KR102462878B1 - Reactive polycarboxylic acid compound, active energy ray curable resin composition using same and cured product thereof, and use thereof - Google Patents

Abstract

(식 중, n은 평균값을 나타내고 0∼10의 수를 나타낸다. P 및 R은 각각 독립적으로 수소 원자, 할로겐 원자, 탄소수 1∼8의 알킬기, 아릴기 중 어느 것을 나타내고, 복수의 P 및 R은 서로 동일해도 상이해도 좋다. G는 글리시딜기를 나타낸다.)

(식 (2) 중 R₁은, 각각 독립적으로 수소 원자, 탄소수 1∼10의 알킬기를 나타낸다. m은 1∼3의 정수를 나타낸다.)(Project) An object of this invention is to provide the active-energy-ray-curable resin composition which provides the cured film excellent in heat resistance and developability.
(Solution means) In the epoxy resin (a) represented by the following formula (1), a carbonic acid compound (b) having a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule, optionally having a hydroxyl group and a carboxyl group in one molecule A reactive polycarboxylic acid compound (A) in which the reactive epoxy carboxylate compound (d) obtained by reacting the compound (c) is reacted with the polybasic acid anhydride (e) represented by the following formula (2) or (3).

(Wherein, n represents an average value and represents a number from 0 to 10. P and R each independently represent any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and a plurality of P and R are They may be the same or different from each other. G represents a glycidyl group.)

(In Formula (2), R ₁ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. m represents an integer of 1 to 3.)

Description

Reactive polycarboxylic acid compound, active energy ray-curable resin composition using same, cured product thereof, and use thereof

The present invention relates to a novel reactive polycarboxylic acid compound (A), an active energy ray-curable resin composition containing the same, and a cured product thereof. In particular, it relates to a novel reactive polycarboxylic acid compound suitable as a resist material applicable also as a color resist, a resist material for a color filter, and a black matrix material, an active energy ray-curable resin composition containing the same, and a cured product thereof.

Printed wiring boards are required to achieve high precision and high density for the purpose of reducing the size and weight of portable devices and improving the communication speed. Furthermore, performance that can withstand substrate adhesion, high insulation, and electroless gold plating while maintaining heat resistance and thermal stability is required, and a film forming material having stronger cured properties is required.

As these materials, a carboxylate compound obtained by reacting a compound having a hydroxyl group and a carboxylic acid group with acrylic acid in a general epoxy resin is known as a material having a low acid value and excellent developability, and it is also known that this compound has resistance ink ability. There is (Patent Document 1).

On the other hand, acid-modified epoxy acrylates based on a phenol aralkyl-type epoxy resin (eg, NC-3000 manufactured by Nippon Kayaku, etc.) as a basic skeleton are generally known as materials exhibiting high toughness after curing, and solder using the same. The use as a resist is also studied (patent document 2).

In addition, carbon black etc. are disperse|distributed to the acid-modified epoxy acrylate which made a phenol aralkyl type epoxy resin basic skeleton, and the trial which applied to the black matrix resist used for liquid crystal display panels etc. is also known (patent document 3).

Japanese Laid-Open Patent Publication No. 06-324490 Japanese Laid-Open Patent Publication No. 09-211860 Japanese Laid-Open Patent Publication No. 2005-055814

However, in acid-modified epoxy acrylates having a phenol aralkyl-type epoxy resin as a basic skeleton, color pigments such as carbon black have good affinity with the resin, and although pigments are dispersed, developability is poor, and development at high paint concentration It is necessary to have a gender.

Then, this invention improves the problem of the said prior art, and is excellent in dispersibility of a colored pigment etc., and also has favorable development characteristic even at high pigment concentration, an acid-modified epoxy acrylate compound, and an active energy ray containing the same. An object of the present invention is to provide a curable resin composition and a cured product thereof.

In order to solve the said subject, as a result of earnestly examining the said inventors, as a result, the reaction product of a phenol aralkyl type epoxy resin, an unsaturated group-containing carboxylic acid, and a compound which has both a hydroxyl group and a carboxy group in one molecule as needed is a specific polybasic acid anhydride. It discovered that the resin composition using the reaction material of the above-mentioned problem was solved, and this invention was reached|attained.

That is, the present invention is

[1] A carboxylic acid compound (b) having both an ethylenically unsaturated group and a carboxy group that can be polymerized in one molecule to the epoxy resin (a) represented by the following formula (1), and optionally a compound having a hydroxyl group and a carboxy group in one molecule A reactive polycarboxylic acid compound (A) in which the reactive epoxycarboxylate compound (d) obtained by reacting (c) is reacted with a polybasic acid anhydride (e) represented by the following formula (2) or (3);

(Wherein, n represents an average value and represents a number from 0 to 10. P and R each independently represent any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and a plurality of P and R are They may be the same or different from each other. G represents a glycidyl group.)

(In Formula (2), R ₁ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. m represents an integer of 1 to 3.)

