KR101482028B1 - Reactive Carboxylate Compound, Active-energy-ray-curable Resin Composition Utilizing the Same and Use of the Same - Google Patents

Abstract

An object of the present invention is to provide a resin composition which can be cured by active energy rays such as ultraviolet rays or the like to obtain a strong coating film or molding material. The present invention also relates to a method for producing an epoxy resin composition, which comprises adding to a phenol-type epoxy resin containing a specific structure in a molecule a compound having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in the molecule and a compound having at least one hydroxyl group and at least one carboxyl group ≪ / RTI > Also, a strong cured product can be obtained from the curable resin composition using the same. This reactive compound also exhibits good pigment dispersibility.

Description

REACTIVE CARBOXYLATATE COMPOUND, ACTIVE ENERGY THERMOPLASTIC RESIN COMPOSITION USING THE SAME, AND USE THEREOF BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reactive carboxylate compound,

The present invention relates to a phenol-type epoxy resin (a) containing a specific structure in a molecule, a compound (b) having both at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in a molecule represented by acrylic acid or the like, (C) having at least one hydroxyl group and at least one carboxyl group, and a reactive polycarboxylic acid compound (B) as an acid-modified product thereof. The reactive epoxycarboxylate compound (A) and the reactive polycarboxylic acid compound (B) have a good affinity with the pigment and can obtain a hardened product from the resin composition containing the same.

The printed wiring board is required to have high accuracy and high density in order to reduce the size and weight of the portable device and to improve the communication speed. As a result, there is a growing demand for solder resists for covering the circuit itself, and it is demanded to have a capability to withstand substrate adhesion, high insulation, and electroless gold plating while maintaining heat resistance and thermal stability higher than conventional requirements, A film-forming material having physical properties is required.

Epoxy resins containing specific structures in molecules have been developed in response to demands for high performance of solder resists, and resins containing them or cured products of acid-modified epoxy carboxylate resins are known.

For example, acid-modified epoxy acrylates having a basic skeleton of a phenol aralkyl type epoxy resin (for example, Nippon Chemical's NC-3000 series, NC-2000 series, etc.) are disclosed in Patent Document 1 or Patent Document 2, It is generally known as a material to represent. The use of solder resists using such solder resists has also been studied.

Patent Document 3 describes an acid-modified epoxy acrylate compound having a basic skeleton of an epoxy resin having a polycyclic hydrocarbon group and a cured product thereof, and has a relatively high toughness after curing. A solder resist using the same is also described. However, this solder resist has a comparatively high reliability, but has not satisfied the performance that can satisfy the higher reliability required by the electronicization of transportation equipment and the like in recent years.

Further, as an application of acid-modified epoxy acrylate by such an epoxy resin, an attempt has been made to apply a color pigment such as carbon black to a black matrix resist used for a liquid crystal display panel or the like.

Examples of application to a black matrix resist in which a color pigment such as carbon black is dispersed in an acid-modified epoxy acrylate having a phenol aralkyl type epoxy resin as a basic skeleton are described in Patent Document 4 and Patent Document 5. [

It is also known to disperse a colored pigment such as carbon black in an acid-modified epoxy acrylate compound having an epoxy resin having a polycyclic hydrocarbon group as a basic skeleton and apply it to a black matrix resist (Patent Document 6).

However, when a coloring pigment such as carbon black is mixed at a high concentration in the use of a black matrix resist used for a liquid crystal display panel or the like, since the pigment is affinity with a resin and is well dispersed, good developability is obtained even if a pigment exists at a high concentration, It is possible to realize a phenomenon in which there is no gap. In this case, developability at a higher pigment concentration, i.e. higher pigment dispersibility, is required. Conventional acid-modified epoxy acrylates exhibit comparatively good pigment dispersibility, but they have disadvantages in that the pigment dispersion is pseudomorphically aggregated and poor in stability.

On the other hand, a carboxylate compound obtained by reacting acrylic acid with a carboxylic acid compound having a hydroxyl group in a general epoxy resin is known as a material having low acid value and excellent developability, and further, the compound has a resist ink suitability is disclosed in Patent Document 7 .

Patent Document 1: JP-A-11-140144 Patent Document 2: JP-A-5-194708 Patent Document 3: JP-A-5-214048 Patent Document 4: JP-A-2005-55814 Patent Document 5: JP-A-2003-183354 Patent Document 6: JP-A-2004-295084 Patent Document 7: JP-A-6-324490

A curable resin composition using an epoxy resin containing a specific structure in the molecule can obtain a comparatively hardened cured product. However, as a material for an application requiring extremely high reliability as a transportation device, a new tough Curing properties are required.

In addition, when the composition is used as a coloring resist composition, there is a demand for an acid-modified epoxy acrylate having a high dispersibility in a coloring pigment, particularly carbon black or the like, and having good developing characteristics even at a high pigment concentration. At this time, there is a demand for a material having a relatively high molecular weight and suitable developing properties. There is also a demand for a colored pigment dispersion resin composition which does not cause aggregation in the pigment dispersion and exhibits long-term storage stability.

In order to solve the above-mentioned problems, the inventors of the present invention have found out that a compound (b) having an epoxy resin containing a specific structure in a molecule and having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in the molecule, And a compound (c) having at least one carboxyl group, and further, a reactive polycarboxylic acid compound obtained by reacting a polybasic acid anhydride (d) with a reactive epoxycarboxylate compound, and particularly a resin property and a resin property .

It has also been found that such a resin composition has a particularly good affinity with a colored pigment and can be a resist material having good developability even at a high pigment concentration.

That is, the present invention relates to an epoxy resin composition comprising (a) an epoxy resin represented by the following general formula (1), (b) a compound having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in one molecule, (A) obtained by reacting a compound (c) having a hydroxyl group and at least one carboxyl group.

Wherein R ₁ is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms, R ₂ is a divalent polycyclic hydrocarbon group having 7 to 16 carbon atoms or an aralkylene group having 7 to 18 carbon atoms, m is an integer of 1 to 4, and n is an integer of 1 to 10, respectively)

The present invention also relates to a reactive epoxycarboxylate compound (A) wherein the epoxy resin (a) is the general formula (2).

(Wherein R ₃ is the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group of 1 to 4 carbon atoms, o represents an integer of 1 to 4, and p represents an integer of 1 to 10, respectively)

The present invention also relates to a reactive epoxycarboxylate compound (A) wherein the epoxy resin (a) is a general formula (3).

(Wherein R ₄ is the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group of 1 to 4 carbon atoms, q represents an integer of 1 to 4, and r represents an integer of 1 to 10, respectively,

The present invention also relates to a reactive epoxycarboxylate compound (A) wherein the epoxy resin (a) is the general formula (4).

(Wherein, R ₅ are the same or different a hydrogen atom, a halogen atom or a hydrocarbon group of a carbon number of 1-4 together, s is an integer of 1 to 4, and t represents an integer of 1 to 10 as a mean value, respectively)

The present invention also relates to a reactive polycarboxylic acid compound (B) obtained by reacting the above-obtained reactive carboxylate compound (A) with a polybasic acid anhydride (d).

