JPWO2020059500A1 - Reactive polycarboxylic acid resin mixture, active energy ray-curable resin composition using it and its cured product, and reactive epoxy carboxylate resin mixture. - Google Patents

Abstract

The epoxy resin (a) represented by the formula (1), the compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, and, if necessary, a hydroxyl group and a carboxy group in one molecule. Reactive polycarboxylic acid resin which is a reaction product of reactive epoxy carboxylate resin obtained by reacting compound (c) and polybasic acid anhydride (d), and formulas (2) to (4). ), The compound (b), and the reactive epoxy carboxylate resin obtained by reacting the compound (c) if necessary, and the polybasic acid anhydride (d). ), A reactive polycarboxylic acid resin mixture containing the reactive polycarboxylic acid resin. (In the formula (1), R1 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

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

Printed wiring boards are required to have high accuracy and high density with the aim of reducing the size and weight of mobile devices and improving the communication speed. Along with this, the demand for solder resists that cover the circuit itself is becoming more and more sophisticated. Compared 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 a film-forming material with tougher cured physical properties is required. It has been demanded.

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

On the other hand, an acid-modified epoxy acrylate having an epoxy resin having a polycyclic hydrocarbon group having a specific structure (for example, XD-1000 manufactured by Nippon Kayaku Co., Ltd.) as a basic skeleton is used as a material showing high toughness after curing. It is generally known. Further, the use as a solder resist using this is also being studied (Patent Document 2).

In addition, acid-modified epoxy acrylate based on epoxy having a TrisP-PA skeleton has excellent heat resistance, developability, and copper plating adhesion, so its use as a photosensitive interlayer insulating layer is also being investigated. Is being done. (Patent Document 3)
However, even with these studies, a resin composition having both high insulating properties and developability has not been realized.

Japanese Patent Application Laid-Open No. 06-324490 Japanese Patent Application Laid-Open No. 2009-102501 International release 2018/003314

The present invention improves the above-mentioned problems of the prior art, and has a reactive polycarboxylic acid resin mixture having good development characteristics without deteriorating high insulation reliability, and an active energy ray-curable resin composition containing the same. The primary purpose is to provide goods. The present invention also provides a reactive epoxy carboxylate resin mixture that improves the above-mentioned problems of the prior art and has good development characteristics and insulation reliability without deteriorating high toughness and heat resistance. The second purpose.

As a result of diligent studies to solve the above-mentioned problems, the present inventors are excellent in an epoxy carboxylate resin having a specific structure, and further, a reactive polycarboxylic acid resin obtained by reacting it with a polybasic acid anhydride. They have found that they have resin properties and have reached the present invention.

That is, the present invention relates to the following [1] to [15].
[1]
An epoxy resin (a) represented by the following formula (1), a compound (b) having a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, and a hydroxyl group and a carboxy group in one molecule as needed. A reactive epoxy carboxylate resin which is a reaction product obtained by reacting the compound (c) having both of the above, a reactive polycarboxylic acid resin which is a reaction product of a polybasic acid anhydride (d), and the epoxy resin. An epoxy resin (a') different from (a'), the compound (b), and a reactive epoxy carboxylate resin which is a reaction product obtained by reacting the compound (c), if necessary, and the above-mentioned poly. A reactive polycarboxylic acid resin that is a reaction product with the basic acid anhydride (d), wherein the epoxy resin (a') is represented by any of the following formulas (2) to (4). A reactive polycarboxylic acid resin mixture containing, which is a reactive polycarboxylic acid resin.

(In the 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.)

（式（２）中、ｐは０〜２の整数を示す。）

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

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

(In the formula (4), Ar is either the formula (5) or the formula (6) independently, and the molar ratio of the formula (5) and the formula (6) is the formula (5) / the 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.)

[2]
A reactive epoxy carboxylate resin mixture that is a reaction product obtained by reacting the epoxy resin (a) and the epoxy resin (a'), the compound (b), and the component (c) if necessary. The reactive polycarboxylic acid resin mixture according to the previous item [1], which is a reaction product of the polybasic acid anhydride (d).
[3]
An active energy ray-curable resin composition containing the reactive polycarboxylic acid resin mixture according to the above item [1] or [2].
[4]
Further, the reactive compound (C) contains a reactive compound (C), and the reactive compound (C) can be used as a radical reaction type acrylate, a cationic reaction type epoxy compound, vinyl compounds sensitive to both of these, or an active energy ray. The active energy ray-curable resin composition according to the preceding item [3], which is a reactive oligomer having a sensitive functional group.
[5]
The active energy ray-curable resin composition according to the above item [3] or [4], further comprising a photopolymerization initiator.
[6]
The active energy ray-curable resin composition according to any one of the above items [3] to [5], further containing a coloring pigment.
[7]
The active energy ray-curable resin composition according to any one of the above items [3] to [6], which is a molding material.
[8]
The active energy ray-curable resin composition according to any one of the above 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 above items [3] to [6], which is a resist material composition.
[10]
The cured product of the active energy ray-curable resin composition according to any one of the above items [3] to [9].
[11]
An article overcoated with the cured product according to the preceding item [10].
[12]
The epoxy resin (a) represented by the following formula (1) contains a compound (b) having a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, and a hydroxyl group and carboxy in one molecule as needed. One or more selected from the group of reactive epoxy carboxylate resins, which are reactants obtained by reacting compound (c) having a group, and epoxy resins represented by the following formulas (2) to (4). A reactive epoxy carboxylate resin mixture containing the compound (b) and a reactive epoxy carboxylate resin which is a reaction product obtained by reacting the compound (c), if necessary, with the epoxy resin.

(In the 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.)

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

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

(In the formula (4), Ar is either the formula (5) or the formula (6) independently, and the molar ratio of the formula (5) and the formula (6) is the formula (5) / the 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.)

The active energy ray-curable resin composition containing a mixture of a reactive epoxy carboxylate resin having a polycyclic hydrocarbon group having a specific structure of the present invention and / or an acid-modified resin thereof can obtain a tough cured product. Furthermore, it has good developability. Further, 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 is suitably used as a film forming material having excellent heat resistance and high insulation reliability. Can be done.

Preferably, for example, a solder resist for a printed wiring board that requires particularly high insulation reliability, a protective film for a multilayer printed wiring board, an interlayer insulating material for a multilayer printed wiring board, a solder resist for a flexible printed wiring board, a plating resist, and photosensitive. It can be used for applications such as optical waveguides.

