KR102668938B1 - Reactive polycarboxylic acid resin mixture, active energy ray-curable resin composition using the same and its cured product, and reactive epoxycarboxylate resin mixture - Google Patents

Abstract

An epoxy resin (a) represented by formula (1), a compound (b) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule, and, if necessary, a compound (c) having both a hydroxyl group and a carboxyl group in one molecule are reacted. A reactive polycarboxylic acid resin that is a reaction product of a reactive epoxycarboxylate resin and a polybasic acid anhydride (d) obtained by and, optionally, a reactive polycarboxylic acid resin mixture containing a reactive polycarboxylic acid resin that is a reaction product of a reactive epoxycarboxylate resin obtained by reacting compound (c) and a polybasic acid anhydride (d).

(R ₁ in formula (1) may be the same or different, and represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 4 carbon atoms, and n represents an integer of 1 to 10.)

Description

Reactive polycarboxylic acid resin mixture, active energy ray-curable resin composition using the same and its cured product, and reactive epoxycarboxylate resin mixture

The present invention relates to a reactive polycarboxylic acid resin mixture, an active energy ray-curable resin composition using the same and its cured product, and a reactive epoxycarboxylate resin mixture.

Printed wiring boards are required to have higher precision and higher density with the goal of making portable devices smaller and lighter and improving communication speeds. Accordingly, the requirements for solder resist that covers the circuit itself are becoming more and more sophisticated. In addition to conventional requirements, performance that can withstand substrate adhesion, high insulation, and electroless gold plating while maintaining heat resistance and thermal stability is required, and materials for film formation with stronger curing properties are required.

As these materials, carboxylate resins obtained by reacting acrylic acid with a general epoxy resin and a carboxylic acid compound having a hydroxyl group are known as materials with a low acid value and excellent developability. Additionally, it is known that this resin has resist ink compatibility (Patent Document 1).

On the other hand, acid-modified epoxy acrylate whose basic skeleton is an epoxy resin having a polycyclic hydrocarbon group of a specific structure (e.g., XD-1000 manufactured by Nippon Kayaku Co., Ltd., etc.) is a general material that exhibits high toughness after curing. This is a notice. In addition, studies are being conducted on the use of this as a soldering resist (patent document 2).

In addition, acid-modified epoxy acrylate, whose basic skeleton is epoxy with a TrisP-PA skeleton, is being studied for use as a photosensitive interlayer insulating layer because it has excellent heat resistance, developability, and copper plating adhesion (patent Document 3).

However, even through these studies, the realization of a resin composition that has both high insulation and developability has not been reached.

Japanese Patent Publication No. 06-324490 Japanese Patent Publication No. 2009-102501 International Publication No. 2018/003314

The first purpose of the present invention is to improve the problems of the prior art and to provide a reactive polycarboxylic acid resin mixture having good development characteristics without compromising high insulation reliability and an active energy ray-curable resin composition containing the same. do. In addition, the present invention has a second purpose to improve the problems of the prior art and to provide a reactive epoxycarboxylate resin mixture having good development characteristics and insulation reliability without deteriorating high toughness and heat resistance.

In order to solve the above-mentioned problem, the present inventors conducted intensive studies and discovered that an epoxycarboxylate resin having a specific structure and a reactive polycarboxylic acid resin obtained by reacting a polybasic acid anhydride have excellent resin physical properties, and the present invention reached.

That is, the present invention relates to the following [1] to [15].

[One]

An epoxy resin (a) represented by the following formula (1), a compound (b) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule, and, if necessary, a compound (c) having both a hydroxyl group and a carboxyl group in one molecule. A reactive epoxycarboxylate resin, which is a reactant obtained by reacting, a reactive polycarboxylic acid resin, which is a reactant of a polybasic acid anhydride (d), an epoxy resin (a') different from the epoxy resin (a), the compound (b), and the necessary A reactive epoxycarboxylate resin, which is a reactant obtained by reacting the compound (c) according to the above, and a reactive polycarboxylic acid resin, which is a reactant of the polybasic acid anhydride (d), wherein the epoxy resin (a') has the following formula (2) ~ A reactive polycarboxylic acid resin mixture containing a reactive polycarboxylic acid resin that is an epoxy resin represented by any of formula (4).

(R ₁ in formula (1) may be the same or different, and represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 4 carbon atoms, and n represents an integer of 1 to 10.)

(In equation (2), p represents an integer from 0 to 2)

(In equation (3), m represents an integer from 0 to 30)

(Ar in equation (4) is each independently either equation (5) or equation (6), and the molar ratio of equations (5) and (6) is equation (5) / equation (6) = 1~3 q is the number of repetitions, and r represents the mantissa and is 1 or 2.

[2]

The reactive epoxycarboxylate according to the preceding item [1], which is a reactant obtained by reacting the epoxy resin (a) and the mixture of the epoxy resin (a'), the compound (b), and, if necessary, the component (c). A reactive polycarboxylic acid resin mixture that is a reaction product of the resin mixture and the polybasic acid anhydride (d).

[3]

An active energy ray-curable resin composition comprising the reactive polycarboxylic acid resin mixture according to the preceding item [1] or [2].

[4]

The method of the preceding item [3], further comprising a reactive compound (C), wherein the reactive compound (C) is a radical-reactive acrylate, a cation-reactive epoxy compound, a vinyl compound sensitive to both, or an active An active energy ray-curable resin composition that is a reactive oligomer having a functional group sensitive to energy rays.

[5]

The active energy ray-curable resin composition according to the preceding item [3] or [4], further comprising a photopolymerization initiator.

[6]

The active energy ray-curable resin composition according to any one of the preceding items [3] to [5], further comprising a coloring pigment.

[7]

The active energy ray-curable resin composition according to any one of the preceding items [3] to [6], which is a molding material.

[8]

The active energy ray-curable resin composition according to any one of the preceding items [3] to [6], which is a material for forming a film.

[9]

The active energy ray-curable resin composition according to any one of the preceding items [3] to [6], which is a resist material composition.

[10]

A cured product of the active energy ray-curable resin composition according to any one of the preceding items [3] to [9].

[11]

An article overcoated with the cured material according to the preceding paragraph [10].

[12]

To the epoxy resin (a) represented by the following formula (1), a compound (b) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule, and, if necessary, a compound (c) having both a hydroxyl group and a carboxyl group in one molecule, The compound (b) and, if necessary, the compound (b) in an epoxy resin selected from the group of reactive epoxycarboxylate resins and epoxy resins represented by the following formulas (2) to (4), which are reactants obtained by reacting A reactive epoxycarboxylate resin mixture containing a reactive epoxycarboxylate resin, which is a reactant obtained by reacting (c).

(R ₁ in formula (1) may be the same or different, and represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 4 carbon atoms, and n represents an integer of 1 to 10.)

(In equation (2), p represents an integer from 0 to 2)

(In equation (3), m represents an integer from 0 to 30)

(Ar in equation (4) is each independently either equation (5) or equation (6), and the molar ratio of equations (5) and (6) is equation (5) / equation (6) = 1~3 q is the number of repetitions, and r represents the mantissa and is 1 or 2.