[2] An active energy ray-curable resin composition comprising the reactive polycarboxylic acid compound (A) according to the preceding item [1];

[3] The active energy ray-curable resin composition according to [2], comprising a reactive compound (B) other than the reactive polycarboxylic acid compound (A);

[4] The active energy ray-curable resin composition according to the preceding [2] or [3] containing a photopolymerization initiator;

[5] The active energy ray-curable resin composition according to any one of [2] to [4], which is a molding material;

[6] The active energy ray-curable resin composition according to any one of [2] to [4], which is a material for forming a film;

[7] The active energy ray-curable resin composition according to any one of [2] to [4], which is a resist material composition;

[8] A cured product of the active energy ray-curable resin composition according to any one of [2] to [7],

[9] An article overcoated with the cured product according to [8] above;

is about

The active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention not only obtains a tough cured product, but also has excellent resin properties even in a state in which the solvent is only dried. In addition, the cured product obtained by curing the active energy ray-curable resin composition of the present invention with active energy rays such as ultraviolet rays, etc., has excellent heat resistance and can develop finely with alkali. suitable for

In addition, from the high affinity with the colored pigment, the reactive polycarboxylic acid compound of the present invention and the active energy ray-curable resin composition containing the same exhibit good developability even at a high pigment concentration, for color resists and color filters. of resist materials, especially black matrix materials, etc.

In addition, the active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention has thermal and mechanical toughness, good storage stability, and high reliability to withstand high temperature, high humidity, and cold thermal shock. It is also used for applications such as solder resists for printed wiring boards requiring high reliability, interlayer insulating materials for multilayer printed wiring boards, solder resists for flexible printed wiring boards, plating resists, and photosensitive optical waveguides.

(Form for implementing the invention)

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The reactive polycarboxylic acid compound (A) of the present invention includes an epoxy resin (a) having a structure represented by the following formula (1), and a carbonic acid compound having both an ethylenically unsaturated group and a carboxyl group that can be polymerized in one molecule (b); If necessary, the compound (c) which has both a hydroxyl group and a carboxy group in 1 molecule is made to react, and a reactive epoxy carboxylate compound (d) is obtained. Then, it can obtain by making the polybasic acid anhydride (e) represented by following formula (2) or Formula (3) react.

(Wherein, n represents an average value and represents a number from 0 to 10. P and R each independently represent any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and a plurality of P and R are They may be the same or different from each other. G represents a glycidyl group.)

(In Formula (2), R ₁ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. m represents an integer of 1 to 3.)

First, the carboxylate-ization process for providing reactivity to a carboxylate compound and obtaining a reactive epoxy carboxylate compound (d) is demonstrated.

Epoxy resin (a) (hereinafter also simply referred to as "epoxy resin (a)") represented by the formula (1) used in the present invention is various brand names, for example, NC-3000 (Nippon Kayaku). (manufactured by Co., Ltd.), etc., are generally available.

In the present invention, the carbonic acid compound (b) having both an ethylenically unsaturated group and a carboxyl group that can be polymerized in one molecule (hereinafter also simply referred to as “carboxylic acid compound (b)”) is used to impart reactivity to an active energy ray. to react for The ethylenically unsaturated group and the carboxy group are not limited as long as there is at least one in each molecule.

As the carbonic acid compound (b) having both an ethylenically unsaturated group and a carboxyl group that can be polymerized in one molecule, for example, (meth)acrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or saturated or unsaturated dibasic acid and unsaturated and a reaction product of a group-containing monoglycidyl compound. In the above (meth)acrylic acids, for example, (meth)acrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, (meth)acrylic acid dimer, saturated or unsaturated dibasic acid anhydride and one molecule per molecule. In one molecule, such as half esters, which are sugar molar reactants with (meth)acrylate derivatives having a hydroxyl group, and half esters, which are sugar molar reactants of saturated or unsaturated dibasic acids and monoglycidyl (meth)acrylate derivatives, etc. A monocarboxylic acid compound containing one carboxyl group, half-esters that are sugar molar reactants with a (meth)acrylate derivative having a plurality of hydroxyl groups in one molecule, and glycidyl having a plurality of epoxy groups with a saturated or unsaturated dibasic acid and polycarboxylic acid compounds having a plurality of carboxyl groups in one molecule, such as half esters which are sugar molar reactants of (meth)acrylate derivatives.

Among these, when the stability of the reaction between the epoxy resin (a) and the carboxylic acid compound (b) is considered, the carbonic acid compound (b) is preferably a monocarboxylic acid, and even when monocarboxylic acid and polycarboxylic acid are used together, mono It is preferable that the value represented by the molar amount of carboxylic acid/molar amount of polycarboxylic acid is 15 or more.

Most preferably, (meth)acrylic acid, the reaction product of (meth)acrylic acid, and (epsilon)-caprolactone, or cinnamic acid is mentioned from the point of sensitivity when it is set as an active energy ray-curable resin composition.

As a compound having at least one polymerizable ethylenically unsaturated group and at least one carboxy group in one molecule, it is preferable not to have a hydroxyl group in the compound.

The compound (c) having both a hydroxyl group and a carboxy group in one molecule used in the present invention (hereinafter, simply referred to as "compound (c)") is made to react 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 two or more hydroxyl groups and one carboxy group in one molecule, and a compound having one or more hydroxyl group and two or more carboxy groups in one molecule. There is this.

As a compound which has one hydroxyl group and one carboxy group in 1 molecule, hydroxypropionic acid, hydroxybutanoic acid, hydroxystearic acid, etc. are mentioned, for example. Moreover, as a compound which has two or more hydroxyl groups and one carboxy group in 1 molecule, dimethylol acetic acid, dimethylol propionic acid, dimethylol butanoic acid, etc. are mentioned. Hydroxyphthalic acid etc. are mentioned as a compound which has 1 or more hydroxyl group and 2 or more carboxy groups in 1 molecule.