Further, the specific structure according to the present invention has a high affinity with a coloring pigment such as carbon black, can exhibit good developability even at a high pigment concentration, and is a resist for a color resist and a color filter. It can also be suitably used for materials, particularly black matrix materials, black column spacers and the like.

The reactive polycarboxylic acid resin mixture of the present invention contains at least two types of reactive polycarboxylic acid resins shown in 1 and 2 below.
1. 1. The epoxy resin (a) represented by the above formula (1) (hereinafter, also simply referred to as “component (a)”), the compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule. (Hereinafter, it is also simply referred to as “component (b)”), and if necessary, the compound (c) having both a hydroxyl group and a carboxy group in one molecule (hereinafter, also simply referred to as “component (c)”) is reacted. A reactive polycarboxylic acid which is a reaction product of a reactive epoxy carboxylate resin which is a reaction product obtained by the above treatment and a polybasic acid anhydride (d) (hereinafter, also simply referred to as “component (d)”).
2. A reaction obtained by reacting an epoxy resin (a') different from the component (a) (hereinafter, also simply referred to as "component (a')"), the component (b), and if necessary, the component (c). A reactive epoxy carboxylate resin which is a product and a reactive polycarboxylic acid resin which is a reaction product of the component (d), wherein the component (a') is any one of the above formulas (2) to (4). Reactive polycarboxylic acid resin which is an epoxy resin represented by.
Similarly, the reactive epoxy carboxylate resin mixture of the present invention contains at least two types of reactive epoxy carboxylate resins shown in 3 to 4 below.
3. 3. A reactive epoxy carboxylate resin which is a reactant obtained by reacting the component (a), the component (b), and the component (c) if necessary.
4. A reactive epoxy carboxylate resin which is a reactant obtained by reacting the component (a'), the component (b), and the component (c) if necessary, and the component (a') is the above formula (2). ) ~ Reactive epoxy carboxylate resin which is an epoxy resin represented by any of the formula (4).

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

_{In R 1} in the formula (1), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. _{In R 1} in the formula (1), examples of the hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group or t-. Butyl groups and the like can be mentioned.

Among them, _{a compound in which R 1} is an all hydrogen atom or a compound in which R 1 is a methyl group is preferable because it can be obtained at low cost.
Further, a method for producing an epoxy resin represented by the above formula (1) is described in Patent Document 3 and the like. 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. In addition, KUKDO CHEMICAL CO ,. LTD. It is also available as KDCP-130 and LDCP-150.
As the component (a), for example, a compound suitable for the softening point grade may be appropriately selected from these products or synthesized.

The component (a') is an epoxy resin other than the component (a), and one type may be used alone or two or more types may be used in combination.
The component (a') is preferably an epoxy resin having three or more epoxy groups in the molecule. Specific examples include aromatic novolac type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol aralkyl type epoxy resin and the like. In the present invention, at least an epoxy resin represented by any of the above formulas (2) to (4) is used as the component (a').
The epoxy equivalent of the component (a') is preferably 180 to 220 g / eq, more preferably 185 to 210 g / eq. When the epoxy equivalent is in the above range, the heat resistance is further excellent.

In the above equations (2) [in equation (2), p represents an integer of 0 to 2. ] Is known, and is generally available as NC-6000 and NC-6300 of Nippon Kayaku Co., Ltd. It is also available as TECMOREVG3101L from Printec. For the compound of the above formula (2), for example, a suitable compound may be appropriately selected from these or synthesized.

In the above equation (3) [in equation (3), m represents an integer from 0 to 30. ] Is known, and is generally available from Nippon Kayaku Co., Ltd. as EPPN-501H, EPPN-501HY, EPPN-502H, and EPPN-503. In addition, KUKDO CHEMICAL CO ,. LTD. It is available as KDMN-1065 from. As the compound of the above formula (3), for example, a suitable compound may be appropriately selected from these or synthesized. In the present invention, m is preferably an integer of 0 to 8 in the above formula (3).

In the above formulas (4) [in the formula (4), Ar is either the formula (5) or the formula (6) independently, and the molar ratio of the formula (5) and the formula (6) is the formula (5). / Equation (6) = 1-3. q is the number of repetitions, which is an integer of 0-5. r represents a valence and is 1 or 2. ] Is known, and a commercially available product is generally available from Nippon Kayaku Co., Ltd. as the NC-3500 series. As the compound of the above formula (4), for example, a suitable compound among the grades of the NC-3500 series may be appropriately selected or synthesized.

Examples of the compound (b) having both an ethylenically unsaturated group and a carboxy group that can be polymerized in one molecule include (meth) acrylic acids, crotonic acid, α-cyanocynic acid, cinnamic acid, or saturated or unsaturated di. Examples thereof include a reaction product of a basic acid and an unsaturated group-containing monoglycidyl compound. In the above, examples of the (meth) acrylic acids include (meth) acrylic acid, β-styrylacrylic acid, β-fulfurylacrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride and 1 Semi-esters that are the molar reactants of (meth) acrylate derivatives having one hydroxyl group in the molecule, and semi-esters that are the molar reactants of saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives. A monocarboxylic acid compound containing one carboxy group in one molecule of esters, etc., a (meth) acrylate derivative having a plurality of hydroxyl groups in one molecule, and semiesters which are the molar reaction products, saturated or unsaturated dibases. Examples thereof include polycarboxylic acid compounds having a plurality of carboxy groups in one molecule such as semiesters which are the molar reaction products of an acid and glycidyl (meth) acrylate derivatives having a plurality of epoxy groups.

Of these, considering the stability of the reaction between the epoxy resin and the component (b), the component (b) is preferably a monocarboxylic acid, and even when the monocarboxylic acid and the polycarboxylic acid are used in combination, the monocarboxylic acid is used. The value represented by the molar amount of the polycarboxylic acid / the molar amount of the polycarboxylic acid is preferably 15 or more.
Most preferably, (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid can be mentioned in terms of sensitivity when made into an active energy ray-curable resin composition.
As the compound having one or more polymerizable ethylenically unsaturated groups and one or more carboxy groups in one molecule, those having no hydroxyl group in the compound are preferable.