(Effects of the Invention)

The active energy ray-curable resin composition comprising a mixture of a reactive epoxycarboxylate resin having a polycyclic hydrocarbon group of a specific structure and/or an acid-modified resin thereof according to the present invention can obtain a strong cured product and has good developability. . 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 has excellent heat resistance and can be suitably used as a film forming material with high insulation reliability.

Suitable applications include, for example, solder resist for printed wiring boards that require particularly high insulation reliability, protective films for multilayer printed wiring boards, interlayer insulating materials for multilayer printed wiring boards, solder resists for flexible printed wiring boards, plating resists, photosensitive optical waveguides, etc. It can be used as

In addition, the specific structure according to the present invention has high affinity with coloring pigments such as carbon black, can exhibit good developability even at high pigment concentrations, and can be used as a color resist, a resist material for color filters, especially a black matrix. It can also be suitably used for materials, black column spacers, etc.

The reactive polycarboxylic acid resin mixture of the present invention contains at least two types of reactive polycarboxylic acid resins shown in 1 to 2 below.

1. Epoxy resin (a) represented by the above formula (1) (hereinafter simply referred to as “component (a)”), compound (b) (hereinafter simply referred to as “component (a)”), which has both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule. Reactive epoxy carboxyl, which is a reactant obtained by reacting “component (b)”) and, if necessary, a compound (c) having both a hydroxyl group and a carboxyl group in one molecule (hereinafter also simply referred to as “component (c)”) A reactive polycarboxylic acid that is a reaction product of late resin and polybasic acid anhydride (d) (hereinafter also simply referred to as “component (d)”).

2. Reactive epoxy, which is a reactant obtained by reacting an epoxy resin (a') different from component (a) (hereinafter also simply referred to as "component (a')"), component (b), and, if necessary, component (c). A reactive polycarboxylic acid resin that is a reaction product of a carboxylate resin and component (d), wherein component (a') is an epoxy resin represented by any of the formulas (2) to (4) above. .

Similarly, the reactive epoxycarboxylate resin mixture of the present invention contains at least two types of reactive epoxycarboxylate resins shown in 3 to 4 below.

3. Reactive epoxycarboxylate resin, which is a reactant obtained by reacting component (a), component (b), and, if necessary, component (c).

4. A reactive epoxycarboxylate resin that is a reactant obtained by reacting component (a'), component (b), and, if necessary, component (c), wherein component (a') is one of the above formulas (2) to (4). ) A reactive epoxycarboxylate resin, which is an epoxy resin represented by any of the following.

The epoxy resin (a) is represented by the above formula (1) [In formula (1), R ₁ may be the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and n represents an integer of 1 to 10. ] is displayed.

In R ₁ in formula (1), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Examples of the hydrocarbon group having 1 to 4 carbon atoms for R ₁ in formula (1) include methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, and t-butyl groups. I can hear it.

Among them, compounds in which all R ₁ is a hydrogen atom or a methyl group are available inexpensively and are preferred.

In addition, the manufacturing method of the epoxy resin represented by the above formula (1) is described in Patent Document 3, etc. Compounds in which R ₁ is all hydrogen atoms and n represents an integer of 1 to 10 are available from Nippon Kayaku Co., Ltd. as the XD-1000 series. Additionally, it is also available as KDCP-130 and LDCP-150 from KUKDO CHEMICAL CO., LTD.

For component (a), for example, a compound suitable for the softening point grade may be appropriately selected or synthesized from among these products.

Component (a') is an epoxy resin other than component (a), and may be used alone or in combination of two or more types.

Component (a') is preferably an epoxy resin having three or more epoxy groups in the molecule. Specific examples include aromatic novolak-type epoxy resin, biphenyl-type epoxy resin, triphenylmethane-type epoxy resin, and phenol aralkyl-type epoxy resin. In the present invention, at least an epoxy resin represented by any of the above formulas (2) to (4) is used as component (a').

Additionally, the epoxy equivalent of component (a') is preferably 180 to 220 g/eq, and more preferably 185 to 210 g/eq. When the epoxy equivalent weight is within the above range, heat resistance is superior.

The manufacturing method of the epoxy resin represented by the above formula (2) [in formula (2), p represents an integer of 0 to 2] is well known, and is generally known as Nippon Kayaku Co., Ltd. Available as NC-6000 and NC-6300. It is also available from Printec Corporation as TECMOREVG 3101L. The compound of the formula (2) can be selected, for example, by appropriately selecting or synthesizing a suitable compound from among these.

The manufacturing method of the epoxy resin represented by the above formula (3) [m in formula (3) represents an integer of 0 to 30] is known, and generally EPPN-501H and EPPN- are manufactured by Nippon Kayaku Co., Ltd. Available as 501HY, EPPN-502H, and EPPN-503. It is also available as KDMN-1065 from KUKDO CHEMICAL CO., LTD. The compound of the formula (3) can be selected, for example, by appropriately selecting or synthesizing a suitable compound from among these. In the present invention, m in the above formula (3) is preferably an integer of 0 to 8.

In the above formula (4) [Ar in formula (4) is each independently either formula (5) or formula (6), and the molar ratio of formula (5) and formula (6) is formula (5) / formula (6) )=1~3. q is the number of repetitions and is an integer from 0 to 5. r represents the valence and is 1 or 2], etc. are known for the production method of the epoxy resin, and generally commercially available products are available from Nippon Kayaku Co., Ltd. as the NC-3500 series. The compound of formula (4) may be appropriately selected or synthesized from, for example, grades of the NC-3500 series.

Compounds (b) that have both an ethylenically unsaturated group and a carboxyl group that can be polymerized in one molecule include, for example, (meth)acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or saturated or unsaturated dibasic acids and unsaturated group-containing mono Reactants of glycidyl compounds, etc. can be mentioned. In the above, (meth)acrylic acids include, for example, (meth)acrylic acid, β-styrylacrylic acid, β-furfuryl acrylic acid, (meth)acrylic acid dimer, saturated or unsaturated dibasic acid anhydride, and one molecule per molecule. One carboxyl group per molecule, such as half-esters, which are molar reactants of (meth)acrylate derivatives with hydroxyl groups, and half-esters, which are molar reactants of saturated or unsaturated dibasic acids and monoglycidyl (meth)acrylate derivatives. monocarboxylic acid compounds, including (meth)acrylate derivatives having multiple hydroxyl groups in one molecule, half-esters that are molar reactants, glycidyl (meth)acrylate having a saturated or unsaturated dibasic acid, and multiple epoxy groups. Examples include polycarboxylic acid compounds having multiple carboxyl groups in one molecule, such as half esters, which are mole reactants of derivatives.

Among these, considering the stability of the reaction between the epoxy resin and component (b), it is preferable that component (b) is a monocarboxylic acid. Even when monocarboxylic acid and polycarboxylic acid are used together, the molar amount of monocarboxylic acid / poly It is preferable that the value expressed in molar amount of carboxylic acid is 15 or more.

