KR20100058450A - Reactive carboxylate compound, curable resin composition using the same, and use of the same - Google Patents

Abstract

Disclosed is a resin composition which is cured by active energy ray such as ultraviolet light and enables to obtain a tough coating film or a molding material. Specifically disclosed is a reactive compound derived from a phenol aralkyl-type epoxy resin having a specific structure with an excellent balance between hydroxy group and epoxy group. A tough cured product can be obtained from a curable resin composition using such a reactive compound. In addition, the reactive compound exhibits good pigment dispersibility.

Description

Reactive carboxylate compound, curable resin composition using the same, and use of the same}

 The present invention provides a phenolaralkyl type epoxy resin (a) having excellent balance of hydroxyl group, epoxy group and softening point, and a compound (b) having at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in a molecule such as acrylic acid. It relates to a reactive epoxy carboxylate compound (A) obtained by reacting and a reactive polycarboxylic acid compound (B) which is an acid modified product thereof. These reactive epoxy carboxylate compounds (A) and reactive polycarboxylic acid compounds (B) have good dispersibility of the pigment, and from the resin composition containing them, a film forming material, a solder resist, a plating resist, a color resist, Various hardened | cured materials suitable for various resists, such as a color filter resist and a black matrix, and an optical waveguide can be obtained.

Printed wiring boards are aimed at reducing the size and weight of mobile devices and improving communication speeds, and demanding high precision and high density. With these, the demands on solder resists covering the circuits themselves are becoming more advanced. Furthermore, the performance which can tolerate board | substrate adhesiveness, high insulation, and electroless gold plating property while maintaining heat resistance and thermal stability is calculated | required more, and the film forming material which has more tough hardened | cured material property was calculated | required.

In these materials, a reactive polycarboxylic acid compound in which a carboxyl group is introduced with an acid anhydride for the purpose of patterning using an alkaline developer after carboxylating an epoxy resin with acrylic acid or the like is applied to a resist use, in particular, a solder resist. It is generally known to do (patent documents 1-2).

Acid-modified epoxy acrylates based on phenol aralkyl type epoxy resins (e.g., NC-3000 manufactured by Nippon Kayaku Co., Ltd.) are generally known as materials showing high toughness after curing, and are used as solder resists using the same. Examination is also performed regarding (patent document 3).

Among these, in film forming applications, in particular solder resist applications, physical properties in a state only by volatilizing a solvent after film formation are also important factors. Specifically, when this step is more flexible than necessary, peeling or fouling of the patterning film occurs. In particular, in the use of what is called a dry film, this characteristic is more important in order to enter the process called transfer.

In order to improve the toughness before and after curing, using a high molecular weight material is a common technique, but in this case, developability is largely impaired.

Moreover, patent document 3 does not disclose the quantitative balance of a hydroxyl group and an epoxy group in an epoxy resin, and cannot obtain the very suitable balance in the case of this invention.

In addition, a test in which carbon black or the like is dispersed in an acid-modified epoxy acrylate based on a phenol aralkyl type epoxy resin (for example, NC-3000 manufactured by Nippon Kayaku Co., Ltd.) as a basic skeleton, and applied to a black matrix resist used in a liquid crystal display panel, etc. It is known (patent document 4).

In this application, in the case of blending colored pigments such as carbon black at high concentrations, the pigments are well dispersed with the resins that are compatible with the resin, and exhibit good developability even when the pigments are present at high concentrations, and there is no pigment residue. Development is possible. Conventional acid-modified epoxy acrylates, especially acid-modified epoxy acrylates having a biphenyl backbone, exhibit relatively good dispersibility, but developability at higher pigment concentrations, ie higher pigment dispersibility, has been called for. In addition, Patent Document 4 also does not disclose a quantitative balance between a hydroxyl group and an epoxy group in the epoxy resin, and in the disclosed method, a very appropriate balance in the case of the present invention cannot be obtained. Although patent document 5 describes the epoxy resin similar to the epoxy resin (a) used by this invention, the reactive epoxy carboxylate compound (A) and the reactive polycarboxylic acid compound (B) are not described.

Patent Document 1: Special Publication No. 56-40329 Patent Document 2: Special Publication No. 57-45795 Patent Document 3: Japanese Patent Application Laid-Open No. 11-140144 Patent Document 4: Japanese Patent Application Laid-Open No. 2005-55814 Patent Document 5: Japanese Patent Application Laid-Open No. 2007-191587

Although the curable resin composition which uses the epoxy resin of the above-mentioned, phenol aralkyl-type can obtain comparatively strong hardened | cured material, it is not enough in the hardening physical property of image development.

In addition, acid-modified epoxy acrylates are desired that have a higher dispersion in color pigments, in particular carbon black and the like, and have good developing properties even at high pigment concentrations. At this time, the material which has comparatively high molecular weight, and has suitable developability is calculated | required.

There is a demand for a material having tough curing properties, good developing properties, and having good developing properties even at high pigment concentrations.

MEANS TO SOLVE THE PROBLEM In order to solve the subject mentioned above, the present inventors obtained the hardened | cured material which the active energy ray hardening-type resin composition derived from the epoxy resin which has a specific structure, ie, the epoxy resin containing many structures represented by General formula (1), is obtained. It was found that the resin had excellent resin properties even in the state of only drying the solvent. It has also been found to have particularly good dispersibility of colored pigments, and that it can be made into a resist material having good developability even at high pigment concentrations.

That is, the present invention relates to a reactive epoxy carboxylate compound (A) obtained by reacting the following epoxy resin (a) with a compound (b) having at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in a molecule. It is about:

In addition, it has a structure represented by the following general formula (2) (In general formula (2), Ar is represented by general formula (3) or (4), m represents the integer of 1-3 as the number of substituent R, n represents the average value of the repeating number of 1-10, R respectively represents a hydrogen atom, a halogen atom, a C1-C15 hydrocarbon group, a trifluoromethyl group, an aryl group, or an aryl group, and each R is respectively They may be the same as or different from each other, and Ar may be the same or different.)

Epoxy resin (a) obtained from the phenol aralkyl resin (P) of the structure shown by;

(i) an epoxy resin (a) formed by partially epoxidizing the phenolaralkyl resin (P)

(ii) An epoxy resin (a) formed by reacting a phenol aralkyl resin (P) and a phenol aralkyl type epoxy resin (E2).

Moreover, the reactive epoxy carboxylate compound (A) characterized by using the epoxy resin (a) which can be obtained using 1.0-5.0 mol of epihalohydrin with respect to 1 mol of hydroxyl groups of a phenol aralkyl resin (P) (A). ).

Moreover, the epoxy resin (a) which can be obtained by making it react so that the hydroxyl group of a phenol aralkyl resin (P) may be 0.01-0.3 mol with respect to 1 mol of epoxy groups of a phenol aralkyl type epoxy resin (E2) is characterized by the above-mentioned reactivity. It relates to an epoxy carboxylate compound (A).

In the case where the epoxy resin (a) has a hydroxyl equivalent of X (g / eq.) And an epoxy equivalent of Y (g / eq.), The respective relationships are represented by the following formula (I)

It relates to a reactive epoxy carboxylate compound (A) which satisfies.

Moreover, it is related with the reactive polycarboxylic acid compound (B) obtained by making a polybasic acid anhydride (c) react with the said carboxylate compound (A).

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

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

Moreover, it is related with the active energy ray hardening type resin composition characterized by including a coloring pigment in the said active energy ray hardening type resin composition.

Moreover, it is related with the said active energy ray hardening-type resin composition which is a molding material.

Moreover, it is related with the said active energy ray hardening-type resin composition which is a film forming material.

Moreover, it is related with the said active energy ray hardening type resin composition which is a resist material composition.

Moreover, it is related with the hardened | cured material of the said active energy ray hardening-type resin composition.

Moreover, it is related with the article overcoat with the hardened | cured material of the said resin composition.