The compound (c) having both a hydroxyl group and a carboxy group in one molecule reacts for the purpose of introducing a hydroxyl group into the carboxylate compound. These include compounds that have one hydroxyl group and one carboxy group in one molecule, compounds that have two or more hydroxyl groups and one carboxy group in one molecule, and one or more hydroxyl groups and two in one molecule. Some compounds have more than one carboxy group.
Examples of the compound having one hydroxyl group and one carboxy group in one molecule include hydroxypropionic acid, hydroxybutanoic acid, hydroxystearic acid and the like. Examples of the compound having two or more hydroxyl groups and one carboxy group in one molecule include dimethylolacetic acid, dimethylolpropionic acid, and dimethylolbutanoic acid. Examples of the compound having one or more hydroxyl groups and two or more carboxy groups in one molecule include hydroxyphthalic acid and the like.
Of these, those containing two or more hydroxyl groups in one molecule are preferable in consideration of the effects of the present invention. Further, it is preferable that the number of carboxy groups is one in one molecule in consideration of the stability of the carboxylation reaction. Most preferably, one molecule having two hydroxyl groups and one carboxy group is preferable. Considering the availability of raw materials, dimethylolpropionic acid and dimethylolbutanoic acid are particularly suitable.
As the compound having one or more hydroxyl groups and one or more carboxy groups in one molecule, those having no polymerizable ethylenically unsaturated group in the compound are preferable.

The charging ratio of the epoxy resin and the component (b) and the component (c) in this carboxylation reaction should be appropriately changed depending on the intended use. That is, when all the epoxy groups are carboxylated, the unreacted epoxy groups do not remain, so that the storage stability as a reactive epoxy carboxylate resin is high. In this case, only the reactivity due to the introduced double bond will be used.

On the other hand, by reducing the amount of the component (b) and the component (c) charged to leave an unreacted residual epoxy group, the reactivity due to the introduced unsaturated bond and the reaction with the remaining epoxy group, for example, due to a photocation 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 storage of the reactive epoxy carboxylate resin and the examination of the production conditions.

In the case of producing a reactive epoxy carboxylate resin in which no epoxy group remains, the total of the components (b) and (c) is 0.9 equivalents or more and 1.2 equivalents or less with respect to 1 equivalent of the total epoxy resin. Is preferable. Within this range, it is possible to manufacture under relatively stable conditions. If the amount of the carboxylic acid compound charged is larger than this, the excess component (b) and the component (c) remain, which is not preferable.

When the epoxy group remains, it is preferable that the total of the component (b) and the component (c) is 0.2 equivalent or more and less than 0.9 equivalent with respect to 1 equivalent of the total of the epoxy resin. If it deviates from this range, the effect of composite curing is diminished. Of course, in this case, sufficient attention must be paid to gelation during the reaction and the stability of the reactive epoxy carboxylate resin over time.

The carboxylate reaction can be carried out without a 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 carboxylation reaction.

The amount of the solvent used is preferably adjusted according to the viscosity of the obtained resin and the intended use, but is preferably used so as to have a solid content of 90 to 30% by mass, more preferably 80 to 50% by mass. Will be done.

Examples of the solvent used for the carboxylate reaction include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane and decane, and petroleum which is a mixture thereof. Examples thereof include ether-based solvents, ether-based solvents, ketone-based solvents, and the like, such as ether, white gasoline, and solvent naphtha.

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

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

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

During the carboxylate reaction, it is preferable to use a catalyst to accelerate the reaction. The amount of the catalyst used is 0.1 to 10% by mass with respect to 100 parts by mass of the total amount of the reaction product to which the epoxy resin, the component (b), the component (c) used as needed, and optionally a solvent or the like are added. It is a department. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalysts that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanate, octane. Examples thereof include known general basic catalysts such as zirconium acid.

Further, 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 and the like are preferably used.

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

As a preferable molecular weight range of the reactive epoxy carboxylate resin thus obtained, the polystyrene-equivalent weight average molecular weight in GPC (gel permeation chromatography) is in the range of 500 to 50,000, and more preferably 800 to 30, It is 000, 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 larger than 50,000, the viscosity becomes high and coating or the like becomes difficult.

Next, the reactive polycarboxylic acid resin according to the present invention is obtained by reacting the reactive epoxy carboxylate resin with the polybasic acid anhydride (d).
The reasons for introducing the carboxyl group by this acid addition step are, for example, to make the active energy ray non-irradiated portion soluble in alkaline water in applications requiring resist patterning and the like, and to add solubility to metals, inorganic substances and the like. For example, to impart adhesion. In this acid addition step, the hydroxyl group of the epoxy carboxylate compound is reacted with the component (d) to introduce a carboxyl group via an ester bond.

As the component (d), for example, any compound having a phthalic anhydride structure in one molecule can be used, but phthalic anhydride having excellent developability, heat resistance, hydrolysis resistance, etc. in an alkaline aqueous solution, Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, hydrogenated trimellitic anhydride, trimellitic anhydride or maleine anhydride Acids are preferred.

The reaction for adding the component (d) can be carried out by adding the component (d) to the solution of the epoxy carboxylate compound. The amount of addition may be appropriately changed according to the intended use.

However, when the reactive polycarboxylic acid resin mixture of the present invention is used as an alkali-developed resist, the component (d) is used as the solid acid value (JISK5601-) of the reactive polycarboxylic acid resin obtained by the above acid addition step. It is preferable to prepare a calculated amount of 20 to 120 mg · KOH / g, more preferably 40 to 100 mg · KOH / g (according to 2-1: 1999).
When the solid content acid value is in this range, the alkaline aqueous solution developability of the active energy ray-curable resin composition of the present invention shows good performance. That is, it has good patterning properties, a wide range of control over overdevelopment, and no excess acid anhydride remains.

At the time of the reaction, it is preferable to use a catalyst to accelerate the reaction, and the amount of the catalyst used is based on the total amount of the reactive epoxy carboxylate resin and the reaction product to which the component (d) and, in some cases, the solvent and the like are added. 0.1 to 10 parts by mass. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalysts that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanate, octane. Examples thereof include zirconium acid.

