JP6576161B2 - Novel reactive epoxycarboxylate compound, derivative thereof, resin composition containing the same, and cured product thereof - Google Patents

Description

  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 polymerizable in one molecule, and if necessary, in one molecule. A reactive epoxycarboxylate compound (A) obtained by reacting a compound (c) having a hydroxyl group and a carboxy group, a reactive polycarboxylic acid compound (B) which is an acid-modified product thereof, a resin composition containing them, and , Related to the cured product. These reactive epoxycarboxylate compound (A) and reactive polycarboxylic acid compound (B) have good affinity for the pigment, and a tough cured product is obtained from the resin composition containing them. I can do it.

  Printed wiring boards are required to have high precision and high density in order to reduce the size and weight of portable devices and improve communication speed. Accordingly, the solder resist that covers the circuit itself is required to have high substrate adhesion, high insulation, and electroless gold plating while maintaining heat resistance and thermal stability. There is also a need for a film-forming material having tougher cured properties.

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

  On the other hand, an acid-modified epoxy acrylate having a phenol aralkyl type epoxy resin as a basic skeleton is disclosed in Patent Document 2 as a material exhibiting high toughness after curing, and the use as a solder resist using this is also studied. Has been done.

  In addition, in Patent Document 3, carbon black or the like is dispersed in an acid-modified epoxy acrylate having a phenol aralkyl type epoxy resin as a basic skeleton and applied to a black matrix resist used for a liquid crystal display panel or the like.

  In the black matrix resist, a color pigment such as carbon black is dispersed with good affinity to the resin, so that even if the color pigment has a high concentration, good developability is exhibited and development without a pigment residue is 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, the rigidity of the rigid structure and the good affinity of the pigment combined with each other, and when the pigment dispersion was made, there was a problem that the dispersion was pseudo-aggregated and the stability was not good. .

  The acid-modified epoxy acrylate compound of the epoxy resin described in Patent Document 4 is not known.

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

  Although the curable resin composition containing the epoxy resin having a polycyclic hydrocarbon group can obtain a relatively tough cured material, it is reliable as a material that requires extremely high reliability such as transportation equipment. Low. Furthermore, there is a need for acid-modified epoxy acrylate compounds that have better dispersibility of colored pigments, especially carbon black, and that have good development characteristics even at high pigment concentrations. Such an acid-modified epoxy acrylate compound is required to have a high molecular weight and an appropriate developability.

  The inventors of the present invention added an epoxy resin (a) having a polycyclic hydrocarbon group to a compound (b) having an ethylenically unsaturated group and a carboxy group polymerizable in one molecule, and if necessary, in one molecule. Reactive epoxycarboxylate compound (A) obtained by reacting with compound (c) having a hydroxyl group and a carboxy group, and further a reactive polycarboxylic acid compound obtained by reacting it with polybasic acid anhydride (d) It was found that (B) has particularly excellent resin properties. Furthermore, it has been found that the reactive epoxycarboxylate compound (A) and the reactive polycarboxylic acid compound (B) have a good affinity with a colored pigment, and a composition containing these compounds has a high pigment. It has been found that the resist material has good developability even at a high concentration.

  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 polymerizable in one molecule, and if necessary, in one molecule. It relates to a reactive epoxycarboxylate compound (A) obtained by reacting a compound (c) having a hydroxyl group and a carboxy group.

(In the formula, each A is independently either (i) or (ii), and the molar ratio of (i) and (ii) is (i) / (ii) = 1-3. G is Represents a glycidyl group, where n is an average value of the number of repetitions and is a positive number of 0 <n ≦ 5.)

  Furthermore, an epoxy resin (a) in which (i) of A in the general formula (1) is a meta isomer, a compound (b) having an ethylenically unsaturated group and a carboxy group polymerizable in one molecule, and further necessary Accordingly, the present invention relates to a reactive epoxycarboxylate compound (A) obtained by reacting a compound (c) having a hydroxyl group and a carboxy group in one molecule.

Furthermore, it is related with the reactive polycarboxylic acid compound (B) obtained by making a polybasic acid anhydride (d) react with the said reactive epoxy carboxylate compound (A).
Furthermore, it is related with the resin composition containing the said reactive epoxy carboxylate compound (A) and / or reactive polycarboxylic acid compound (B).

Furthermore, it is related with said resin composition containing reactive compounds (C) other than the said reactive epoxy carboxylate compound (A) and reactive polycarboxylic acid compound (B).
Furthermore, it is related with said curable resin composition containing a photoinitiator.
Furthermore, it is related with said resin composition containing a coloring pigment.

Furthermore, it is related with said resin composition which is a molding material.
Furthermore, it is related with said resin composition which is a film forming material.
Furthermore, it is related with said resin composition which is a resist material.

Furthermore, it is related with the hardened | cured material of said resin composition.
Further, the present invention relates to an article overcoated with a cured product of the above resin composition.