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. Moreover, when the stability of a carboxylation reaction is taken into consideration that a carboxyl group is one in 1 molecule, it is preferable. Most preferably, it is preferable to have two hydroxyl groups and one carboxy group in one molecule. Considering the availability of raw materials, dimethylolpropionic acid and dimethylolbutanoic acid are particularly suitable.

As a compound which has both a 1 or more hydroxyl group and 1 or more carboxy group in 1 molecule, it is preferable not to have an ethylenically unsaturated group which can superpose|polymerize in a compound.

As an injection|throwing-in ratio of the epoxy resin (a) in this carboxylation reaction, a carbonic acid compound (b), and a compound (c), it should change suitably according to a use. That is, since an unreacted epoxy group does not remain|survive when all the epoxy groups are carboxylate-ized, the storage stability as a reactive epoxy carboxylate compound (d) is high. In this case, only the reactivity due to the introduced double bond is utilized.

On the other hand, by reducing the input amount of the carbonic acid compound (b) and compound (c) to leave an unreacted residual epoxy group, the reactivity by the introduced unsaturated bond and the reaction by the remaining epoxy group, for example, a photocationic catalyst It is also possible to use a polymerization reaction or a thermal polymerization reaction in combination. However, in this case, attention should be paid to the preservation of the reactive epoxycarboxylate compound (d) and examination of the production conditions.

In the case of producing a reactive epoxy carboxylate compound (d) that does not leave an epoxy group, it is preferable that the total amount of the carbonic acid compound (b) and the compound (c) is 90 to 120 equivalent % with respect to 1 equivalent of the epoxy resin (a). do. If it is this range, manufacture under relatively stable conditions is possible. When there is much input amount of a carbonic acid compound than this, since excess carbonic acid compound (b) and compound (c) will remain|survive, it is unpreferable.

Moreover, when leaving an epoxy group, it is preferable that the total of a carbonic acid compound (b) and a compound (c) is 20-90 equivalent% with respect to 1 equivalent of an epoxy resin (a). When it deviates from this range, the effect of composite hardening becomes weak. Of course, in this case, sufficient attention is required for gelation during the reaction and stability over time of the reactive epoxycarboxylate compound (d).

Carboxylation reaction may be made to react without a solvent, or it can also be made to react by diluting with a solvent. As a solvent which can be used here, if it is an inert solvent with respect to a carboxylation reaction, there will be no limitation in particular.

Although the preferable usage-amount of a solvent should be suitably adjusted according to the viscosity and use of resin obtained, Preferably it is 90-30 mass % of solid content content, More preferably, it is used so that it may become 80-50 mass %.

Specifically, for example, 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, solvent naphtha etc., an ester solvent, an ether solvent, a ketone solvent, etc. are mentioned.

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, diethylene glycol monomethyl ether monoacetate, and diethylene glycol monoacetate. Mono or polyalkylene glycol monoalkyl ethers such as ethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, and butylene glycol monomethyl ether acetate and polycarboxylic acid alkyl esters such as monoacetates, dialkyl glutarate, dialkyl succinate, and dialkyl adipic acid.

As an ether solvent, alkyl ethers, such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene Glycol ethers, such as glycol diethyl ether, Cyclic ethers, such as tetrahydrofuran, etc. are mentioned.

Acetone, methyl ethyl ketone, cyclohexanone, isophorone etc. are mentioned as a ketone type solvent.

In addition to this, the reaction can be carried out alone or in a mixed organic solvent such as a reactive compound (B) other than the reactive polycarboxylic acid compound (A) described later (hereinafter also simply referred to as “reactive compound (B)”). In this case, when used as a curable resin composition, since it can use directly as a composition, it is preferable.

In the reaction, it is preferable to use a catalyst in order to promote the reaction, and the amount of the catalyst used depends on the reactants, namely, the epoxy resin (a), the carbonic acid compound (b) and the compound (c), and, in some cases, the solvent. It is 0.1-10 mass parts with respect to 100 mass parts of total amounts of the reactant which added others. The reaction temperature in that case is 60-150 degreeC, and reaction time becomes like this. Preferably it is 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, and methyltriphenylstibine. and a known general basic catalyst such as bean, chromium octanoate, and zirconium octanoate.

Moreover, a thermal polymerization inhibitor can also be used. As the thermal polymerization inhibitor, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4-hydroxytoluene, etc. are used. it is preferable

The carboxylation reaction is 5 mgKOH/g or less, preferably 3 mgKOH/g or less, when the acid value of a sample is made into the end point, sampling appropriately.

As a preferable molecular weight range of the reactive epoxy carboxylate compound (d) obtained in this way, the polystyrene conversion weight average molecular weight in GPC is the range of 500-50,000, More preferably, it is 1,000-30,000, Especially preferably, it is 1000-10000. to be.

When it is smaller than this molecular weight, the toughness of hardened|cured material is not fully exhibited, and when it is too large than this, a viscosity becomes high and coating etc. become difficult.

