KR102286273B1 - Novel reactive epoxy carboxylate compound, derivative thereof, resin composition containing them, cured product thereof, and article - Google Patents

Abstract

(Problem) The present invention is an excellent resin that is cured by active energy rays such as ultraviolet rays, etc., is excellent in photosensitivity and has good developability, and the obtained cured product has sufficient curability, flexibility, toughness, flame retardancy, and pigment dispersibility. It aims to provide a composition.
(Solution Means) Compound (b) having both an ethylenically unsaturated group and a carboxy group that can be polymerized in one molecule to the epoxy resin (a) represented by the general formula (1), and, if necessary, a compound having a hydroxyl group and a carboxy group in one molecule A reactive epoxy carboxylate compound (A) obtained by reacting (c) and a reactive polycarboxylic acid compound (B) obtained by reacting a polybasic acid anhydride (d) with the reactive epoxy carboxylate compound (A). Moreover, it is a resin composition containing the said reactive epoxy carboxylate compound (A) and/or the said reactive polycarboxylic acid compound (B).

Description

Novel reactive epoxycarboxylate compounds, derivatives thereof, resin compositions containing the same, cured products thereof, and articles

The present invention relates to an epoxy resin (a) having a polycyclic hydrocarbon group, a compound (b) having an ethylenically unsaturated group and a carboxy group that can be polymerized in one molecule, and a compound (c) having a hydroxyl group and a carboxy group in one molecule if necessary It relates to a reactive epoxy carboxylate compound (A) obtained by reacting an acid-modified reactive polycarboxylic acid compound (B), a resin composition containing them, and a cured product thereof. These reactive epoxy carboxylate compound (A) and reactive polycarboxylic acid compound (B) have favorable affinity to a pigment, and a tough hardened|cured material can be obtained from the resin composition containing them.

Printed wiring boards are required to have high precision and high density in order to reduce the size and weight of portable devices and to improve communication speed. As a result, the solder resist covering the circuit itself requires high substrate adhesion, high insulation and electroless gold plating while maintaining heat resistance and thermal stability. Further, there is a demand for a material for forming a film having stronger curing properties.

As these materials, Patent Document 1 discloses a carboxylate compound obtained by reacting an epoxy resin with an acrylic acid and a carboxylic acid compound having a hydroxyl group as a material having excellent developability while having a low acid value. It is also disclosed that this compound has resist ink ability.

On the other hand, the acid-modified epoxy acrylate which made a phenol aralkyl type epoxy resin into basic frame|skeleton is disclosed by patent document 2 as a material which shows high toughness after hardening, Furthermore, examination is performed by making these into a soldering resist.

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

In a black matrix resist, when color pigments, such as carbon black, are favorably compatible with resin and disperse|distribute, even if a color pigment is high density|concentration, favorable developability will be shown, and image development without a pigment residue will become possible. Although conventional acid-modified epoxy acrylates, particularly acid-modified epoxy acrylates having a biphenyl skeleton, exhibit relatively good dispersibility, further pigment dispersibility has been demanded. However, when the skeleton of the rigid structure and the good affinity for the pigment are interlocked, and when it is set as a pigment dispersion, the dispersion liquid pseudo aggregates, and there existed a difficulty that stability was not good.

The acid-modified epoxy acrylate compound of the epoxy resin of patent document 4 is not known.

Japanese Laid-Open Patent Publication No. 06-324490 Japanese Laid-Open Patent Publication No. 11-140144 Japanese Laid-Open Patent Publication No. 2005-055814 Japanese Laid-Open Patent Publication No. 2013-043958

Although the above-mentioned curable resin composition containing the epoxy resin having a polycyclic hydrocarbon group can obtain a relatively strong cured product, the reliability is low as a material requiring very high reliability, such as a transport device. Moreover, the acid-modified epoxy acrylate compound which is more excellent in the dispersibility of a colored pigment, especially carbon black, etc. and has favorable development characteristics even if it is a high pigment concentration is calculated|required. Such an acid-modified epoxy acrylate compound needs to have appropriate developability while having a high molecular weight.

The present inventors react with an epoxy resin (a) having a polycyclic hydrocarbon group, a compound (b) having an ethylenically unsaturated group and a carboxy group that can be polymerized in one molecule, and a compound (c) having a hydroxyl group and a carboxy group in one molecule if necessary It discovered that the reactive epoxy carboxylate compound (A) obtained by making it make it, and also the reactive polycarboxylic acid compound (B) obtained by making it react with polybasic acid anhydride (d) have especially excellent resin physical properties. Furthermore, it was discovered that the said reactive epoxy carboxylate compound (A) and reactive polycarboxylic acid compound (B) have favorable affinity with a color pigment, and even if the composition containing these compounds has a high pigment concentration, favorable developability It was discovered that it becomes a resist material etc. which have

The present invention relates to an epoxy resin (a) represented by the following general formula (1), a compound (b) having an ethylenically unsaturated group and a carboxy group that can be polymerized in one molecule, and a compound having a hydroxyl group and a carboxy group in one molecule if necessary It relates to a reactive epoxycarboxylate compound (A) obtained by reacting (c):

(Wherein, A is each independently any one of (i) or (ii), and the molar ratio of (i) and (ii) is (i)/(ii) = 1 to 3; G is a glycidyl group ; n is the number of repetitions and is an integer of 0 to 5 as an average value).

In addition, in the epoxy resin (a) in which (i) of A of the general formula (1) is a meta body, a compound (b) having an ethylenically unsaturated group and a carboxyl group that can be polymerized in one molecule, and, if necessary, a hydroxyl group in one molecule and It is related with the reactive epoxy carboxylate compound (A) obtained by making the compound (c) which has a carboxy group react.

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

Moreover, it relates to the resin composition containing the said reactive epoxy carboxylate compound (A) and/or a reactive polycarboxylic acid compound (B).

Moreover, it is related with the said resin composition containing the reactive compound (C) other than the said reactive epoxy carboxylate compound (A) and reactive polycarboxylic acid compound (B).

In addition, it relates to the above-described curable resin composition comprising a photopolymerization initiator.

Moreover, it is related with the above-mentioned resin composition containing a colored pigment.