The present invention also relates to an active energy ray-curable resin composition characterized by comprising the reactive carboxylate compound (A) and / or the reactive polycarboxylic acid compound (B).

The present invention also relates to an active energy ray-curable resin composition, which further comprises a reactive compound (C) other than (A) and (B).

The present invention also relates to an active energy ray-curable resin composition characterized by further comprising a coloring pigment.

The present invention also relates to an active energy ray-curable resin composition characterized by further comprising a photopolymerization initiator.

The present invention also relates to an active energy ray-curable resin composition which is a molding material.

The present invention also relates to an active energy ray-curable resin composition which is a film-forming material.

The present invention also relates to an active energy ray-curable resin composition which is a resist material composition.

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

The present invention also relates to an article overcoated with the active energy ray-curable resin composition.

The active energy ray-curable resin composition containing an epoxy resin having a specific structure in the molecule of the present invention not only provides a strong cured product, but also has excellent resin properties even when the solvent is dried. The cured product obtained from the active energy ray-curable resin composition of the present invention can be suitably used as a film-forming material requiring thermal and mechanical toughness. Particularly preferable applications include solder resists for printed wiring boards, interlayer insulating materials for multilayer printed wiring boards, solder resists for flexible printed wiring boards, plating resists, photosensitive optical waveguides, and the like.

Also, the obtained active energy ray-curable resin composition has high affinity with colored pigments such as carbon black, so that it exhibits good pigment dispersibility even at high pigment concentration and can exhibit high developability. It is possible to provide a resin composition capable of maintaining the dispersion state of the pigment of the colored pigment dispersion for a long period of time and ensuring high dispersion state storage stability. Therefore, it can be suitably used for a color resist and a resist material for a color filter, particularly, a black matrix material as a particularly preferable use.

BEST MODE FOR CARRYING OUT THE INVENTION

The reactive epoxycarboxylate compound (A) of the present invention is obtained by reacting a phenolic epoxy group with a hydrocarbon group having a specific structure to give a reactive group to the phenolic epoxy resin (a) having a characteristic skeleton represented by the following formula (1) (B) having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in the molecule and a compound (c) having at least one hydroxyl group and at least one carboxyl group in one molecule. That is, the characteristics of the present invention are exhibited by introducing an ethylenically unsaturated group and a hydroxyl group into the molecular chain at the same time by epoxycarboxylation.

Epoxy resin (a) represented by the general formula (1) used in the present invention is a two-carbon number 7-16 represented by phenol type epoxy group and R _2, a cyclic hydrocarbon group or aralkyl group hydrocarbon of a carbon number of 7-18 Is a phenol-type epoxy resin formed by repeating skeletons of the formula (I).

In the formula, R ₁ represents the same or different hydrogen atom, halogen atom or hydrocarbon group of 1 to 4 carbon atoms. Here, the halogen atom represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. The hydrocarbon group having 1 to 4 carbon atoms is preferably a methyl group, an ethyl group, a vinyl group, an n-propyl group, an i-propyl group, a propenyl group, Or a saturated or unsaturated hydrocarbon group.

R ₂ represents a divalent polycyclic hydrocarbon group having 7 to 16 carbon atoms or an aralkylene group having 7 to 18 carbon atoms. The divalent polycyclic hydrocarbon group having 7 to 16 carbon atoms is preferably a bicyclo [2,2,1] heptanediyl group, a bicyclo [2,2,2] octanediyl group, an octahydronaphthalenediyl group, a decahydronaphthalenediyl group, a tetra Hydroiodicycloheptadienediyl group, tetrahydrodicyclopentadienediyl group, and tetrahydrodicyclopentadienediyl group. Among them, a tetrahydrodicyclopentadienediyl group is preferably used.

The aralkylene group having 7 to 18 carbon atoms is preferably a phenylene group, a phenylene group, an naphthylene group, a naphthylene group, an naphthylene group, an anthracene group, Group, a pyrenebis methylene group, and the like. Among them, a phenylene bismethylene group and a biphenylene bismethylene group are suitably used.

In the general formula (1), m represents an integer of 1 to 4 and represents the number of functional groups introduced. n represents an average value of an integer of 1 to 10, preferably 1 to 6, When n is less than 10, preferably less than 6, a suitable viscosity range is obtained. The average value of n represents the average number of repeats and can be calculated from the measurement value by gel permeation chromatography (GPC).

The epoxy resin (a) used in the present invention may preferably be an epoxy resin having a characteristic biphenyl skeleton represented by the general formula (2) as described below.

In the formula, R ₃ represents the same or different hydrogen atom, halogen atom or hydrocarbon group of 1 to 4 carbon atoms. The halogen atom represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. O represents an integer of 1 to 4, and p represents an average value of an integer of 1 to 10, preferably 1 to 6, When the value of p is less than 10, preferably less than 6, a suitable viscosity range is obtained.

Among the epoxy resins (a) represented by the general formula (2), it is preferable that all of R ₃ are hydrogen atoms at a low cost. In general, a commercially available product is available as a NC-3000 series in Japanese explosives. In the NC-3000 series, R ₃ is a hydrogen atom and p is an average of an integer of 1 to 10, respectively. In the present invention, a suitable one among the grades of the series can be appropriately selected.

The epoxy resin (a) used in the present invention is preferably a phenol aralkyl type epoxy resin represented by the general formula (3).

In the formula, R ₄ are the same or different and each represents a hydrogen atom, a halogen atom or a hydrocarbon group of 1 to 4 carbon atoms. Q is a substitution number and is an integer of 1 to 4, and r is an average value of an integer of 1 to 10, respectively.

Among the epoxy resins represented by the general formula (3), it is preferable that R ₄ is a hydrogen atom or a methyl group. The epoxy resin represented by the general formula (3) is generally available as a NC-2000 series in Japanese explosives. In the NC-2000 series, R ₄ is a hydrogen atom and r is an integer of 1 to 10 on average. In the present invention, a suitable one among the grades of the series can be appropriately selected.

The epoxy resin (a) used in the present invention is preferably an epoxy resin having a polycyclic hydrocarbon group represented by the general formula (4).

In the formula, R ₅ is the same or different and is a hydrogen atom, a halogen atom or a hydrocarbon group of 1 to 4 carbon atoms, s is an integer of 1 to 4 which is a substitution number, and t is an integer of 1 to 10 .

Among them, a compound in which all of R < ₅ > are hydrogen atoms or a compound in which R < ₅ > R ₅ are all hydrogen atoms, and t represents an integer of 1 to 10 on average, is available as XD-1000 series from Japan Chemical Industry Co., Ltd. In the present invention, suitable compounds among the grades of the series can be appropriately selected.

The compound (b) having at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in the molecule used in the present invention is reacted to give reactivity to an active energy ray. These include monocarboxylic acid compounds and polycarboxylic acid compounds.

Examples of the monocarboxylic acid compound having one carboxyl group in one molecule include (meth) acrylic acid, crotonic acid,? -Cyano cinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and a monoglycidyl compound containing an unsaturated group . Examples of the acrylic acids include (meth) acrylic acid,? -Styryl acrylic acid,? -Furfuryl acrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride, and Semi-esters, which are reaction products of mono-glycidyl (meth) acrylate with unsaturated dicarboxylic acids and mono-glycidyl (meth) acrylate derivatives, and the like.