Moreover, it is related with the manufacturing method of the reactive epoxy carboxylate compound (A) which makes the said epoxy resin (a) react with the compound (b) which has one or more polymerizable ethylenically unsaturated group and 1 or more carboxyl group in a molecule | numerator.

Moreover, it is related with the manufacturing method of the reactive polycarboxylic acid compound (B) which makes the said carboxylate compound (A) and polybasic acid anhydride (c) react.

The active-energy-ray-curable resin composition containing the epoxy resin which has the specific structure of this invention has the outstanding resin physical property not only in obtaining hardened hardened | cured material but also in the state which dried only the solvent. The hardened | cured material obtained from the active-energy-ray-curable resin composition of this invention can be used suitably for the film forming material which requires thermal and mechanical toughness.

Furthermore, it can suitably be used for the application which requires especially high characteristics, such as the soldering resist for printed wiring boards, the interlayer insulation material for multilayer printed wiring boards, the soldering resist for flexible printed wiring boards, a plating resist, and the photosensitive optical waveguide.

Moreover, since it has high dispersibility of colored pigments, such as carbon black, and can exhibit favorable developability even at high pigment concentration, it is suitable also for color resist, the resist material for color filters, especially a black matrix material. Can be used.

In the active energy ray-curable resin composition of the present invention, the epoxy resin (a), which is an essential component, has a structure in which at least phenols or naphthols are bonded to an aralkyl group as a bonding group and the following general formula (1)

It is a phenol aralkyl type epoxy resin which has a structure represented by these.

The epoxy resin (a) partially epoxidizes the phenol aralkyl resin (P) (single step) or reacts (fusion method) the phenol aralkyl resin (P) and the phenol aralkyl type epoxy resin (E2). Can be obtained by The phenol aralkyl resin (P) used as a raw material is a resin having a molecular structure in which an aromatic ring is bonded to phenols and naphthols having a substituent through a methylene bond, an ethylidene bond, a propylidene bond, or the like. Examples of the aromatic ring include bishalogenomethyl, bishalogenoethyl, and bishalogenopropyl of phenyl, biphenyl, fluorenyl and naphthyl; bisalkoxymethyl, bisalkoxyethyl and bisalkoxy Propyl; bishydroxymethyl, bishydroxyethyl, bishydroxypropyl and the like. The phenol aralkyl resin (P) used by this invention can be obtained by condensation reaction of the phenols, naphthol which have a substituent, and an electroaromatic ring. In the present invention, phenols, particularly preferably those obtained by condensation reaction between a compound having a phenol and a biphenyl skeleton, and a phenyl aralkyl resin of the biphenyl type such as the formula (2) is particularly preferable.

In the formula (2), each R independently represents a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, a trifluoromethyl group, an aryl group or an aryl group, or a halogen atom. Herein, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, a sec-butyl group, and a tert- are specifically a hydrocarbon group having 1 to 15 carbon atoms, more preferably 1 to 7 carbon atoms. Butyl group, isobutyl group, cyclobutyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group And linear or cyclic alkyl groups such as cycloheptyl group, n-octyl group and cyclooctyl group. Moreover, as an aryl group, C6-C11 is preferable. Specifically, a phenyl group, a naphthyl group, toluyl group, etc. are mentioned. Moreover, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned as a halogen atom.

Among them, a hydrogen atom, a methyl group, a phenyl group or a tert-butyl group is preferable, and a hydrogen atom is particularly preferable. Although the substitution position of R is not specifically limited, Ortho position or meta position of a hydroxyl group are respectively taken independently. n represents 1-10 as an average value, and 1.0-5.0 are preferable.

Such phenol aralkyl resins are also available commercially available, specifically, the Mitsui Chemical Industries, Ltd. XLC series, the Showa Chemical Industries, Ltd. MEH-7851, and Nippon Kayaku Co., Ltd. KAYAHARD GPH65 by Shikigaisha Co., Ltd. is mentioned:

(N is 1 to 10 as the average value of the number of repetitions)

The phenol aralkyl type epoxy resin (E2) used as a raw material of an epoxy resin (a) in the fusion method is a structure which has the structure which glycidylated the phenolic hydroxyl group of the said phenol aralkyl resin, and is represented by following General formula (6) Preferred compounds are:

(N is 1 to 10 as the average value of the number of repetitions)

Among them, for example, the formula (7)

(Wherein n is 1 to 10 as the average value of the number of repetitions)

The epoxy resin represented by this is mentioned. In recent years, this epoxy resin is excellent in various characteristics, such as its flame retardance, adhesiveness, and water resistance, and is especially preferable.

The raw material phenol aralkyl resin (P) and the raw material phenol aralkyl type epoxy resin (E2) of the epoxy resin (a) are generally synthesized by the method as described in Patent No. 3122834 or Japanese Patent Laid-Open No. 2001-40053. Specifically, substituted methylene biphenyl such as condensation of 4,4'-bismethoxymethylbiphenyl and phenols under acidic conditions, or condensation of 4,4'-bishalogenomethylbiphenyl and phenols under acidic conditions. Condensation reaction of a compound and phenols is mentioned. By reacting the obtained preferable phenol aralkyl resin with epihalohydrin, the raw material phenol aralkyl type epoxy resin, Preferably the compound represented by General formula (7) can be obtained. As resin represented by General formula (7), Nippon Kayaku Co., Ltd. NC-3000 and NC-3000H are mentioned as a commercial item.

The manufacturing method of an epoxy resin (a) is demonstrated below.

As mentioned above, the single-stage method and the fusion method can be applied to the manufacturing method of an epoxy resin (a). However, conventional one-stage and fusion methods are intended for bifunctional epoxy resins and phenolic resins, and when polyfunctionality is used as a raw material thereof as in epoxy resin (a), polyfunctional phenolic resins and epitaxial ones can be used in one-stage. In addition, it is necessary to consider the reaction rate of rodrin with respect to the reaction rate of a polyfunctional epoxy resin and a polyfunctional phenol resin by the fusion method. Hereinafter, although it distinguishes and describes epoxy resin (a) (i) and epoxy resin (a) (ii) by a manufacturing method, the same epoxy resin (a) can be obtained even if it uses any manufacturing method.

First, the case of a one-stage method is explained in full detail. Epoxy resin (a) (i) can be obtained by making phenol aralkyl resin (P) and epihalohydrin react in presence of an alkali metal hydroxide. In this one-step method, the amount of epihalohydrin and alkali metal hydroxide used is a factor for determining the introduction rate of the structure of the general formula (1).

In the reaction for obtaining the epoxy resin (a), epichlorohydrin, α-methyl epichlorohydrin, γ-methyl epichlorohydrin, epibromohydrin and the like can be used as the epihalohydrin. In the process, epichlorohydrin which is industrially available is preferable. The usage-amount of epihalohydrin is 1.0-5.0 mol normally with respect to 1 mol of hydroxyl groups of raw material phenol aralkyl resin (P), Preferably it is 1.5-3.5 mol.

Examples of the alkali metal hydroxide that can be used in the electrical reaction include sodium hydroxide and potassium hydroxide, and may be used as a solid or an aqueous solution thereof. In the case of using an aqueous solution, an aqueous solution of the alkali metal hydroxide is continuously added into the reaction system, and water and epihalohydrin are continuously discharged under reduced pressure or under normal pressure, followed by separation to remove water. In addition, a method of continuously returning epihalohydrin into the reaction system may be used. The use amount of alkali metal hydroxide is 0.3-2.5 mol normally with respect to 1 mol of hydroxyl groups of a raw material phenol aralkyl resin, Preferably it is 0.5-2.0 mol.

In order to accelerate the reaction, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride are preferably added as a catalyst. As the usage-amount of a quaternary ammonium salt, it is 0.1-15 g normally with respect to 1 mol of hydroxyl groups of a phenol aralkyl resin, Preferably it is 0.2-10 g.