Moreover, it relates to the above-mentioned resin composition which is a molding material.

Moreover, it relates to the above-mentioned resin composition which is a material for film formation.

Furthermore, it relates to the above-mentioned resin composition which is a resist material.

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

It also relates to an article overcoated with a cured product of the above-mentioned resin composition.

The acid-modified compound of an epoxy resin having a polycyclic hydrocarbon group of the present invention has good affinity with a colored pigment. The resin composition containing the said acid-modified compound has the outstanding resin physical property also in the state which only dried the solvent. Moreover, the hardened|cured material obtained by hardening|curing the resin composition of this invention by active energy rays, such as an ultraviolet-ray, etc. has thermal and mechanical toughness, favorable storage stability, and also has high reliability which endures high temperature, high humidity, and cold-heat shock. Therefore, the resin composition of the present invention is suitable for a material for molding, a material for forming a film, and a resist material.

From the high affinity with the color pigment, the acid-modified compound of the present invention and the composition containing the acid-modified compound exhibit good developability even at high pigment concentrations, and are color resists and resist materials for color filters, particularly black matrix. suitable for materials, etc.

The acid-modified compound of the present invention and the composition containing the acid-modified compound are solder resists for printed wiring boards in which particularly high reliability is required from thermal and mechanical toughness, good storage stability, and further high resistance to high-temperature, high-humidity, and cold-heat shock. , an interlayer insulating material for multilayer printed wiring boards, solder resists for flexible printed wiring boards, plating resists, photosensitive optical waveguides, and the like.

(Form for implementing the invention)

The reactive epoxy carboxylate compound (A) of the present invention is a compound (b) having both an ethylenically unsaturated group and a carboxyl group that can be polymerized in one molecule in the epoxy resin (a) represented by the general formula (1), and, if necessary, It is obtained by making the compound (c) which has both a hydroxyl group and a carboxy group react in 1 molecule.

That is, the characteristic of this invention is exhibited by introduce|transducing an ethylenically unsaturated group and a hydroxyl group into the molecular chain of an epoxy resin in arbitrary ratios.

About the manufacturing method etc. of the epoxy resin (a) represented by General formula (1), it is well-known and it describes in patent document 4. However, the manufacturing method is not limited to what was described in patent document 4. Epoxy resin (a) is available as NC-3500 (Nippon Kayaku Co., Ltd.).

In A in the general formula (1), (i) may be any of an ortho-form, meta-form, and para-form. In this invention, the meta body represented by the following general formula (2) is preferable.

The softening point (circular ball method) of the epoxy resin (a) is 50 to 150°C, preferably 52 to 100°C, particularly preferably 52 to 95°C. If it is less than 50 degreeC, stickiness is severe, handling is difficult, and there exists a subject in productivity. Moreover, when it exceeds 150 degreeC, it is a temperature close to a shaping|molding temperature, and it is unpreferable from the point which cannot ensure the fluidity|liquidity at the time of shaping|molding.

The epoxy equivalent of the epoxy resin (a) is 180-350 g/eq. In particular, 190-300 g/eq. is preferable. When an epoxy equivalent is less than 180 g/eq., since there are too many functional groups, in the hardened|cured material after hardening, water absorption is high, and it is brittle. When the epoxy equivalent exceeds 350 g/eq., the softening point becomes very large, or the epoxidation does not proceed sufficiently, which is not preferable in that the amount of chlorine becomes very large.

Moreover, the amount of chlorine of an epoxy resin (a) is 200-1500 ppm in total chlorine (hydrolysis method), Especially preferably, it is set as 200-900 ppm. From the standard of JPCA, it is desired not to exceed 900 ppm even as an epoxy single-piece. When there is much chlorine content in an epoxy resin (a), since electric reliability is affected, it is unpreferable. When it is less than 200 ppm, an excessive purification process for dechlorination is required, and a subject arises in productivity.

In addition, the melt viscosity in 150 degreeC of an epoxy resin (a) is 0.05-5 Pa.s. Preferably it is 0.05-2.0 Pa*s. When a viscosity is high, a subject arises in fluidity|liquidity, and a problem arises in the flowability and embedding property at the time of a press. When less than 0.05 Pa*s, since molecular weight is too small, heat resistance runs short.

In the present invention, it is particularly preferable to use the epoxy resin (a) in which the ratio between the formulas (i) and (ii) is (i)/(ii)=1 to 3 in terms of molar ratio. In the above formula, the molar ratio of (i) and (ii) is (i)/(ii) = 1 to 3. That is, it is characterized in that at least half are disubstituted glycidyl ether groups. The reactive epoxycarboxylate compound (A) and the reactive polycarboxylic acid compound (B) of the present invention obtained from the epoxy resin (a) in this molar ratio range are excellent in developability and pigment dispersibility, and the cured product of the present invention is It has excellent heat resistance, water absorption and toughness.

In the above formula, n is a repeating unit and is an integer of 0 to 5 as an average value. When n is in this range, it is excellent in developability and coatability at the time of setting it as the resin composition of this invention. When n exceeds 5, the developability of the resin composition of this invention and the solubility to a solvent fall.

The compound (b) which has 1 or more polymerizable ethylenically unsaturated group and 1 or more carboxy group in 1 molecule used in this invention is used in order to provide the reactivity to an active energy ray. As the compound (b) having at least one polymerizable ethylenically unsaturated group and at least one carboxy group in one molecule, it is preferable not to have a hydroxyl group in the compound. As such a compound (b), a monocarboxylic acid compound and a polycarboxylic acid compound are mentioned.

Examples of the monocarboxylic acid compound include (meth)acrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound. In the above, the acrylic acids include, for example, (meth)acrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, (meth)acrylic acid dimer, saturated or unsaturated dibasic acid anhydride and one hydroxyl group per molecule. and half-esters, which are (meth)acrylate derivatives and sugar molar reactants, and half-esters, which are sugar molar reactants of saturated or unsaturated dibasic acids and monoglycidyl (meth)acrylate derivatives.