Most preferably, in terms of sensitivity when used as an active energy ray-curable resin composition, (meth)acrylic acid, a reaction product of (meth)acrylic acid and ε-caprolactone, or cinnamic acid are used.

As a compound having both one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule, it is preferable that the compound does not have a hydroxyl group.

Compound (c), which has both a hydroxyl group and a carboxyl group in one molecule, is reacted for the purpose of introducing a hydroxyl group into the carboxylate compound. These include compounds that have both one hydroxyl group and one carboxyl group in one molecule, compounds that have both two or more hydroxyl groups and one carboxyl group in one molecule, and compounds that have both one or more hydroxyl groups and two or more carboxyl groups in one molecule. there is.

Examples of compounds having both one hydroxyl group and one carboxyl group in one molecule include hydroxypropionic acid, hydroxybutanoic acid, and hydroxystearic acid. Additionally, compounds having both two or more hydroxyl groups and one carboxyl group in one molecule include dimethylolacetic acid, dimethylolpropionic acid, and dimethylolbutanoic acid. Examples of compounds having both one or more hydroxyl groups and two or more carboxyl groups in one molecule include hydroxyphthalic acid.

Among these, it is preferable that two or more hydroxyl groups are included in one molecule, considering the effect of the present invention. Additionally, considering the stability of the carboxylate reaction, it is preferable that there is only one carboxyl group per molecule. Most preferably, it has two hydroxyl groups and one carboxyl group in one molecule. Considering the availability of raw materials, dimethylolpropionic acid and thimethylolbutanoic acid are particularly suitable.

As a compound having both one or more hydroxyl groups and one or more carboxyl groups in one molecule, it is preferable that the compound does not have a polymerizable ethylenically unsaturated group.

The injection ratio of the epoxy resin and component (b) and component (c) in this carboxylate reaction should be appropriately changed depending on the application. That is, when all epoxy groups are carboxylated, no unreacted epoxy groups remain, so the storage stability as a reactive epoxycarboxylate resin is high. In this case, only the reactivity due to the introduced double bond is used.

On the other hand, by reducing the injection amount of component (b) and component (c) to leave unreacted remaining epoxy groups, the reactivity due to the introduced unsaturated bond and the reaction due to the remaining epoxy group, for example, polymerization reaction using a photo cation catalyst It is also possible to use a combination of thermal polymerization reactions. However, in this case, care must be taken to review the storage and manufacturing conditions of the reactive epoxycarboxylate resin.

When producing a reactive epoxy carboxylate resin that does not retain epoxy groups, it is preferable that the total of component (b) and component (c) is 0.9 equivalent to 1.2 equivalent based on 1 equivalent of the total epoxy resin. Within this range, manufacturing is possible under relatively stable conditions. If the amount of the carboxylic acid compound injected is greater than this, excess component (b) and component (c) remain, which is not preferable.

In addition, when the epoxy group is left, it is preferable that the total of component (b) and component (c) is 0.2 equivalent to less than 0.9 equivalent based on 1 equivalent of the total epoxy resin. If it deviates from this range, the effect of composite hardening becomes weaker. Of course, in this case, sufficient attention must be paid to gelation during the reaction and the stability over time of the reactive epoxycarboxylate resin.

The carboxylate reaction can be carried out using a non-solvent or diluted with a solvent. The solvent that can be used here is not particularly limited as long as it is a solvent that is inert to the carboxylate reaction.

The amount of the preferred solvent must be adjusted appropriately depending on the viscosity of the resulting resin and its intended use, but it is preferably used so that the solid content is 90 to 30% by mass, more preferably 80 to 50% by mass.

Solvents used in the carboxylate reaction include, 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 and white. Gasoline, solvent naphtha, etc., ester-based solvents, ether-based solvents, ketone-based solvents, etc. can be mentioned.

Ester-based solvents include alkyl acetates such as ethyl acetate, propyl acetate, butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, and diethylene glycol mono. Mono or polyalkylene glycol monoalkyl ether monoacetate such as ethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, butylene glycol monomethyl ether acetate, etc. and polycarboxylic acid alkyl esters such as acetates, dialkyl glutarate, dialkyl succinate, and dialkyl adipic acid.

Ether-based solvents include 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, and triethylene glycol. Glycol ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran, etc. are mentioned.

Examples of ketone-based solvents include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

During carboxylate reaction, it is preferable to use a catalyst to promote the reaction. The amount of the catalyst used is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the reactant to which the epoxy resin, component (b), component (c) used as needed, and solvent and others are added as the case may be. The reaction temperature at that time is 60 to 150°C, and the reaction time is preferably 5 to 60 hours. Specific examples of catalysts that can be used include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstivine, and methyltriphenylstivine. Common basic catalysts such as bean, chromium octanoate, and zirconium octanoate can be mentioned.

Additionally, a thermal polymerization inhibitor can also be used. It is recommended to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4-hydroxytoluene, etc. as thermal polymerization inhibitors. desirable.

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

A preferable molecular weight range of the reactive epoxycarboxylate resin obtained in this way is a polystyrene-equivalent weight average molecular weight in GPC (gel permeation chromatography) of 500 to 50,000, more preferably 800 to 30,000, and especially preferably 800 to 30,000. is 800~10,000.

If the molecular weight is less than 500, the toughness of the cured product is not sufficiently exhibited, and if it is greater than 50,000, the viscosity increases and coating becomes difficult.

Next, the reactive polycarboxylic acid resin according to the present invention is obtained by reacting the reactive epoxycarboxylate resin with a polybasic acid anhydride (d).

The reason for introducing a carboxyl group through this acid addition process is to provide solubility in alkaline water to the area not irradiated with active energy rays and adhesion to metals, inorganic substances, etc. in applications requiring resist patterning, etc. What to do, etc. This acid addition process involves reacting component (d) with the hydroxyl group of the epoxycarboxylate compound to introduce a carboxyl group through an ester bond.

As component (d), for example, any compound that has a cyclic acid anhydride structure in one molecule can be used, but succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrate, which are excellent in alkaline aqueous solution developability, heat resistance, and hydrolysis resistance, etc. Hydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, hydrogenated trimellitic anhydride, trimellitic anhydride or maleic anhydride are preferred.

The reaction for adding component (d) can be performed by adding component (d) to the solution of the epoxycarboxylate compound. The amount added may be appropriately changed depending on the intended use.

However, when the reactive polycarboxylic acid resin mixture of the present invention is used as an alkali-developable resist, component (d) is adjusted to the solid acid value of the reactive polycarboxylic acid resin obtained by the acid addition process (JISK5601-2-1: 1999). It is desirable to inject a calculated amount such that the standard) is 20 to 120 mg·KOH/g, more preferably 40 to 100 mg·KOH/g.

When the solid acid value is within this range, the active energy ray-curable resin composition of the present invention exhibits good alkaline aqueous solution developability. In other words, it has good patterning properties and a wide range of control over over-development, and there is no case where excess acid anhydride remains.