At this time, it is preferable to carry out the reaction by adding alcohols such as methanol, ethanol and isopropyl alcohol, aprotic polar solvents such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane and the like.

When using alcohols, the usage-amount is 2-50 weight part normally with respect to the usage-amount of epihalohydrin, Preferably it is 4-20 weight part. Moreover, when using an aprotic polar solvent, it is 5-100 weight part normally with respect to the usage-amount of epihalohydrin, Preferably it is 10-80 weight part.

The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours. The reaction product of these epoxidation reactions is removed after washing with or without water washing to remove epihalohydrin, a solvent and the like. Then, in order to obtain an epoxy resin containing less hydrolyzable halogen, the recovered epoxy resin is dissolved in a solvent such as toluene, methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to carry out the reaction. The closure can be assured. In this case, the usage-amount of alkali metal hydroxide is 0.01-0.3 mol normally, Preferably it is 0.05-0.2 mol with respect to 1 mol of hydroxyl groups of the phenol aralkyl resin (P) used for epoxidation. Reaction temperature is 50-120 degreeC normally, and reaction time is 0.5 to 2 hours normally.

After completion | finish of reaction, the produced | generated salt is removed by filtration, water washing, etc., and then an epoxy resin (a) (i) can be obtained by distilling a solvent off under reduced pressure under heating.

Next, the fusion method will be described in detail. This method is a method of obtaining an epoxy resin (a) (ii) by reacting a phenol aralkyl type epoxy resin (E2) and a phenol aralkyl resin (P). In this fusion method, the ratio of phenol aralkyl type epoxy resin (E2) and phenol aralkyl resin (P) becomes a factor which determines the introduction ratio of the structure of General formula (1). A commercially available compound may be used for the phenol aralkyl type epoxy resin (E2), and phenol aralkyl resin (P) may be epoxidized and used. When synthesize | combining, it can carry out by the following method, for example.

A phenol aralkyl type epoxy resin (E2) can be obtained by making phenol aralkyl resin (P) and epihalohydrin react. As epihalohydrin, epichlorohydrin, (alpha) -methyl epichlorohydrin, (gamma) -methyl epichlorohydrin, epibromohydrin, etc. can be used, Epichlorohydrin which is industrially available is preferable. Do. The usage-amount of epihalohydrin is 2.0-20.0 mol normally with respect to 1 mol of hydroxyl groups of a phenol aralkyl resin (P), Preferably it is 2.5-10.0 mol.

Examples of the alkali metal hydroxide that can be used in the electrical reaction include sodium hydroxide and potassium hydroxide, and may be used as a solid or an aqueous solution thereof. In the case of using an aqueous solution, an aqueous solution of the alkali metal hydroxide is continuously added into the reaction system, and water and epihalohydrin are continuously discharged under reduced pressure or under normal pressure, followed by separating the water to remove water. In addition, a method of continuously returning epihalohydrin into the reaction system may be used. The use amount of alkali metal hydroxide is 0.9-2.5 mol normally with respect to 1 mol of hydroxyl groups of a phenol aralkyl resin, Preferably it is 0.95-2.0 mol.

In order to accelerate the reaction, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride are preferably added as a catalyst. As the usage-amount of a quaternary ammonium salt, it is 0.1-15 g normally with respect to 1 mol of hydroxyl groups of a phenol aralkyl resin, Preferably it is 0.2-10 g.

At this time, it is preferable to carry out the reaction by adding alcohols such as methanol, ethanol and isopropyl alcohol, aprotic polar solvents such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane and the like.

When using alcohols, the usage-amount is 2-50 weight part normally with respect to the usage-amount of epihalohydrin, Preferably it is 4-20 weight part. Moreover, when using an aprotic polar solvent, it is 5-100 weight part normally with respect to the usage-amount of epihalohydrin, Preferably it is 10-80 weight part.

The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours. The reaction product of these epoxidation reactions is removed after washing with or without water washing to remove epihalohydrin, a solvent and the like. Then, in order to obtain an epoxy resin containing less hydrolyzable halogen, the recovered epoxy resin is dissolved in a solvent such as toluene, methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to carry out the reaction. The closure can be assured. In this case, the usage-amount of alkali metal hydroxide is 0.01-0.3 mol normally, Preferably it is 0.05-0.2 mol with respect to 1 mol of hydroxyl groups of the phenol aralkyl resin (P) used for epoxidation. Reaction temperature is 50-120 degreeC normally, and reaction time is 0.5 to 2 hours normally.

After completion | finish of reaction, the produced | generated salt is removed by filtration, water washing, etc., and then a solvent is distilled off under heating pressure reduction, and a phenol aralkyl type epoxy resin (E2) can be obtained. Epoxy resin (a) (ii) can be obtained by making obtained phenol aralkyl type epoxy resin (E2) and phenol aralkyl resin (P) react. Usually, it is made to react so that the hydroxyl group of phenol aralkyl resin (P) may be 0.01-0.3 mol with respect to 1 mol of epoxy groups of phenol aralkyl-type epoxy resin (E2).

The reaction of a phenol aralkyl type epoxy resin (E2) and a phenol aralkyl resin (P) uses a catalyst as needed. Specific examples of the catalyst that can be used include quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride; quaternary phosphonium salts such as triphenylethylphosphonium chloride and triphenylphosphonium bromide; sodium hydroxide; Alkali metal salts such as potassium hydroxide, potassium carbonate and cesium carbonate; imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole Tertiary amines such as 2- (dimethylaminomethyl) phenol, triethylenediamine, triethanolamine, and 1,8-diazabicyclo (5,4,0) undecene-7; triphenylphosphine and diphenylphosph Organic phosphines such as pin and tributyl phosphine; metal compounds such as octylic acid tin; tetrasubstituted foams such as tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, etc. Phosphonium · tetra-substituted borate is a, 2-ethyl-4-methylimidazole, and the like tetraphenyl boron salts such as imidazole, tetraphenylborate, N- methyl morpholine, tetraphenylborate. Although the usage-amount when using these catalysts changes with kinds of catalysts, generally 10 ppm-30000 ppm with respect to total resin amount, Preferably 100 ppm-5000 ppm are used as needed. Since the reaction proceeds without adding a catalyst in the present reaction, it is preferable to use a suitable reaction temperature and the amount of the reaction solvent in combination.

In this fusion method, it is also possible to react with a solvent or to dilute with a solvent for reaction. As a solvent which can be used here, it will not specifically limit, if it is an inetato solvent with respect to this reaction. In addition, in the case of using the solvent in the next step of carboxylating reaction and the acid addition reaction in the next step, it is provided to the reaction in the next step directly without removing the solvent provided that it is inert to both reactions thereof. can do.

Specifically, for example, aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane, and decane, and petroleum ethers such as petroleum ether, white gasoline, solvent naphtha, etc. Can be mentioned.

Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate and diethylene glycol mono Mono or polyalkylene glycol monoalkyl ether mono such as ethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate Polycarboxylic acid alkyl esters, such as acetates, dialkyl glutaric acid, dialkyl succinate, and adipic acid dialkyl, etc. are mentioned.

Examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether and triethylene Glycol ethers, such as glycol diethyl ether, Cyclic ethers, such as tetrahydrofuran, etc. are mentioned.

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

In addition, reaction can be performed in single or mixed organic solvents, such as other reactive compound (C) mentioned later. In this case, when used as a curable composition, since it can use directly as a composition, it is preferable.

The amount of the solvent used is 0 to 300 parts by weight, preferably 0 to 100 parts by weight based on the total resin weight.

Although reaction temperature and reaction time need to be selected suitably according to resin concentration and catalyst amount, it cannot be limited uniformly, but reaction time is 1 to 200 hours normally, Preferably it is 1 to 100 hours. Shorter reaction times are desirable in terms of productivity. Moreover, reaction temperature is 0-250 degreeC normally, Preferably it is 30-200 degreeC.