Examples of the polycarboxylic acid compound include (meth)acrylate derivatives having a plurality of hydroxyl groups in one molecule and half-esters that are sugar molar reactants, and glycidyl (meth)acrylate derivatives having a plurality of epoxy groups with a saturated or unsaturated dibasic acid. and half-esters which are sugar molar reactants with

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

The compound (c) which has 1 or more hydroxyl group and 1 or more carboxy group in 1 molecule used in this invention is used in order to introduce|transduce a hydroxyl group in a carboxylate compound. These include compounds having one hydroxyl group and one carboxy group in one molecule, compounds having two or more hydroxyl groups and one carboxy group in one molecule, and compounds having one or more hydroxyl groups and two or more carboxy groups in one molecule. .

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

Among these, those containing two or more hydroxyl groups in one molecule are preferable in consideration of the effect of the present invention. Moreover, when the stability of a carboxylation reaction is taken into consideration that a carboxyl group is one in 1 molecule, it is preferable. Most preferably, it is preferable to have two hydroxyl groups and one carboxy group in one molecule. Considering the availability of raw materials, dimethylolpropionic acid and dimethylolbutanoic acid are particularly suitable. As the compound (c) having at least one hydroxyl group and at least one carboxy group in one molecule, it is preferable not to have a polymerizable ethylenically unsaturated group in the compound.

Among them, in consideration of the stability of the reaction between the epoxy resin (a) and the compound (b) and the compound (c), the compound (b) and the compound (c) are preferably monocarboxylic acid, and monocarboxylic acid and polycarbonate Even when an acid is used together, it is preferable that the value represented by the total molar amount of monocarboxylic acid/total molar amount of polycarboxylic acid is 15 or more.

The ratio of the total amount of the epoxy resin (a), the compound (b), and the total carboxylic acid of the compound (c) in this reaction should be changed appropriately according to the use. That is, since there is no unreacted epoxy group when all the epoxy groups are carboxylated, the storage stability as a reactive carboxylate compound is high. In this case, only the reactivity due to the introduced double bond is utilized.

On the other hand, by reducing the input amount of the carbonic acid compound and leaving an unreacted epoxy group, the reactivity by the introduced unsaturated bond and the reaction by the remaining epoxy group, for example, a polymerization reaction or thermal polymerization reaction by a photocationic catalyst, are complex. It is also possible to use as However, in this case, attention should be paid to the preservation|save of a reactive carboxylate compound, and examination of manufacturing conditions.

In the case of producing a reactive epoxy carboxylate compound (A) that does not leave an epoxy group, it is preferable that the total amount of the compound (b) and the compound (c) is 90 to 120 equivalent % with respect to 1 equivalent of the epoxy resin (a). . If it is within this range, gelation does not occur in the reaction, and production under relatively stable conditions is possible.

Moreover, when leaving unreacted epoxy groups, it is preferable that the total of a compound (b) and a compound (c) is 20-90 equivalent% with respect to 1 equivalent of the said epoxy resin (a). When it deviates from this range, the effect of composite hardening will fade. In addition, in this case, sufficient attention is required about the gelatinization during reaction and time-lapse|temporal stability of a reactive epoxy carboxylate compound (A).

The use ratio of compound (b) and compound (c) is preferably in the range of (b):(c) 9:1 to 1:9, further 4:6 to 8:2 in molar ratio to carboxylic acid. do. If it is this range, a sensitivity, developability, and pigment dispersibility are favorable.

This carboxylation reaction may be made to react without a solvent, or it can also be made to react by diluting with a solvent. As a solvent which can be used here, if it is an inert solvent with respect to a carboxylation reaction, there will be no limitation in particular. Although the preferable usage-amount of a solvent should be adjusted suitably according to the viscosity and use of resin obtained, 90-30 mass % with respect to solid content in the resin composition of this invention, A solvent is used so that it may become preferably 80-50 mass %.

Specific examples of the solvents that can be used as the above solvent include, for example, aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane, and decane, and mixtures thereof. Petroleum ether, white gasoline, solvent naphtha, etc. are mentioned. Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene Mono or polyalkylene glycol monoalkyl, such as glycol monoethyl 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 ether monoacetate, dialkyl glutarate, dialkyl succinate, and dialkyl adipic acid. 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, Glycol ethers, such as triethylene glycol diethyl ether, Cyclic ethers, such as tetrahydrofuran, etc. are mentioned. Moreover, acetone, methyl ethyl ketone, cyclohexanone, isophorone, etc. are mentioned as a ketone type solvent.

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

In the reaction, it is preferable to use a catalyst in order to promote the reaction, and the amount of the catalyst used is the total amount of the reactants, that is, the epoxy resin (a), the compound (b), and, in some cases, a solvent plus others. It is 0.1-10 mass % with respect to it. The reaction temperature in that case is 60-150 degreeC, and reaction time becomes like this. Preferably it is 5-60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, and methyltriphenylstibine. and a known general basic catalyst such as bin, chromium octanoate, and zirconium octanoate.

Further, as the thermal polymerization inhibitor, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4-hydroxytoluene, etc. It is preferable to use

This reaction makes an end point when the acid value of a sample became 5 mg-KOH/g or less, Preferably it became 2 mg-KOH/g or less, sampling appropriately.

As a molecular weight range of the reactive epoxy carboxylate compound (A) obtained in this way, the polystyrene conversion mass average molecular weight in GPC is the range of 1,000-30,000, Preferably it is 1,500-20,000. When it is smaller than this molecular weight, the toughness of hardened|cured material is not fully exhibited, and when it is too large than this, a viscosity becomes high and coating etc. become difficult.

Next, the acid addition step will be described in detail. An acid addition process introduce|transduces a carboxy group as needed into the reactive epoxy carboxylate compound (A) obtained in the previous process, and is performed for the purpose of obtaining a reactive polycarboxylic acid compound (B). As the reason for introducing a carboxy group, for example, in applications requiring resist patterning, etc., the purpose of imparting solubility in alkaline water to a portion not irradiated with active energy rays, and imparting adhesion to metals, inorganic substances, etc. introduced with A carboxy group is introduce|transduced through an ester bond by making polybasic acid anhydride (d) addition-react specifically, to the hydroxyl group which generate|occur|produced by the carboxylation reaction.

Specific examples of the polybasic acid anhydride (d) include, for example, any compound having an acid anhydride structure in one molecule, but excellent in aqueous alkali solution developability, heat resistance, hydrolysis resistance, etc. Particular preference is given to phthalic acid, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride.