During the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is 0.1 to 10 based on the total amount of reactants to which the reactive epoxycarboxylate resin, component (d), and, in some cases, solvent and others are added. It is the mass part. The reaction temperature at that time is 60 to 150°C, and the reaction time is preferably 5 to 60 hours. Specific examples of catalysts that can be used include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstivine, and methyltriphenylstivine. Examples include bean, chromium octanoate, and zirconium octanoate.

This acid addition reaction can be carried out without a solvent or by diluting with a solvent. There is no particular limitation as to the solvent as long as it is a solvent that does not affect the acid addition reaction. Additionally, when a solvent is used in the epoxy carboxylate reaction, which is the previous step, it can be directly applied to the acid addition reaction without removing the solvent, provided that it does not affect the acid addition reaction. The solvent that can be used may be the same as that that can be used in the carboxylation reaction.

The amount of the preferred solvent must be adjusted appropriately depending on the viscosity and use of the resulting resin, but is preferably used so that the solid content is 90 to 30% by mass, more preferably 80 to 50% by mass.

In addition to this, it can be carried out alone or in mixed organic solvents. In this case, when used as a curable resin composition, it is preferable because it can be used directly as a composition.

Additionally, the use of a thermal polymerization inhibitor is preferable, and examples of the thermal polymerization inhibitor include those similar to the thermal polymerization inhibitor in the epoxycarboxylation reaction.

This acid addition reaction is sampled appropriately and the end point is set at the point where the acid value of the reactant falls within plus or minus 10% of the set acid value.

As a preferable molecular weight range of the reactive polycarboxylic acid resin obtained in this way, the polystyrene conversion weight average molecular weight in GPC measurement is in the range of 500 to 50,000, more preferably 800 to 30,000, and particularly preferably 800 to 10,000.

If the molecular weight is less than 500, the toughness of the cured product is not sufficiently exhibited, and if it is greater than 50,000, the viscosity increases, making coating difficult.

The active energy ray-curable resin composition of the present invention contains a reactive polycarboxylic acid resin mixture, and there is no problem even if a reactive epoxycarboxylate resin is used in combination.

The reactive polycarboxylic acid resin mixture of the present invention is

Manufacturing method 1: a reactive epoxycarboxylate resin as a reactant obtained by reacting component (a), component (b), and optionally component (c), a reactive polycarboxylic acid resin as a reactant of component (d), and components Reactive epoxycarboxylate resin, which is a reactant obtained by reacting (a'), component (b), and, if necessary, component (c), and reactive polycarboxylic acid resin, which is a reactant of component (d), are synthesized and mixed, respectively. method,

Manufacturing Method 2: A method of reacting component (d) with a reactive epoxycarboxylate resin mixture, which is a reactant obtained by reacting component (a), component (a'), component (b), and, if necessary, component (c). It can be obtained by any manufacturing method.

When using Production Method 1, the mixing ratio of the reactive polycarboxylic acid resin obtained from component (a) and the reactive polycarboxylic acid resin obtained from component (a') should be appropriately changed depending on the intended use. As the proportion of the reactive polycarboxylic acid resin obtained from component (a') increases, developability improves, but the insulation reliability of the cured product deteriorates.

The reactive polycarboxylic acid resin obtained from component (a') is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, and 1 to 20% by mass relative to the total amount of 100% by mass of the reactive polycarboxylic acid resin mixture. Mass percent is more preferable.

Since the reactive polycarboxylic acid resin mixture obtained in Production Method 2 has good insulation reliability and developability, it is more preferable to use Production Process 2.

This is believed to be because, through manufacturing method 2, a structure is obtained in which component (a) and component (a') are bonded via component (c) and/or component (d).

The mixing ratio of component (a) and component (a') should be appropriately changed depending on the intended use. As the ratio of component (a') increases, developability improves, but the insulation reliability of the cured product deteriorates.

Component (a') is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, and still more preferably 1 to 20% by mass, based on 100% by mass of the total amount of component (a) and component (a'). do.

Additionally, the reactive epoxycarboxylate resin mixture of the present invention can be obtained as an intermediate product of Production Method 2 above. In addition, the epoxycarboxylate resin mixture of the present invention is a reactive epoxycarboxylate resin obtained by reacting component (a), component (b), and, if necessary, component (c), and component (a') and component (c). (b) and, if necessary, the reactive epoxy carboxylate resin, which is a reactant obtained by reacting component (c), may be synthesized and mixed, respectively.

The acid value of the reactive polycarboxylic acid mixture of the present invention is preferably 50 to 70 mg·KOH/g, more preferably 55 to 65 mg·KOH/g, and especially 58 to 62 mg·KOH/g. desirable. When the acid value is within the above range, developability becomes good.

In addition, the active energy ray-curable resin composition of the present invention may contain a reactive compound (C) (hereinafter also simply referred to as “component (C)”). Component (C) is not particularly limited as long as it is a compound other than the above reactive polycarboxylic acid resin, and specific examples include radically reactive acrylates, cationic reactive epoxy compounds, vinyl compounds sensitive to both, etc. So-called reactive oligomers can be mentioned.

Acrylates that can be used include monofunctional (meth)acrylates, polyfunctional (meth)acrylates, epoxy acrylates, polyester acrylates, and urethane acrylates.

Monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol (meth)acrylate, and polyethylene glycol (meth)acrylate. ) Acrylate monomethyl ether, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, etc. I can hear it.

Polyfunctional (meth)acrylates include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, and ethylene glycol di(meth)acrylate. ) Acrylate, diethylene di(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 adduct of hydroxypivalic acid neopen glycol Di(meth)acrylate, poly(meth)acrylate of the reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylolpropane 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 Rate and its ethylene oxide adduct, etc. can be mentioned.

Vinyl compounds that can be used include vinyl ethers, styrenes, and other vinyl compounds. Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Styrenes include styrene, methyl styrene, and ethyl styrene. Other vinyl compounds include triallyl isocyanurate and trimetalyl isocyanurate.

In addition, so-called reactive oligomers include urethane acrylate, which has both a functional group that is sensitive to active energy rays and a urethane bond in the same molecule, polyester acrylate, which also has a functional group that is sensitive to active energy rays and an ester bond, etc., in the same molecule. In addition, epoxy acrylates derived from epoxy resins and having functional groups sensitive to active energy rays in the same molecule, reactive oligomers in which these bonds are used in combination, etc.

Additionally, there is no particular limitation as to the cation-reactive monomer, as long as it is generally a compound having an epoxy group. For example, glycidyl (meth)acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3, 4-Epoxycyclohexanecarboxylate (“CYRACURE UVR-6110” manufactured by Union Carbide Corporation, etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexenedioxide (Union Carbide Corporation's "ELR-4206", etc.), limonene dioxide (DAICEL CHEMICAL INDUSTRIES, LTD.'s "CELLOXIDE 3000", etc.), allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide Seed, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl)adipate (manufactured by Union Carbide Corporation) "CYRACURE UVR-6128", etc.), bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxycyclohexyl)ether, bis(3,4-epoxycyclohexylmethyl)ether, bis( 3,4-epoxycyclohexyl)diethylsiloxane, etc. are mentioned.