 After the completion of the reaction, the epoxy resin solution obtained by using the solvent may be adjusted as necessary to the concentration of the solution as it is, and proceed to the carboxylating step of the next step as a solution containing the epoxy resin (a) (ii). . If necessary, the catalyst or the like may be removed by washing with water, and then the solvent may be isolated by heating and distilled off under reduced pressure to proceed to the next step.

One of the epoxy resins (a) used in the present invention may be represented by the following general formula (10):

(Wherein j, k and l are the average values of the repetition number, and 0 ≦ j ≦ 39, 0 ≦ k ≦ 39, and 0 ≦ l ≦ 39)

When the phenolaralkyl resin (P) which can be used in the present invention is monofunctional (when j = 0 in the above formula (10)), the epoxy resin (a) has a linear structure, but is polyfunctional (0 <j≤39), the epoxy resin (a) takes a branched structure. In the case of polyfunctionality, the branched chain branched again from the branched chain may arise, resulting in a complicated structure.

Other examples of the epoxy resin (a) used in the present invention include the following general formula (8)

(Wherein k and l are the same as in formula (10)).

The sum of the average value of the number of repetitions, the value represented by (k + 2j + l) or (k + l), is infinitely large in order to derive from the phenol aralkyl resin (the average value of the repetition number n is 1 to 10) as a raw material. There is a possibility that it is possible, but preferably either (k + 2j + l) or (k + l) is 2-40 as an average value, More preferably, it is 2-30. When larger than 2, the effect of the hydroxyl group of this invention is exhibited effectively, and when it is smaller than 40, Preferably it is less than 30, the viscosity of an unhardened state will become a suitable range.

Specific examples of the compound represented by the formula (8) include the following formula (9)

(In formula, k and l are the same as that of General formula (8)), Although it is mentioned, It is not limited to these.

In the present invention, the hydroxyl equivalent of the epoxy resin (a) is determined (the epoxy equivalent of the corresponding epoxy resin and the epoxy group in the epoxy resin (a) are reacted with the phenol of the equivalent, and the epoxy group is closed, and the hydroxyl equivalent ( Value calculated from JIS K # 0070: 1992. Unit: g / eq.), And when the epoxy equivalent of the epoxy resin is Ｙ (based on JIS K-7236: 2001. Unit: g / eq.) The epoxy resin (a) in which each relationship satisfy | fills following formula (I) is preferable. Hereinafter, it is set as (Ｘ / Ｙ) = α.

Now, X, Y and j, k and l have the following relationship:

X = (molecular weight of epoxy resin) / (j + l)

Y = (molecular weight of epoxy resin) / (j + k + l)

From there, j, k and l have a relationship between the α value and the following formula (II):

In the epoxy resin (a) used in the present invention, the balance between the epoxy equivalent and the hydroxyl equivalent is important. That is, the ratio of the epoxy group and hydroxyl group contained in a molecule | numerator becomes an important parameter.

Bonding of the said Formula (1) is a structure obtained when an epoxy resin, a phenol compound, or an alcohol compound reacts. In general, a high molecular weight grade, for example, is a bond formed when synthesizing a solid bisphenol A epoxy resin (or phenoxy resin), and the method is a one-stage method and a fusion method (also known as an advanced method or a two-stage method). , Dannaehong, pp. 24-25, 30-31). An epoxy resin (a) is a compound using this one step method or the fusion method. In the present invention, any one-stage method or a fusion method may be used. However, when synthesized in one-stage method, it is preferable to use a fusion method because the side products tend to increase.

In the epoxy carboxylate compound (A) or the reactive polycarboxylic acid compound (B) of the present invention, the amount of a bond containing a hydroxyl group such as the formula (1) contained in the molecular skeleton of the epoxy resin (a), For example, in the case of an alkali developing solder resist, it contributes to the physical property of developability and sensitivity. Many hydroxyl groups enter the molecular chain, causing a similar crosslinking effect by the hydroxyl groups. However, when there are too many binding patterns, the density | concentration of the epoxy group in molecular skeleton will become low, and the problem will arise in the hardenability. Therefore, the ratio of hydroxyl equivalent and epoxy group becomes important. In addition, the softening point contributes to the tack property, but not only contributes to the functional group density of the electric epoxy equivalent and the hydroxyl equivalent, but also contributes to the developability during alkali development. Therefore, the softening point is too big or too small. When the molecular weight and the epoxy value increase, the softening point also increases. That is, the balance of epoxy equivalent, hydroxyl equivalent, and molecular weight (softening point) becomes important.

When the value of X / Y exceeds 15, the effect of the structure (I) is not fully exhibited, and physical properties, such as favorable developability and toughness of hardened | cured material and pigment dispersibility, are not exhibited. In addition, when it is less than 2 in reverse, a reactive site cannot fully be introduced in a carboxylation reaction, and sufficient curability cannot be exhibited. In the case where the epoxy resin (a) is polyfunctional, if it is less than 2, it is likely to gel, and the problem according to the present invention cannot be solved. It is also assumed that the effect of structure (I) is an interaction between the polymer chains by hydroxyl groups or between the polymer and the pigment. The more preferable range of X / Y is in the range of 3 to 10.

Next, the carboxylate process aimed at giving reactivity to a carboxylate compound and obtaining a reactive carboxylate compound (A) is demonstrated.

This reaction is obtained by reacting the obtained epoxy resin (a) with a compound (b) having a polymerizable ethylenically unsaturated group and at least one carboxyl group to obtain a reactive carboxylate compound (A).

The compound (b) shown here was reacted to impart reactivity to an active energy ray. Specifically, the reactant of (meth) acrylic acid or crotonic acid, (alpha)-cyanocinnamic acid, cinnamic acid, or a saturated or unsaturated dibasic acid and an unsaturated-group-containing monoglycidyl compound is mentioned, for example. In the above, as the acrylic acid, for example, (meth) acrylic acid, β-styrylacrylic acid, β-furfuryl acrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic anhydride and (meth) acryl having one hydroxyl group in one molecule Monocarboxylic acid compounds containing one carboxyl group in one molecule, such as the half esters of the acrylate derivatives and the sugar molar reactants thereof, the half esters of the saturated or unsaturated dibasic acids and the monoglycidyl (meth) acrylate derivatives, It is also a half-molecular reactant of a (meth) acrylate derivative having a plurality of hydroxyl groups in one molecule and a half ester of a sugar mole reactant, and a glycidyl (meth) acrylate derivative having a saturated or unsaturated dibasic acid and a plurality of epoxy groups. The polycarboxylic acid compound which has two or more carboxyl groups in 1 molecule, such as ester, is mentioned.

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

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

In this reaction, the addition ratio of the epoxy resin (a) and the carboxylic acid compound (b) should be appropriately changed depending on the use. In other words, when the entire epoxy group is carboxylated, the storage stability as a reactive carboxylate compound is high because no unreacted epoxy group remains. In this case, only reactivity by the introduced double bond is used.

On the other hand, by reducing the amount of the carboxylic acid compound charged to leave the unreacted residual epoxy group, the reaction by the introduced unsaturated bond and the reaction by the remaining epoxy group, such as a polymerization reaction or a thermal polymerization reaction by a photo cation catalyst, are combined. It is also possible to use. In this case, however, attention should be paid to the preservation of the reactive carboxylate compound and the examination of the production conditions.

When producing the reactive carboxylate compound (A) which does not remain an epoxy group, it is preferable that a carboxylic acid compound (b) is 90-120 equivalent% with respect to 1 equivalent of epoxy resin (a). If it is this range, manufacture on comparatively stable conditions is possible. This is not preferable because the excess amount of the carboxylic acid compound (b) remains even when the amount of the carboxylic acid compound is large.

