoxy resin (a) are used. Compound (c) is sufficient. In the present invention, the total amount of the above compound (b) or (b) and (c) is preferably 20 to 90 equivalent% based on 1 equivalent of the epoxy resin (a). When the loading amount of the carboxylic acid compound is too small, the efficiency of the composite hardening becomes low. At this time, it must be fully retained. The gelation in the reaction or the stability over time of the reactive carboxylate compound (A).

When the reactive carboxylic acid ester compound (A) is produced, the compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups and a compound having one or more hydroxyl groups and one or more carboxyl groups ( c) The use ratio is in the molar ratio with respect to the carboxyl group (b): (c) is from 9:1 to 1:9, and further preferably in the range of from 4:6 to 8:2. If it is in this range, the sensitivity of the compound (b) is too small to be lowered, and the effect of (c) when the compound (c) is too small can be prevented from becoming thin. In the carboxylic acid esterification reaction (hereinafter referred to as "the present carboxylic acid esterification reaction") in the present invention, the order of loading of (b) and (c) is not particularly limited.

The carboxylic acid esterification reaction system does not require a solvent, but may be reacted by dilution with a solvent. The solvent which can be used here is the same as the solvent used for the synthesis of the above-mentioned epoxy resin (a), and is not particularly limited as long as it does not exhibit a reaction for the esterification reaction of the present carboxylic acid. The amount of the solvent to be used may be appropriately adjusted depending on the viscosity and use of the obtained resin, but is preferably from 30 to 90% by weight, more preferably from 50 to 80% by weight based on the total amount of the reactants.

Examples of the solvent to be used include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane, and decane; and petroleum ethers of such mixtures; , white gasoline, solvent oil, etc. Further, examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate; cyclic esters such as γ-butyrolactone; ethylene glycol monomethyl ether acetate; and diethyl ether. Glycol monomethyl ether monoacetate, Diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, dibutyl Mono- or polyalkylene glycol monoalkyl ether monoacetate such as alcohol monomethyl ether acetate; polyalkyl carboxylate such as dialkyl glutarate, dialkyl succinate or dialkyl adipate Esters and the like. Further, examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol. a glycol ether such as diethyl ether, triethylene glycol dimethyl ether or triethylene glycol diethyl ether; or a cyclic ether such as tetrahydrofuran. Further, examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

Others may be carried out in a separate or mixed organic solvent such as the reactive carboxylic acid ester compound (A) or the reactive polyvalent carboxylic acid compound (B). In this case, when it is used as a curable resin composition, it can be used as a composition as it is, and it is preferable.

In the reaction, in order to promote the reaction, it is preferred to use a catalyst, and the epoxy resin (a), the compound (b), and/or the compound (c), and optionally the solvent, may be added to the reactant. The catalyst is used in an amount of from 0.1 to 10% by weight based on the total amount of the reactants. The reaction temperature at this time is 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst which can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethyl iodide. Ammonium, triphenylphosphine, triphenylstibine, methyltriphenylphosphonium, chromium octoate, zirconium octylate, etc., are generally known as basic catalysts.

Further, the thermal polymerization inhibitor is preferably hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenyl bitteramine, diphenylamine, 3,5-di-tert-butyl-4hydroxytoluene, and the like.

In the present reaction, the acid value of the sample is set to be 5 mgKOH/g or less, preferably 2 mgKOH/g or less, as the end point.

The preferred molecular weight range of the reactive carboxylic acid ester compound (A) of the present invention obtained in this manner is a polystyrene-equivalent weight average molecular weight (Mw) in the GPC measurement of from 1,000 to 30,000, more preferably from 1,500 to 20,000.

When the molecular weight is less than this molecular weight, the toughness of the cured product cannot be sufficiently exhibited, and when it is larger than this, the viscosity becomes high and coating is difficult.

The reactive carboxylic acid ester compound (A) of the present invention contains a structure represented by the following formula (3), but is not limited thereto.

(Wherein, R _{1, 1,} R _2, and R ₂ and the same system with a formula (R 1) in the a)

Next, the reactive polycarboxylic acidification of the present invention will be described. Compound (B).