This acid addition reaction can be carried out without solvent or diluted with a solvent. The solvent is not particularly limited as long as it does not affect the acid addition reaction. Further, when a solvent is used in the epoxy carboxylate reaction which is the previous step, it can be directly subjected to the acid addition reaction without removing the solvent on the condition 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 solvent used is preferably adjusted according to the viscosity of the obtained resin and the intended use, but is preferably used so that the solid content is 90 to 30% by mass, more preferably 80 to 50% by mass. Be done.

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

Further, it is preferable to use a thermal polymerization inhibitor, and examples of the thermal polymerization inhibitor include the same as the thermal polymerization inhibitor in the epoxy carboxylate reaction.

The end point of this acid addition reaction is the point where the acid value of the reaction product falls within the range of plus or minus 10% of the set acid value while sampling as appropriate.
The preferred molecular weight range of the reactive polycarboxylic acid resin thus obtained is such that the polystyrene-equivalent weight average molecular weight in the GPC measurement is in the range of 500 to 50,000, more preferably 800 to 30,000, and particularly preferably. It is 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 larger than 50,000, the viscosity becomes high and coating or the like becomes 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 epoxy carboxylate resin is used in combination.

The reactive polycarboxylic acid resin mixture of the present invention is
Production method 1: A reaction product of a reactive epoxy carboxylate resin, which is a reaction product obtained by reacting the component (a), the component (b), and the component (c) if necessary, and the component (d). A reactive polycarboxylic acid resin, a reactive epoxy carboxylate resin which is a reaction product obtained by reacting a component (a'), a component (b), and a component (c) if necessary, and a component (d). ), A method of separately synthesizing and mixing a reactive polycarboxylic acid resin.
Production method 2: A mixture of a reactive epoxy carboxylate resin, which is a reaction product obtained by reacting the component (a) and the component (a'), the component (b), and the component (c) if necessary, and the component (d). ) And how to react,
Any manufacturing method may be used.

When the production method 1 is used, the mixing ratio of the reactive polycarboxylic acid resin obtained from the component (a) and the reactive polycarboxylic acid resin obtained from the component (a') should be appropriately changed depending on the intended use. be. When the proportion of the reactive polycarboxylic acid resin obtained from the component (a') is increased, the developability is improved, but the insulation reliability of the cured product is lowered.
The reactive polycarboxylic acid resin obtained from the component (a') is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, based on 100% by mass of the total amount of the reactive polycarboxylic acid resin mixture. ~ 20% by mass is more preferable.

It is more preferable to use the production method 2 because the reactive polycarboxylic acid resin mixture obtained by the production method 2 has good insulation reliability and developability.
It is considered that this is because the production method 2 provides a structure in which the component (a) and the component (a') are bonded via the component (c) and / or the component (d).
The mixing ratio of the component (a) and the component (a') should be appropriately changed according to the intended use. When the proportion of the component (a') is increased, the developability is improved, but the insulation reliability of the cured product is lowered.
The component (a') is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, and further 1 to 20% by mass with respect to 100% by mass of the total amount of the component (a) and the component (a'). preferable.

The reactive epoxy carboxylate resin mixture of the present invention can be obtained as an intermediate product of the above-mentioned production method 2. Further, the epoxy carboxylate resin mixture of the present invention is a reactive epoxy carboxylate resin which is a reaction product obtained by reacting the component (a), the component (b), and the component (c) if necessary, and the component. The reactive epoxy carboxylate resin, which is a reaction product obtained by reacting (a'), the component (b), and the component (c) if necessary, may be synthesized and mixed separately.

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 58 to 62 mg · KOH / g. Is particularly preferable. When the acid value is in the above range, the developability is good.

Further, the active energy ray-curable resin composition of the present invention may further contain a reactive compound (C) (hereinafter, also simply referred to as “component (C)”). The component (C) is not particularly limited as long as it is a compound other than the reactive polycarboxylic acid resin, and specific examples thereof include radical reaction type acrylates, cationic reaction type other epoxy compounds, and vinyl sensitive to both. Examples thereof include so-called reactive oligomers such as compounds.

Examples of acrylates that can be used include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, and other epoxy acrylates, polyester acrylates, urethane acrylates, and the like.

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, and the like. Examples thereof include phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

Examples of 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. , Diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, epoxydi (meth) acrylate, bisphenolethylene oxide di (meth) acrylate, Di (meth) acrylate of bisphenol ethylene oxide di (meth) acrylate, bisphenol di (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of neopenglycol hydroxybivariate, poly of the reaction product of dipentaerythritol and ε-caprolactone. (Meta) Acrylate, Dipentaerythritol Poly (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Triethylol Propanetri (Meta) Acrylate, and Ethylene Oxide Adducts, Pentaerythritol Tri (Meta) Acrylate, and Ethylene Examples thereof include an oxide adduct, a pentaerythritol tetra (meth) acrylate, and an ethylene oxide adduct thereof, a dipentaerythritol hexa (meth) acrylate, and an ethylene oxide adduct thereof.

Examples of 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, ethylene glycol divinyl ether and the like. Examples of styrenes include styrene, methylstyrene, ethylstyrene and the like. Examples of other vinyl compounds include triallyl isocyanurate and trimetaallyl isocyanurate.

Further, as so-called reactive oligomers, urethane acrylate having a functional group sensitive to active energy rays and a urethane bond in the same molecule, and similarly a functional group sensitive to active energy rays and an ester bond in the same molecule. Examples thereof include polyester acrylates having both of them, epoxy acrylates having functional groups derived from other epoxy resins and having a functional group sensitive to active energy rays in the same molecule, and reactive oligomers in which these bonds are used in combination.

The cationic reaction type monomer is not particularly limited as long as it is a compound generally 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 manufactured by Union Carbide). UVR-6110 "etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide ("ELR-4206 "manufactured by Union Carbide, etc.), limonendioxide (Dycel Chemical Industries, Ltd.) Made by "Ceroxide 3000" etc.), Allylcyclohexenedioxide, 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 ("Cyracure UVR-6128" manufactured by Union Carbide, etc.), bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-) Examples thereof include epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, and bis (3,4-epoxycyclohexyl) diethylsiloxane.

Of these, as the component (C), radically curable acrylates are most preferable. In the case of the cationic type, since the carboxylic acid reacts with the epoxy group, it is necessary to make a two-component mixed type.