Examples of the polycarboxylic acid compound having a plurality of carboxyl groups in one molecule include half esters, which are monovalent reactants of a (meth) acrylate derivative having a plurality of hydroxyl groups in one molecule with a dibasic acid anhydride, a saturated or unsaturated dibasic acid and a plurality of epoxy groups And half esters, which are the reaction products of the glycidyl (meth) acrylate with a noble metal moiety, and the like.

Of these, the most preferable ones are reaction products of (meth) acrylic acid, (meth) acrylic acid and? -Caprolactone, or cinnamic acid in terms of sensitivity when made into an active energy ray curable resin composition.

The compound (b) having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in one molecule is preferably free of a hydroxyl group in the compound.

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

Examples of the compound having one hydroxyl group and one carboxyl group in one molecule include hydroxypropionic acid, hydroxybutanoic acid, and hydroxystearic acid.

Examples of the compound having two or more hydroxyl groups and one carboxyl group in one molecule include dimethylol acetic acid, dimethylol propionic acid, dimethylolbutanoic acid and the like.

Examples of the compound having at least one hydroxyl group and at least two carboxyl groups in one molecule include hydroxyphthalic acid and the like.

Among them, it is preferable that two or more hydroxyl groups are contained in one molecule in consideration of the effect of the present invention. The carboxyl group is preferably one in one molecule in consideration of the stability of the carboxylation reaction. Most preferably two hydroxyl groups and one carboxy group in one molecule. Dimethylolpropionic acid and dimethylolbutanoic acid are particularly suitable considering the raw material availability.

The compound (c) having at least one hydroxyl group and at least one carboxyl group in one molecule preferably has no ethylenic unsaturated group polymerizable in the compound.

Among them, in consideration of the stability of the reaction between the epoxy resin (a) and the two types of carboxylic acid compounds (b) and (c), (b) and (c) are preferably monocarboxylic acids, and monocarboxylic acids and polycarboxylic acids , It is preferable that the value represented by the total molar amount of the monocarboxylic acid / the total molar amount of the polycarboxylic acid is 15 or more.

In this reaction, the injection ratio of the total amount of the carboxylic acid of the epoxy resin (a) and the carboxylic acid compounds (b) and (c) should be appropriately changed depending on the application. That is, when all the epoxy groups are carboxylated, unreacted epoxy groups do not remain, so that the storage stability of the reactive carboxylate compound is high. In this case, only the reactivity due to the introduced double bond is used.

On the other hand, by reducing the amount of the carboxylic acid compounds (b) and (c) intentionally left unreacted residual epoxy groups, the reactivity by the introduced unsaturated bonds and the reaction by the remaining epoxy groups, Or a thermal polymerization reaction may be used in combination. In this case, however, care must be taken to examine the preservation and production conditions of the reactive carboxylate compound.

(B) and (c) is 90 to 120 equivalent% based on 1 equivalent of the epoxy group of the epoxy resin (a) when the reactive epoxycarboxylate compound (A) . Within this range, production under relatively stable conditions is possible. When the amount of the carboxylic acid compound to be injected is larger than this, the excess carboxylic acid compound (b) remains, which is not preferable.

When the epoxy group is intentionally left to remain, the total amount of the carboxylic acid compounds (b) and (c) is preferably 20 to 90 equivalent% based on 1 equivalent of the epoxy resin (a). Outside this range, the effect of complex curing is reduced. Of course, in this case, it is necessary to pay sufficient attention to the gelation during the reaction and the stability with time of the carboxylate compound (A).

The ratio of the compound (b) having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group and the compound (c) having at least one hydroxyl group and at least one carboxyl group is preferably selected from the group consisting of (b) (c) is in the range of 9: 1 to 1: 9 or 4: 6 to 8: 2. Within this range, it is possible to prevent a decrease in sensitivity when the amount of (b) is too small, and to prevent the effect of (c) from becoming less effective when the amount of (c) is too small.

The carboxylation reaction may be carried out in the absence of a solvent or may be carried out by dilution with a solvent. The solvent usable here is not particularly limited as long as it is a solvent inert to the carboxylation reaction.

The amount of the solvent to be used is appropriately adjusted depending on the viscosity and the purpose of the resin to be obtained, but a solvent is preferably used so that the solid content is 90 to 30 mass%, more preferably 80 to 50 mass%.

Specific examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane and decane, and mixtures thereof, petroleum 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? -Butylolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol mono Mono or polyalkylene glycol monoalkyl ether monoacetates such as ethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, and butylene glycol monomethyl ether acetate; Polycarboxylic acid alkyl esters such as diethyl glutarate, dialkyl succinate, dialkyl adipate and the like.

Examples of the ether solvent include alkyl ethers such as diethyl ether and ethylbutyl ether; ketones such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, Glycol ethers such as glycol diethyl ether, and cyclic ethers such as tetrahydrofuran.

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

And the reactive compound (C) other than (A) and (B) to be described later. In this case, when the composition is used as a curable composition, it can be used directly as a composition, which is preferable.

In the reaction, it is preferable to use a catalyst in order to accelerate the reaction. The amount of the catalyst to be used is preferably in the range of 1 to 20 parts by weight per 100 parts by weight of the epoxy compound (a), the compound (b) Based on the total amount of the reactants. The reaction temperature is 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstilbine, methyltriphenylstilbene, Chromium octanoate, zirconium octanoate, and the like.

In addition, the use of hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenyl picrylhydrazine, diphenylamine, 3,5-di-t-butyl-4-hydroxytoluene, .

The reaction is terminated when the acid value of the sample becomes 5 mgKOH / g or less, preferably 2 mgKOH / g or less while appropriately sampling.

The preferred molecular weight range of the reactive carboxylate compound (A) thus obtained is in the range of 1,000 to 30,000, more preferably 1,500 to 20,000 in terms of polystyrene-equivalent weight average molecular weight in GPC.

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

Next, the reactive polycarboxylic acid compound (B) of the present invention obtained by the acid part process will be explained. The acid part treatment is carried out for the purpose of obtaining a reactive polycarboxylic acid compound (B) by introducing a carboxyl group into the reactive carboxylate compound (A) obtained in the previous step, if necessary. Carboxy groups are introduced for the purpose of imparting solubility to alkaline water to the active energy beam unexposed sites in applications where resist patterning or the like is required, and for imparting adhesion to metals, minerals, and the like.

Specifically, a carboxyl group is introduced through an ester bond by subjecting a hydroxyl group formed by an epoxycarboxylation reaction to an addition reaction of a polybasic acid anhydride (d).

Specific examples of the polybasic acid anhydride (d) can be any compound having an acid anhydride structure in a molecule, but examples thereof include anhydrous succinic acid, anhydrous phthalic acid, tetrahydrophthalic anhydride, hexa Particularly preferred are phthalic anhydride, itaconic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride.

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

However, when the polycarboxylic acid compound (B) of the present invention is to be used as an alkali developing type resist, the solid acid value of the reactive polycarboxylic acid compound (B) finally obtained from the polybasic acid anhydride (d) (JIS K5601-2-1: 1999 Is in the range of 30 to 120 mg · KOH / g, and more preferably 40 to 105 mg · KOH / g. When the solid acid value is in this range, the developability of the aqueous alkali solution of the active energy ray-curable resin composition of the present invention is satisfactory. That is, the patterning property and the phenomenon of overexposure are wide and the excess acid anhydride does not remain.