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

In the following, the acid addition step will be described in detail. The acid addition step is carried out by introducing a carboxyl group as needed in the reactive carboxylic acid ester compound (A) obtained in the previous step to obtain a reactive polyvalent carboxylic acid (B). The reason why the carboxyl group is introduced is introduced for the purpose of imparting solubility to alkali water to the non-irradiated portion of the active energy ray, and imparting adhesion to metals, inorganic substances, and the like, for example, in the use of the resist patterning. Specifically, the polyprotonic acid anhydride (d) is subjected to an addition reaction by a hydroxyl group generated by a carboxylic acid esterification reaction, and a carboxyl group is introduced via an ester bond.

The reaction of adding the polyprotic anhydride (d) can be carried out by adding the polyprotic anhydride (d) to the above-mentioned carboxylic acid esterification reaction liquid. The amount of addition can be appropriately changed depending on the use.

The multi-protonic acid anhydride (d) which can be used, for example, can be used as long as it is a compound having an acid anhydride structure in one molecule, but is excellent in succinic anhydride or phthalic anhydride which is excellent in alkali developability, heat resistance, hydrolysis resistance and the like. Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride are particularly preferred.

When the polycarboxylic acid compound (B) of the present invention is used as a resist for an alkali developing type, it is preferably a solid acid value of the finally obtained reactive polycarboxylic acid compound (B) (according to JIS K5601-2-1) :1999) is calculated as a value of 30 to 120 mg ‧ KOH / g and charged with polyprotonic anhydride (d), more preferably 40 Up to 105 mg ‧ KOH / g. When the solid content acid value at this time is in this range, the alkali aqueous solution developability of the active energy ray-curable resin composition of the present invention is shown to be good developability. That is, the alkali water-soluble developability is good, which means good patterning property and a wide management range for over-development, and no excessive acid anhydride remains.

In order to promote the reaction during the reaction, it is preferred to use a catalyst, and the carboxylate compound (A) obtained from the reactant, that is, the epoxy compound (a), the compound (b) and/or the compound (c). And the polyprotonic anhydride (d), if necessary, the total amount of other reactants added, the catalyst is used in an amount of 0.1 to 10% by weight. The reaction temperature at this time is 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst which can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethyl iodide. Ammonium, triphenylphosphine, triphenylsulfonium, methyltriphenylphosphonium, chromium octoate, zirconium octoate, and the like.

The acid addition reaction can be carried out in the absence of a solvent or by diluting with a solvent. The solvent which can be used herein can be the same as the solvent used in the synthesis of the above epoxy resin (a) and in the esterification reaction of the carboxylic acid, as long as it is a solvent which does not exhibit a reaction for the acid addition reaction, and Specially limited. Further, when a solvent is used in the carboxylic acid esterification reaction belonging to the previous step, the reaction may not be shown as a condition, and the solvent may be directly supplied to the acid addition reaction belonging to the second step without removing the solvent.

The amount of the solvent to be used may be appropriately adjusted depending on the viscosity and use of the obtained resin, and is preferably from 90 to 30% by weight, more preferably from 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 petroleum ethers of such mixtures; , white oil, solvent oil, etc.

Further, examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate; cyclic esters such as γ-butyrolactone; ethylene glycol monomethyl ether acetate; and diethyl ether. Glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, Mono- or polyalkylene glycol monoalkyl ether monoacetate such as propylene glycol monomethyl ether acetate or butanediol monomethyl ether acetate; dialkyl glutarate, dialkyl succinate, A polyvalent alkyl carboxylate such as a dialkyl adipate.

Further, examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol. a glycol ether such as diethyl ether, triethylene glycol dimethyl ether or triethylene glycol diethyl ether; or a cyclic ether such as tetrahydrofuran.

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

Others may be carried out in a separate or mixed organic solvent such as the reactive compound (C) described later. In this case, when it is used as a hardening type composition, it can be used as a composition as it is, and it is preferable.

Further, a thermal polymerization inhibitor or the like is preferably used in the same manner as in the above-described carboxylic acid esterification reaction.

The reaction is appropriately sampled while taking the acid value of the reactant The time point in the range of plus or minus 10% of the acid value set is used as the end point.

The polyvalent carboxylic acid compound (B) of the present invention contains a compound represented by the following formula (4) as a structural example, but is not limited thereto.

(Wherein the R _{1, 1,} R _2, and R ₂ and the same system with a formula (R 1) in the 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 has a reactive carboxylate compound (A) and/or a reactive polycarboxylic acid compound (B) in the composition of 5 to 97% by weight, preferably 10 to 87. weight%.

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 use.