In the active energy ray-curable resin composition of the present invention, the reactive polycarboxylic acid resin is contained in the composition in an amount of 97 to 5% by mass, preferably 87 to 10% by mass, and the component (C) is preferably 3 to 95% by mass. Contains 3 to 80% by mass. If necessary, other components may be contained up to about 70% by mass. Examples of other components include photopolymerization initiators, other additives, coloring materials, curing accelerators, and volatile solvents added for viscosity adjustment for the purpose of imparting coating suitability. Other ingredients that may be used are illustrated 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 presumed 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. Further, in a composition that requires development, dispersibility is more preferable, good patterning characteristics are exhibited, and development residue in a developing and dissolving portion is small, which is suitable.

Examples of the coloring pigment include organic pigments such as phthalocyanine, azo and quinacridone, and inorganic pigments such as carbon black and titanium oxide. Of these, carbon black is preferable because of its high dispersibility.

The active energy ray-curable resin composition of the present invention may further contain 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, and 1,1-dichloro. Acetophenone, 2-hydroxy-2-methyl-phenylpropane-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 Acetophenones such as -one; anthraquinones such as 2-ethylanthraquinone, 2-t-butyl anthraquinone, 2-chloroanthraquinone, 2-amyl anthraquinone; 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone and the like. Thioxanthones; acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals; benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bismethylaminobenzophenone and other benzophenones; 2,4,6-trimethyl Known general radical photopolymerization initiators such as phosphine oxides such as benzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide can be mentioned.

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

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

Other halides include 2,2,2-trichloro- [1-4'-(dimethylethyl) phenyl] etanone (TRIgonal PI manufactured by AKZO, etc.), 2,2-dichloro-1-4- (phenoxyphenyl). Examples thereof include etanone (Sandray 1000 manufactured by Sandoz Co., Ltd.), α, α, α-tribromomethylphenyl sulfone (BMPS manufactured by Steel Chemical Co., Ltd., etc.) and the like. Examples of the triazine-based initiator include 2,4,6-triazine (trichloromethyl) -triazine, 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine (TriazineA manufactured by Panchim, etc.), 2,4. -Trichloromethyl- (4'-methoxystyryl) -6-triazine (Panchim's TriazinePMS, etc.), 2,4-trichloromethyl- (pipronyl) -6-triazine (Panchim's TriazinePP, etc.), 2,4-trichloro Methyl- (4'-methoxynaphthyl) -6-triazine (TriazineB manufactured by Panchim, etc.), 2 [2'(5-methylfuryl) ethylidene] -4,6-bis (trichloromethyl) -s-triazine (Sanwa) Chemicals, etc.), 2 (2'-frillethylidene) -4,6-bis (trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd.) and the like.

Examples of the borate-based photopolymerization initiator include NK-3876 and NK-3881 manufactured by Nippon Photosensitizing Dye, and examples of other photoacid generators include 9-phenylaclydin and 2,2'-bis (o-chlorophenyl). ) -4,4', 5,5'-tetraphenyl-1,2-biimidazole (biimidazole manufactured by Kurokin Kasei Co., Ltd., etc.), 2,2-azobis (2-amino-propane) dihydrochloride (Wako Pure Chemical Industries, Ltd.) V50, etc. manufactured by Wako), 2,2-azobis [2- (imidazolin-2yl) propane] dihydrochloride (VA044, etc. manufactured by Wako Pure Chemical Industries, Ltd.), [Eta-5-2-4- (cyclopentadecyl) (1) , 2,3,4,5,6, eta)-(methylethyl) -benzene] iron (II) hexafluorophosphonate (Irgacure261, manufactured by CibaGeigy, etc.), bis (y5-cyclopentadienyl) bis [2,6 -Difluoro-3- (1H-pyri-1-yl) phenyl] Titanium (CGI-784, etc. manufactured by Ciba Geigy) and the like can be mentioned.

In addition, an azo-based initiator such as azobisisobutyronitrile and a peroxide-based radical-type initiator such as benzoyl peroxide that is sensitive to heat may be used in combination. Moreover, both radical type and cationic type photopolymerization initiators may be used together. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

Of these, the radical photopolymerization initiator is particularly preferable in consideration of the characteristics of the reactive polycarboxylic acid resin mixture of the present invention.

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

Furthermore, the active energy ray-curable resin composition of the present invention may contain other additives, if necessary. Other additives include, for example, thermosetting catalysts such as melamine, thixotropy-imparting agents such as Aerosil, silicone-based and fluorine-based leveling agents and defoamers, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, and oxidation. Inhibitors and the like can be used.

Other resins that do not react to active energy rays (so-called inert polymers) include, for example, other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, etc. Styrene resin, guanamine resin, natural and synthetic rubber, acrylic resin, polyolefin resin, and modified products thereof can also be used. These are preferably used in the range of up to 40 parts by mass in the resin composition.

In particular, when a reactive polycarboxylic acid resin is to be used for solder resist applications, it is preferable to use a known general epoxy resin as resins that do not show reactivity with active energy rays. This is because the carboxy group derived from the reactive polycarboxylic acid resin remains even after the reaction and curing by the active energy rays, and as a result, the cured product is inferior in water resistance and hydrolyzability. Therefore, by using an epoxy resin, the remaining carboxy groups are further carboxylated to form a stronger crosslinked structure. As the known general epoxy resin, the cationic reaction type monomer can be used.

Further, for the purpose of adjusting the viscosity according to the purpose of use, a volatile solvent can be added to the resin composition in a range of up to 50 parts by mass, more preferably 35 parts by mass.

The active energy ray-curable resin composition of the present invention is easily cured by the active energy ray. Here, specific examples of the active energy ray include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays and laser beams, and particle beams such as alpha rays, beta rays and electron beams. Considering the preferred use of the present invention, among these, ultraviolet rays, laser beams, visible rays, or electron beams are preferable.

In the active energy ray-curable resin composition of the present invention, the glass transition temperature by the viscoelasticity measuring device is preferably 150 to 250 ° C, more preferably 160 to 180 ° C. When the glass transition temperature is within the above range, heat resistance and developability are improved.

In the present invention, the molding material is a material in which an uncured composition is placed in a mold or the mold is pressed to form an object, and then a curing reaction is caused by active energy rays to form the uncured composition. It refers to a material used for molding by irradiating with focal light such as a laser to cause a curing reaction.