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

However, when the reactive polycarboxylic acid compound (B) of the present invention is used as an alkali developing resist, the solid content acid value (JIS K5601-2-) of the reactive polycarboxylic acid compound (B) finally obtained by using the polybasic acid anhydride (d) 1: Based on 1999) is 30 to 120 mg·KOH/g, preferably 40 to 105 mg·KOH/g. When the solid content acid value at this time is this range, the developability with favorable alkali aqueous solution developability of the resin composition of this invention is shown. In other words, good patterning properties and a wide range of management for excessive development are obtained, and excessive acid anhydride does not remain.

In the reaction, it is preferable to use a catalyst to promote the reaction. The usage-amount of the said catalyst is 0.1-10 mass % with respect to the total amount of the reactive epoxy carboxylate compound (A), a polybasic acid anhydride (d), and the reaction product which added a solvent and others in some cases. The reaction temperature in that case is 60-150 degreeC, and reaction time becomes like this. Preferably it is 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, and methyltriphenylstibine. Vienna, chromium octanoate, zirconium octanoate, etc. are mentioned.

This acid addition reaction can also be made to react without a solvent, or can also be made to react by diluting with a solvent. As a solvent which can be used here, if it is an inert solvent which does not react with respect to an acid addition reaction, there will be no limitation in particular. In addition, when it manufactures using a solvent in the carboxylation reaction which is a previous process, it can also use for the acid addition reaction which is a next process directly without removing a solvent on condition that it is an inert for the both reaction. Although the preferable usage-amount of a solvent should be suitably adjusted according to the viscosity and use of resin obtained, Preferably it is 90-30 mass % as solid content, A solvent is used so that it may become 80-50 mass % more preferably.

In addition to this, the reaction can be carried out alone or in a mixed organic solvent such as a reactive compound (C) described later. In this case, after reaction, it can use directly as a composition.

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

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

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

Examples of the acrylates that can be used include monofunctional (meth)acrylates, polyfunctional (meth)acrylates, 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 heard

Examples of the polyfunctional (meth)acrylates include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, glycol di(meth)acrylate. ) acrylate, diethylene di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanurate, polypropylene glycol di(meth)acrylate, adipic acid epoxy Di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogenated bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, di of ε-caprolactone adduct of neophene glycol hydroxypivalate (meth)acrylate, poly(meth)acrylate of a reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylolpropane Tri(meth)acrylate and its ethylene oxide adduct, pentaerythritol tri(meth)acrylate and its ethylene oxide adduct, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acryl rate and its ethylene oxide adduct, etc. are mentioned.

Examples of usable vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds. Examples of the vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Styrene, methyl styrene, ethyl styrene, etc. are mentioned as styrene. As other vinyl compounds, triallyl isocyanurate, trimethallyl isocyanurate, etc. are mentioned.

Moreover, as so-called reactive oligomers, a urethane acrylate having both a functional group and a urethane bond functional to an active energy ray in the same molecule, and a polyester acrylate having both a functional group and an ester bond functional to an active energy ray in the same molecule in the same molecule , and other epoxy acrylates derived from an epoxy resin and having a functional group capable of being functional with an active energy ray in the same molecule, and reactive oligomers in which these bonds are used in combination.

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

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

The resin composition of the present invention by mixing the reactive epoxycarboxylate compound (A) and/or the reactive polycarboxylic acid compound (B) of the present invention and a reactive compound (C) other than (A) and (B) if necessary can be obtained At this time, you may add another component suitably according to a use.

The resin composition of this invention is 97-5 mass % of a reactive epoxy carboxylate compound (A) and/or a reactive polycarboxylic acid compound (B) in a composition, Preferably 87-10 mass %, (A), (B) 3-95 mass % of other reactive compounds (C), More preferably, 3-90 mass % is included. You may contain other components up to about 70 mass % as needed.

The reactive epoxy carboxylate compound (A) or reactive polycarboxylic acid compound (B) in the resin composition of this invention can be used properly according to the use. For example, a reactive epoxycarboxylate compound ( ( When using A) and developing with alkaline water, the reactive polycarboxylic acid compound (B) is used. In general, the reactive polycarboxylic acid compound (B) is often used for this purpose from the viewpoint that the alkaline water developing type is easier to form a fine pattern. Of course, there is no problem at all even if (A) and (B) are used together.

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

The color pigment which can be used in this invention is used in order to make the resin composition of this invention into a coloring material.

In this invention, since dispersion|distribution of a colored pigment is favorable, a pigment density|concentration can be thickened. Also in the case of developing, since the dispersion is in a good state, the patterning characteristics are excellent, and there are few development residues in the developing and dissolving part.

As a color pigment, inorganic pigments, such as organic pigments, such as a phthalocyanine type, an azo type, a quinacridone type, carbon black, and titanium oxide, are mentioned. Among these, carbon black has high dispersibility and is most preferred.

In the present invention, the molding material is formed by putting an uncured composition in a mold, or by pressing the mold to the uncured composition to shape an object and then causing a curing reaction with an active energy ray, or It refers to a material used for molding by irradiating an uncured composition with a focused light such as a laser to cause a curing reaction.

Specific uses include a sheet molded into a planar shape, an encapsulant for protecting an element, a so-called nanoprinting material that is finely molded by pressing a microfabricated "frame" to an uncured composition, and furthermore, a particularly thermal requirement. A suitable use is mentioned as a peripheral sealing material, such as a strict light emitting diode and a photoelectric conversion element.

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

Among these, the reactive polycarboxylic acid compound (B) of the reaction for coating a plastic base material or a metal base material is alkali, since the adhesiveness to a base material increases by introduction of a carboxy group of a reactive polycarboxylic acid compound (B). Taking advantage of the property of being soluble in aqueous solution, the resin composition of the present invention can also be used as an alkaline water developing resist material.

In the present invention, the resist material is intended to form a film layer of the composition on a substrate, and then partially irradiate active energy rays such as ultraviolet rays, and draw using the difference in physical properties between the irradiated portion and the unirradiated portion. Specifically, the irradiated part or the unirradiated part is removed by some method, for example, by dissolving it with a solvent or an alkali solution, etc., and drawing is performed.