Moreover, when leaving an epoxy group, it is preferable that a carboxylic acid compound (b) is 20-90 equivalent% with respect to 1 equivalent of epoxy resin (a). When it deviates from these ranges, the effect of composite hardening becomes light. In this case, of course, sufficient attention should be paid to the gelation during the reaction and the time stability of the carboxylate compound (A).

The carboxylation reaction can be carried out by reacting without solvent or by diluting with a solvent. The solvent that can be used herein is not particularly limited as long as it is an inert solvent with respect to the carboxylation reaction.

Although the usage-amount of a preferable solvent should be adjusted suitably by the viscosity and the use of resin obtained, it is used so that it may become 90-30 weight part, more preferably 80-50 weight part with respect to a preferable solid content.

Specifically, for example, aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane, decane, and mixtures thereof, petroleum ether, white gasoline, solvent naphtha Ester solvents, ether solvents, ketone solvents, and the like.

Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, and diethylene glycol monoethyl. Mono or polyalkylene glycol monoalkyl ether monoacetate, such as ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate And polycarboxylic acid alkyl esters such as dialkyl glutaric acid, dialkyl succinate, and adipic acid dialkyl.

Examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether and triethylene Glycol ethers, such as glycol diethyl ether, Cyclic ethers, such as tetrahydrofuran, etc. are mentioned.

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

In addition, it can carry out in single or mixed organic solvents, such as other reactive compound (C) mentioned later. In this case, when used as a curable composition, since it can use directly as a composition, it is preferable.

In the reaction, it is preferable to use a catalyst in order to accelerate the reaction, and the amount of the catalyst used is a reactant, that is, an epoxy compound (a), a carboxylic acid compound (b), and optionally a solvent or the like. It is 0.1-10 weight part with respect to the total amount. The reaction temperature at that time is 60-150 degreeC, and reaction time is 5 to 60 hours preferably. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibin, methyltriphenylstibin, Known general basic catalysts, such as chromium octanoate and zirconium octanoate, are mentioned.

As the thermal polymerization inhibitor, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4-hydroxytoluene and the like are used. It is preferable.

This reaction has an end point at which the acid value of the sample is 1 mgKOH / g or less, preferably 0.5 mgKOH / g or less, with appropriate sampling.

As a preferable molecular weight range of the reactive carboxylate compound (A) thus obtained, it is the range whose polystyrene conversion weight average molecular weight is 5,000-30,000 in GPC, More preferably, it is 6,000-20,000.

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

Next, an acid addition process is explained in full detail. An acid addition process is performed in order to introduce a carboxyl group into the reactive carboxylate compound obtained at the previous process as needed, and to obtain reactive polycarboxylic acid (B). That is, a carboxyl group is introduce | transduced through ester bond by addition-reacting polybasic acid anhydride (c) to the hydroxyl group produced by the carboxylation reaction.

As a specific example of the polybasic acid anhydride (c), any compound having an acid anhydride structure can be used, for example, but succinic anhydride, phthalic anhydride, tetrahydro phthalic anhydride, and hexahydro excellent in alkaline aqueous solution developability, heat resistance, and hydrolysis resistance. Especially preferred are phthalic anhydride, itaconic anhydride, 3-methyl-tetrahydro phthalic anhydride, 4-methylhexahydro phthalic anhydride, trimellitic anhydride or maleic anhydride.

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

The amount of the polybasic acid anhydride (c) added is, for example, in the case where the polycarboxylic acid compound (B) of the present invention is to be used as an alkali developing resist, the solid acid value of the reactive polycarboxylic acid compound (B) which can finally obtain the polybasic acid anhydride (c). It is preferable to add the calculated value (based on JIS K5601-2-1: 1999) to 40-120 mgKOH / g, More preferably, it is 60-110 mgKOH / g. When solid content acid value at this time is this range, the alkali aqueous solution developability of the photosensitive resin composition of this invention shows favorable developability. In other words, a wide range of management of good patterning properties and excessive phenomena, and no excess acid anhydride remains.

In the reaction, it is preferable to use a catalyst in order to promote the reaction, and the amount of the catalyst used is a reactant, that is, a carboxylated compound obtained from an epoxy compound (a), a carboxylic acid compound (b), and other basic anhydrides (c). ), 0.1 to 10 parts by weight, based on the total amount of the reactants, optionally added solvent. The reaction temperature at that time is 60-150 degreeC, and reaction time becomes like this. Preferably it is 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibin, methyltriphenylstibin, jade Chromium carbonate, zirconium octanoate and the like.

The acid addition reaction can be carried out by reacting with a solvent or by diluting with a solvent. It can be used here as a solvent, if an acid addition reaction is an inert solvent, it will not specifically limit. In addition, when manufactured using a solvent in the carboxylation reaction which is the previous process, the acid addition which is the next process can be directly provided to reaction, without removing a solvent, provided that it is inert to both reactions. The solvent which can be used should be the same as that which can be used for a carboxylation reaction.

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

In addition, it can carry out in single or mixed organic solvents, such as an electroreactive compound (C). In this case, when used as a curable composition, since it can use directly as a composition, it is preferable.

Moreover, it is preferable to use the thing similar to the example in an electric carboxylate reaction as a thermal polymerization inhibitor.

This reaction makes an endpoint by taking the point which became the range of plus and minus 10% of the acid value set by the acid value of the reactant, sampling suitably.

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

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

As monofunctional (meth) acrylates, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol ( Meth) acrylate monomethyl ether, phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc. Can be mentioned.

As polyfunctional (meth) acrylates, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) ) Acrylate, diethylenedi (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, adipic acid epoxydi Di of (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogenated bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, the ε-caprolactone adduct of hydroxybivalic acid neofenglycol (Meth) acrylate, poly (meth) acrylate of reactant of dipentaerythritol and ε-caprolactone, dipentaerythritol poly (meth) acrylate, Limethylolpropane tri (meth) acrylate, triethylolpropane tri (meth) acrylate, and its ethylene oxide adduct, pentaerythritol tri (meth) acrylate, and its ethylene oxide adduct, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, and its ethylene oxide adduct.

Examples of vinyl compounds that can be used include vinyl ethers, styrenes, and other vinyl compounds. As vinyl ether, ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, etc. are mentioned. As styrene, styrene, methyl styrene, ethyl styrene, etc. are mentioned. Other vinyl compounds include triaryl isocyanurate, trimetharyl isocyanurate, and the like.

Moreover, as what are called reactive oligomers, urethane acrylate which has a functional group and urethane bond which can be functionally activated to an active energy ray in the same molecule, polyester acrylate which has a functional group and ester bond which can be functionally equivalent to an active energy ray in the same molecule, In addition, the epoxy acrylate which has a functional group derived from an epoxy resin, and has a functional group which can be functional to an active energy ray in the same molecule, the reactive oligomer which these bonds are used compositely, etc. are mentioned.

Moreover, as a cationic reaction type monomer, if the compound generally has an epoxy group, it will not specifically limit. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4- Epoxycyclohexane carboxylate ("Suracure VR-6111" by Union Carbide Co., Ltd.), 3, 4- epoxycyclohexyl ethyl-3, 4- epoxy cyclohexane carboxylate, vinyl cyclohexene dioxide (Union Carbide Co., Ltd. "ELL-42600" etc.), limonene dioxide ("Ceroxide 300" by Daicel Chemical Co., Ltd.), arylcyclohexene dioxide, 3, 4- epoxy- 4-methylcyclohexyl 2- propylene Oxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate (union carbide) `` Siracure Cure JR-6131 '', etc.), Bis (3,4-Epoxy) Rohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane have.

Among these, as reactive compound (c), the radical hardening type acrylate is the most preferable. In the case of the cationic type, since the carboxylic acid and the epoxy react, there is a need for a two-liquid mixed type.