Specific applications include a sheet molded into a flat surface, a sealing material for protecting an element, and a so-called nanoimprint material in which a finely processed "mold" is pressed against an uncured composition to perform fine molding. Further, light emitting diodes having particularly strict thermal requirements, peripheral sealing materials such as photoelectric conversion elements, and the like can be mentioned as suitable applications.

In the present invention, the film-forming material is used for the purpose of coating the surface of the base material. Specific applications 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 for laminating and optical disks. Adhesive materials such as agents and adhesives, resist materials such as solder resists, etching resists, and resists for micromachines fall under this category. Furthermore, a so-called dry film, in which a film-forming material is temporarily applied to a peelable base material to form a film and then bonded to the originally intended base material to form a film, is also a film-forming material. ..

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

Of these, the introduction of the carboxy group of the reactive polycarboxylic acid resin enhances the adhesion to the base material, so that it is preferably used for coating a plastic base material or a metal base material.

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

In the present invention, the resist material composition is such that a film layer of the composition is formed on a base material, and then active energy rays such as ultraviolet rays are partially irradiated, and the physical characteristics of the irradiated portion and the non-irradiated portion are different. Refers to an active energy ray-sensitive composition to be drawn using. Specifically, it is a composition used for the purpose of drawing by removing the irradiated portion or the unirradiated portion by dissolving it in some method, for example, a solvent or an alkaline solution.

The active energy ray-curable resin composition, which is the resist material composition of the present invention, can be applied to various materials capable of patterning, and is particularly useful for solder resist materials and interlayer insulating materials for build-up methods. Furthermore, it is also used as an optical waveguide for printed wiring boards, electric / electronic / optical substrates such as optoelectronic boards and optical substrates.

Particularly suitable applications include photosensitive films, photosensitive films with supports, insulating resin sheets such as prepregs, and circuit boards (laminated board applications, multilayer printed wiring boards) by taking advantage of their good heat resistance and developability. Applications), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, fill-in-the-blank resins, component-embedded resins, etc., which can be used in a wide range of applications in which a resin composition is required. Among them, since good developability can be exhibited even at a high pigment concentration, it can be suitably used for color resists, resist materials for color filters, particularly black matrix materials and the like.

Further, a resin composition for an insulating layer of a multilayer printed wiring board (a multilayer printed wiring board in which a cured product of a photosensitive resin composition is used as an insulating layer) and a resin composition for an interlayer insulating layer (a cured product of a photosensitive resin composition) are used. It can also be suitably used for a multi-layer printed wiring board having an interlayer insulating layer), a resin composition for forming a plating (a multi-layer printed wiring board in which plating is formed on a cured product of a photosensitive resin composition), and the like.

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 onto a substrate with a film thickness of 0.1 to 200 μm by a method such as a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a curtain coating method, or a spin coating method. The coating film can be formed by drying the coating film at a temperature of usually 50 to 110 ° C., preferably 60 to 100 ° C. Then, the coating film is directly or indirectly irradiated with high-energy rays such as ultraviolet rays at ^{an intensity of about 10 to 2000 mJ / cm 2} through a photomask on which an exposure pattern is formed, and a developing solution described later is used, for example, spraying. A desired pattern can be obtained by vibration immersion, paddle, brushing and the like.

The alkaline aqueous solution used for the above development includes an inorganic alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate, potassium phosphate and the like, and tetramethylammonium hydroxide. , Tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine and other organic alkaline aqueous solutions can be used. The aqueous solution can further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

In addition, it is particularly preferably used as a dry film application in which mechanical strength before a curing reaction by active energy rays is required. That is, since the balance of the hydroxyl group and the epoxy group of 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.

The method for forming the film is not particularly limited, but intaglio printing methods such as gravure, letterpress printing methods such as flexography, stencil printing methods such as silk screen, lithographic printing methods such as offset, roll coaters, knife coaters, die coaters, etc. Various coating methods such as curtain coater and spin coater can be arbitrarily adopted.

The cured product of the active energy ray-curable resin composition of the present invention refers to a product obtained by irradiating the active energy ray-curable resin composition of the present invention with active energy rays and curing it.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Further, in the examples,% indicates mass% unless otherwise specified.

The softening point, epoxy equivalent, and acid value were measured under the following conditions.
1) Epoxy equivalent: Measured according to JISK7236: 2001.
2) Softening point: Measured according to JISK7234: 1986.
3) Acid value: Measured according to JISK0070: 1992.
4) The measurement conditions of GPC are as follows.
Model: TOSOH HLC-8320GPC
Column: Super HZM-N
Eluent: THF (tetrahydrofuran); 0.35 ml / min, 40 ° C.
Detector: RI (Differential Refractometer)
Molecular weight standard: polystyrene

(Example 1, Reference Example 1, Comparative Example 1): Synthesis of reactive epoxy carboxylate resin XD-1000 (manufactured by Nippon Kayaku Co., Ltd., softening point 74 ° C., epoxy equivalent 252 g / eq. ), EPPN-201 (manufactured by Nippon Kayaku Co., Ltd., softening point 70 ° C., epoxy equivalent 193 g / eq.) As component (a'-1), EPPN-503 (Nippon Kayaku) as component (a'-2). Made by Nippon Kayaku Co., Ltd., softening point 94 ° C., epoxy equivalent 185 g / eq.), NC-3500 as component (a'-3) (Nippon Kayaku Co., Ltd., softened point 70 ° C., epoxy equivalent 206 g / eq.) NC-6000 (manufactured by Nippon Kayaku Co., Ltd., softening point 60 ° C., epoxy equivalent 208 g / eq.) As component (a'-4), acrylic acid (AA) or methacrylic acid (MAA) as component (b). Was added in the amount described in Table 1, and dimethylolpropionic acid (hereinafter abbreviated as “DMPA”) was added as the component (c) in 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 as to have a solid content of 80% by mass, and the mixture was reacted at 100 ° C. for 24 hours to obtain a solution of a reactive epoxy carboxylate resin mixture.

(Example 2, Reference Example 2, Comparative Example 2): Preparation of composition for hard coating For each of 20 g of each reactive epoxy carboxylate resin mixture solution synthesized in Example 1, Reference Example 1, and Comparative Example 1. Then, 4 g of dipentaerythritol hexaacrylate, which is a radical curing type reactive compound, and 1.5 g of Irgacure 184 as an ultraviolet reaction type photopolymerization initiator were dissolved by heating.
Next, the polycarbonate plate was coated with a hand applicator so that the film thickness at the time of drying was 20 microns, and solvent drying was carried out in an electric oven at 80 ° C. for 30 minutes. After drying, a film-forming product was obtained by irradiating and curing ultraviolet rays with an irradiation dose of 1000 mJ by an ultraviolet vertical exposure apparatus (manufactured by ORC Manufacturing Co., Ltd.) equipped with a high-pressure mercury lamp.