The resin composition of the present invention can be applied to various materials that can be patterned, and is useful, for example, as a solder resist material and an interlayer insulating material for a build-up method, and furthermore, as an optical waveguide, a printed wiring board, an optoelectronic board, or an optical device. It is also used for electric, electronic and optical substrates such as plates.

As a particularly suitable use, by making use of the characteristic of obtaining a tough cured product, by taking advantage of the characteristic of being used in permanent resists such as solder resists and having good pigment dispersibility, color resists such as printing inks and color filters, especially resists for black matrix. use is preferred.

The resin composition of this invention is used especially suitably as a dry film use by which the mechanical strength before hardening reaction by an energy ray is calculated|required. That is, since the balance of the hydroxyl group and the epoxy group of the epoxy resin (a) used in the present invention is within a specific range, the reactive epoxycarboxylate compound (A) and the reactive polycarboxylic acid compound (B) of the present invention have a relatively high molecular weight. In spite of this, good developability can be exhibited.

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

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

In addition, for the purpose of making the resin composition of this invention suitable for various uses, 70 mass % can also be added as an upper limit in a resin composition. As other components, a photoinitiator, other additives, other color pigments, and the volatile solvent etc. which are added for viscosity adjustment for the purpose of providing coating suitability etc. are mentioned. Other components that can be used below are exemplified.

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

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

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

Examples of other halides include 2,2,2-trichloro-[1-4'-(dimethylethyl)phenyl]ethanone (such as Trigonal PI manufactured by AKZO), 2.2-dichloro-1--4-(phenoxyphenyl) ) ethanone (Sandray 1000 manufactured by Sandoz, etc.), α,α,α-tribromomethylphenylsulfone (BMPS manufactured by Seitetsu Chemical, etc.), and the like. Examples of the triazine-based initiator include 2,4,6-tris(trichloromethyl)-triazine, 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine (such as Triazine A manufactured by Panchim). , 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine (such as Triazine PMS manufactured by Panchim), 2,4-trichloromethyl-(fipronyl)-6-triazine (Triazine PP manufactured by Panchim, etc.), 2,4-trichloromethyl-(4'-methoxynaphthyl)-6-triazine (Triazine B manufactured by Panchim, etc.), 2[2'(5"-methylfuryl) )ethylidene]-4,6-bis(trichloromethyl)-s-triazine (manufactured by Sanwa Chemical, etc.), 2(2'-furylethylidene)-4,6-bis(trichloromethyl)- s-triazine (manufactured by Sanwa Chemical) and the like.

Examples of the borate-based initiator include NK-3876 and NK-3881 manufactured by Nippon Photosensitive Dye, and examples of other photoacid generators include 9-phenylacridine, 2,2'-bis(o-chlorophenyl)- 4,4',5,5'-tetraphenyl-1,2-biimidazole (biimidazole, etc. manufactured by Kurogane Kasei Co., Ltd.), 2,2-azobis(2-amino-propane)dihydro Chloride (V50, etc. manufactured by Wako Pure Chemical Industries, Ltd.), 2,2-azobis[2-(imidazolin-2yl)propane]dihydrochloride (VA044 manufactured by Wako Pure Chemical Industries, Ltd., etc.), (η ⁵ -2-4-cyclo pentadien-1-yl)[(1,2,3,4,5,6-η)-(1-methylethyl)benzene]iron(II)hexafluorophosphate (Irgacure 261 manufactured by Ciba Geigy, etc.); bis(η ⁵ -cyclopentadien-1-yl)-bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium (CGI-784 manufactured by Ciba Geigy, etc.) can be heard

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

Examples of other additives include thermosetting catalysts such as melamine, thixotropy imparting agents such as aerosol, silicone-based and fluorine-based leveling agents and defoamers, hydroquinone and hydroquinone monomethyl ether, polymerization inhibitors, stabilizers, and antioxidants. etc. can be used.

Moreover, as another coloring material, what is not intended for coloring, what is called an extender, can also be used, for example. For example, talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay, etc. are mentioned.

In addition, resins that do not show reactivity to active energy rays (so-called inert polymers), such as other epoxy resins, phenol resins, urethane resins, polyester resins, ketoneformaldehyde resins, cresol resins, xylene resins, Allyl phthalate resins, styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof can also be used. It is preferable to use these in the resin composition of this invention in the range to 40 mass %.

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

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

[Example]

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

A softening point and an epoxy equivalent were measured on condition of the following.

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

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) GPC measurement conditions are as follows.

Model: TOSOH HLC-8220GPC

Column: TSKGEL Super HZM-N

Solvent: THF (tetrahydrofuran); 0.35 ml every minute. 40℃

Detector: Differential Refractometer

Molecular Weight Standard: Polystyrene

Synthesis Example 1

In a flask equipped with a thermometer, a cooling tube, and a stirrer, 316 parts of phenol and 158 parts of resorcin were put, and the temperature was raised to 100 ° C. Then, 201 parts of 4,4'-bischloromethylbiphenyl were added in portions over 2 hours, and the copper It was made to react at the same temperature for further 5 hours. Then, it heated up to 160 degreeC, and all 4,4'- bischloromethyl biphenyl was reacted. In the meantime, the generated HCl was distilled off by trapping with an alkali. After completion of the reaction, unreacted phenol and unreacted resorcin were distilled off at 180°C under reduced pressure using a rotary evaporator to obtain 266 parts of phenol resin (P-1). The obtained phenol resin (P-1) had a hydroxyl equivalent of 137 g/eq., a softening point of 94°C, an ICI viscosity of 470 mPa·s, and a dihydric phenol introduction ratio of 64%.