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

The reactive compound (C) which can be used in the present invention is preferably a reactive epoxy carboxylate compound (A) or a reactive polycarboxylic acid compound (B). Specific examples include so-called reactive oligomers such as a radical reaction type acrylate, a cationic reaction type other epoxy compound, and a vinyl compound which is induced to both.

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

Examples of the monofunctional (meth) acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, and polyethylene glycol ( Methyl) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, phenyl ethyl (meth) acrylate, isodecyl (meth) acrylate, cyclohexyl (meth) acrylate, ( Methyl methacrylate, tetrahydrofuran methyl (meth)acrylate, and the like.

Examples of the polyfunctional (meth) acrylate include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and decanediol. Di(meth) acrylate, glycol di(meth) acrylate, diethylene di(meth) acrylate, polyethylene glycol di(meth) acrylate, ginseng (meth) propylene oxy group B Trimeric isocyanate, polypropylene glycol di(meth)acrylate, adipic acid di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide (meth) acrylate, bisphenol di(meth) acrylate, hydroxytrimethyl acetic acid a poly(meth) acrylate of a ε-caprolactone adduct of a diol, a poly(meth) acrylate of dipentaerythritol and ε-caprolactone, and a neopentyl alcohol poly( Methyl)acrylate, trimethylolpropane tri(meth)acrylate, trishydroxyethylpropane tri(meth)acrylate, and its ethylene oxide adduct, pentaerythritol tris(methyl) An acrylate, an ethylene oxide adduct thereof, neopentyl alcohol tetra(meth) acrylate, dipentaerythritol hexa(meth) acrylate, an ethylene oxide adduct thereof, and the like.

Examples of the vinyl compound 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 styrenes include styrene, methylstyrene, and ethylstyrene. Examples of the other vinyl compound include triallyl tripolyisocyanate and trimethylallyl trimer isocyanate.

Further, the reactive oligomers may, for example, be urethane acrylates having both an active energy ray-functional functional group and a urethane bond in the same molecule, and in the same molecule. A polyester acrylate having a functional group and an ester bond functionally functionalized with an active energy ray, an epoxy acrylate derived from another epoxy resin and having an active energy ray functional functional group in the same molecule, These bonds are reactive oligomers and the like which are used in combination.

Further, the cationically reactive 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-epoxy group Cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Cyracure UVR-6110, manufactured by Union Carbide Co., Ltd.), 3,4-epoxycyclohexylethyl-3,4-epoxy Cyclohexane carboxylate, vinyl cyclohexene dioxide ("ELR-4206" manufactured by Union Carbide Co., Ltd.), limonene dioxide ("Celoxide 3000" manufactured by Daicel Chemical Co., Ltd.), allyl ring Hexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propene oxide, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4- Epoxy group) cyclohexane-m-two Alkane, bis(3,4-epoxycyclohexyl) adipate (Cyracure UVR-6128, manufactured by Union Carbide Co., Ltd.), bis(3,4-epoxycyclohexylmethyl) adipate , bis(3,4-epoxycyclohexyl)ether, bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexyl)diethyloxane, etc. .

Among these, the reactive compound (C) is preferably an acrylate having a radical curing type. In the case of a cationic type, since the carboxylic acid reacts with the epoxy group, it must be a two-liquid mixing type.

The active energy ray-curable resin composition of the present invention contains the reactive carboxylic acid ester compound (A) and/or the reactive polycarboxylic acid compound (B) in the composition of 5 to 97% by weight, preferably 10 to 87. The weight %, the reactive compound (C) other than (A) and (B) is 3 to 95% by weight, more preferably 3 to 90% by weight. Other components may be contained as an upper limit of about 70% by weight as needed.

The reactive carboxylic acid ester compound (A) and/or the reactive polyvalent carboxylic acid compound (B) of the present invention can be suitably used separately depending on the use of the active energy ray-curable resin composition of the present invention. For example, even if it is the same as the solder resist, it is not developed, and when the pattern is formed by printing, or by solvent, etc. The solvent-developing type in which the unreacted portion flows is a carboxylate compound (A), and the reactive polycarboxylic acid compound (B) is used for development by alkali water. In general, an alkaline water developing type is easy to produce a fine pattern, and therefore, a reactive polycarboxylic acid compound (B) is often used in this application. Of course, it can also be used in any combination according to the use/performance of requirements (A) and (B).

The active energy ray-curable resin composition of the present invention is easily cured by an active energy ray. Here, specific examples of the active energy ray include ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, electromagnetic waves such as laser rays, particle lines such as α rays, β rays, and electron beams. In view of the suitable use of the present invention, among these, ultraviolet rays, laser rays, visible rays, or electron beams are preferred.