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

The active energy ray-curable resin composition of the present invention is 97 to 5 parts by weight, preferably 87 to 10 parts by weight of the carboxylate compound (A) and / or the reactive polycarboxylic acid compound (B) in the composition, and other reactive compounds (C ) 3 to 95 parts by weight, and preferably 3 to 90 parts by weight. As needed, you may contain 0-80 weight part of other components.

In the active energy ray-curable resin composition of the present invention, the carboxylate compound (A) or the reactive polycarboxylic acid compound (B) can be suitably used in accordance with its use. For example, in the case of the so-called solvent developing type in which the patterning is molded by a printing method or the unreacted site is removed by a solvent or the like, the carboxylate compound (A) is used in alkaline water, for example, even if the same solder resist is not developed. In the case of developing by using, a reactive polycarboxylic acid compound (B) is used. Generally, a reactive polycarboxylic acid compound (B) is used for this use from a viewpoint of the alkali water developing type which is easy to produce a fine pattern. Of course, using (A) and (B) together does not cause any problem.

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 rays include ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, and other types of particle beams such as alpha rays, beta rays, and electron beams. In consideration of the suitable use of the present invention, among these, ultraviolet rays, laser beams, visible rays, or electron beams are preferable.

As a coloring pigment used by this invention, it is used in order to make the active energy ray resin composition of this invention a coloring material. Since the balance of the hydroxyl group and epoxy group of the epoxy resin (a) used by this invention exists in a specific range, the dispersibility, ie dispersibility of especially excellent pigment is exhibited.

Although it is not limited about this apparatus, in order to disperse | distribute well, a pigment concentration can be concentrated as a result, and in the composition which requires image development, a favorable patterning characteristic is exhibited in order to disperse | distribute to a more suitable state, and develops It is suitable because there is also little developing residue in the melting part.

As a coloring pigment, inorganic pigments, such as titanium oxide, such as organic pigments, such as a phthalocyanate type, an azo type, and quinacridone type, carbon black, are mentioned. Of these, carbon black is most preferred because of its high dispersibility.

In the present invention, the molding material means that the uncured composition is put into a mold, or the mold is pressed to mold an object, followed by molding by causing a curing reaction with an active energy ray, or the uncured composition. The material used for the use which irradiates focus light, such as a laser, etc., raises hardening reaction, and shape | molds.

Specific uses include so-called nano-printed materials, in particular those formed with a planar sheet, an encapsulant for protecting the device, and a micro molding by pressing a "form" finely processed into an uncured composition, and particularly a luminescent light with particularly high thermal demands. Peripheral sealing materials, such as a diode and a photoelectric conversion element, are mentioned as a suitable use.

In this invention, it is used for the purpose of coat | covering the surface of a base material as a film forming material. Specific applications include ink materials such as gravure inks, flexi inks, silk screen inks and offset inks, coating materials such as hard coats, top coats, overprint varnishes, clear coats, adhesives for adhesives, adhesives, etc. Such materials include resist materials such as materials, solder resists, etching resists, and micromash resists. In addition, what is called a dry film which apply | coats a film shaping | molding material to a peelable base material temporarily, and forms a film after bonding to a base material made into the original target also corresponds to a film forming material.

Among these, since adhesiveness to a base material becomes high by introduction of the carboxyl group of a reactive polycarboxylic acid compound (B), it is preferable to use it as a use for coating a plastic base material or a metal base material.

Moreover, it is also preferable to use as an alkali water developing type resist material composition utilizing the conditions by which an unreacted reactive polycarboxylic acid compound (B) becomes soluble in aqueous alkali solution.

In the present invention, the resist material composition refers to an active energy intended to form a coating layer of the composition on a substrate, and then partially irradiate active energy rays such as ultraviolet rays, and draw using the physical properties of the irradiated portion and the unirradiated portion. Refers to a composition of the line sensitization. Specifically, it is a composition used for the purpose of carrying out drawing by removing an irradiation part or an unirradiated part by arbitrary methods, for example, melt | dissolving by a solvent etc., an alkaline solution, etc., and to draw.

The active energy ray-curable resin composition for resists of the present invention can be adapted to various materials that can be patterned, and is particularly useful as an interlayer insulating material for solder resist materials, build-up methods, and as printed waveguides, optoelectronic substrates, It is also used in electrical, electronic and optical materials such as optical substrates.

Particularly suitable applications include the use of permanent resists such as solder resists, and the use of color resists such as printing inks and color filters, in particular, black matrix resists, utilizing the properties of obtaining a strong cured product and utilizing pigment dispersibility. Is preferred.

In addition, it is especially suitably used as a dry film application in which the mechanical strength before the curing reaction by the active energy ray is required. That is, since the balance of the hydroxyl group and epoxy group of the epoxy resin (a) used by this invention exists in a specific range, although the reactive carboxylate compound of this invention is comparatively high molecular weight, favorable developability can be exhibited.

Although it does not specifically limit as a film forming method, Intaglio printing methods, such as radicals, Iron plate printing methods, such as a flexible, Engraving printing methods, such as a silk screen, Plate printing methods, such as an offset, Roll coater, and knife coater Various coating methods, such as a die coater, a curtain coater, and a spin coater, can be arbitrarily employed.

The hardened | cured material of the active energy ray hardening-type resin composition of this invention refers to what hardened | cured by irradiating an active energy ray to the active energy ray hardening-type resin composition of this invention.

The article overcoated with the resin composition of this invention represents the material which has at least 2 or more layers which can be obtained by film-forming and hardening the active energy ray hardening-type resin composition shown by this invention on a base material.

In addition, in order to make the active energy ray hardening-type resin composition of this invention suitable for various uses, another component can be added to a composition with an upper limit of 70 weight part. As another component, the photoinitiator, another additive, a coloring material, the volatile solvent added for viscosity adjustment for the purpose of providing application | coating suitability, etc. are mentioned. Other components which can be used below are illustrated.

As a radical type photoinitiator, For example, benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propylether, benzoin isobutyl ether; acetophenone, 2, 2- diethoxy 2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone Acetophenones such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one; Anthraquinones, such as 2-ethyl anthraquinone, 2-tet-butyl anthraquinone, 2-chloroanthraquinone and 2-amyl anthraquinone; Thioxanthones such as 2,4-diethyl thioxanthone, 2-isopropyl thioxanthone, and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone; Well-known general radical photoreaction initiators, such as phosphine oxides, such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, are mentioned. have.

Moreover, as a cationic photoinitiator, the diazonium salt of Lewis acid, the iodonium salt of Lewis acid, the sulfonium salt of Lewis acid, the phosphonium salt of Lewis acid, other halides, the triazine type initiator, the borate type initiator, and the other Photoacid generators;

Examples of diazonium salts of Lewis acids include p-methoxyphenyldiazonium fluorophosphonate and N, N-diethylaminophenyldiazonium hexafluorophosphonate (manufactured by Samshin Chemical Co., Ltd. -90L / SI-100L etc.), As a iodonium salt of Lewis acid, diphenyl iodonium hexafluorophosphonate, diphenyl iodonium hexafluoro antimonate, etc. are mentioned, Lewis acid Examples of the sulfonium salts thereof include triphenylsulfonium hexafluorophosphonate (such as Union Carbide Co., Ltd.) and triphenylsulfonium hexafluoroantimonate (such as Union Carbide Company, Co., Ltd. The phosphonium salt of Lewis acid etc. can be mentioned, Triphenyl phosphonium hexafluoro antimonate, etc. are mentioned.