Among these, as component (C), radically curable acrylates are most preferable. In the case of the cationic type, the carboxylic acid and epoxy group react, so it is necessary to use a two-liquid mixed type.

The active energy ray-curable resin composition of the present invention contains 97 to 5% by mass of reactive polycarboxylic acid resin, preferably 87 to 10% by mass, and 3 to 95% by mass of component (C), preferably 3 to 10% by mass. Contains 80% by mass. If necessary, other components may be included at an upper limit of about 70% by mass. Other components include photopolymerization initiators, other additives, coloring materials, curing accelerators, and volatile solvents added to adjust viscosity for the purpose of providing coating suitability, etc. Other components that can be used are exemplified below.

The active energy ray-curable resin composition of the present invention may further contain a coloring pigment, and the coloring pigment is used to use the resin composition of the present invention as a coloring material. It is assumed that the hydroxyl group of the reactive polycarboxylic acid resin mixture used in the active energy ray-curable resin composition of the present invention exhibits particularly excellent affinity for pigments, that is, dispersibility. As a result of good dispersibility, the pigment concentration can be increased. In addition, for compositions that require development, the dispersibility is more suitable, good patterning characteristics are exhibited, and the development residue in the development and dissolution area is small, so it is suitable.

Examples of the coloring pigment include organic pigments such as phthalocyanine-based, azo-based, and quinacridone-based pigments, and inorganic pigments such as carbon black and titanium oxide. Among these, carbon black is preferable due to its high dispersibility.

The active energy ray-curable resin composition of the present invention may further include a photopolymerization initiator. As the photopolymerization initiator, a radical type photopolymerization initiator and a cationic photopolymerization initiator are preferable.

Examples of the radical photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; Acetophenone, 2,2-diethoxy-2-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; Known general radical type photopolymerization initiators such as phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide can be mentioned.

Additionally, cationic photopolymerization initiators include diazonium salts of Lewis acids, iodonium salts of Lewis acids, sulfonium salts of Lewis acids, phosphonium salts of Lewis acids, other halides, triazine initiators, borate initiators, and other mineral acids. Generating agents, etc. can be mentioned.

Examples of diazonium salts of Lewis acids include p-methoxyphenyldiazonium fluorophosphonate and N,N-diethylaminophenyldiazonium hexafluorophosphonate (SAN-AID SI manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD. -60L/SI-80L/SI-100L, etc.), etc., and examples of iodonium salts of Lewis acids include diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroantimonate, etc. , Sulfonium salts of Lewis acids include triphenylsulfonium hexafluorophosphonate (CYRACURE UVI-6990, etc., manufactured by Union Carbide Corporation) and triphenylsulfonium hexafluoroantimonate (CYRACURE UVI-6974, etc., manufactured by Union Carbide Corporation). and the like, and examples of phosphonium salts of Lewis acids include triphenylphosphonium hexafluoroantimonate and the like.

Other halides include 2,2,2-trichloro-[1-4'-(dimethylethyl)phenyl]ethanone (TRIGONAL PI manufactured by Akzo Corporation, etc.), 2,2-dichloro-1-4-(phenoxy Phenyl)ethanone (SANDRAY1000 manufactured by Sandoz AG, etc.), α,α,α-tribromomethylphenylsulfone (BMPS manufactured by Seitetsu Kagaku Co., Ltd., etc.), etc. are mentioned. Triazine-based initiators include 2,4,6-tris(trichloromethyl)-triazine, 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine (TRIAZINE A manufactured by Panchim S.A., etc.), 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine (TRIAZINE PMS, manufactured by Panchim S.A., etc.), 2,4-trichloromethyl-(fipronil)-6-triazine ( TRIAZINE PP manufactured by Panchim S.A., etc.), 2,4-trichloromethyl-(4'-methoxynaphthyl)-6-triazine (TRIAZINE B manufactured by Panchim S.A., etc.), 2[2'(5-methylfuryl)ethyl Liden]-4,6-bis(trichloromethyl)-s-triazine (manufactured by SANWA CHEMICAL CO., LTD., etc.), 2(2'-furylethylidene)-4,6-bis(trichloromethyl) )-s-triazine (manufactured by SANWA CHEMICAL CO., LTD.), etc. can be mentioned.

Borate-based photopolymerization initiators include NK-3876 and NK-3881 manufactured by Japanese Research Institute for Photosensitizing Dyes Co., Ltd. Other photoacid generators include 9-phenylacridine and 2,2'-bis. (o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole (biimidazole manufactured by KUROGANE KASEI Co., Ltd., etc.), 2,2-azobis (2 -Amino-propane) dihydrochloride (V50, etc. manufactured by Wako Pure Chemical Industries, Ltd.), 2,2-azobis[2-(imidazoline-2yl) propane] dihydrochloride (Wako Pure Chemical Industries, Ltd. .VA044, etc.), [Ita-5-2-4-(cyclopentadecyl)(1,2,3,4,5,6,Ita)-(methylethyl)-benzene]Iron(II)hexafluoro Phosphonate (IRGACURE 261, etc. manufactured by Ciba-Geigy AG), bis(y5-cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyri-1-yl)phenyl]titanium (Ciba- CGI-784 manufactured by Geigy AG, etc.).

In addition, azo-based initiators such as azobisisobutyronitrile and heat-sensitive peroxide-based radical-type initiators such as benzoyl peroxide may be used together. Additionally, both radical and cationic photopolymerization initiators may be used together. One type of photopolymerization initiator may be used individually, or two or more types may be used together.

Among these, considering the characteristics of the reactive polycarboxylic acid resin mixture of the present invention, a radical-type photopolymerization initiator is particularly preferable.

Additionally, the active energy ray-curable resin composition of the present invention may contain an extender pigment. Examples of extender pigments include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, and clay.

Additionally, the active energy ray-curable resin composition of the present invention may contain other additives as needed. Other additives include, for example, heat curing catalysts such as melamine, thixotropy imparting agents such as Aerosil, silicone-based and fluorine-based leveling agents and anti-foaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, and antioxidants. etc. can be used.

In addition, resins that do not show reactivity to active energy rays (so-called inner polymers) include, for example, other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, and dia. Relyl phthalate resin, styrene resin, guanamine resin, natural and synthetic rubber, acrylic resin, polyolefin resin, and their modified products can also be used. These are preferably used in an amount of up to 40 parts by mass in the resin composition.

In particular, when it is desired to use a reactive polycarboxylic acid resin for soldering resist purposes, it is preferable to use a known general epoxy resin as a resin that does not show reactivity to active energy rays. Even after reacting and curing with active energy rays, the carboxyl group derived from the reactive polycarboxylic acid resin remains, and as a result, the cured product has poor water resistance and hydrolysis properties. Therefore, by using an epoxy resin, the remaining carboxyl groups are further carboxylated and a strong crosslinked structure is formed. The known general epoxy resin may use the cation reactive monomer.