Next, the acid addition step (hereinafter also simply referred to as "the present acid addition reaction") will be described in detail. An acid addition process introduce|transduces a carboxy group as needed into the reactive epoxy carboxylate compound (d) obtained in the previous process, and is performed for the purpose of obtaining a reactive polycarboxylic acid compound (A). That is, by addition-reacting the polybasic acid anhydride (e) represented by the formula (2) or (3) (hereinafter simply referred to as "polybasic acid anhydride (e)") to the hydroxyl group generated by the carboxylation reaction, an ester bond is formed A carboxyl group is introduced through

Examples of the alkyl group having 1 to 10 carbon atoms in the formula (2) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group. In the formula (2), R ₁ is preferably a hydrogen atom or a methyl group.

As said polybasic acid anhydride (e), the compound represented by following formula (4) is preferable.

The reaction to add the polybasic acid anhydride (e) can be performed by adding the polybasic acid anhydride (e) to the carboxylation reaction liquid. The amount of addition should be appropriately changed according to the use.

The amount of the polybasic acid anhydride (e) added is, for example, when the reactive polycarboxylic acid compound (A) of the present invention is used as a resist material of an aqueous alkali solution development type, the polybasic acid anhydride (e) is finally obtained as a reactive poly The solid content acid value (according to JISK5601-2-1:1999) of the carbonic acid compound (A) is preferably 20 to 120 mgKOH/g, more preferably 30 to 110 mgKOH/g. It is preferable to do When the solid content acid value at this time is this range, the developability with favorable alkali aqueous solution developability of the active energy ray-curable resin composition of this invention is shown. That is, good patterning property and the control range for overdevelopment are wide, and an excess acid anhydride does not remain.

In the reaction, it is preferable to use a catalyst in order to promote the reaction, and the amount of the catalyst used is the reactive epoxy carboxylate compound obtained from the reactants, that is, the epoxy compound (a), the carbonic acid compound (b) and the compound (c). It is 0.1-10 mass parts with respect to the total amount of the reactant which added (d) and polybasic acid anhydride (e), and a solvent and others in some cases. The reaction temperature in that case is 60-150 degreeC, and reaction time becomes like this. Preferably it is 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, and methyltriphenylstibine. Vienna, chromium octanoate, zirconium octanoate, etc. are mentioned.

This acid addition reaction may be reacted without a solvent, or may be reacted after being diluted with a solvent. As a solvent which can be used here, if it is an inert solvent with respect to an acid addition reaction, there will be no limitation in particular. In addition, when it is produced using a solvent in the carboxylation reaction that is the previous step, it can be directly used in the next step, the acid addition reaction, without removing the solvent, provided that it is an inert for the positive reaction. . The solvent that can be used is preferably the same one that can be used in the carboxylation reaction.

Although the preferable usage-amount of a solvent should be suitably adjusted according to the viscosity of resin obtained and a use, Preferably it is 90-30 mass % of solid content content, More preferably, it is used so that it may become 80-50 mass %.

In addition, the reaction can be carried out alone or in a mixed organic solvent such as the reactive compound (B). In this case, when used as a curable resin composition, since it can use directly as a composition, it is preferable.

In addition, it is preferable to use the thing similar to the illustration in the said carboxylation reaction as a thermal polymerization inhibitor etc.

This acid addition reaction takes as an end point the point where the acid value of a reactant became the range of plus or minus 10% of the set acid value while sampling appropriately.

As a preferable molecular weight range of the reactive polycarboxylic acid compound (A) obtained in this way, the polystyrene conversion weight average molecular weight in GPC (gel permeation chromatography) measurement is the range of 500-50,000, More preferably, it is 1,000-30,000, Especially preferably, it is 1000-10000.

When it is smaller than this molecular weight, the toughness of hardened|cured material is not fully exhibited, and when it is too large than this, a viscosity becomes high and coating etc. become difficult.

Specific examples of the reactive compound (B) that can be used in the present invention include so-called reactive oligomers such as radical-reactive acrylates, other cation-reactive epoxy compounds, and vinyl compounds that react to both. can

Examples of the acrylates that can be used include monofunctional (meth)acrylates, polyfunctional (meth)acrylates, and 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 monomethyl ether, phenyl ethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc. can be heard

Examples of the polyfunctional (meth)acrylates include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, ethylene glycol di( Meth)acrylate, diethylenedi(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanurate, polypropylene glycol di(meth)acrylate, adipic acid Epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide di(meth)acrylate, bisphenol di(meth)acrylate, ε-caprolactone addition of hydroxybivalic acid neophenglycol Di(meth)acrylate of water, poly(meth)acrylate which is a reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethyl Allpropane tri (meth) acrylate and its ethylene oxide adduct, pentaerythritol tri (meth) acrylate and its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate and its ethylene oxide adduct; Dipentaerythritol hexa(meth)acrylate, its ethylene oxide adduct, etc. are mentioned.

Examples of usable 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. Styrene, methyl styrene, ethyl styrene, etc. are mentioned as styrene. As other vinyl compounds, triallyl isocyanurate, trimallyl isocyanurate, etc. are mentioned.

In addition, the so-called reactive oligomers include urethane acrylates having both a functional group and a urethane bond sensitive to active energy ray in the same molecule, polyester acrylate having a functional group sensitive to active energy ray and an ester bond in the same molecule, In addition, an epoxy acrylate derived from an epoxy resin and having a functional group sensitive to an active energy ray in the same molecule, a reactive oligomer in which these bonds are used in combination, etc. are mentioned.