Synthesis Example 2

266 parts of the phenol resin (P-1) obtained in Synthesis Example 1, 719 parts of epichlorohydrin, 72 parts of methanol, and 21 parts of water were added to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device while purging with nitrogen, It heated up to 75 degreeC. Then, after adding 83 parts of flake-shaped sodium hydroxide in portions over 90 minutes, reaction was further performed at 75 degreeC for 75 minutes. After completion of the reaction, water washing was performed, and an excess solvent such as epichlorohydrin was distilled off from the organic layer under reduced pressure at 140°C using a rotary evaporator. 750 parts of methyl isobutyl ketone was added to the residue, it melt|dissolved, and it heated up to 75 degreeC. After adding 52 parts of 30% sodium hydroxide aqueous solution under stirring and reacting for 1 hour, the organic layer was washed with water until the washing water became neutral. By distilling off the solvent, 338 parts of epoxy resins (EP1) were obtained. The epoxy equivalent of the obtained epoxy resin (EP1) was 209 g/eq., the softening point was 71 degreeC, the viscosity in 150 degreeC was 370 mPa*s, and the introduction ratio of the divalent glycidyl-substituted phenyl group was 68%.

Synthesis Example 3

In a flask equipped with a thermometer, a cooling tube and a stirrer, 316 parts of phenol and 126 parts of resorcin were put, and the temperature was raised to 100°C, and then 201 parts of 4,4'-bischloromethylbiphenyl were added in portions over 2 hours. It was further reacted at temperature for 5 hours. Then, it heated up to 160 degreeC, and all 4,4'- bischloromethyl biphenyl was reacted. In the meantime, the generated HCl was distilled off by trapping with an alkali. After completion of the reaction, unreacted phenol and unreacted resorcin were distilled off under reduced pressure at 180°C using a rotary evaporator to obtain 194 parts of phenol resin (P-2). The obtained phenol resin (P-2) had a hydroxyl equivalent of 141 g/eq., a softening point of 89°C, an ICI viscosity of 446 mPa·s, and a dihydric phenol introduction ratio of 51%.

Synthesis Example 4

282 parts of the phenol resin (P-2) obtained in Synthesis Example 3, 719 parts of epichlorohydrin, 72 parts of methanol, and 21 parts of water were added to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device while purging with nitrogen, It heated up to 75 degreeC. Then, after adding 83 parts of flake-shaped sodium hydroxide in portions over 90 minutes, reaction was further performed at 75 degreeC for 75 minutes. After completion of the reaction, water washing was performed, and an excess solvent such as epichlorohydrin was distilled off from the organic layer under reduced pressure at 140°C using a rotary evaporator. 750 parts of methyl isobutyl ketone was added to the residue, it melt|dissolved, and it heated up to 75 degreeC. After adding 52 parts of 30% sodium hydroxide aqueous solution under stirring and reacting for 1 hour, the organic layer was washed with water until the washing water became neutral. 352 parts of epoxy resins (EP2) were obtained by distilling off a solvent. The epoxy equivalent of the obtained epoxy resin (EP2) was 215 g/eq., the softening point was 78 degreeC, the viscosity in 150 degreeC was 410 mPa*s, and the introduction ratio of a divalent glycidyl-substituted phenyl group was 55 %.

Synthesis Example 5

In a flask equipped with a thermometer, a cooling tube, and a stirrer, 316 parts of phenol and 179 parts of resorcin were put, and the temperature was raised to 100 ° C. Then, 201 parts of 4,4'-bischloromethylbiphenyl were added in portions over 2 hours. It was further reacted at temperature for 5 hours. Then, it heated up to 160 degreeC, and all 4,4'- bischloromethyl biphenyl was reacted. In the meantime, the generated HCl was distilled off by trapping with an alkali. After completion of the reaction, 300 parts of phenol resin (P-3) was obtained by distilling off unreacted phenol and unreacted resorcin under reduced pressure at 180°C using a rotary evaporator. The obtained phenol resin (P-3) had a hydroxyl equivalent of 127 g/eq., a softening point of 112°C, an ICI viscosity of 2.0 Pa·s, and a dihydric phenol introduction ratio of 70%.

Synthesis Example 6

254 parts of the phenol resin (P-3) obtained in Synthesis Example 5, 719 parts of epichlorohydrin, 72 parts of methanol, and 21 parts of water were added to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device while purging with nitrogen, It heated up to 75 degreeC. Then, after adding 83 parts of flake-shaped sodium hydroxide in portions over 90 minutes, reaction was further performed at 75 degreeC for 75 minutes. After completion of the reaction, water washing was performed, and an excess solvent such as epichlorohydrin was distilled off from the organic layer under reduced pressure at 140°C using a rotary evaporator. 750 parts of methyl isobutyl ketone was added to the residue, it melt|dissolved, and it heated up to 75 degreeC. After adding 52 parts of 30% sodium hydroxide aqueous solution under stirring and reacting for 1 hour, the organic layer was washed with water until the washing water became neutral. 312 parts of epoxy resins (EP3) were obtained by distilling off a solvent. The epoxy equivalent of the obtained epoxy resin (EP3) was 194 g/eq., the softening point was 91 degreeC, the viscosity in 150 degreeC was 1.2 Pa.s, and the introduction ratio of the divalent glycidyl-substituted phenyl group was 74%.

Example 1: Synthesis of reactive epoxycarboxylate compound (A)

As the epoxy resin (a), the epoxy resin obtained in Synthesis Example 2, Synthesis Example 4, and Synthesis Example 6 was described in the amount in Table 1, and as the compound (b), acrylic acid (abbreviated AA, Mw=72) was in Table 1, the amount described in Table 1, the compound As (c), dimethanol propionic acid (abbreviated abbreviation DMPA, Mw=134) was added in Table 1 in the stated amount. 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that it might become 80 mass % of solid content of a reaction liquid, it was made to react at 100 degreeC for 24 hours, and the reactive epoxy carboxylate compound (A) solution was obtained. The reaction end point was determined by the solid content acid value (AV), and the measured value was described in Table 1. The acid value measurement was measured with the reaction solution and converted into the acid value as solid content.

Comparative Example 1-1: Synthesis of Comparative Reactive Epoxycarboxylate Compound

NC-3000H (manufactured by Nippon Kayaku Co., Ltd., softening point 70° C., epoxy equivalent 288 g/eq.) is 288 g, AA as compound (b) is the amount described in Table 1, and dimethanol pyropionic acid as compound (c) (c) The abbreviation DMPA, Mw=134) was added in Table 1. As a catalyst, propylene glycol monomethyl ether monoacetate was added so that it might become 80 mass % of solid content as 3 g of triphenylphosphine and a solvent, and it was made to react at 100 degreeC for 24 hours, and the carboxylate compound solution was obtained. The reaction endpoint was determined from the solid content acid value (AV), and the measured values are described in Table 1. The acid value measurement was measured with the reaction solution and converted into the acid value as solid content.