The coloring pigment which can be used in the present invention is used to make the active energy ray resin composition of the present invention as a coloring material. Since the reactive carboxylic acid ester compound (A) and the reactive polyvalent carboxylic acid compound (B) of the present invention have excellent affinity for a pigment, that is, have dispersibility, they can be dispersed well and have a rich pigment concentration. Further, since the composition to be developed is dispersed in a more suitable state, it is excellent in patterning properties, and the development residue in the developing and dissolving portion is also small, which is preferable.

Examples of the coloring pigment include inorganic pigments such as phthalocyanine, azo, and quinacrid, inorganic pigments such as carbon black, and titanium oxide. Among these, carbon black is highly dispersible and is optimal.

The material for molding in the present invention refers to a material in which an uncured composition is placed in a mold or a mold is pressed to form an object, and a hardening reaction is caused by an active energy ray to cause formation, or an unhardened composition is irradiated with a ray. A material used for the purpose of causing a hardening reaction and forming it, such as focusing light.

For the specific use, for example, a sheet formed into a flat shape, a sealing material for protecting the element, and a micro-molded nano-substrate by pressing the micro-machined "die" on the uncured composition may be mentioned. The embossing material is further provided as a peripheral sealing material such as a light-emitting diode or a photoelectric conversion element which is particularly required to be heat-sensitive.

In the present invention, the material for forming a film is used for the purpose of covering the surface of the substrate. The specific uses are ink printing materials such as gravure ink, flexographic ink, screen printing ink, lithographic ink, etc.; coating materials such as hard coating, top coating, overprint varnish, transparent coating, etc.; The optical disc is made of other various adhesives, pressure-sensitive adhesives, and the like; solder resists, etching resists, and resists for micromachines are suitable. Further, after the film forming material is temporarily applied to the release substrate and film-formed, it is bonded to the original target substrate to form a film, and the dry film also conforms to the film forming material.

The carboxyl group of the reactive polycarboxylic acid compound (B) improves the adhesion to the substrate. Further, since the reactive polycarboxylic acid compound (B) is soluble in an aqueous alkali solution, the composition of the present invention containing the reactive polycarboxylic acid compound (B) is used as an alkali water for coating a plastic substrate or a metal substrate. The composition of the resist material is also good.

In the present invention, the composition of the resist material refers to a film layer on which a composition is formed on a substrate, and then partially irradiates an active energy ray such as an ultraviolet ray, and is characterized by a difference in physical properties between the illuminating portion and the unirradiated portion. Active energy line sensing type composition. Specifically, the illuminating unit or the unirradiated portion is removed by some methods, for example, by a solvent or the like, an alkali solution, or the like, and the composition used for the purpose of drawing is drawn.

The active energy ray-curable resin composition for a resist of the present invention can be applied to various materials which can be patterned, for example, an interlayer insulating material which is particularly useful for a solder resist material, a buildup method, and further It can be used as an optical waveguide for an electrical/electronic/optical substrate such as a printed wiring board, an optoelectronic substrate, or an optical substrate.

Particularly suitable for use is to obtain the characteristics of tough and hardened materials, the use of permanent resists such as solder resists, the use of pigments with good dispersibility, printing of color resists such as inks and color filters, especially for black matrix. Agent.

The active energy ray-curable resin composition of the present invention is also used for a dry film application requiring mechanical strength before a hardening reaction by an energy ray. 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, although the reactive carboxylate compound (A) of the present invention has a relatively high molecular weight, Play a good developability.

The method of forming the film is not particularly limited, but may be arbitrarily used: a gravure printing method such as a gravure, a letterpress printing method such as flexography, a stencil printing method such as a screen, a lithographic printing method such as a lithography, a roll coater, a knife coater, Various coating methods such as a die coater, a curtain coater, and a spin coater.

The active energy ray-curable resin composition of the present invention The cured product refers to an active energy ray-curable resin composition of the present invention which is irradiated with an active energy ray and hardened.

In addition, the active energy ray-curable resin composition of the present invention is suitable for various purposes, and other components may be added to the resin composition at an upper limit of 70% by mass. Other components include, for example, a photopolymerization initiator, other additives, a coloring material, a volatile solvent added for viscosity adjustment, and the like for imparting coating suitability. The other ingredients that can be used are exemplified below.