The hardness of the coating film of this product was measured by JISK5600-5-4: 1999, and the cold and thermal impact resistance test was further measured by JISK5600-7-4: 1999. The results are shown in Table 2. The meanings of the symbols shown in Table 2 are as follows.
○: No scratches or peeling △: Slightly scratched ×: Peeled off

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

(Example 3, Reference Example 3, Comparative Example 3): Synthesis of reactive polycarboxylic acid resin 200 g of each reactive epoxy carboxylate resin mixture solution obtained in Example 1, Reference Example 1, and Comparative Example 1 respectively. In contrast, THPA (1,2,3,6-tetrahydrophthalic anhydride, manufactured by Shin Nihon Rika Co., Ltd.) was used as the component (d) at 30.9 (g), and the solid content was 65% as the solvent. A solution of a reactive polycarboxylic acid resin mixture was obtained by adding propylene glycol monomethyl ether monoacetate and heating to 100 ° C. and then acid addition reaction. 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 into a solid content value.

(Synthetic 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 218 g / eq.), Acrylic acid (AA) as component (b), dimethylol propionic acid (DMPA) as component (c). ) Was added in the amount described in Table 4. 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so as to have a solid content of 80% by mass, and the mixture was reacted at 100 ° C. for 24 hours to obtain a reactive epoxy carboxylate resin solution. In the obtained reactive epoxycarboxylate resin solution, propylene glycol monomethyl ether monoacetate was added so that THPA as the component (d) was added to the amount (g) shown in Table 4 and the solid content was 65% as the solvent. After addition, the mixture was heated to 100 ° C. and then subjected to an acid addition reaction 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 into a 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 blended in the weight ratio shown in Table 5, and the reactive polycarboxylic acid solution was blended. A mixture of

(Comparative Example 4): Formulation of Reactive Polycarboxylic Acid Resin The reactive polycarboxylic acid resin solution synthesized in Synthesis Examples 1 and 3 and other reactive polycarboxylic acid resins were blended in the weight ratio shown in Table 6 for comparison. An example reactive polycarboxylic acid mixture solution was obtained.

ＫＡＹＡＲＡＤ ＺＡＲ−２００１Ｈ；ビスフェノールＡ型反応性ポリカルボン酸樹脂（日本化薬株式会社製）
ＫＡＹＡＲＡＤ ＺＦＲ−１５５４Ｈ；ビスフェノールＦ型反応性ポリカルボン酸樹脂（日本化薬株式会社製）
ＫＡＹＡＲＡＤ ＺＣＲ−１７６１Ｈ；ビフェニルアラルキル型反応性ポリカルボン酸樹脂（日本化薬株式会社製、式（４）で表されＡｒが式（６）である構造を有する。）
ＫＡＹＡＲＡＤ ＵＸＥ−３０２４Ｈ；カルボン酸変性ビスフェノールＡ／ウレタン型エポキシアクリレート（日本化薬株式会社製）

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., represented by formula (4) and having a structure in which 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 Solutions of each reactive polycarboxylic acid resin mixture obtained in Examples 3, 4, Reference Examples 3, 4, and Comparative Example 4 56. For each of .73 g, DPCA-60 (trade name: polyfunctional acrylate manufactured by Nippon Kayaku Co., Ltd.) 5.67 g as the other reactive compound (C), and Irgacure 907 (manufactured by BASF) as the photopolymerization initiator. 2.92 g and KayaCure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) 0.58 g, NC-3000H (manufactured by Nippon Kayaku Co., Ltd.) 17.54 g as a curing component, and 0 melamine as a heat curing catalyst. .73 g and 5.67 g of propylene glycol monomethyl ether monoacetate as a concentration adjusting solvent were added and kneaded with a bead mill to uniformly disperse to obtain a resist resin composition.
The obtained composition was uniformly applied to a polyethylene terephthalate film to be a support film using a wire bar coater # 20, passed through a hot air drying furnace at a temperature of 70 ° C. to form a resin layer having a thickness of 20 μm, and then this was formed. A polyethylene film serving as a protective film was attached on the resin layer to obtain a dry 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., and a resin layer was attached to the entire surface of the substrate while peeling off the protective film.

Next, in order to estimate the mask on which the circuit pattern was drawn and the sensitivity using an ultraviolet exposure device (ORC Manufacturing Co., Ltd., model HMW-680GW), Kodak Step Tablet No. The ultraviolet rays of 500 mJ / cm ^{2 were irradiated through 2.} Then, the film on the dry film was peeled off and the peeled state was confirmed. Then, spray development was carried out with a 1% aqueous sodium carbonate solution to remove the resin in the ultraviolet-unirradiated portion. After washing and drying with water, the printed circuit board was heat-cured for 60 minutes in a hot air dryer at 150 ° C. to obtain a cured film.

[Evaluation of insulation reliability]
The prepared resist resin composition is applied to a thickness of 20 μm on a comb-tooth type electrode (material: copper, pattern pitch: 18 μm, L / S = 100 μm / 100 μm) formed on a substrate (polyimide film). After prebaking at 80 ° C. for 30 minutes, ^{it was exposed at 500 mJ / cm 2} 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 Kasei Co., Ltd.) at 130 ° C. and 85% humidity, and a migration tester (ETAC SIR-13mini Kusumoto Kasei Co., Ltd.) was used to connect the electrodes to 100 V. A DC voltage was applied and the resistance between the electrodes was measured. The insulation reliability was judged according to the following criteria. In the case of the judgment criteria of ◯ and Δ, the insulation reliability is judged to be acceptable, the insulation retention is not hindered in actual use, and the insulation reliability is excellent.