Additionally, for the purpose of adjusting the viscosity depending on the intended use, a volatile solvent may be added to the resin composition in the range of 50 parts by mass, more preferably up to 35 parts by mass.

The active energy ray-curable resin composition of the present invention is easily cured by active energy rays. Here, 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 preferred.

The active energy ray-curable resin composition of the present invention preferably has a glass transition temperature of 150 to 250°C, as determined by a viscoelasticity measuring device, and more preferably 160 to 180°C. When the glass transition temperature is in the above range, heat resistance and developability become good.

In the present invention, the material for molding refers to an object that is molded by placing an uncured composition in a mold or pressing the mold and causing a curing reaction using active energy rays, or a focused light such as a laser is applied to the uncured composition. It refers to a material used for molding by causing a hardening reaction through irradiation.

Specific uses include sheets molded into a flat shape, sealants to protect elements, so-called nanoimprint materials in which fine molding is performed by pressing a “mold” finely processed into an uncured composition, and light emitting diodes with particularly stringent thermal requirements. , peripheral sealing materials for photoelectric conversion elements, etc. can be cited as suitable uses.

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, silk screen ink, and offset ink, coating materials such as hard coat, top coat, overprint varnish, and clear coat, and various adhesives and adhesives for laminating and optical disks, etc. These include resist materials such as adhesive materials, solder resist, etching resist, and micro machine resist. In addition, a so-called dry film in which a film-forming material is temporarily applied to a peelable substrate to form a film and then bonded to the intended substrate to form a film also corresponds to a film-forming material.

The present invention includes a cured product obtained by irradiating the curable resin composition with active energy rays, and also includes a multilayer material having layers of the cured product.

Among these, the introduction of the carboxyl group of the reactive polycarboxylic acid resin increases adhesion to the substrate, so it is preferable to use it for coating a plastic substrate or a metal substrate.

Additionally, it is also preferable to use the unreacted reactive polycarboxylic acid resin as an alkaline water-developable resist material composition, taking advantage of the characteristic of being soluble in aqueous alkaline solutions.

In the present invention, the resist material composition refers to forming a film layer of the composition on a substrate, then partially irradiating active energy rays such as ultraviolet rays, and using the difference in physical properties of the irradiated area and the unradiated area to draw the active energy ray. Refers to a sensitive composition. Specifically, it is a composition used for the purpose of removing irradiated or unradiated areas by any method, such as dissolving them with a solvent or an alkaline solution, and performing drawing.

The active energy ray-curable resin composition, which is the resist material composition of the present invention, can be adapted to a variety of materials capable of patterning, and is particularly useful for solder resist materials and interlayer insulating materials for build-up methods, and is also useful as an optical waveguide for printed wiring boards, It is also used in electrical, electronic, and optical materials such as optoelectronic boards and optical boards.

In particular, suitable applications include photosensitive films with good heat resistance and developability, photosensitive films with supports, insulating resin sheets such as prepreg, circuit boards (laminated boards, multilayer printed wiring boards, etc.), solder resists, and underfill materials. It can be used in a wide range of applications that require a resin composition, such as die bonding material, semiconductor sealing material, hole filling resin, and component filling resin. In particular, since it can exhibit good developing properties even at high pigment concentrations, it can be suitably used for color resists, resist materials for color filters, and especially black matrix materials.

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 a 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 also be suitably used in a resin composition for forming plating (a multilayer printed wiring board in which plating is formed on a cured product of a photosensitive resin composition).

Patterning using the active energy ray-curable resin composition of the present invention can be performed, for example, as follows. The curable resin composition of the present invention is applied to a substrate with a film thickness of 0.1 to 200 ㎛ by a method such as screen printing, spraying, roll coating, electrostatic coating, curtain coating, spin coating, etc., and the coating film is usually 50 μm thick. A coating film can be formed by drying at a temperature of ~110°C, preferably 60~100°C. Afterwards, high-energy rays such as ultraviolet rays are irradiated directly or indirectly to the coating film through a photomask on which an exposure pattern is formed, usually at an intensity of about 10 to 2000 mJ/cm2, using a developer described later, for example, spray or vibration. The desired pattern can be obtained by dipping, paddling, brushing, etc.

Alkaline aqueous solutions used in the above phenomenon include inorganic alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, and potassium phosphate, or tetramethylammonium hydroxide and tetraethylammonium hydroxide. Organic alkali aqueous solutions such as tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine can be used. This aqueous solution may further contain organic solvents, buffers, complexing agents, dyes or pigments.

In addition, it is particularly suitably used for dry film applications that require mechanical strength before curing reaction by active energy rays. That is, since the balance of hydroxyl groups and epoxy groups in the epoxy resin used in the present invention is within a specific range, the reactive polycarboxylic acid resin mixture of the present invention can exhibit good developability.

There are no particular restrictions on the method of forming the film, but it includes intaglio printing methods such as gravure, raised plate printing methods such as flexo, stencil printing methods such as silk screen, flat printing methods such as offset, roll coater, knife coater, die coater, and curtain coater. , various coating methods such as spin coater can be arbitrarily adopted.

The cured product of the active energy ray-curable resin composition of the present invention refers to the product cured by irradiating active energy rays to the active energy ray-curable resin composition of the present invention.

(Example)

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

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

1) Epoxy equivalent weight: measured by a method according to JISK7236: 2001.

2) Softening point: Measured by a method according to JISK7234: 1986.

3) Acid value: Measured by a method according to JISK0070: 1992.

4) GPC measurement conditions are as follows.

Model: TOSOH HLC-8320GPC

Column: Super HZM-N

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

Detector: RI (differential refractometer)

Molecular Weight Standard: Polystyrene

(Example 1, Reference Example 1, Comparative Example 1): Synthesis of reactive epoxycarboxylate resin

As component (a), , softening point 70°C, epoxy equivalent weight 193 g/eq.), EPPN-503 (manufactured by Nippon Kayaku Co., Ltd., softening point 94°C, epoxy equivalent weight 185 g/eq.) as component (a'-2), component (a' -3) as NC-3500 (manufactured by Nippon Kayaku Co., Ltd., softening point 70°C, epoxy equivalent weight 206 g/eq.), and as component (a'-4), NC-6000 (manufactured by Nippon Kayaku Co., Ltd., Softening point 60°C, epoxy equivalent weight 208 g/eq.), acrylic acid (AA) or methacrylic acid (MAA) as component (b) in the amounts listed in Table 1, and dimethylolpropionic acid (hereinafter referred to as “DMPA”) as component (c). (abbreviated) was added in the amount listed in Table 1. 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content was 80% by mass, and the mixture was reacted at 100°C for 24 hours to obtain a solution of a reactive epoxycarboxylate resin mixture.