In addition, as a cation-reactive monomer, if it is a compound which generally has an epoxy group, there will be no limitation in particular. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate (“Sylacure UVR-6110” manufactured by Union Carbide, etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (Union Carbide) "ELR-4206", etc.), limonene dioxide ("Celoxide 3000" manufactured by Daisel Chemical Co., Ltd., etc.), allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2 -(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl)adipate (Union Carbide Co., Ltd. "Syler" Cure UVR-6128, etc.), bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxycyclohexyl)ether, bis(3,4-epoxycyclohexylmethyl)ether, bis(3 and 4-epoxycyclohexyl)diethylsiloxane.

Among these, as a reactive compound (B), the acrylates of a radical hardening type are the most preferable. In the case of a cationic type, since carbonic acid and an epoxy group will react, it is necessary to set it as a two-component mixing type.

The reactive polycarboxylic acid compound (A) of the present invention and other reactive compounds (B) can be mixed to obtain the active energy ray-curable resin composition of the present invention. At this time, you may add another component suitably according to a use.

The active energy ray-curable resin composition of the present invention contains 97 to 5 parts by mass of the reactive polycarboxylic acid compound (A) in the composition, preferably 87 to 10 parts by mass, and 3 to 95 parts by mass of other reactive compounds (B); More preferably, 3-90 mass parts is included. You may contain 0-80 mass parts of other components as needed.

In addition, for the purpose of making the active-energy-ray-curable resin composition of this invention suitable for various uses, 70 mass parts can also be added as an upper limit in a composition with an upper limit. As other components, a photoinitiator, other additives, a coloring material, a thermosetting catalyst, and the volatile solvent etc. which are added for viscosity adjustment for the purpose of providing coating suitability etc. are mentioned.

The active energy ray-curable resin composition of this invention may contain a photoinitiator further. As a photoinitiator, a radical type photoinitiator and a cationic photoinitiator are preferable.

As a radical type photoinitiator, For example, Benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether; Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclo acetophenones such as hexylphenyl ketone and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; thioxanthone such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-bismethylaminobenzophenone; and phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. .

Examples of the cationic photopolymerization initiator include a diazonium salt of a Lewis acid, an iodonium salt of a Lewis acid, a sulfonium salt of a Lewis acid, a phosphonium salt of a Lewis acid, other halides, a triazine-based initiator, a borate-based initiator, and and other photoacid generators.

As the diazonium salt of Lewis acid, p-methoxyphenyldiazonium fluorophosphonate, N,N-diethylaminophenyldiazonium hexafluorophosphonate (San-Aid SI-60L/ by Sanshin Chemical Co., Ltd.) SI-80L/SI-100L, etc.) and the like, and examples of the iodonium salt of Lewis acid include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate. and, as the sulfonium salt of Lewis acid, triphenylsulfonium hexafluorophosphonate (Cyracure UVI-6990 manufactured by Union Carbide, etc.), triphenylsulfonium hexafluoroantimonate (Cyracure UVI-6974 manufactured by Union Carbide) etc.) etc. are mentioned, and triphenylphosphonium hexafluoroantimonate etc. are mentioned as a phosphonium salt of a Lewis acid.

Examples of other halides include 2,2,2-trichloro-[1-4'-(dimethylethyl)phenyl]ethanone (such as Trigonal PI manufactured by AKZO), 2,2-dichloro-1--4-(phenoxy) cyphenyl)ethanone (Sandray 1000 manufactured by Sandoz, etc.), α,α,α-tribromomethylphenylsulfone (BMPS manufactured by Seitetsu Chemical, etc.), and the like. Examples of the triazine-based initiator include 2,4,6-tris(trichloromethyl)-triazine, 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine (such as Triazine A manufactured by Panchim). , 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine (such as Triazine PMS manufactured by Panchim), 2,4-trichloromethyl-(fipronyl)-6-triazine (Triazine PP manufactured by Panchim, etc.), 2,4-trichloromethyl-(4'-methoxynaphthyl)-6-triazine (Triazine B manufactured by Panchim, etc.), 2[2'(5-methylfuryl) ethylidene]-4,6-bis(trichloromethyl)-s-triazine (manufactured by Sanwa Chemical, etc.), 2(2'-furylethylidene)-4,6-bis(trichloromethyl)-s -triazine (made by Sanwa Chemical) etc. are mentioned.

Examples of the borate-based photopolymerization initiator include NK-3876 and NK-3881 manufactured by Nippon Photoresist, and examples of other photoacid generators include 9-phenylacridine and 2,2'-bis(o-chloro). Phenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole (biimidazole manufactured by Kurogane Kasei, etc.), 2,2-azobis(2-amino-propane)dihydro Chloride (V50 manufactured by Wako Pure Chemical Industries, Ltd., etc.), 2,2-azobis[2-(imidazolin-2yl)propane]dihydrochloride (VA044 manufactured by Wako Pure Chemical Industries, Ltd., etc.), [Eta-5-2-4 (Cyclopentadecyl)(1,2,3,4,5,6,etha)-(methylethyl)-benzene]iron(II)hexafluorophosphonate (Irgacure 261 manufactured by CibaGeigy, etc.), bis(y5) -cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyri-1-yl)phenyl]titanium (CGI-784 manufactured by CibaGeigy, etc.), etc. are mentioned.