[Criteria for insulation reliability]
◯: Resistance lasts for 100 hours or more when the resistance is 1 × 10 ⁹ Ω or more, and the insulation is very good. Δ: Resistance lasts for 100 hours or more when the resistance is 1 × 10 ⁸ Ω or more and less than ^{1 × 10 9 Ω, and the insulation is very good.} good ×: less than 100 hours in the resistance drops below 1 × 10 ⁸ Ω, it is considered poor insulation

[Sensitivity evaluation]
The sensitivity was determined based on the number of steps of the density portion remaining in the exposed portion transmitted through the step tablet during development. The larger the number of stages (value), the higher the sensitivity is judged in the dark part of the tablet (unit: stage).

[Developability evaluation]
The developability was evaluated based on the so-called break time, which is the time until the pattern shape portion is completely developed when the exposed portion transmitted through the pattern mask is developed (unit: seconds).

[Evaluation of heat resistance]
The resist resin composition is uniformly applied to the polyimide film, 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 an ultraviolet exposure apparatus (Oak Manufacturing Co., Ltd., model HMW-680GW). To obtain a cured product. The produced cured product is cut out with a width of 5 mm. After that, it was set in a viscoelasticity measuring device RSA-G2 manufactured by TA instruments, and the frequency was 10 Hz and the temperature rising rate was 2 ° C./min in an air atmosphere. The temperature at the maximum value of tan δ was taken as Tg.

From the above results, the resist material composition using the reactive polycarboxylic acid resin mixture of the present invention has better resist physical characteristics than the composition using the mixture of the reactive polycarboxylic acid resins for comparison. It was confirmed that it had.

(Example 6, Reference Example 6, Comparative Example 6): Evaluation of Pigment Dispersibility For each of 20 g of each reactive polycarboxylic acid resin mixture obtained in Example 3, Reference Example 3, and Comparative Example 4. , DPHA (trade name: acrylate monomer manufactured by Nippon Kayaku Co., Ltd.) 5.0 g as component (C), propylene glycol monomethyl ether acetate 10 g as organic solvent, and Mitsubishi Carbon Black MA-100 as coloring pigment 15 g or 10 g. In addition, it was stirred. Further, 35 g of glass beads were added and dispersed with a paint shaker for 1 hour. The dispersion liquid after completion of the dispersion was coated on a polyethylene terephthalate film with a wire bar coater # 2, and dried in a warm air dryer at 80 ° C. for 10 minutes. The gloss of the coating film surface after drying was measured using a 60 ° reflection gloss meter (HORIBA, Ltd. IG-331 gloss meter), and the dispersibility of carbon black was evaluated. The results are shown in Table 8. 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 did not change the gloss value even when the content of the coloring pigment was large. It was confirmed that the pigment dispersibility of the reactive polycarboxylic acid resin mixture of the present invention is excellent regardless of the content of the coloring pigment, although the developability and heat resistance are improved.

Based on 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, can be finely alkaline-developed, and has good insulation reliability. Suitable for materials for film formation, resist materials, and interlayer insulating materials. In particular, since it exhibits good developability even at a high pigment concentration, it is suitable for color resists, resist materials for color filters, particularly black matrix materials, black column spacer materials, and the like.

This application is based on a Japanese patent application filed on September 18, 2018 (Japanese Patent Application No. 2018-173665) and a Japanese patent application filed on October 11, 2018 (Japanese Patent Application No. 2018-192527). The contents of are taken here as a reference.

Claims (12)

An epoxy resin (a) represented by the following formula (1), a compound (b) having a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, and a hydroxyl group and a carboxy group in one molecule as needed. A reactive epoxy carboxylate resin which is a reaction product obtained by reacting the compound (c) having both of the above, a reactive polycarboxylic acid resin which is a reaction product of the polybasic acid anhydride (d), and
An epoxy resin (a') different from the epoxy resin (a), the compound (b), and a reactive epoxy carboxylate resin which is a reaction product obtained by reacting the compound (c) as needed. A reactive polycarboxylic acid resin which is a reaction product with the polybasic acid anhydride (d), and the epoxy resin (a') is represented by any of the following formulas (2) to (4). Reactive polycarboxylic acid resin, which is an epoxy resin,
Reactive polycarboxylic acid resin mixture containing.

(In the 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.)

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

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

(In the formula (4), Ar is either the formula (5) or the formula (6) independently, and the molar ratio of the formula (5) and the formula (6) is the formula (5) / the 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.) A reactive epoxy carboxylate resin mixture that is a reaction product obtained by reacting the epoxy resin (a) and the epoxy resin (a'), the compound (b), and the component (c) if necessary. And the reaction product with the polybasic acid anhydride (d).
The reactive polycarboxylic acid resin mixture according to claim 1. An active energy ray-curable resin composition containing the reactive polycarboxylic acid resin mixture according to claim 1 or 2. In addition, it contains the reactive compound (C) and contains
The reactive compound (C) is a radical-reactive acrylate, a cationic-reactive epoxy compound, a vinyl compound that is sensitive to both of these, or a reactive oligomer having a functional group that is sensitive to active energy rays. Is,
The active energy ray-curable resin composition according to claim 3. In addition, it contains a photopolymerization initiator,
The active energy ray-curable resin composition according to claim 3 or 4. In addition, it contains colored pigments,
The active energy ray-curable resin composition according to any one of claims 3 to 5. The active energy ray-curable resin composition according to any one of claims 3 to 6, which is a molding material. The active energy ray-curable resin composition according to any one of claims 3 to 6, which is a material for forming a film. The active energy ray-curable resin composition according to any one of claims 3 to 6, which is a resist material composition. A cured product of the active energy ray-curable resin composition according to any one of claims 3 to 9. An article overcoated with the cured product according to claim 10. A compound (b) having both an ethylenically unsaturated group and a carboxy group that can be polymerized in one molecule is added to the epoxy resin (a) represented by the following formula (1), and a hydroxyl group and a carboxy group are contained in one molecule if necessary. Reactive epoxy carboxylate resin, which is a reactant obtained by reacting compound (c) having a group, and
The compound (b) is reacted with the compound (c), if necessary, with one or more epoxy resins selected from the group of epoxy resins represented by the following formulas (2) to (4). Reactive epoxy carboxylate resin, which is the resulting reactant,
Reactive epoxy carboxylate resin mixture containing.

(In the 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.)

(In equation (2), n represents an integer of 0 to 2.)

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

(In the formula (4), Ar is either the formula (5) or the formula (6) independently, and the molar ratio of the formula (5) and the formula (6) is the formula (5) / the 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.)