In the reaction, it is preferable to use a catalyst in order to accelerate the reaction. The amount of the catalyst to be used is not particularly limited, and the amount of the catalyst to be used may be appropriately selected depending on the kind of the reaction product, namely the carboxylate compound (A) obtained from the epoxy compound (a), the carboxylic acid compound (b) (D) 0.1 to 10% by mass, based on the total amount of reactants added to the solvent and other substances depending on the case. At this time, the reaction temperature is 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstilbine, methyltriphenylstilbene, Chromium octanoate, zirconium octanoate, and the like.

The acid part of the acid part may be reacted with a solvent or diluted with a solvent. The solvent which can be used here is not particularly limited as long as the acid part is a solvent inert to the reaction. Specifically, the same solvent as the one exemplified in the carboxylation reaction of the previous step can be used. When the solvent is prepared by using a solvent in the carboxylation reaction of the previous step, the acid may be directly supplied to the reaction by the next step without removing the solvent, provided that the reaction is inert to both reactions.

The amount of the solvent to be used is appropriately adjusted depending on the viscosity and the purpose of the resin to be obtained, but a solvent is preferably used so that the solid content is 90 to 30 mass%, more preferably 80 to 50 mass%.

And other reactive compounds (C) described later, and the like. In this case, when the composition is used as a curable composition, it is preferable because it can be used as a direct composition.

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

This reaction is defined as the point where the acid value of the reactant is in the range of plus or minus 10% of the set acid value while appropriately sampling.

The active energy ray-curable resin composition of the present invention comprises an epoxycarboxylate compound (A) and / or a polycarboxylic acid compound (B). The epoxycarboxylate compound (A) and / or the polycarboxylic acid compound (B) can be appropriately used in accordance with the intended use. For example, the epoxy carboxylate compound (A) may be used in the case of a so-called solvent developing type in which a pattern is formed by a printing method without developing in the use of a solder resist or in the case of a so-called solvent developing type in which an unreacted portion is disturbed by a solvent, In the case of developing with alkaline water, the polycarboxylic acid compound (B) may be used. In general, the polycarboxylic acid compound (B) is often used in this application since an alkaline water developing type is easy to form a fine pattern. Of course, there is no problem with using it together.

The active energy ray-curable resin composition of the present invention may further contain a reactive compound (C) other than the epoxycarboxylate compound (A) and the polycarboxylic acid compound (B).

Specific examples of the reactive compound (C) usable in the present invention include so-called reactive oligomers such as radical reaction type acrylates, cationic reaction type other epoxy compounds, and vinyl compounds sensitive to both of them .

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

Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (Meth) acrylate, phenylethyl (meth) acrylate, isobonyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate and tetrahydrofurfuryl .

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

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

Examples of the so-called reactive oligomers include urethane acrylate which combines a functional group capable of forming an active energy ray and a urethane bond in the same molecule, a polyester acrylate having both a functional group capable of forming an active energy ray and an ester bond in the same molecule, Epoxy acrylates derived from other epoxy resins and having functional groups capable of reacting with 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 so long as it is a compound having an epoxy group in general. Such as glycidyl (meth) acrylate, methyl glycidyl ether, ethylene glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxy Cyclohexanecarboxylate ("SAIRACURE UVR-6110" manufactured by Union Carbide Corp.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (union carbide ELR-4206 "manufactured by Daicel Chemical Industries, Ltd.), limonene dioxide (" Vertical Side 3000 "manufactured by Daicel Chemical Industries, Ltd.), allyl cyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane, and the like.

Of these, as the reactive compound (C), acrylate which is in the radical curing type is most preferable. In the case of the cationic type, since a carboxylic acid and an epoxy group react with each other, it is necessary to prepare a two-liquid mixture type.

The active energy ray-curable resin composition (B) of the present invention is prepared by mixing the carboxylate compound (A) and / or the reactive polycarboxylic acid compound (B) of the present invention with the reactive compound (C) Can be obtained. At this time, other components may be appropriately added depending on the application.

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

A coloring pigment usable in the present invention is used to make the active energy ray-curable resin composition of the present invention as a coloring material. Since the balance of the hydroxyl groups of the carboxylate compound (A) and the reactive polycarboxylic acid compound (B) used in the present invention falls within a specific range, it is presumed that the compatibility with the pigment, that is, the dispersibility is excellently exerted. The pigment can be thickened as a result because the dispersion is satisfactorily progressed although it is not sure about the mechanism, and in a composition requiring development, the dispersion is in a more suitable state, so that good patterning characteristics are exhibited, It is suitable because there are few residual phenomena.

Examples of the color pigment include organic pigments such as phthalocyanine pigments, azo pigments and quinacridone pigments, and inorganic pigments such as carbon black and titanium oxide. Of these, the dispersibility of carbon black is most preferred.

A photopolymerization initiator can be added to efficiently and sufficiently cure the active energy ray-curable resin composition of the present invention. Examples of the photopolymerization initiator include a radical photopolymerization initiator, a cationic photopolymerization initiator, and other polymerization initiators.

Examples of the radical type photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy- Acetophenones such as diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one; Anthraquinones such as 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 2-chloro anthraquinone, and 2-amylanthraquinone; Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone; And phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and the like.

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 initiator, a borate initiator, And the like.

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

Other halides include 2,2,2-trichloro- [1-4 '- (dimethylethyl) phenyl] ethanone (such as Trigonal PI from AKZO), 2,2-dichloro- Phenyl) ethanone (Sandray 1000 manufactured by Sandoz Co., Ltd.), and alpha, alpha, alpha -tribromomethylphenylsulfone (BMPS manufactured by Iron & Steel Chemistry Co., Ltd.). Examples of triazine initiators include 2,4,6-tris (trichloromethyl) -triazine, 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine (Triazine A, (2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine (Triazine PMS from Panchim, etc.), 2,4-trichloromethyl- (fiphenyl- 6,4'-methoxynaphthyl) -6-triazine (manufactured by Panchim Corp., etc.), 2- [2 '- (5 "-methylpyryl) ethyl (Trichloromethyl) -s-triazine (manufactured by Sampling Chemical Co., Ltd.), 2- (2'-pryethylidene) -4,6-bis (trichloromethyl) And triazine (manufactured by Samhwa Chemical Co., Ltd.).

Examples of the borate initiator include NK-3876 and NK-3881, which are Japanese photosensitive dyes, and other photoacid generators include 9-phenyl acridine, 2,2'-bis (o-chlorophenyl) 4,4 ', 5,5'-tetraphenyl-1,2-biimidazole (biimidazole, manufactured by KKM Ltd.), 2,2-azobis (2-aminopropane) dihydrochloride V50 and the like), 2,2-azobis [2- (imidazolin-2-yl) propane] dihydrochloride (VA044 and the like), [ita-5-2-4- (cyclopentadecyl) (II) hexafluorophosphonate (Irgacure 261 manufactured by Ciba Geigy, etc.), bis (cyclopentadienyl) bis (cyclopentadienyl) Bis [2,6-difluoro-3- (1H-pyryl-1-yl) phenyl] titanium (CGI-784 manufactured by Ciba Geigy).