The radical photopolymerization initiator may, for example, be a benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether or benzoin isobutyl ether; Acetophenone, 2,2-diethoxy-2-phenylethylbenzene, 2,2-diethoxy-2-phenylethylbenzene, 1,1-dichloroethylbenzene, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyethyl benzene, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio) Ethyl benzene such as phenyl]-2-morpholinyl-propan-1-one; 2-ethyl hydrazine, 2-tert-butyl fluorene, 2-chloroindole, 2-amino hydrazine, etc. Terpenes; thiaoxalinones such as 2,4-diethylthianone, 2-isopropylthioxanthone, 2-chlorothiazolone; acetophenone ketal, benzene Ketals such as methyl dimethyl ketal; benzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 4,4'-bismethylaminodiphenyl Benzophenones such as ketone; 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, etc. A well-known general radical type photoreaction initiator such as phosphorus oxide.

Further, the cationic photopolymerization initiator may, for example, be a diazonium salt of Lewis acid, a strontium salt of Lewis acid, a strontium salt of Lewis acid, a strontium salt of Lewis acid, other halides, or the like. An initiator, a borate initiator, and other photoacid generators.

The diazonium salt of Lewis acid may, for example, be p-methoxyphenyldiazonium fluorophosphate or N,N-diethylaminophenyldiazonium hexafluorophosphate (San-Aid, Sanshin Chemical Industry Co., Ltd.) For example, SI-60L/SI-80L/SI-100L, etc., and the Lewis acid salt may be, for example, diphenylphosphonium hexafluorophosphate or diphenylphosphonium hexafluoroantimonate. Examples of the salt system include triphenylsulfonium hexafluorophosphate (Cyracure UVI-6990 manufactured by Union Carbide Co., Ltd.), triphenylsulfonium hexafluoroantimonate (Cyracure UVI-6974 manufactured by Union Carbide Co., Ltd.), and the like, and Lewis acid. Examples of the sulfonium salt include triphenylsulfonium hexafluoroantimonate.

Other halides include, for example, 2,2,2-trichloro-[1-4'-(dimethylethyl)phenyl]ethanone (Trigonal PI, manufactured by AKZO Co., Ltd.), 2,2-dichloro -1-4-(phenoxyphenyl)ethanone (Sandray 1000, manufactured by Sandoz Co., Ltd.), α, α, α-tribromomethylphenyl hydrazine (BMPS, manufactured by Seiko Chemical Co., Ltd.), and the like. three The initiator is 2,4,6-gin (trichloromethyl)-three 2,4-trichloromethyl-(4'-methoxyphenyl)-6-three (Triazine A, manufactured by Panchim, etc.), 2,4-trichloromethyl-(4'-methoxystyryl)-6-three (Triazine PMS made by Panchim, etc.), 2,4-trichloromethyl-(piperidinyl)-6-three (Triazine PP manufactured by Panchim Co., Ltd.), 2,4-trichloromethyl-(4'-methoxynaphthyl)-6-three (Triazine B, manufactured by Panchim, etc.), 2[2'(5"-methylfuranyl)ethylidene]-4,6-bis(trichloromethyl)-s-three (made by Sanwa Chemical Co., Ltd.), 2(2'-furylethylidene)-4,6-bis(trichloromethyl)-s-three (Sanhe Chemical Co., Ltd.) and so on.

Examples of the borate-based initiators include NK-3876 and NK-3881, which are made of Japanese photosensitive pigments, and other photoacid generators, such as 9-phenyl acridine and 2,2'-bis(o-chlorobenzene). , 4,4',5,5'-tetraphenyl-1,2-biimidazole (biimidazole, etc., manufactured by Heijin Chemical Co., Ltd.), 2,2-azobis(2-amino-propane) di-salt Acid salt (V50, etc., manufactured by Wako Pure Chemical Co., Ltd.), 2,2-azobis[2-(imidazolin-2-yl)propane] dihydrochloride (VA044, etc., manufactured by Wako Pure Chemical Industries, Ltd.), [η-5- 2-4-(cyclopentadecyl)(1,2,3,4,5,6,η)-(methylethyl)-benzene]iron(II) hexafluorophosphate (Irgacure 261, manufactured by Ciba Geigy Co., Ltd.) Et.), bis(y5-cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyridin-1-yl)phenyl]titanium (CGI-784, manufactured by Ciba Geigy Co., Ltd.) and the like.