Comparative Example 1-2: Synthesis of Comparative Reactive Epoxycarboxylate Compound

200 g of cresol novolak type epoxy resin EOCN-103S (manufactured by Nippon Kayaku Co., Ltd., softening point 80° C., epoxy equivalent 200 g/eq.) as compound (b), AA as the amount described in Table 1, as compound (c) DMPA was added to the amount described in Table 1. 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that it might become 80 mass % of solid content, and it was made to react at 100 degreeC for 24 hours, and the reactive epoxy carboxylate compound solution was obtained. The reaction endpoint was determined from the solid content acid value (AV), and the measured values are described in Table 1. The acid value measurement was measured with the reaction solution and converted into the acid value as solid content.

Note) The molar ratio of the amount of AA is the molar ratio of AA (b) to the epoxy resin (a).

The molar ratio of the amount of DMPA is the molar ratio of DMPA (c) to the epoxy resin (a).

Example 2: Synthesis of reactive polycarboxylic acid compound (B)

In the reactive epoxycarboxylate compound (A) solution obtained in Example 1, tetrahydrophthalic anhydride (abbreviated THPA) as the polybasic acid anhydride (d) was added in Table 2 as the amount and as the solvent, and the solid content in the reaction solution was 65% by mass. Propylene glycol monomethyl ether monoacetate was added so as to become

Comparative Example 2: Synthesis of reactive polycarboxylic acid compound

In the reactive epoxycarboxylate compound solution obtained in Comparative Examples 1-1 and 1-2, THPA as the polybasic acid anhydride (d) in Table 2, and propylene glycol monomethyl ether mono so that the solid content is 65 mass% as the solvent and Acetate was added, and the reaction product was subjected to acid addition reaction by heating at 100° C. to obtain a reactive polycarboxylic acid compound solution.

Example 3 and Comparative Example 3: Preparation of a composition for hard coating

20 g of the reactive epoxycarboxylate compound (A) synthesized in Example 1 and Comparative Example 1, 6.0 g of dipentaerythritol hexaacrylate, which is a radical curing monomer as the other reactive compound (C), and Irga as a UV-reactive initiator 1.5 g of IRGACURE 184 was added, and it was heat-dissolved. Moreover, this was coated on the polycarbonate board with a hand applicator so that it might become the film thickness at the time of drying 20 micrometers, and the solvent was dried in the electric oven at 80 degreeC for 30 minute(s). After drying, an ultraviolet vertical exposure apparatus (manufactured by Oaksei Co., Ltd.) equipped with a high-pressure mercury lamp was irradiated with ultraviolet rays having an irradiation dose of 1000 mJ and cured to obtain a multilayer material. The hardness of the coating film of this multilayer material was measured according to JIS K5600-5-4: 1999, and the impact resistance test was further performed according to ISO6272-1: 2002.

○: No scratches or peeling

△: Slightly scratched

×: peeling off

As is clear from the above results, the Example improved hardness and impact resistance compared with Comparative Examples 3-1 and 3-2. As this reason, it is thought that it depends on what the crosslinking density improved with introduction of the component (a) in the epoxy resin (a) represented by General formula (1).

Example 4 and Comparative Example 4: Preparation of dry film resist composition

56.73 g of the reactive polycarboxylic acid compound (B) obtained in Example 2 and Comparative Example 2, and DPCA-60 (trade name: Nippon Kayaku Co., Ltd. polyfunctional acrylate) as the other reactive compound (C) 5.67 g, 2.92 g of Irgacure 907 (manufactured by BASF) as a photoinitiator, and 0.58 g of KAYACURE-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) as a curing component NC-3000H (Nippon Kayaku) 17.54 g (manufactured by Co., Ltd.), 0.73 g of melamine as a thermosetting catalyst, and 5.67 g of propylene glycol monomethyl ether monoacetate as a concentration adjusting solvent were added, kneaded with a bead mill and uniformly dispersed to obtain a resist resin composition. The obtained composition is uniformly applied to a polyethylene terephthalate film serving as a support film using a wire bar coater #20, passed through a hot air drying furnace at a temperature of 70° C. to form a resin layer having a thickness of 20 μm, and then this resin layer The polyethylene film used as a protective film was adhere|attached on it, and the dry film was obtained. The obtained dry film was applied to a polyimide printed circuit board (copper circuit thickness: 12 µm, polyimide film thickness: 25 µm) using a heating roll having a temperature of 80° C., and the resin layer was adhered to the entire surface of the substrate while peeling the protective film. . In addition, the (A), (B) mixture used in Example 4-4 is what was shown in Example 1-2 as a reactive epoxy carboxylate compound (A), and Example 2 as a reactive polycarboxylic acid compound (B) -2 is a mixture of 50:50 by mass of the solution.

Next, in order to estimate the mask and the sensitivity on which the circuit pattern was drawn using the ultraviolet exposure apparatus (Oak Seisakusho Co., Ltd., model HMW-680GW), it passed through Kodak manufacturing step tablet No. 2 and 500 mJ/cm<2> UV irradiated. Then, the film on a dry film was peeled and the peeling state was confirmed. Then, spray development was performed with 1% sodium carbonate aqueous solution, and resin of the ultraviolet-ray non-irradiated part was removed. After washing-drying with water, the printed circuit board was heat-hardened with a 150 degreeC hot-air dryer for 60 minutes, and the cured film was obtained.

<Sensitivity evaluation>

Sensitivity was judged by whether the density|concentration part of which level remained in the exposure part which permeate|transmitted the step tablet at the time of development. The one with a larger number (value) is judged with high sensitivity by the farmer of the tablet (unit: step).

<Evaluation of developability>

When developing the exposed part which passed through the pattern mask, developability was evaluated as developability (unit: second) with the time until development of a patterned part completes completely, what is called a break time.

<Curability evaluation>

Sclerosis|hardenability evaluation was shown with the pencil hardness of the cured film after completion|finish of 150 degreeC heating. The evaluation method was based on JIS K5600-5-4: 1999.