In addition, you may use together an azo-type initiator, such as azobisisobutyronitrile, a peroxide-type radical-type initiator sensitive to heat, such as benzoyl peroxide, etc. Moreover, you may use both the photoinitiator of a radical type and a cationic type together. A photoinitiator may be used individually by 1 type, and may use 2 or more types together.

Among these, when the characteristic of the reactive polycarboxylic acid compound (A) of this invention is considered, a radical type photoinitiator is especially preferable.

Moreover, the active-energy-ray-curable resin composition of this invention can contain a coloring pigment. As a color pigment, what is not intended for coloring, what is called an extender, can also be used, for example. For example, talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay, carbon black, etc. are mentioned.

Moreover, the active-energy-ray-curable resin composition of this invention can contain other additives as needed. Examples of other additives include thermosetting catalysts such as melamine, thixotropy imparting agents such as Aerosil, silicone-based and fluorine-based leveling agents and defoamers, hydroquinone and hydroquinone monomethyl ether, polymerization inhibitors, stabilizers, and antioxidants. etc. can be used.

Other resins that do not show reactivity to active energy rays (so-called inert polymer) include, for example, other epoxy resins, phenol resins, urethane resins, polyester resins, ketoneformaldehyde resins, cresol resins, xylene resins, Diallyl phthalate resins, styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof can also be used. It is preferable to use these in the range to 40 mass parts in a resin composition.

In particular, when it is going to use a reactive polycarboxylic acid compound (A) for a soldering resist use, it is preferable to use well-known general epoxy resin as resins which do not show reactivity to an active energy ray. Even after making this react and harden|cure this with an active energy ray, the carboxy group derived from a reactive polycarboxylic acid compound (A) will remain, and as a result, the hardened|cured material will be inferior to water resistance and hydrolysis property. Therefore, by using an epoxy resin, the carboxyl group which remains is further carboxylated, and a stronger crosslinked structure is formed. The said cation-reactive monomer can be used for the said well-known general epoxy resin.

Moreover, it is 50 mass parts in a resin composition for the purpose of adjusting a viscosity according to an intended use, More preferably, it is the range to 35 mass parts. WHEREIN: A volatile solvent can also be added.

The active energy ray-curable resin composition of this invention hardens|cures easily with an active energy ray. Specific examples of active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X rays, gamma rays, and laser rays, and particle rays such as alpha rays, beta rays and electron rays. Considering the suitable use of the present invention, among these, ultraviolet rays, laser rays, visible rays, or electron rays are preferable.

In the present invention, the molding material means that an uncured composition is put into a mold, or an object is molded by pressing a mold, and then a curing reaction is caused by an active energy ray to cause a molding, or an uncured product. It refers to the material used for the use of irradiating focal light, such as a laser, etc. to a composition, causing hardening reaction, and shaping|molding.

Specific uses include a sheet molded into a planar shape, an encapsulant for protecting an element, a so-called nanoimprint material in which a micro-processed "mould" is pressed against an uncured composition to perform micro-molding, and by extension, a particularly thermal demand. A suitable use is given to peripheral sealing materials, such as a strict light emitting diode and a photoelectric conversion element, etc.

In the present invention, the film-forming material is used for the purpose of coating the surface of the substrate. Specific uses include ink materials such as gravure ink, flexo ink, silkscreen ink, and offset ink, coating materials such as hard coating, top coating, overprint varnish, clear coating, lamination, optical disk, and various other adhesives, pressure-sensitive adhesives These include adhesive materials such as adhesive materials, solder resists, etching resists, resist materials such as resists for micromachines, and the like. Furthermore, a so-called dry film in which a film-forming material is temporarily coated on a releasable substrate to form a film and then bonded to an intended substrate to form a film is also a film-forming material.

The present invention includes a cured product obtained by irradiating an active energy ray to the curable resin composition, and also includes a multilayer material having a layer of the cured product.

Among these, since the adhesiveness to a base material becomes high by introduction|transduction of the carboxy group of a reactive polycarboxylic acid compound (A), it is preferable to use as a use for coat|covering a plastic base material or a metal base material.

Furthermore, it is also preferable to use the unreacted reactive polycarboxylic acid compound (A) as an alkaline water developing type resist material composition by taking advantage of the property of being soluble in aqueous alkali solution.

In the present invention, the resist material composition refers to an activity to be drawn by forming a coating layer of the composition on a substrate, and then partially irradiating active energy rays such as ultraviolet rays, using the difference in physical properties of the irradiated and unirradiated parts. It refers to an energy ray-sensitive composition. Specifically, it is a composition used for the purpose of removing an irradiated part or an unirradiated part by some method, for example, dissolving in a solvent etc., an alkali solution, etc., and performing drawing.

The active energy ray-curable resin composition which is a resist material composition of this invention can adapt to various materials which can be patterned, For example, it is useful especially for a soldering resist material and the interlayer insulating material for build-up methods, and furthermore, As a waveguide, it is also used for an electric/electronic/optical substrate such as a printed wiring board, an optoelectronic substrate, or an optical substrate.

Particularly suitable applications include insulating resin sheets such as photosensitive films, photosensitive films with a support, prepregs, circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, It can be used for a wide range of uses requiring a resin composition, such as a die bonding material, a semiconductor sealing material, hole filling resin, and component embedding resin. Especially, since favorable developability can be exhibited also in a high pigment density|concentration, it can utilize suitably also for a color resist, the resist material for color filters, especially a black matrix material, etc.