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

In addition, in order to suitably use the active energy ray-curable resin composition of the present invention for various applications, other components may be added to the resin composition at an upper limit of 70% by mass. Examples of the other components include other additives, pigment materials, coloring materials, and volatile solvents added for viscosity adjustment for the purpose of imparting a coating property. Other ingredients that can be used are illustrated below.

Examples of other additives include thermosetting catalysts such as melamine, thixotropy imparting agents such as errors in quality, polymerization inhibitors such as silicones, fluorine leveling agents and defoamers, hydroquinone and hydroquinone monomethyl ether, stabilizers, and antioxidants .

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

(So-called inner polymer) such as an epoxy resin, a phenol resin, a urethane resin, a polyester resin, a ketone formaldehyde resin, a cresol resin, a xylene resin, a diallyl phthalate resin, Styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins and modified products thereof. These are preferably used in the range of up to 40% by mass.

Particularly when a reactive polycarboxylic acid compound (B) is used for a solder resist, it is preferable to use a known general epoxy resin as a resin which does not show reactivity with an active energy ray. This is because the carboxyl group derived from (B) remains after the reaction and curing by the active energy ray, and as a result, the cured product is poor in water resistance and hydrolysis resistance. Therefore, by using an epoxy resin, the remaining carboxyl groups are further carboxylated to form a stronger crosslinked structure.

A volatile solvent may be added to the resin composition in an amount of up to 50% by mass, more preferably up to 35% by mass for the purpose of adjusting the viscosity depending on the purpose of use.

The present invention is an active energy ray curable resin composition which is a molding material, a film forming material, or a resist material composition.

In the present invention, the molding material may be obtained by forming the uncured composition in a mold or by molding the mold by pressing the mold, causing the curing reaction to occur by an active energy ray, or forming the uncured composition by focusing light such as a laser And irradiating the material to cause a curing reaction.

Specific examples thereof include a sheet formed in a plane shape, a sealing material for protecting the element, a so-called nano-print material for finely molding by pressing a " mold " finely processed in the uncured composition, , A surrounding encapsulating material such as a photoelectric conversion element or the like can be used as a suitable use.

In the present invention, the film-forming material is used for coating the substrate surface. Specific applications include ink materials such as gravure ink, flexo ink, silkscreen ink and offset ink, coating materials such as hard coat, dope coat, over coat, overprint varnish and clear coat, laminates, , Adhesive materials such as pressure-sensitive adhesives, resist materials such as solder resists, etching resists, and resists for micromachines. Called dry film film forming material in which a film forming material is temporarily coated on a releasable substrate to form a film, and then the film is formed by bonding to a substrate intended for the original purpose.

Among them, since the adhesion of the reactive polycarboxylic acid compound (B) to the substrate is enhanced by the introduction of the carboxyl group, it is preferably used as an application for coating a plastic substrate or a metal substrate.

It is also preferable to utilize the unreacted reactive polycarboxylic acid compound (B) as an alkaline water-developing resist composition by taking advantage of its solubility in an aqueous alkali solution.

In the present invention, a resist material composition is an active energy ray-sensitive composition which is formed by forming a coating layer of a composition on a substrate, partially irradiating an active energy ray such as ultraviolet rays, and drawing the difference in physical properties of an irradiated portion and a non- irradiated portion . Specifically, the composition is used for the purpose of performing drawing by removing the irradiating unit or the non-irradiating unit by any method, for example, dissolving with a solvent, an alkali solution or the like.

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

The active energy ray-curable resin composition of the present invention can be applied to various materials capable of patterning, and is useful, for example, as an interlayer insulating material particularly for a solder resist material and a build-up method, and is also useful as an optical waveguide in a printed wiring board, an optoelectronic substrate, It is also used for electric, electronic, and optical substrates.

Particularly, it is preferable to use a permanent resist such as solder resist or a color resist such as a color filter such as a printing ink and a black matrix, Do.

In addition, it is particularly suitably used as a dry film application requiring mechanical strength before curing reaction by an active energy ray. That is, since the balance of the hydroxyl group and the epoxy group of the epoxy resin (a) used in the present invention falls within a specific range, the reactive carboxylate compound of the present invention can exhibit good developability in spite of a relatively high molecular weight.

There are no particular restrictions on the method of forming the film, but it is possible to use various methods such as intaglio printing method such as gravure, iron plate printing method such as Furekiso, stencil printing method such as silk screen, flat plate printing method such as offset, , A curtain coater, a spin coater, and the like can be arbitrarily employed.

The cured product of the active energy ray-curable resin composition of the present invention indicates that the active energy ray-curable resin composition of the present invention is cured by irradiation with an active energy ray for use in the above-mentioned use.

The article overcoated with the active energy ray-curable resin composition of the present invention may be obtained by forming a coat layer of the active energy ray-curable resin composition of the present invention on a suitable substrate and partially irradiating active energy rays such as ultraviolet rays to form a coat- . In this case, whether the cured product of the resin composition is formed on the substrate with the film-cured layer or the film-cured layer formed by drawing for the resist pattern is not particularly limited.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified in the Examples, "parts" means "parts by mass".

Softening point, epoxy equivalent, etc. were measured under the following conditions.

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

2) Softening point: Measured by the method according to JIS K 7234: 1986.

3) Acid value: Measured by the method according to JIS K 0070: 1992.

4) The measurement conditions of GPC are as follows.

Model: TOSOH HLC-8220GPC

Column: TSKGEL Super HZM-N

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

Detector: differential refractometer

Molecular weight standard: Polystyrene

Example 1: Preparation of carboxylate compound (A) with epoxy resin represented by general formula (2)

288 g of NC-3000H (Japanese Chemical Medicines, softening point 70 ° C, epoxy equivalent 288 g / eq, R ₃ represented by the general formula (2) are all hydrogen atoms and p is an average value of 3) as the epoxy resin (a) Acrylic acid (abbreviated AA, Mw = 72) as the compound (b) having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in the molecule, at least one hydroxyl group and at least one carboxyl group in the molecule Dimethylolpropionic acid (abbreviated as DMPA, Mw = 134) was added as the compound (c) capable of serving as the starting material. The molar ratio of each AA and DMPA injection equivalents to the epoxy groups was described.

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 reacted at 100 DEG C for 24 hours to obtain a carboxylate compound (A) solution of the present invention.

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

Example 2: Preparation of carboxylate compound (A) with epoxy resin represented by general formula (3)

230 g of NC-2000 (Japanese chemical, softening point 60 ° C, epoxy equivalent 230 g / eq, R ₄ represented by the general formula (3) are all hydrogen atoms and r is an average value of 5) as the epoxy resin (a) (b) and dimethylol propionic acid as the compound (c) were added in the amounts shown in Table 1. The molar ratio of each AA and DMPA injection equivalents to the epoxy groups was described.

3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content became 80% by mass of the reaction solution, and reacted at 100 占 폚 for 24 hours to obtain a carboxylate compound (A) solution.