Further, a peroxide-based radical initiator such as an azo-based initiator such as azobisisobutyronitrile or a benzoyl peroxide group may be used in combination. Further, an initiator of both a radical type and a cationic type may be used in combination. The initiator may be used singly or in combination of two or more.

As other additives, for example, a thermal curing catalyst such as melamine, a shake imparting agent such as Aerosil, a polyfluorene-based, a fluorine-based leveling agent or an antifoaming agent, a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether, or the like may be used. Stabilizers, antioxidants, etc.

Further, other pigment materials may be, for example, so-called body pigments which are not intended for coloring. For example, talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, cerium oxide, clay, and the like.

Others, resins which do not exhibit reactivity to the active energy ray (so-called inert polymers), such as other epoxy resins, phenol resins, urethane resins, polyester resins, ketone-formaldehyde resins, cresol resins, may also be used. ,two Toluene resin, diallyl phthalate resin, styrene resin, guanamine resin, natural and synthetic rubber, acrylic resin, polyolefin resin, and the like. These are preferably used in the range of up to 40% by mass in the resin composition.

In particular, when the reactive polycarboxylic acid compound (B) is used in the use of a solder resist, it is preferred to use a known general epoxy resin as a resin which does not exhibit reactivity to the active energy ray. When the reaction is carried out and hardened by the active energy ray, the carboxyl group derived from the compound (B) remains, and as a result, the cured product is inferior in water resistance or hydrolysis property. An epoxy resin is used to further carboxylate the remaining carboxyl groups to further form a strong crosslinked structure.

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

[Examples]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples. Further, in the examples, "parts" means parts by weight unless otherwise specified.

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

1) Epoxy equivalent: determined according to the method of JIS K 7236:2001.

2) Softening point: determined according to the method of JIS K 7234:1986

3) Acid value: determined according to the method of JIS K 0070:1992

4) The measurement conditions of GPC are as follows.

Model: TOSOH HLC-8220GPC

Column: TSKGEL Super HZM-N

Lysate: THF (tetrahydrofuran); 0.35 ml per minute. 40 ° C

Detector: differential refractometer

Molecular weight standard: polystyrene

5) Total chlorine content: The resin is burned and measured by ion chromatography (machine, measurement conditions) after adsorption of gas pure water.

(Synthesis Example 1)

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 25 parts by mass of water, 500 parts by mass of dimethyl hydrazine, and a phenol resin (phenol-biphenylene type hydroxyl equivalent) are added while applying nitrogen purge. 200 g/eq. softening point 65 ° C) 500 parts by mass, and the temperature was raised to 45 ° C to dissolve. Then, it was cooled to 38 to 40 ° C, and it was directly added for 16 minutes to add 130.0 parts by mass of a caustic soda (purity of 99% Tosoh) (1.3 molar equivalents based on the hydroxyl group equivalent of the phenol resin). Thereafter, 294.3 parts by mass of methyl methacrylate (purity: 99% by Tokyo Chemical Industry Co., Ltd.) was added dropwise for 60 minutes (1.3 molar equivalents per 1 hydroxy equivalent of the phenol resin), directly from 38 to 40. The reaction was carried out at ° C for 5 hours and at 60 to 65 ° C for 1 hour.

After completion of the reaction, water, dimethyl hydrazine, and the like were distilled off using a rotary evaporator at 125 ° C or lower under heating and reduced pressure. Then, 740 parts by mass of methyl isobutyl ketone was added, and the water washing was repeated to confirm that the aqueous layer became neutral. Then, the solvent was distilled off from the oil layer using a rotary evaporator under reduced pressure while purging with nitrogen to obtain a methyl allyl ether resin of the above formula (2) of n = 2.0 (hereinafter referred to as "MEP") 600 parts by mass.

(Synthesis Example 2)

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 1000 parts by mass of an ethyl acetate solution (concentration of MEP: 50% by mass) of MEP obtained in Synthesis Example 1 was charged while applying nitrogen gas to degas. In a molar amount of 0.04 mol parts of potassium tungstate as a tungstic acid compound and 0.06 mol parts of potassium phosphate as a phosphoric acid compound, per 100 parts by mass of the MEP, and then as an organic carboxylic acid per 100 parts by mass of the MEP. 60.0 parts by mass of acetic acid, and the mixture was heated to 50 °C. After the temperature was raised, while stirring, it took 20 minutes to add a 35% aqueous hydrogen peroxide solution with respect to the methylallyl 1 molar equivalent in the MEP and hydrogen peroxide to 2 molar equivalents. After the end of the addition, the mixture was stirred at 50 ° C for 24 hours.