In addition, a resin composition for an insulating layer of a multilayer printed wiring board (a multilayer printed wiring board using a cured product of the photosensitive resin composition as an insulating layer), a resin composition for an interlayer insulating layer (a multilayer printed wiring board using a cured product of a photosensitive resin composition as an interlayer insulating layer), It can use suitably also for the resin composition for metal-plating formation (multilayer printed wiring board in which plating was formed on the hardened|cured material of the photosensitive resin composition) etc.

Patterning using the active energy ray-curable resin composition of the present invention can be performed, for example, as follows. On a substrate, the curable resin composition of the present invention is applied to a film thickness of 0.1 to 200 µm by a method such as screen printing, spraying, roll coating, electrostatic painting, curtain coating, spin coating, and the like, and the coating film is usually 50 -110 degreeC, A coating film can be formed by drying at the temperature of preferably 60-100 degreeC. Then, through the photomask on which the exposure pattern is formed, high energy rays such as ultraviolet rays are irradiated to the coating film directly or indirectly at an intensity of about 10 to 2000 mJ/cm 2 , and using a developer described later, for example, spray, A desired pattern can be obtained by vibration immersion, paddle, brushing, or the like.

Examples of the aqueous alkali solution used for the above development include an inorganic aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like. , tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and an organic aqueous alkali solution such as triethanolamine can be used. The aqueous solution may further contain organic solvents, buffers, complexing agents, dyes or pigments.

In addition, it is used especially suitably as a dry film use by which the mechanical strength before hardening reaction by an active energy ray is calculated|required. 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 polycarboxylic acid compound (A) of the present invention exhibits good developability despite a relatively high molecular weight. can do it

Although there is no restriction|limiting in particular as a method of forming a film, Intaglio printing method, such as gravure, convex printing method, such as flexo, stencil printing method, such as silkscreen, Flatbed printing method, such as offset, roll coater, knife coater, die Various coating methods, such as a coater, a curtain coater, and a spin coater, can be employ|adopted arbitrarily.

The hardened|cured material of the active energy ray-curable resin composition of this invention points out what irradiated and hardened active energy ray to the active energy ray-curable resin composition of this invention.

The article overcoated with the active energy ray-curable resin composition of the present invention refers to a material comprising at least two or more layers obtained by coating and curing the active energy ray-curable resin composition shown in the present invention on a substrate.

(Example)

Hereinafter, the present invention will be described in more detail by way of Examples, but the present invention is not limited by these Examples. In addition, in the Example, unless otherwise indicated, % represents mass %.

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

1) Epoxy equivalent: It measured by the method according to JISK7236:2001.

2) Softening point: It was measured by the method according to JISK7234:1986.

3) Acid value: It measured by the method according to JISK0070:1992.

4) GPC (gel permeation chromatography) measurement conditions are as follows.

Model: TOSOH HLC-8220GPC

Column: Super HZM-N

Eluent: THF (tetrahydrofuran); 0.35ml/min, 40℃

Detector: RI (Differential Refractometer)

Molecular Weight Standard: Polystyrene

(Synthesis Examples 1-3): Synthesis of reactive epoxy carboxylate compound (d)

288 g of phenol aralkyl type epoxy resin (NC-3000H Nippon Kayaku Co., Ltd. softening point 70° C., epoxy equivalent 288 g/eq.) acrylic acid (AA) or methacrylic acid (MAA) as carbonic acid compound (b) The amount described in Table 1, and dimethylolpropionic acid (hereinafter abbreviated as “DMPA”) as the compound (c) was added to the amount described in Table 1. 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that it might become 80 mass % of solid content content, and it was made to react at 100 degreeC for 24 hours, and the reactive epoxy carboxylate compound (d) solution was obtained.

(Example 1, Comparative Example 1): Preparation of reactive polycarboxylic acid compound (A)

To 200 g of the obtained reactive epoxy carboxylate compound (d) solution, propylene glycol monomethyl ether monoacetate was added so that the compound described in Table 2 as the polybasic acid anhydride (e), the amount (g), and the solid content as a solvent became 65%, , after heating to 100°C, acid addition reaction was carried out to obtain a reactive polycarboxylic acid compound (A) solution. Table 2 shows the solid content acid value (AV: mgKOH/g) of the obtained reactive polycarboxylic acid compound (A). The solid content acid value (mg·KOH/g) measurement was performed as a solution and converted into a value in the solid content.

HTMA: 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, manufactured by Mitsubishi Chemical Co., Ltd.

NTA: norbornane tricarboxylic anhydride, see Japanese Patent Publication No. 5532123 Synthetic product

THPA: 1,2,3,6-tetrahydrophthalic anhydride, manufactured by Shin Nippon Rica Co., Ltd.

SA: Ricaside SA succinic anhydride, manufactured by Shin Nippon Rica Co., Ltd.

(Example 2 and Comparative Example 2): Preparation of resist material composition

54.44 g of the reactive polycarboxylic acid compound (A) obtained in Example 1 and Comparative Example 1, and 3.54 g of HX-220 (trade name: Nippon Kayaku Co., Ltd. diacrylate monomer) as other reactive compounds (B); 4.72 g of Irgacure 907 (manufactured by Chiba Specialty Chemicals) and 0.47 g of Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) as a photoinitiator, NC-3000 (Nippon Kayaku Co., Ltd.) as a curing agent component 14.83 g), 1.05 g of melamine as a thermal curing catalyst, and 20.95 g of methyl ethyl ketone as a concentration adjustment solvent were added, kneaded with a bead mill and uniformly dispersed to obtain a resist material resin composition.