Other halides include 2,2,2-trichloro- [1,4 '-(dimethylethyl) phenyl] ethanol (such as Trigonal PI manufactured by AKZO), 2,2-dichloro-1-4- (phenoxyphenyl ) Ethanol (Sandray 1000 by Sandoz, etc.), (alpha), (alpha), (alpha)-tribromomethylphenyl sulfone (BMPS etc. by Steel Chemical Co., Ltd.), etc. are mentioned. Examples of the triazine initiator include 2,4,6-tris (trichloromethyl) -triazine, 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine (such as Triazine A manufactured by Panchim), 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine (Triazine PMS manufactured by Panchim, etc.), 2,4-trichloromethyl- (pipronyl) -6-triazine ( Triazine PP, etc. by Panchim, Inc.), 2,4-trichloromethyl- (4'-methoxynaphthyl) -6-triazine (Triazine B, etc. by Panchim, Inc.), 2 [2 '(5-methylfuryl) ethyl Lidene] -4,6-bis (trichloromethyl) -s-triazine (manufactured by Samwha Chemical Co., Ltd.), 2 (2'-furylethylidene) -4,6-bis (trichloromethyl) -s- Triazine (manufactured by Samwha Chemical Co., Ltd.) and the like.

Examples of borate-based photopolymerization initiators include NK-3876 and NK-3881 manufactured by Nippon Dye, and other light generating agents include 9-phenylacridine, 2,2'-bis (o-chlorophenyl) -4, and the like. , 4 ', 5,5'-tetraphenyl-1,2-biimidazole (Bimidazole, etc. manufactured by Black Gold Co., Ltd.), 2,2-azobis (2-aminopropane) bihydrochloride (Hwagwang Pure Chemical Co., Ltd.) Manufactured V50), 2,2-azobis [2- (imidazolin-2-yl) propane] bihydrochloride (VA044 manufactured by Hwagwang Pure Chemical Co., Ltd., etc.), [ita-5-2-4- (cyclopenta) Decyl) (1,2,3,4,5,6-ita)-(methylethyl) -benzene] iron (II) hexabromophosphonate (such as Irgacure 261 from Ciba Geigy), bis (y5-cyclopenta) Diphenyl) bis [2,6-difluoro-3- (1H-pyri-1-yl) phenyl] titanium (CGI-784 manufactured by Ciba Geigy, etc.) and the like.

In addition, you may use together azo initiators, such as azobisisobutyronitrile, peroxide type radical initiators sensitive to heat, such as benzoyl peroxide. Moreover, you may use together the initiator of both a radical system and a cation system. An initiator may be used individually by 1 type and may use two or more types together.

Other additives include, for example, thermosetting catalysts such as melamine, thixotropy-imparting agents such as aerodyl, silicone- and fluorine-based leveling agents, antifoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers and antioxidants. Etc. can be used.

As other pigment materials, those which are not intended for coloring, for example, so-called extender pigments can be used. For example, talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay, etc. are mentioned.

Other resins (so-called inert polymers) that do not exhibit reactivity to an active energy ray include, for example, other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diaryl phthalate resins, Styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified substances thereof can be used. It is preferable to use these in the range up to 40 weight part in a resin composition.

When using a reactive polycarboxylic acid compound (B) especially for a soldering resist use, it is preferable to use a well-known general epoxy resin as resins which do not show reactivity to an active energy ray. The carboxyl group derived from (B) remain | survives even after these react and harden | cure with an active energy ray, As a result, its hardened | cured material becomes worse in water resistance or hydrolysis resistance. Therefore, the use of an epoxy resin also carboxylates the remaining carboxyl groups, further forming a robust crosslinked structure. The well-known general epoxy resin can use an electric cationic reaction type monomer.

Moreover, a volatile solvent can be added in 50 weight part, more preferably up to 35 weight part in a resin composition for the purpose of adjusting a viscosity according to a use purpose.

Example

Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. Moreover, unless otherwise indicated in a Example, a part shows a weight part.

Softening point and epoxy equivalent were measured on condition of the following.

1) Epoxy equivalent: It measured by the method according to JIS-K-7236: 2001.

2) Hydroxyl equivalent: The epoxy equivalent of the corresponding epoxy resin and the epoxy group in the epoxy resin were made to react with the equivalent of acetic acid, and the epoxy group was closed, and it calculated from the hydroxyl equivalent measured by the method according to JISKK0070: 1992.

3) Softening point: It measured by the method according to JIS K-7234: 1986.

4) The measurement conditions of GPC are as follows.

Model: TOSOH HLC-8220GPC

Column: Super HZM-N

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

Detector: Differential Refractometer

Molecular Weight Standard: Polystyrene

Synthetic example 1: Synthesis of Epoxy Resin

A phenolbiphenyl novolak-type epoxy resin (NC-3000H manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288) as an epoxy resin of the formula (8) while carrying out a nitrogen purge to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device. g / eq., softening point 70 DEG C, compound represented by formula (7), n'3) 576 g, phenol biphenyl novolak resin (KAYAHARD GPH 65 hydroxyl equivalent equivalent 197 manufactured by Nippon Kayaku Co., Ltd.) g / eq., the compound shown by the said General formula (5), n'2) were put into the quantity of Table 1, and also methyl isobutyl ketone (MI ') was added as a solvent so that solid content might be 60 weight part. After dissolving uniformly at 70 degreeC, 0.5 g of triphenylphosphines were added, and it stirred at 100 degreeC for 20 hours. After the reaction was completed, oxygen purge was performed to oxidize triphenylphosphine to obtain an epoxy resin (a) resin solution.

In addition, the solvent was removed by drying the obtained resin solution under reduced pressure, an epoxy resin (a) was obtained, the epoxy equivalent, the hydroxyl equivalent, and the softening point were measured and put together in the table | surface. From this value, the value of alpha (kV / kV of formula (I)) was obtained.

week:

JP: Epoxy equivalent (g / eq) = Y

OHH: hydroxyl equivalent (g / eq) = X

ｓｐ ： softening point (℃)

In Table 1, molar ratio of pH-665 shows the molar ratio of the hydroxyl group with respect to the epoxy group of NC-3000H.

Comparative Synthesis Example 1-1 shows the data of NC-3000H itself.

In Comparative Synthesis Example 1-2, the α value exhibited due to gelation could not be measured and was represented by a calculated value. When the value of α is less than 2, it can be seen that it is not suitable for the present invention.

Example  One: Carboxylate  Preparation of Compound (A)

Compounds having at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in the amounts and molecules of the epoxy resins (a) prepared in Synthesis Examples 1-1, 1-2, 1-3 and 1-4 ( b) As the amount of acrylic acid (abbreviated AA, M２ = 72) in the table, 3 g of triphenylphosphine as a catalyst, propylene glycol monomethyl ether monoacetate as a solvent was added so as to have a solid content of 90%, and allowed to react at 100 ° C for 24 hours. And the carboxylate compound (A) solution were obtained.

Comparative example 1: compared Carboxylate  Preparation of compounds

Each of NC-3000H (manufactured by Nippon Kayaku Co., Ltd.) is a compound (b) having at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in the amounts and molecules shown in Table 2, respectively. The amount described in 2, 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%, and reacted at 100 ° C for 24 hours to obtain a carboxylate compound (A) solution.

Example ２ ： Reactive polycarboxylic acid  Preparation of Compound (B)

To 2 kg of the carboxylate compound (A) solution obtained in Example 1, tetrahydrophthalic anhydride (c) was used as the amount of tetrahydrophthalic anhydride (abbreviated THPA) as shown in Table 3, and the solid content was 65 parts by weight of propylene glycol mono Methyl ether monoacetate was added, and after heating at 100 degreeC, acid addition reaction was carried out and the reactive polycarboxylic acid compound (B) solution was obtained.

Example ３ ： For hard coat  Preparation of the composition

20 g of the reactive carboxylate compound (A) synthesized in Examples 1 and 2, 4 g of dipentaerythritol hexaacrylate, which is a radical curable monomer (C), and Irgacure 184 as a UV-responsive initiator were heated and dissolved in 1.5 g.

This was then applied onto a polycarbonate plate by a hand applicator so as to have a film thickness of 20 microns at the time of drying, and solvent drying was performed at 80 ° C. for 30 minutes in an electric oven. After drying, an ultraviolet-ray having an irradiation dose of 1000 mJ was irradiated and cured by an ultraviolet ray vertical exposure apparatus (manufactured by Oak Works) equipped with a high-pressure mercury lamp to obtain an article overcoated with the resin composition.