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

(Example 1): Synthesis of Reactive Carboxylic Acid Compound (A)

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 274 g of an epoxy resin (a1) obtained in Synthesis Example 2 as an epoxy resin (a) was added as a compound (b). The acrylic acid (abbreviated as AA, Mw=72) is used as the amount described in Table 1 as the dimethanol propionic acid (abbreviated as DMPA, Mw=134) of the compound (c), as the amount described in Table 1, 3 g of triphenylphosphine as a catalyst, propylene glycol monomethyl ether monoacetate as a solvent, and the reaction is carried out at 100 ° C for 24 hours in an amount of 80% to obtain a reactive epoxy carboxylate compound of the present invention. (A1) solution. The perchlorinated fraction of the obtained reactive epoxy carboxylate compound (A1) solution is 10 ppm or less. The weight average molecular weight is 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 was measured by a reaction solution and converted into an acid value as a solid content.

(Comparative Example 1): Synthesis of Reactive Carboxylic Acid Compounds

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, a phenol-biphenol novolak type epoxy resin (the Nippon Chemical Co., Ltd. NC-3000H) was added as an epoxy resin (a) while nitrogen gas was degassed. , a softening point of 70 ° C, an epoxy equivalent of 288 g / eq, a total chlorine content of 500 ppm) of 288 g, and the acrylic acid (abbreviated as AA, Mw = 72) as the compound (b) in the amount shown in Table 1, as the compound (c) The methacrylic acid (abbreviated as DMPA, Mw=134) is in the amount shown in Table 1, 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent to make the solid content 80%. The amount was reacted at 100 ° C for 24 hours to obtain 452 g of a comparative carboxylate compound (A2). The weight average molecular weight is 1400.

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

(Example 2): Synthesis of Reactive Polycarboxylic Acid Compound (B)

In 434 g of the reactive carboxylic acid ester compound (A1) solution obtained in Example 1, tetrahydrofurfuric anhydride (referred to as THPA) as the polyprotonic acid anhydride (d) was added in an amount described in Table 2, and a propylene glycol monomer as a solvent was added. Methyl ether monoacetate was heated to 100 ° C in an amount of 65 wt%, and an acid addition reaction was carried out to obtain a reactive polycarboxylic acid compound (B1) solution of the present invention. The perchlorinated fraction of the obtained reactive polycarboxylic acid compound (B1) solution is 10 ppm or less.

(Comparative Example 2): Synthesis of Reactive Polycarboxylic Acid Compounds

In 452 g of the reactive carboxylic acid ester compound (A2) solution obtained in Comparative Example 1, tetrahydrophthalic anhydride (referred to as THPA) as the polyprotonic acid anhydride (d) was added in the amounts described in Table 2, and propylene glycol as a solvent. Monomethyl ether monoacetate was heated to 100 ° C in an amount of 65 wt%, and an acid addition reaction was carried out to obtain a reactive polycarboxylic acid compound (B2) solution. The perchlorinated fraction of the obtained reactive polycarboxylic acid compound solution was 300 ppm.

(Example 3, Comparative Example 3): Modulation 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: Nippon Kayaku Co., Ltd.) as another reactive compound (C) Acrylate monomer: 5.67 g, Irgacure 907 (manufactured by BASF) 2.92 g as a photopolymerization initiator, and 0.58 g of Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.), NC-3000H as a hardening component (Nipponization) 17.54 g of a pharmaceutical product, 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 kneaded by a particle mill to uniformly disperse to obtain a resin composition.

(Example 4, Comparative Example 4)

The resin compositions obtained in Example 3 and Comparative Example 3 were uniformly applied to a polyethylene terephthalate film to be a support film using a wire bar coater #20, and passed through a hot air drying oven at a temperature of 70 ° C. After forming a resin layer having a thickness of 20 μm, a polyethylene film to be a protective film was attached to the resin layer to obtain a dry film. The resulting dry film is printed on a polyimide substrate (copper circuit thickness: 12 μm, polyimide film thickness: 25 μm), using a heating roller at a temperature of 80 ° C, the resin layer was attached to the entire substrate while peeling off the protective film.