The obtained said composition was apply|coated uniformly to the film of the copper foil used as a support film by the roll coating method, it was made to pass through the hot-air drying furnace with a temperature of 70 degreeC, and the 30-micrometer-thick resin layer was formed. Then, spray development was performed with 1% sodium carbonate aqueous solution, and developability was evaluated with time until complete development, a so-called break time (unit: seconds).

From the above results, the resist material composition using the reactive polycarboxylic acid compound (A) of the present invention has good developability.

(Example 3 and Comparative Example 3): Evaluation of thermal decomposition resistance

8 g of the reactive polycarboxylic acid compound (A) obtained in Example 1 and Comparative Example 1, 0.24 g of Irgacure 907 (manufactured by Chiba Specialty Chemicals) as a photopolymerization initiator, and Kayacure DETX-S (Nippon Kayaku Co., Ltd.) ) of 0.01 g, NC-3000 (manufactured by Nippon Kayaku) as a curing agent component, 0.403 g, as a thermal curing catalyst, 0.017 g of triphenylphosphine, and 0.446 g of propylene glycol monomethyl ether monoacetate were added to the polyimide film The cured product was uniformly applied to the surface and passed through a hot air drying furnace at a temperature of 80° C. to form a resin layer having a thickness of 20 μm, and then exposed with an ultraviolet light exposure apparatus (Okseisakusho Co., Ltd., model HMW-680GW). got The produced cured product is cut out to a width of 5 mm. Thereafter, it was set in a viscoelasticity measuring device RSA-G2 manufactured by TA Instruments, and tan δ was measured in an air atmosphere at a frequency of 10 Hz and a temperature increase rate of 2° C./min., and the temperature at the maximum value of tan δ was Tg.

From said result, it turns out that the active energy ray-curable resin composition using the reactive polycarboxylic acid compound (A) of this invention is excellent in heat resistance compared with the resin composition for a comparison.

(Example 4 and Comparative Example 4): Evaluation of pigment dispersibility

20 g of the reactive polycarboxylic acid compound (A) obtained in Example 1 and Comparative Example 1, 5.0 g of DPHA (trade name: Nippon Kayaku Co., Ltd. acrylate monomer) as the other reactive compound (B), propylene as an organic solvent 10 g of glycol monomethyl ether acetate and 15 g or 10 g of Mitsubishi Carbon Black MA-100 as a color pigment were added and stirred. Furthermore, 35 g of glass beads were put, and it disperse|distributed for 1 hour with a paint shaker. The dispersion liquid after completion|finish of dispersion was coated on the polyethylene terephthalate film with wire bar coater #2, and it dried for 10 minutes with an 80 degreeC warm air dryer. The gloss of the surface of the coating film after drying was measured using a 60° reflective gloss meter (Horiba Seisakusho IG-331 gloss meter), and dispersibility of carbon black was evaluated. Table 5 shows the results. The higher the value of gloss, the better the pigment dispersibility.

As is evident from the above results, the coating film obtained from the resin composition containing the reactive polycarboxylic acid compound (A) obtained in Example 1 had no change in the value of the gloss even when the content of the color pigment was high. On the other hand, it can be confirmed that the luster of the reactive polycarboxylic acid compound of Comparative Example 1-1 is decreased when the content of the color pigment is increased. It can be seen that the reactive polycarboxylic acid compound of Comparative Example 1-2 has a low gloss value even when the content of the color pigment is small, and thus the content dispersibility is low. Therefore, it can be said that the pigment dispersibility of the reactive polycarboxylic acid compound (A) of this invention is excellent, without depending on content of a color pigment.

Claims (9)

In the epoxy resin (a) represented by the following formula (1), a carbonic acid compound (b) having a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule, and optionally a compound having a hydroxyl group and a carboxyl group in one molecule (c) A reactive polycarboxylic acid compound (A) obtained by reacting a reactive epoxy carboxylate compound (d) obtained by reacting with a polybasic acid anhydride (e) represented by the following formula (2) or (3) In the synthesis of compound (d), at least one fatty acid having 10 or more carbon atoms per carboxyl group is not reacted):

(Wherein, n represents an average value and represents a number from 0 to 10; P and R each independently represent any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and a plurality of P and R are may be the same or different from each other; G represents a glycidyl group);

(In formula (2), R ₁ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; m represents an integer of 1 to 3). An active energy ray-curable resin composition comprising the reactive polycarboxylic acid compound (A) according to claim 1 . 3. The method of claim 2,
An active energy ray-curable resin composition comprising a reactive compound (B) other than the reactive polycarboxylic acid compound (A). 3. The method of claim 2,
An active energy ray-curable resin composition comprising a photoinitiator. 5. The method according to any one of claims 2 to 4,
An active energy ray-curable resin composition as a molding material. 5. The method according to any one of claims 2 to 4,
An active energy ray-curable resin composition which is a material for film formation. 5. The method according to any one of claims 2 to 4,
An active energy ray-curable resin composition which is a resist material composition. Hardened|cured material of the active-energy-ray-curable resin composition in any one of Claims 2-4. An article overcoated with a cured product of the active energy ray-curable resin composition according to claim 8.