(Example 2, Reference Example 2, Comparative Example 2): Preparation of composition for hard coat

For each 20 g of each reactive epoxycarboxylate resin mixture solution synthesized in Example 1, Reference Example 1, and Comparative Example 1, 4 g of dipentaerythritol hexaacrylate, a radically curable reactive compound, and IRGACURE as an ultraviolet-reactive photopolymerization initiator. 1.5 g of 184 was dissolved by heating.

Next, it was applied on a polycarbonate plate using a hand applicator so that the film thickness at the time of drying was 20 microns, and solvent dried in an electric oven at 80°C for 30 minutes. After drying, the film was cured by irradiating it with ultraviolet rays at an irradiation dose of 1000 mJ using an ultraviolet vertical exposure device (manufactured by ORC Manufacturing Co., Ltd.) equipped with a high-pressure mercury lamp to obtain a film-forming product.

The hardness of the coating film of this formation was measured according to JISK5600-5-4: 1999, and the cold and heat shock resistance test was also measured according to JISK5600-7-4: 1999. The results are shown in Table 2. The meaning of each symbol shown in Table 2 is as follows.

○: No scratches or peeling

△: Slight scratches

×: peeled off

As is clear from the results in Table 2, it was confirmed that Examples 2-1 to 2-4 had excellent cold and heat shock resistance.

(Example 3, Reference Example 3, Comparative Example 3): Synthesis of reactive polycarboxylic acid resin

THPA (1,2,3,6-tetrahydrophthalic anhydride, New Japan Chemical) as component (d) for 200 g of each reactive epoxycarboxylate resin mixture solution obtained in Example 1, Reference Example 1, and Comparative Example 1. Co., Ltd.) to 30.9 (g) and propylene glycol monomethyl ether monoacetate as a solvent to a solid content of 65%, heated to 100°C, and then subjected to acid addition reaction to form a reactive polycarboxylic acid resin mixture. A solution was obtained. The solid acid value (mgKOH/g) of the obtained reactive polycarboxylic acid resin mixture is shown in Table 3. The solid content acid value (AV: mgKOH/g) was measured as a solution and converted to the solid content value.

(Synthesis Examples 1 to 5): Synthesis of reactive polycarboxylic acid resin

Component (a), component (a'-1), component (a'-2), component (a'-3), component (a'-5) (EOCN-104S, manufactured by Nippon Kayaku Co., Ltd., Softening point 92°C, epoxy equivalent weight 218 g/eq.), acrylic acid (AA) as component (b), and dimethylolpropionic acid (DMPA) as component (c) were added in the amounts listed in Table 4. 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content was 80% by mass, and the mixture was reacted at 100°C for 24 hours to obtain a reactive epoxycarboxylate resin solution. To the obtained reactive epoxycarboxylate resin solution, THPA as component (d) in the amount (g) shown in Table 4 and propylene glycol monomethyl ether monoacetate as a solvent were added to a solid content of 65%, and heated to 100°C. An acid addition reaction was performed to obtain a reactive polycarboxylic acid resin solution. The solid acid value (AV: mgKOH/g) of the obtained reactive polycarboxylic acid resin is shown in Table 4. The solid content acid value (mgKOH/g) was measured as a solution and converted to the solid content value.

(Example 4, Reference Example 4): Formulation of reactive polycarboxylic acid resin

The reactive polycarboxylic acid resin solutions synthesized in Synthesis Examples 1 to 5 were mixed in the weight ratio shown in Table 5 to obtain a mixture of reactive polycarboxylic acid solutions.

(Comparative Example 4): Formulation of reactive polycarboxylic acid resin

The reactive polycarboxylic acid resin solution synthesized in Synthesis Example 1, Synthesis Example 3, and other reactive polycarboxylic acid resins were mixed in the weight ratio shown in Table 6 to obtain a reactive polycarboxylic acid mixture solution as a comparative example.

KAYARAD ZAR-2001H; Bisphenol A type reactive polycarboxylic acid resin (manufactured by Nippon Kayaku Co., Ltd.)

KAYARAD ZFR-1554H; Bisphenol F type reactive polycarboxylic acid resin (manufactured by Nippon Kayaku Co., Ltd.)

KAYARAD ZCR-1761H; Biphenyl aralkyl type reactive polycarboxylic acid resin (manufactured by Nippon Kayaku Co., Ltd., has a structure represented by formula (4) and Ar is formula (6))

KAYARAD UXE-3024H; Carboxylic acid-modified bisphenol A/urethane type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd.)

(Example 5, Reference Example 5, Comparative Example 5): Dry film type resist composition

For each of 56.73 g of each reactive polycarboxylic acid resin mixture solution obtained in Example 3, Example 4, Reference Example 3, Reference Example 4, and Comparative Example 4, DPCA-60 (Product name: 5.67 g of multifunctional acrylate (manufactured by Nippon Kayaku Co., Ltd.), 2.92 g of IRGACURE 907 (manufactured by BASF Japan Ltd.) and 0.58 g of KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) as a photopolymerization initiator, 17.54 g of NC-3000H (manufactured by Nippon Kayaku Co., Ltd.) was added as a curing component, 0.73 g of melamine was added as a heat curing catalyst, and 5.67 g of propylene glycol monomethyl ether monoacetate was added as a concentration adjusting solvent, and then added by a bead mill. It was kneaded and dispersed uniformly to obtain a resist resin composition.

The obtained composition was uniformly applied to a polyethylene terephthalate film as a support film using wire bar coater #20, passed through a hot air drying furnace at a temperature of 70°C to form a 20㎛ thick resin layer, and then protected on this resin layer. A dry film was obtained by attaching a polyethylene film to be used as a film. The obtained dry film was applied to a polyimide printed circuit board (copper circuit thickness: 12 µm, polyimide film thickness: 25 µm) using a heating roll at a temperature of 80°C to peel off the protective film while attaching the resin layer to the entire surface of the substrate.

Next, using an ultraviolet exposure device (ORC Manufacturing Co., Ltd., model HMW-680GW), a mask on which the circuit pattern was drawn was used, and in order to estimate the sensitivity, 500 mJ/cm2 was applied through step tablet No. 2 manufactured by Kodak Japan Ltd. Ultraviolet rays were irradiated. Afterwards, the film on the dry film was peeled off to check the peeling state. After that, spray development was performed with a 1% sodium carbonate aqueous solution to remove the resin in the ultraviolet irradiated area. After washing with water and drying, the printed circuit board was heat-cured for 60 minutes using a hot air dryer at 150°C to obtain a cured film.

[Evaluation of insulation reliability]

The prepared resist resin composition was applied to a film thickness of 20 ㎛ on a comb-shaped electrode (material: copper, pattern pitch: 18 ㎛, L/S = 100 ㎛/100 ㎛) formed on a substrate (polyimide film) and incubated at 80°C. After performing a prebake for 30 minutes, it was exposed to 500 mJ/cm2 and heat-cured at 150°C for 1 hour to obtain a test piece. The heated test piece was placed in a tank (ETAC PLAMOUBT HAST CHAMBER PM220 Kusumoto Chemicals, Ltd.) at 130°C and 85% humidity, and a direct current voltage of 100V was applied between the electrodes using a migration tester (ETAC SIR-13mini Kusumoto Chemicals, Ltd.). was applied, and the resistance between the electrodes was measured. Insulation reliability was judged based on the following standards. In the case of the judgment criteria of ○ and △, the insulation reliability is judged to be acceptable, and there is insulation maintenance without any problem in actual use, and the insulation reliability is excellent.