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

Example 3: Production of Epoxycarboxylate Compound (A) by Epoxy Resin Represented by General Formula (4)

250 g of XD-1000 (Japanese chemical, softening point 70 캜, epoxy equivalent 250 g / eq, R ₅ represented by the general formula (4) are all hydrogen atoms and t is an average value of 3) as the epoxy resin (a) (b) and dimethylol propionic acid as the compound (c) were added in the amounts shown in Table 1. The molar ratio of each AA and DMPA injection equivalents to the epoxy groups was described.

3 g of triphenylphosphine was used as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent was added so as to have a solid content of 80% by mass and reacted at 100 占 폚 for 24 hours to obtain an epoxy carboxylate compound (A) solution.

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

Comparative Example 1: Preparation of Comparative Carboxylate Compound

(Molar ratio: 1.0) as a compound (b), 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent at a solid content of 80% by mass, And reacted for a time to obtain a carboxylate compound solution.

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

Comparative Example 2: Preparation of Comparative Carboxylate Compound

(Molar ratio: 1.0) as the compound (b), 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent in an amount of 80% by weight of the reaction liquid And reacted at 100 DEG C for 24 hours to obtain a carboxylate compound solution.

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

Comparative Example 3: Preparation of comparative epoxy carboxylate compound

Propylene glycol monomethyl ether monoacetate was added as a solvent to 80% by mass of solids, and the mixture was heated at 100 占 폚 for 24 hours at a temperature of 100 占 폚, to which 250g of XD-1000, 72g of acrylic acid as a compound (b) Hour reaction to obtain an epoxy carboxylate compound solution.

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

Comparative Example 4-1: Preparation of Comparative Carboxylate Compound

200 g of cresol novolak type epoxy resin EOCN-103S (Japanese chemical, softening point 80 캜, epoxy equivalent of 200 g / eq) as a compound (b) having both at least one polymerizable ethylenic unsaturated group and at least one carboxyl group 36 g (molar ratio: 0.5) of acrylic acid, and 67 g (molar ratio: 0.5) of dimethylolpropionic acid as a compound (c) having at least one hydroxyl group and at least one carboxyl group in the molecule.

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 reacted at 100 DEG C for 24 hours to obtain a comparative carboxylate compound solution.

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

Comparative Example 4-2: Preparation of Comparative Carboxylate Compound

(Molar ratio: 0.5) as the compound (c), 18 g of the acrylic acid (molar ratio: 0.5) as the component (b), 20 g of the component (c), and 20 g of the cresol novolac epoxy resin jER-1002 (manufactured by Japan Epoxy Resin, epoxy equivalent: 400 g / Respectively.

3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content became 80% by mass of the reaction solution, and reacted at 100 ° C for 24 hours to obtain a comparative carboxylate compound solution.

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

[Table 1]

Test Example 1: Storage stability of the epoxycarboxylate compound (A)

The epoxycarboxylate compound solutions obtained in Example 1 and Comparative Example 1 were stored in a freezer at a temperature of minus 5 캜 to compare the times until crystals were formed.

[Table 2]

From the above results, it can be clearly seen that the storage stability of the resin solution improves with the introduction of the compound (c) having at least one hydroxyl group and at least one carboxyl group in the molecule.

Example 4: Preparation of reactive polycarboxylic acid compound (B) with epoxy resin represented by general formula (2)

Tetrahydrophthalic anhydride (abbreviated as THPA) as a polybasic acid anhydride (d) was added to 299 g of the carboxylate compound (A) solution obtained in each of Examples 1-1, 1-2 and 1-3, Propylene glycol monomethyl ether acetate was added to 65% by mass of propylene glycol monomethyl ether acetate, and the mixture was heated to 100 占 폚 to react with an acid moiety to obtain a solution of the reactive polycarboxylic acid compound (B) of the present invention (Examples 4-1, 4-2, 4-3, 4-4). The solid acid value (mg KOH / g) is shown in Table 3.

Example 5: Preparation of reactive polycarboxylic acid compound (B) with epoxy resin represented by general formula (3)

Tetrahydrophthalic anhydride as the polybasic acid anhydride (d) was added to 299 g of the carboxylate compound (A) solution obtained in each of Examples 2-1, 2-2, 2-3 and 2-4, Propylene glycol monomethyl ether monoacetate was added to 65% by mass of the reaction solution, and the mixture was heated to 100 占 폚 for 3 hours to give a reactive polycarboxylic acid compound (B) solution of the present invention (Examples 5-1, 5-2, 5-3, 5-4, 5-5). The solid acid value (mg KOH / g) is shown in Table 3.

Example 6: Production of polycarboxylic acid compound (B) with epoxy resin represented by general formula (4)

Tetrahydrophthalic anhydride as the polybasic acid anhydride (d) was added to 299 g of the epoxy carboxylate compound (A) solution obtained in each of Examples 3-1, 3-2 and 3-3 in an amount of 65 g %, And the acid part was reacted by heating to 100 ° C to obtain a solution of the polycarboxylic acid compound (B) (Examples 6-1, 6-2, 6-3, 6-4) . The solid acid value (mg KOH / g) is shown in Table 3.

Comparative Example 5: Preparation of comparative reactive polycarboxylic acid compound

Propylene glycol monomethyl ether monoacetate was added to 299 g of the carboxylate compound solution obtained in Comparative Example 1 so as to have a solid content of 65% by mass as the amount of the base material and solvent of tetrahydrophthalic anhydride as the polybasic acid anhydride (d) in Table 3, To give a reactive polycarboxylic acid compound solution (Comparative Examples 5-1 and 5-2). The solid acid value (mg KOH / g) is shown in Table 3.

Comparative Example 6: Preparation of comparative reactive polycarboxylic acid compound

To 299 g of the carboxylate compound solution obtained in Comparative Example 2, tetrahydrophthalic anhydride as the polybasic acid anhydride (d) was added in the amount shown in Table 3 and propylene glycol monomethyl ether monoacetate was added as a solvent so that the solid content became 65% And heated at 100 ° C. for 3 hours to react with the acid moiety to obtain a reactive polycarboxylic acid compound solution (Comparative Examples 6-1 and 6-2). The solid acid value (mg KOH / g) is shown in Table 3.

Comparative Example 7: Preparation of comparative reactive polycarboxylic acid compound

Propylene glycol monomethyl ether monoacetate was added to 299 g of the epoxy carboxylate compound solution obtained in comparative example 3 so as to have a solid content of 65% by mass as the amount of the base material and solvent of tetrahydrophthalic anhydride as the polybasic acid anhydride (d) And the acid part was reacted to obtain a polycarboxylic acid compound solution (Comparative Examples 7-1 and 7-2). The solid acid value (mg KOH / g) is shown in Table 3.

Comparative Example 8: Preparation of comparative reactive polycarboxylic acid compound

Tetrahydrophthalic anhydride as the polybasic acid anhydride (d) was added to 299 g of the epoxy carboxylate compound solution obtained in Comparative Examples 4-1 and 4-2 in the amount shown in Table 3 and propylene glycol monomethyl ether Monoacetate was added and heated at 100 캜 to react with an acid moiety to obtain a polycarboxylic acid compound solution (Comparative Examples 8-1, 8-2, 8-3). The solid acid value (mg KOH / g) is shown in Table 3.