Then, ultraviolet rays of 500 mJ/cm ^{2 were} irradiated by Kodak Step Tablet No. 2 in order to estimate the mask and sensitivity drawn by the circuit pattern using an ultraviolet exposure apparatus (manufactured by ORK Co., Ltd., model HMW-680GW). Thereafter, the film on the dry film was peeled off, and the peeled state was confirmed. Thereafter, the film was spray-developed with a 1% sodium carbonate aqueous solution to remove the resin in the ultraviolet non-irradiated portion. After washing with water, the printed substrate was subjected to a heat curing reaction at 150 ° C for 60 minutes to obtain a cured film. With respect to the obtained cured film, sensitivity, developability, hardenability, dielectric constant, and dielectric tangent were measured in accordance with the following measurement conditions. The results are shown in Table 3.

‧ Sensitivity evaluation: The sensitivity system remains on the exposure portion penetrating the Step Tablet until the concentration portion of the first segment is determined. The larger the number of segments (value) is, the higher the sensitivity of the rich portion of the tablet (unit: segment).

‧ Development property evaluation: The developability is evaluated by the so-called Break Time as the developability (unit: second) when the exposed portion of the through-pattern mask is developed, and the time when the pattern-shaped portion is completely developed.

‧ Hardenability evaluation: The evaluation of the hardenability was expressed by the pencil hardness of the cured film after completion of heating at 150 °C. The evaluation method is based on JIS K5600-5-4:1999.

‧ Dielectric Rate Evaluation: Dielectric Tangent Evaluation: The 1 GHz cavity resonator manufactured by Kanto Electronics Application Development Co., Ltd. was tested by the cavity resonator perturbation method. However, the sample size was set to 1.7 mm in width × 100 mm in length and 1.7 mm in thickness, and the test was carried out. (Dielectric rate unit: %)

From the above results, it was confirmed that the resist composition of the present invention does not show a difference in superiority, but it is cured by an active energy ray such as ultraviolet rays, and has excellent light sensitivity and good developability, and the obtained cured product is obtained. It is excellent in various properties such as hardenability and dielectric properties.

(Example 5, Comparative Example 5)

For the reliability evaluation of temperature and humidity, the electrical characteristics under high temperature and high humidity were evaluated. The evaluation substrate (cured film) obtained in Example 4 and Comparative Example 4 was subjected to a bias voltage of 100 V DC in a high-temperature and high-humidity bath at 120 ° C and 85% RH, and the presence or absence of migration phenomenon after 100 hours and 150 hours was confirmed. .

From the above results, the cured product using the resin composition of the present invention can obtain excellent results in evaluation of electrical characteristics under high temperature and high humidity with respect to the cured product using the comparative resin composition.

The electrical reliability evaluation under high temperature and high humidity requires that the bias voltage of DC 100V is applied for only 150 hours under the environment of 120 ° C and 85% R.H. From the above, it is understood that the epoxy carboxylic acid ester compound of the present invention using the epoxy resin (a) represented by the formula (1) has the same sensitivity and development as compared with the case of using the comparative epoxy carboxylic acid ester compound. Sexuality, hardenability, and further excellent electrical reliability under high temperature and high humidity.

Claims (11)

A reactive epoxy carboxylate compound (A) obtained by copolymerizing an epoxy resin (a) represented by the following formula (1) with a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule. a compound (b) and/or a compound (c) having both a hydroxyl group and a carboxyl group in one molecule; In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and a represents 1 to 3, respectively, and the number of n-number repeats is 1 to 10. A reactive polycarboxylic acid compound (B) obtained by reacting the reactive epoxy carboxylate compound (A) described in claim 1 with a polyprotonic acid anhydride (d). An active energy ray-curable resin composition comprising the reactive epoxy carboxylate compound (A) according to claim 1 and/or the reactive polycarboxylic acid compound described in claim 2 (B). The active energy ray-curable resin composition according to claim 3, further comprising a reactive compound (C). The active energy ray-curable resin composition according to claim 3, further comprising a photopolymerization initiator. The active energy ray-curable resin composition according to any one of claims 3 to 5, which further contains a coloring pigment. The active energy ray-curable resin composition according to any one of claims 3 to 6, which is a molding material. The active energy ray-curable resin composition according to any one of claims 3 to 6, which is a material for forming a film. The active energy ray-curable resin composition according to any one of claims 3 to 6, which is a resist material composition. A cured product which is a cured product of the active energy ray-curable resin composition according to any one of claims 3 to 9. An article which is a cured product of an active energy ray-curable resin composition according to claim 10 of the patent application.