The hardness of the coating film of the article overcoat with this resin composition was measured by JISK5600-5-4: 1999, and the impact test was done by ISO6272-1: 2002.

From the above result, in the case of (A) using the epoxy resin (a) whose alpha value exceeds 10 (comparative example 3-1), it was clear that sclerosis | hardenability was favorable but inferior impact resistance. This is considered that the hydroxyl group contained in the epoxy resin (a) serving as a basic skeleton exhibits impact resistance.

Example  4: dry film type Resist  Preparation of the composition

54.44 g of the reactive polycarboxylic acid compound (B) obtained in Example 2, 3.54 g of HX-220 (trade name: Nihon Chemical Co., Ltd. diacrylate monomer) as a reactive compound (C), Irgacure 907 as a photopolymerization initiator 4.72 g of (Ciba Specialty Chemicals Co., Ltd.) and 0.47 g of Kayakure DETX-S (manufactured by Nippon Kayaku Co., Ltd.), 14.83 g of GTR-1800 (Nihon Chemical Co., Ltd.) as a curing ingredient, melamine as a thermosetting catalyst 20.95 g of methyl ethyl ketone was added as 1.05 g and a concentration adjusting solvent, and it knead | mixed and mixed uniformly by the bead mill, and obtained the resist resin composition.

The obtained composition was uniformly applied to a polyethylene terephthalate film serving as a supporting film by a roll coat method, and passed through a hot air drying furnace at a temperature of 70 ° C. to form a resin layer having a thickness of 30 μm, followed by a protective film on the resin layer. The polyethylene film to which it adheres was attached, and the dry film was obtained. The resin layer was adhere | attached on the whole board | substrate, peeling a protective film on the obtained dry film on the polyimide printed substrate (copper thickness: 12 micrometers, polyimide film thickness: 25 micrometers) using the heating roll of temperature 80 degreeC.

 Subsequently, ultraviolet rays were irradiated through a Kodak tablet tablet No. 2 in order to approximate a mask in which a circuit pattern was drawn and a sensitivity using an ultraviolet exposure apparatus (Oak Manufacturing Co., Ltd., model HMW-680GW). Then, the film on the dry film was peeled off and the peeling state was confirmed. Thereafter, spray development was carried out with an aqueous 1% sodium carbonate solution to remove the resin from the non-ultraviolet irradiation part. After washing with water, the printed circuit board was heat-cured for 60 minutes by the 150 degreeC hot air dryer, and the cured film was obtained.

Peelability  evaluation

Peelability was judged by the ease of the film peeling after completion | finish of exposure.

(Circle) +: It peels in an interface very neatly.

(Circle): It peels at an interface beautifully.

(Triangle | delta): Peeling is possible by peeling carefully.

Δ-: It cannot be peeled off unless it is peeled very carefully.

X: There exists a part which peels partially (or entirely)

Sensitivity evaluation

The sensitivity was determined by how many stages the concentration portion remained in the exposed portion that passed through the tablet. The larger the number of stages (value), the higher sensitivity is determined by the farmer of the tablet (unit: stage).

Developability  evaluation

The developability was an evaluation of development in units of seconds until the pattern shape was fully developed, the so-called break time, when developing the exposed portion passing through the pattern mask (unit: seconds).

Curability Evaluation

Curability evaluation was shown as the pencil hardness of the cured film after 150 degreeC heating completion.

The evaluation method was based on JISK5600-5-4: 1999.

As apparent from the above results, when the α value is too large (Comparative Example 4-1), the peelability of the dry film is poor.

Example  5: Evaluation on Pigment Dispersibility

20 g of the reactive polycarboxylic acid compound (B) obtained in Example 2, 5.0 g of DPHA (trade name: acrylate monomer manufactured by Nippon Kayaku Co., Ltd.) as a reactive compound (C), and 10 g of propylene glycol monomethyl ether acetate as an organic solvent And Mitsubishi carbon black MA-100: 10 g was mixed and stirred as a coloring pigment. 35 g of glass beads were added thereto and dispersed for 1 hour with a paint shaker.

The dispersion liquid after completion | finish of dispersion was apply | coated on the polyethylene terephthalate film with the wire bar coater # 2, and it dried for 10 minutes by the 80 degreeC warm air dryer.

The glossiness of the coating film surface after completion of drying was measured using a 60 ° reflecting gloss system to evaluate the dispersibility of carbon black. At this time, the higher the measured value of glossiness indicates good pigment dispersibility.

As apparent from the above results, in the present invention, when the α value of the epoxy resin (a) serving as the basic skeleton of the reactive polycarboxylic acid (B) exceeds 10, it was clear that the dispersibility of carbon black was inferior.

Industrial availability

As the active energy ray-curable resin of the present invention, a hard coat material, an alkali developable resist material, and a good pigment dispersibility are exhibited as a material having both curability and toughness. In particular, it can be used suitably as a black matrix for LCD etc. as a material which has resist suitability, such as pigment dispersibility and developability.

Claims (13)

A reactive epoxy carboxylate compound (A) obtained by reacting the following epoxy resin (a) with compound (b) having at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in a molecule:

In addition, it has a structure represented by the following general formula (2) (In general formula (2), Ar is represented by general formula (3) or (4), m represents the integer of 1-3 as the number of substituent R, n represents the average value of the repeating number of 1-10, R respectively represents a hydrogen atom, a halogen atom, a C1-C15 hydrocarbon group, a trifluoromethyl group, an aryl group, or an aryl group, and each R is respectively They may be the same as or different from each other, and Ar may be the same or different.)

Epoxy resin (a) obtained from the phenol aralkyl resin (P) of the structure shown by;
(i) an epoxy resin (a) formed by partially epoxidizing the phenolaralkyl resin (P)
(ii) An epoxy resin (a) formed by reacting a phenol aralkyl resin (P) and a phenol aralkyl type epoxy resin (E2). The reactive epoxy carboxyl according to claim 1, wherein an epoxy resin (a) obtained by using 1.0 to 5.0 mol of epihalohydrin is used for 1 mol of the hydroxyl group of the phenol aralkyl resin (P). Rate compound (A). The epoxy resin (a) according to claim 1, wherein the epoxy resin (a) obtained by reacting the hydroxyl group of the phenol aralkyl resin (P) with respect to 1 mol of the epoxy group of the phenol aralkyl type epoxy resin (E2) to be 0.01 to 0.3 mol is used. Reactive epoxy carboxylate compound (A) characterized by the above-mentioned. The epoxy resin (a) according to any one of claims 1 to 3, wherein the hydroxyl equivalent of the epoxy resin (a) is X (g / eq.) And the epoxy equivalent is Y (g / eq.). In each case, the relationship

Reactive epoxy carboxylate compound (A) which satisfies. The reactive polycarboxylic acid compound (B) obtained by making a polybasic acid anhydride (c) react with the carboxylate compound (A) in any one of Claims 1-4. The active-energy-ray-curable resin composition containing the carboxylate compound (A) of any one of Claims 1-4, and / or the reactive polycarboxylic acid compound (B) of Claim 5. The active energy ray-curable resin composition according to claim 6, further comprising a reactive compound (C) other than the above (A) and (B). The active energy ray-curable resin composition according to claim 6 or 7, further comprising a colored pigment. The active energy ray-curable resin composition according to any one of claims 6 to 8, which is a molding material. The active energy ray-curable resin composition according to any one of claims 6 to 9, which is a material for forming a film. The active energy ray curable resin composition according to any one of claims 6 to 10, which is a resist material composition. Hardened | cured material of the active-energy-ray-curable resin composition in any one of Claims 6-11. The article overcoat with the hardened | cured material obtained by hardening | curing the resin composition of any one of Claims 6-11.