[Table 3]

Examples 7, 8 and 9 and Comparative Examples 9, 10, 11 and 12: Preparation of a composition for a hard coat and a cured product thereof, a hardness evaluation test thereof,

20 g of the reactive carboxylate compound (A) prepared in Examples 1, 2 and 3 and Comparative Examples 1, 2, 3 and 4, 4 g of dipentaerythritol hexaacrylate as the radical-curable monomer (C) Irgacure 184 was dissolved by heating in an amount of 1.5 g (1.0 g of UVI-6990 was added as a cationic initiator in Examples 7-4, 8-4 and 9-4).

Subsequently, this was coated on a polycarbonate plate with a hand applicator so as to have a film thickness of 20 microns upon drying, and the solvent was dried in an electric oven at 80 DEG C for 30 minutes. After drying, ultraviolet rays having an irradiation dose of 1000 mJ were irradiated and cured by an ultraviolet vertical exposure apparatus (manufactured by OAK) equipped with a high-pressure mercury lamp to obtain a multi-layer material.

The coating film hardness of this multilayered material was measured by JIS K5600-5-4: 1999 (Test Example 2), followed by impact test by ISO 6272-1: 2002 (Test Example 3), and by cold and heat impact test by JIS K5600-7 -4: 1999 (Test Example 4). The test samples (Examples 7 to 9, Comparative Examples 9 to 12) and the respective evaluation test results (Test Examples 2 to 4) were shown in Table 4.

[Table 4]

As can be seen from the above results, the hard coat materials prepared in Examples 7, 8, and 9 were prepared in the same manner as in Comparative Example 9 (Comparative Example 9) in which all of the epoxy groups were acrylated without using the compound (c) having a hydroxyl group and a carboxyl group in one molecule. , 10 and 11, respectively. The reason for the improvement of the impact resistance is that the density of the double bond is appropriately lowered according to the introduction of the compound (c) and that the gentle cross-linking structure due to hydrogen bonding has a good influence upon the introduction of the hydroxyl group.

In addition, in Comparative Examples 12-1 and 12-2 derived from a conventional bifunctional epoxy resin, the curability was markedly deteriorated and the impact resistance was low.

Examples 10, 11 and 12 and Comparative Examples 13, 14, 15 and 16: Preparation of a dry film type resist composition and a cured product thereof

54.44 g of the reactive polycarboxylic acid compound (B) obtained in Examples 4, 5 and 6 and Comparative Examples 5, 6, 7 and 8, and HX-220 (trade name: Acrylate monomer), 4.72 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, 0.47 g of Kayacure-DETX-S (manufactured by Nippon Gakuen Kogyo Co., Ltd.) (Manufactured by JASCO Corporation), 1.05 g of melamine as a thermosetting catalyst, and 20.95 g of methyl ethyl ketone as a concentration adjusting solvent were kneaded in a bead mill and uniformly dispersed to obtain a resist resin composition.

The resulting composition was uniformly applied to a polyethylene terephthalate film as a support film using a wire bar coater # 20 and passed through a hot air drying oven at 70 캜 to form a resin layer having a thickness of 20 탆. Then, A polyethylene film as a film was stuck to obtain a dry film. The obtained dry film was adhered to the entire surface of the substrate while peeling off the protective film using a heating roll having a temperature of 80 占 폚 on a polyimide print substrate (coater thickness 12 占 퐉, polyimide film thickness 25 占 퐉).

(A) and (B) used in Examples 10-5, 11-6 and 12-5 were the same as those of the acid-modified carboxylate compound (A) prepared in Examples 1-1, And the polycarboxylic acid compound (B) using the corresponding epoxy resin prepared in Example 4-1, 5-1 or 6-1 were mixed 50:50 by the weight of the solution.

Next, ultraviolet rays of 500 mJ / cm ² were irradiated through Kodak Step Tablet No. 2 in order to estimate the mask and sensitivity of the circuit pattern by using an ultraviolet exposure apparatus (manufactured by OAK Corporation, type HMW-680GW) . Thereafter, the film on the dry film was peeled off and the peeling state was confirmed. Thereafter, spraying was performed with a 1% aqueous solution of sodium carbonate to remove the resin from the unexposed portion. After washing with water, the printed board was heated and cured by a hot air drier at 150 ° C for 60 minutes to obtain a cured film.

The performance evaluation of the dry film type resist cured films obtained in Examples 10, 11 and 12 and Comparative Examples 13, 14, 15 and 16 was carried out by the following evaluation methods (Test Examples 5 to 10). The evaluation test results of the respective cured films are shown in Table 5.

Test Example 5: Evaluation of bending resistance

The polyimide printed substrate on which the cured film of the resist was formed was spread out on the side of the cured film and pulled with a finger. The folded-back portion was returned to its original state and the resist film was observed with a magnifying glass.

Evaluation criteria:?: No crack?: Partly crack observed?: Peeled off

Test Example 6: Evaluation of cold and heat impact resistance

A polyimide printed substrate having a cured film of a resist formed thereon was subjected to a cold shock test in the range of -65 to 120 캜. The test method was in accordance with JIS C5012-9.1: 1993. After the completion of the test, a peel test with a cellophane tape (registered trademark) was carried out.

Evaluation criteria:?: No peeling?: Some peeling was observed 占: Peeling was observed

Test Example 7: Evaluation of High Temperature Moisture Resistance

The polyimide printed substrate on which the cured film of the resist was formed was placed in an autoclave at 120 캜 for 1 hour. The substrate was taken out and air-dried at room temperature, and then subjected to a peeling test using Cellophane Tape (registered trademark).

Evaluation criteria:?: No peeling,?: Some peeling was observed, X: Peeling was observed

Test Example 8: Sensitivity evaluation

The degree of sensitivity was judged as to whether or not the exposure to the exposed portion passing through the step tablet up to the concentration level at the second stage had remained at the time of development. It is judged that the one having a larger number (the value) is highly sensitive in the farmer of the tablet (unit: step).

Test Example 9: Developability Evaluation

Developability was evaluated in terms of developability (unit: second) with the time until the pattern portion was completely developed when the exposed portion passed through the pattern mask was developed, that is, the so-called break time.

Test Example 10: Evaluation of Curability

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

[Table 5]

As can be seen from the above results, the resist composition in the present invention can obtain a cured product having a relatively high hardness and has good developability and sensitivity as a resist. Furthermore, in Examples 10 and 11, it has a high bendability. Also, in Example 12, it has high resistance to cold and heat and high-temperature moisture resistance. The resist compositions and cured products of the comparative examples did not show satisfactory evaluation results on the resistance to kneading, impact resistance due to thermal changes, developability and sensitivity, and were unsatisfactory as a dry film resist material.