[Judgment criteria for insulation reliability]

○: Resistance is more than 1×10 ⁹ Ω, lasts for more than 100 hours, and has very good insulation properties.

△: Resistance is more than 1×10 ⁸ Ω and less than 1×10 ⁹ Ω, and lasts for more than 100 hours, so the insulation is good.

×: Less than 100 hours, the resistance decreases to less than 1×10 ⁸ Ω and is considered to be an insulation defect.

[Sensitivity evaluation]

Sensitivity was determined by what level of density portion remained in the exposed area that passed through the step tablet at the time of development. The larger the number (value) of the tablet, the smaller the tablet, and is judged to have higher sensitivity (unit: unit).

[Development evaluation]

Developability was evaluated using the so-called break time, which is the time until the pattern shape part is completely developed when developing the exposed part that passed through the pattern mask (unit: seconds).

[Evaluation of heat resistance]

The resist resin composition was uniformly applied to the polyimide film, passed through a hot air drying furnace at a temperature of 80°C to form a 20㎛ thick resin layer, and then dried using an ultraviolet ray exposure device (ORC Manufacturing Co., Ltd., model HMW-680GW). It was exposed to light and a cured product was obtained. Cut the produced cured product into 5 mm wide pieces. Afterwards, the viscoelasticity measuring device RSA-G2 manufactured by TA Instruments, Inc. was set to measure tanδ 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 tanδ was designated as Tg. .

From the above results, it was confirmed that the resist material composition using the reactive polycarboxylic acid resin mixture of the present invention had better resist physical properties compared to the composition using the comparative reactive polycarboxylic acid resin mixture.

(Example 6, Reference Example 6, Comparative Example 6): Evaluation of pigment dispersibility

5.0 g of DPHA (brand name: acrylate monomer manufactured by Nippon Kayaku Co., Ltd.) as component (C) for each 20 g of each reactive polycarboxylic acid resin mixture obtained in Example 3, Reference Example 3, and Comparative Example 4. , 10 g of propylene glycol monomethyl ether acetate as an organic solvent, and 15 g or 10 g of MITSUBISHI carbon black MA-100 as a coloring pigment were added and stirred. Additionally, 35 g of glass beads were added and dispersed using a paint shaker for 1 hour. The dispersion liquid after completion of dispersion was coated on a polyethylene terephthalate film using wire bar coater #2, and dried in a warm air dryer at 80°C for 10 minutes. The gloss of the surface of the coating film after completion of drying was measured using a 60° reflection gloss meter (HORIBA, Ltd. IG-331 gloss meter), and the dispersibility of the carbon black was evaluated. Table 8 shows the results. The higher the gloss value, the better the pigment dispersibility.

From the above results, the coating film obtained from the resin composition containing the reactive polycarboxylic acid resin mixture obtained in Example 3 showed no change in gloss value even when the content of the coloring pigment was high. It was confirmed that the pigment dispersibility of the reactive polycarboxylic acid resin mixture of the present invention was excellent without being dependent on the content of the color pigment, despite improved developability and heat resistance.

From the above, the cured product of the active energy ray-curable resin composition using the reactive polycarboxylic acid resin mixture of the present invention has excellent heat resistance, is capable of fine alkali development, and has good insulation reliability, so it can be used as a molding material and film formation. Suitable for materials, resist materials, and interlayer insulation materials. In particular, since it exhibits good developability even at high pigment concentrations, it is suitable for color resists, resist materials for color filters, especially black matrix materials, black column spacer materials, etc.

This application is based on the Japanese patent application (patent application 2018-173665) filed on September 18, 2018 and the Japanese patent application (patent application 2018-192527) filed on October 11, 2018, the contents of which are provided here. It is incorporated by reference.

Claims (12)

A mixture of an epoxy resin (a) represented by the following formula (1) and an epoxy resin (a') different from the epoxy resin (a), a compound (b) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule, and A reactive epoxycarboxylate resin mixture, which is a reactant obtained by reacting a compound (c) having both a hydroxyl group and a carboxyl group in one molecule as necessary, and a reactive polycarboxylic acid resin mixture, which is a reactant of a polybasic acid anhydride (d),
A reactive polycarboxylic acid resin mixture containing a reactive polycarboxylic acid resin wherein the epoxy resin (a') is an epoxy resin represented by any of the following formulas (2) to (4).

(R ₁ in formula (1) may be the same or different, and represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 4 carbon atoms, and n represents an integer of 1 to 10.)

(In equation (2), p represents an integer from 0 to 2)

(In equation (3), m represents an integer from 0 to 30)

(Ar in equation (4) is each independently either equation (5) or equation (6), and the molar ratio of equations (5) and (6) is equation (5) / equation (6) = 1~3 q is the number of repetitions, and r represents the mantissa and is 1 or 2. delete An active energy ray-curable resin composition comprising the reactive polycarboxylic acid resin mixture according to claim 1. According to claim 3,
further comprising a reactive compound (C),
An active energy ray-curable resin composition in which the reactive compound (C) is a radical-reactive acrylate, a cation-reactive epoxy compound, a vinyl compound sensitive to both, or a reactive oligomer having a functional group capable of being sensitive to active energy rays. . According to claim 3 or 4,
An active energy ray-curable resin composition further comprising a photopolymerization initiator. According to claim 3 or 4,
An active energy ray-curable resin composition further comprising a coloring pigment. According to claim 3 or 4,
Active energy ray-curable resin composition as a molding material. According to claim 3 or 4,
An active energy ray-curable resin composition that is a material for forming a film. According to claim 3 or 4,
An active energy ray-curable resin composition that is a resist material composition. A cured product of the active energy ray-curable resin composition according to claim 3 or 4. An article overcoated with the cured material according to claim 10. A mixture of an epoxy resin (a) represented by the following formula (1) and one or more epoxy resins selected from the group of epoxy resins represented by the following formulas (2) to (4), an ethylenic polymer that can be polymerized in one molecule. A reactive epoxycarboxylate resin mixture that is a reactant obtained by reacting a compound (b) having both an unsaturated group and a carboxyl group with a compound (c) having both a hydroxyl group and a carboxyl group in one molecule as needed.

(R ₁ in formula (1) may be the same or different, and represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 4 carbon atoms, and n represents an integer of 1 to 10.)

(In equation (2), p represents an integer from 0 to 2)

(In equation (3), m represents an integer from 0 to 30)

(Ar in equation (4) is each independently either equation (5) or equation (6), and the molar ratio of equations (5) and (6) is equation (5) / equation (6) = 1~3 q is the number of repetitions, and r represents the mantissa and is 1 or 2.