  The acid-modified compound of an epoxy resin having a polycyclic hydrocarbon group of the present invention has a good affinity with a color pigment. The resin composition containing the acid-modified compound has excellent resin properties even when the solvent is simply dried. In addition, the cured product obtained by curing the resin composition of the present invention with an active energy ray such as ultraviolet rays has thermal and mechanical toughness, good storage stability, and further, high temperature and high humidity and cold shock. High reliability to withstand. Therefore, the resin composition of the present invention is suitable for molding materials, film forming materials, and resist materials.

  Due to its high affinity with colored pigments, 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 resist materials for color resists and color filters, particularly black Suitable for matrix materials.

  The acid-modified compound of the present invention and the composition containing the acid-modified compound are particularly reliable because of thermal and mechanical toughness, good storage stability, and high reliability withstanding high temperature and high humidity and thermal shock. Are used for applications such as solder resists for printed wiring boards, interlayer insulating materials for multilayer printed wiring boards, solder resists for flexible printed wiring boards, plating resists, and photosensitive optical waveguides.

The reactive epoxycarboxylate compound (A) of the present invention is a compound (b) having both an ethylenically unsaturated group and a carboxy group polymerizable in one molecule on the epoxy resin (a) represented by the general formula (1). And a compound (c) having both a hydroxyl group and a carboxy group in one molecule as required. The reactive epoxycarboxylate compound (A) of the present invention is not integrated into one due to the structure of the epoxy resin (a).
That is, the characteristics of the present invention are exhibited by introducing ethylenically unsaturated groups and hydroxyl groups into the molecular chain of the epoxy resin at an arbitrary ratio.

  About the manufacturing method etc. of the epoxy resin (a) shown by General formula (1), it is well-known and described in patent document 4. FIG. However, the manufacturing method is not limited to that described in Patent Document 4. The epoxy resin (a) is also available as NC-3500 (Nippon Kayaku Co., Ltd.).

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

  The softening point (ring and ball method) of the epoxy resin (a) is 50 ° C. or higher and 150 ° C. or lower, preferably 52 to 100 ° C., particularly preferably 52 to 95 ° C. Below 50 ° C., stickiness is severe, handling is difficult, and productivity is problematic. Moreover, when it exceeds 150 degreeC, it is a temperature near molding temperature, and since the fluidity | liquidity at the time of shaping | molding cannot be ensured, it is unpreferable.

  The epoxy equivalent of the epoxy resin (a) is 180 to 350 g / eq. It is. Especially 190-300 g / eq. Is preferred. Epoxy equivalent is 180 g / eq. When the ratio is less than 1, since the functional group is too much, the cured product after curing has a high water absorption rate and tends to be brittle. Epoxy equivalent is 350 g / eq. In the case where it exceeds 1, the softening point becomes very large, or the epoxidation does not proceed sufficiently and the amount of chlorine becomes very large.

  In addition, the chlorine amount of an epoxy resin (a) is 200-1500 ppm by total chlorine (hydrolysis method), Most preferably, it will be 200-900 ppm. From the JPCA standard, it is desired that epoxy alone does not exceed 900 ppm. A large amount of chlorine in the epoxy resin (a) is not preferable because it affects the electrical reliability. When the concentration is less than 200 ppm, an excessive purification step for dechlorination is required, which causes a problem 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 to 2.0 Pa · s. If the viscosity is high, there will be a problem with fluidity, and there will be a problem with flowability and embedding during pressing. When it is less than 0.05 Pa · s, the molecular weight is too small, and the heat resistance is insufficient.

In the present invention, it is particularly preferable to use an epoxy resin (a) in which the ratio of the formula (i) to the formula (ii) is (i) / (ii) = 1 to 3 in the molar ratio. In the above formula, the molar ratio of (i) to (ii) is (i) / (ii) = 1-3. That is, more than half is a disubstituted glycidyl ether. The reactive epoxycarboxylate compound (A) and reactive polycarboxylic acid compound (B) of the present invention obtained from the epoxy resin (a) within this molar ratio range are excellent in developability and pigment dispersibility, and are cured according to the present invention. The product is excellent in heat resistance, water absorption and toughness.
In the above formula, n is an average value of repeating units and is a positive number of 0 <n ≦ 5. When n is in this range, the developability and coatability are excellent when the resin composition of the present invention is used. When n exceeds 5, the developability and solubility in a solvent of the resin composition of the present invention are lowered.

  The compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxy groups in one molecule used in the present invention is used for imparting reactivity to active energy rays. As the compound (b) having at least one polymerizable ethylenically unsaturated group and at least one carboxy group in one molecule, those having no hydroxyl group in the compound are preferable. Examples of such a compound (b) include a monocarboxylic acid compound and a polycarboxylic acid compound.

  Examples of the monocarboxylic acid compound include (meth) acrylic acids, 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, examples of the acrylic acid include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride and 1 molecule. Half-esters that are (meth) acrylate derivatives having one hydroxyl group and equimolar reactants, half-esters that are equimolar reactants of saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives, etc. Is mentioned.