Example 13 and Comparative Examples 17 and 18: Preparation of flame retardant resin and comparative resin

9.5 g of the resist composition prepared in Example 10-2 and Comparative Examples 13-1 and 16-1 and 0.5 g of a phosphate ester flame retardant (Shikoku Chemical SP-703H) were mixed and stirred to obtain a curable resin composition. The composition was coated on a polyimide film having a thickness of 25 microns with a wire bar coater # 20 and passed through a hot air drying oven at 70 캜 to form a resin layer having a thickness of about 15 탆. And irradiated with ultraviolet light of 500 mJ / cm ² using an ultraviolet exposure apparatus (OAK Corporation, type HMW-680GW). After irradiation, the printed board was heated and cured by a hot-air dryer at 150 캜 for 60 minutes to obtain a cured film (Example 13, Comparative Examples 17 and 18, respectively).

Test Example 11: Evaluation of Flame Retardancy

The cured films obtained in Example 13 and Comparative Examples 17 and 18 were cut out together with a polyimide base film in a monolithic form having a length of 20 cm and a width of 2 cm. The exfoliated film was hanged in the longitudinal direction, and the flame retardancy was evaluated by lighting from the bottom to the lighter. In order to compare the abrasion resistance, the abrasion resistance test data of Example 10-2 and Comparative Examples 13-1 and 16-1 are shown in Table 6 as follows.

[Table 6]

From the above results, it can be seen that the carboxylate compound of the present invention is a material capable of achieving compatibility between flame retardancy and abrasion resistance.

Examples 14, 15 and 16 and Comparative Examples 19, 20, 21 and 22: Preparation of colored pigment dispersion resin

20 g of the reactive polycarboxylic acid compound (B) obtained in Examples 4, 5 and 6 and Comparative Examples 5, 6, 7 and 8 and 20 g of DPHA (trade name: Acrylate Monomer ), 10 g of propylene glycol monomethyl ether acetate as an organic solvent, and 10 g of Mitsubishi carbon black MA-100 as a color pigment were mixed and stirred. Then, 35 g of glass beads were put therein and dispersed for 1 hour with a paint shaker.

After the dispersion was completed, the dispersion was coated on a polyethylene terephthalate film with a wire bar coater # 2 and dried in a hot air drier at 80 ° C for 10 minutes to obtain respective carbon black dispersion resins.

Test Example 12: Evaluation of pigment dispersibility

The gloss of the surface of the coating film of the carbon black dispersion resin obtained in Examples 14, 15 and 16 and Comparative Examples 19, 20, 21 and 22 was measured using a 60 ° reflection gloss meter (HORIBA IG-331 gloss system) Was evaluated. At this time, the higher gloss indicates that the pigment dispersion is good. The results are shown in Table 7.

[Table 7]

From the above results, it can be clearly seen that the reactive polycarboxylic acid compound (B) of the present invention has improved pigment dispersibility. From the difference from the polycarboxylic acid of the comparative example, the pigment dispersing action is considered to be a difference in the effect of adding the epoxy resin and the compound (c) contained in the basic skeleton to the specific structure in the molecule.

Example 17 and Comparative Examples 23 and 24: Preparation of colored pigment dispersion resin

Except that 20 g of the reactive polycarboxylic acid compound (B) obtained in Example 4-2 and Comparative Examples 5-1 and 8-1 and 5.0 g of a DPHA (trade name: Acrylate Monomer, manufactured by Nippon Gakuin KK) as the other reactive compound (C) 10 g of propylene glycol monomethyl ether acetate as an organic solvent, and 10 g of Mitsubishi carbon black MA-100 as a coloring pigment were mixed and stirred. Then, 35 g of glass beads were put therein and dispersed for 1 hour with a paint shaker. The resulting carbon black dispersion resin solution was taken in a sample bottle to obtain a colored pigment dispersion.

Test Example 13: Evaluation of storage stability of a colored pigment dispersion

The colored pigment dispersions prepared in Example 17 and Comparative Examples 23 and 24 were kept at 40 占 폚 for 2 weeks, and the state of the dispersions was evaluated. The results are shown in Table 8.

[Table 8]

As can be seen from the above results, the dispersion of the coloring pigment according to the example maintains a uniform state without separation of the dispersion even after 2 weeks at 40 占 폚. On the other hand, in Comparative Example 23, a transparent layer (varnish suspension) was observed in the upper layer and the dispersion state was unstable. In Comparative Example 24, precipitation of the coloring pigment occurred, and even when stirred, the state was not uniform.

From the above results, it was confirmed that the compound (b) having an ethylenic unsaturated group having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group added to the epoxy resin (a) having a specific structure as a basic skeleton of the reactive polycarboxylic acid compound (B) And the compound (c) having at least one hydroxyl group and at least one carboxyl group in the molecule, thereby improving the dispersibility of the pigment and improving the storage stability of the pigment dispersion.

Industrial availability

The active energy ray-curable resin of the present invention is a material having both hardenability, flexibility, toughness and flame retardancy, and is used as a hard coat material, a resist material requiring flexibility capable of developing alkali, and an application for exhibiting good pigment dispersibility, And can be suitably used for a color resist for LCDs, in particular, a black matrix, as a material that combines a line-hardening type of printing ink and a color resist, particularly resist properties such as pigment dispersibility and developability.

Claims (14)

(B) an epoxy resin (a) represented by the general formula (1), a compound (b) having both at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in one molecule and at least one hydroxyl group and at least one carboxyl group (B) a reactive polycarboxylic acid compound (B) obtained by reacting a reactive epoxycarboxylate compound (A) obtained by reacting a compound (c) having a functional group (EN) Resin composition for line - curable color resist.

Wherein R ₁ is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms, R ₂ is a divalent polycyclic hydrocarbon group having 7 to 16 carbon atoms or an aralkylene group having 7 to 18 carbon atoms, m is an integer of 1 to 4, and n is an average value of an integer of 1 to 10, respectively) The active energy ray-curable color resist composition according to claim 1, wherein the epoxy resin (a) is represented by the general formula (2).

(Wherein, R ₃ is the same or different from each other a hydrogen atom, a halogen atom or a hydrocarbon group of a carbon number of 1 to 4, o is an integer of 1-4, and p represents an integer of 1 to 10 as a mean value, respectively) The active energy ray-curable color resist composition according to claim 1, wherein the epoxy resin (a) is represented by the general formula (3).

(Wherein R ₄ is the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group of 1 to 4 carbon atoms, q represents an integer of 1 to 4, and r represents an integer of 1 to 10, respectively, The active energy ray-curable color resist composition according to claim 1, wherein the epoxy resin (a) is represented by the general formula (4).

(Wherein R ₅ is the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group of 1 to 4 carbon atoms, s represents an integer of 1 to 4, and t represents an integer of 1 to 10, respectively, 5. The resin composition for active energy ray-curable color resist according to any one of claims 1 to 4, further comprising a reactive compound (C) other than (B). 5. The resin composition for active energy ray-curable color resists according to any one of claims 1 to 4, further comprising a photopolymerization initiator. The active energy ray-curable color resist composition according to any one of claims 1 to 4, which is a molding material. The resin composition for active energy ray-curable color resist according to any one of claims 1 to 4, which is a film-forming material. The resin composition for active energy ray-curable color resist according to any one of claims 1 to 4, which is a resist material composition. A cured product of the resin composition for active energy ray-curable color resist according to any one of claims 1 to 4. An article overcoated with a resin composition for an active energy ray-curable color resist according to any one of claims 1 to 4.
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