<Evaluation of folding resistance>

The polyimide printed circuit board on which the cured film of the resist was formed was acid-folded with the cured film side facing up, and the bent part was pulled well with a finger. The bent part was returned to the original state, and the resist film was observed with a loupe.

○: No cracks

(triangle|delta): slight crack is observed

x: peels off

As is clear from the above results, the resin composition of the present invention has high bending resistance while having high hardness. Moreover, it has favorable developability and sensitivity as a resist.

Example 5 and Comparative Example 5: Evaluation of flame retardancy

10.0 g of the resin compositions prepared in Examples 4-1 to 4-3, 4-5 and 4-6 and Comparative Examples 4-1 and 4-2, phosphorus-based reactive flame retardant (FRM-1000 manufactured by Nippon Kayaku Co., Ltd.) 0.5 g was mixed and stirred. The composition was applied to a polyimide film having a thickness of 25 µm with a wire bar coater #20 and passed through a hot air drying furnace at a temperature of 70°C to form a resin layer having a thickness of approximately 15 µm. This resin layer was irradiated with an ultraviolet-ray of 500 mJ/cm<2> using the ultraviolet-ray exposure apparatus (Oak Seisakusho, model HMW-680GW). After irradiation, the resin layer was subjected to a heat curing reaction with a hot air dryer at 150°C for 60 minutes to obtain a cured film. The obtained cured film was cut out together with a polyimide base film in strip shape of 20 cm in length and 2 cm in width. The cut-out film was hung vertically long, and the fire was ignited with a lighter from the lower end, and flame retardancy was evaluated (Table 5).

○: It is ignited, but is extinguished before being burned.

x: It burns out.

For comparison with the folding resistance, the data of Example 4 were combined and described for reference. Evaluation and evaluation results are based on Example 4.

From the above results, it became clear that the reactive polycarboxylic acid compound (B) of this invention is a material compatible with a flame retardance and fold resistance.

Example 6 and Comparative Example 6: Evaluation of Pigment Dispersibility

20 g of the reactive polycarboxylic acid compound (B) obtained in Example 2 and Comparative Example 2, 5.0 g of DPHA (trade name: Nippon Kayaku Co., Ltd. acrylate monomer) as the other reactive compound (C), propylene as an organic solvent 10 g of glycol monomethyl ether acetate and 15 g or 10 g of Mitsubishi carbon black MA-100 as a color pigment were added and stirred. Furthermore, 35 g of glass beads were put, and it disperse|distributed for 1 hour with a paint shaker. The dispersion liquid after completion|finish of dispersion was coated on the polyethylene terephthalate film with wire bar coater #2, and it dried for 10 minutes with an 80 degreeC warm air dryer. The gloss of the surface of the coating film after drying was measured using a 60° reflective gloss meter (Horiba Seisakusho IG-331 gloss meter), and dispersibility of carbon black was evaluated. Table 6 shows the results. The higher the value of gloss, the better the pigment dispersibility.

As is evident from the above results, in the coating film obtained from the resin composition containing the reactive polycarboxylic acid compound (B) obtained in Example 2, even when the content of the color pigment was high, the value of gloss did not change. On the other hand, the luster of the reactive polycarboxylic acid compound of Comparative Example 2-1 decreased when the content of the colored pigment increased. The reactive polycarboxylic acid compound of Comparative Example 2-2 has a low gloss value even when the content of the color pigment is small, and the content dispersibility is low. The pigment dispersibility of the reactive polycarboxylic acid compound (B) of the present invention is excellent, without being dependent on the content of the colored pigment.

The resin composition of this invention is a material which has hardenability, flexibility, toughness, and flame retardance, Comprising: A hard-coat material, the resist material which alkali-developable flexibility is required, and the use which exhibits favorable pigment dispersibility is shown. In particular, as a material having both active energy ray-curable printing inks, color resists, and resist properties such as pigment dispersibility and developability, it is suitable for color resists for LCDs, black matrices, and the like.

Claims (12)

In the epoxy resin (a) represented by the following general formula (1), a compound (b) having an ethylenically unsaturated group and a carboxy group that can be polymerized in one molecule, and a compound (c) having a hydroxyl group and a carboxy group in one molecule if necessary Reactive epoxycarboxylate compound (A) obtained by reacting:

(Wherein, A is each independently any one of (i) or (ii), and the molar ratio of (i) and (ii) is (i)/(ii) = 1 to 3; G is a glycidyl group represents; n is the number of repetitions and is an integer of 0 to 5 as an average value). According to claim 1,
Reactive epoxy carboxylate compound (A) whose (i) is (i) represented by following General formula (2).

A reactive polycarboxylic acid compound (B) obtained by reacting the reactive epoxycarboxylate compound (A) according to claim 1 or 2 with a polybasic acid anhydride (d). In the epoxy resin (a) represented by the following general formula (1), a compound (b) having an ethylenically unsaturated group and a carboxy group that can be polymerized in one molecule, and a compound (c) having a hydroxyl group and a carboxy group in one molecule if necessary Reactive epoxy carboxylate compound (A) obtained by reacting

(Wherein, A is each independently any one of (i) or (ii), and the molar ratio of (i) and (ii) is (i)/(ii) = 1 to 3; G is a glycidyl group n is the number of repetitions and is an integer of 0 to 5 on average) and either or both of the reactive polycarboxylic acid compound (B) obtained by reacting the reactive epoxycarboxylate compound (A) with the polybasic acid anhydride (d) A resin composition including all. 5. The method of claim 4,
A resin composition comprising a reactive epoxy carboxylate compound (A) and a reactive compound (C) other than the reactive polycarboxylic acid compound (B). 5. The method of claim 4,
A resin composition comprising a photoinitiator. 5. The method of claim 4,
A resin composition comprising a colored pigment. 8. The method according to any one of claims 4 to 7,
A resin composition as a molding material. 8. The method according to any one of claims 4 to 7,
A resin composition which is a material for forming a film. 8. The method according to any one of claims 4 to 7,
A resin composition which is a resist material. Hardened|cured material of the resin composition in any one of Claims 4-7. An article overcoated with the cured product of claim 11 .