  Polycarboxylic acid compounds include (meth) acrylate derivatives having a plurality of hydroxyl groups in one molecule and half-esters as equimolar reactants, glycidyl (meth) having a saturated or unsaturated dibasic acid and a plurality of epoxy groups. And half-esters which are equimolar reactants with acrylate derivatives.

  Of these, most preferable are (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid in terms of sensitivity when an active energy ray-curable resin composition is used.

  The compound (c) having one or more hydroxyl groups and one or more carboxy groups in one molecule used in the present invention is used for introducing a hydroxyl group into the reactive epoxycarboxylate 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, one or more hydroxyl groups and two or more in one molecule There are compounds having a carboxy group.

  Examples of the compound having one hydroxyl group and one carboxy group in one molecule include hydroxypropionic acid, hydroxybutanoic acid, hydroxystearic acid and the like. Examples of the compound having two or more hydroxyl groups and one carboxyl group in one molecule include dimethylolacetic acid, dimethylolpropionic acid, and dimethylolbutanoic acid. Examples of the compound having one or more hydroxyl groups and two or more carboxy groups in one molecule include hydroxyphthalic acid.

  Among these, those containing two or more hydroxyl groups in one molecule are preferable in view of the effects of the present invention. Furthermore, it is preferable that the carboxyl group is one in one molecule in view of the stability of the carboxylation reaction. Most preferably, those having two hydroxyl groups and one carboxy group in one molecule are preferred. Considering the availability of raw materials, dimethylolpropionic acid and dimethylolbutanoic acid are particularly suitable. As the compound (c) having one or more hydroxyl groups and one or more carboxy groups in one molecule, those having no polymerizable ethylenically unsaturated group in the compound are preferable.

  Among these, considering the stability of the reaction of the epoxy resin (a) with the compound (b) and the compound (c), the compound (b) and the compound (c) are preferably monocarboxylic acids, Even when carboxylic acid and polycarboxylic acid are used in combination, the value represented by the total molar amount of monocarboxylic acid / the total molar amount of polycarboxylic acid is preferably 15 or more.

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

  On the other hand, by reducing the amount of carboxylic acid compound charged and leaving an unreacted epoxy group, the reactivity due to the introduced unsaturated bond and the reaction due to the remaining epoxy group, for example, a polymerization reaction or thermal polymerization reaction by a photocationic catalyst, can be performed. It can also be used in combination. In this case, however, attention should be paid to the storage of the reactive epoxycarboxylate compound and the examination of the production conditions.

  When producing the reactive epoxycarboxylate compound (A) that does not leave an epoxy group, 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). Is preferred. If it is this range, it will not gelatinize in reaction and manufacture on comparatively stable conditions is possible.

  Moreover, when leaving an unreacted epoxy group, it is preferable that the sum 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 deviating from this range, the effect of the composite curing is reduced. In this case, sufficient attention must be paid to the gelation during the reaction and the temporal stability of the reactive epoxycarboxylate compound (A).

  The use ratio of the compound (b) to the compound (c) is preferably in the range of (b) :( c) from 9: 1 to 1: 9, and more preferably from 4: 6 to 8: 2, in the molar ratio to the carboxylic acid. Within this range, sensitivity, developability and pigment dispersibility are good.

  This carboxylation reaction can be carried out without a solvent or diluted with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the carboxylation reaction. The amount of the solvent used is preferably adjusted as appropriate depending on the viscosity and use of the resin obtained, but is 90 to 30% by mass, preferably 80 to 50% by mass, based on the solid content in the resin composition of the present invention. % Solvent is used.

  Specific examples of what can be used as the above solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane and decane, and Examples thereof include petroleum ether, white gasoline, and solvent naphtha. Examples of ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, Mono- or polyalkylene glycol monoalkyl ether monoacetates such as triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, adipine Polyesters of polycarboxylic acids such as dialkyl acids Kind, and the like. Examples of ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether. Glycol ethers, and cyclic ethers such as tetrahydrofuran. Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

  In addition, it can carry out in single or mixed organic solvents, such as reactive compounds (C) other than (A) and (B). In this case, when it is used as a curable composition, it can be used directly as a composition, which is preferable.

  In the reaction, it is preferable to use a catalyst to promote the reaction. The amount of the catalyst used is a reaction product, that is, a reaction product to which the epoxy resin (a), the compound (b), and optionally a solvent or the like are added. It is 0.1-10 mass% with respect to the total amount of. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, Examples include known general basic catalysts such as zirconium octoate.

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

  The end point of this reaction is the time when the acid value of the sample is 5 mg · KOH / g or less, preferably 2 mg · KOH / g or less, while sampling appropriately.

  The molecular weight range of the reactive epoxycarboxylate compound (A) thus obtained is a polystyrene-reduced mass average molecular weight in GPC in the range of 1,000 to 30,000, preferably 1,500 to 20,000. . When the molecular weight is smaller than this, the toughness of the cured product is not sufficiently exhibited, and when it is larger than this, the viscosity becomes high and coating or the like becomes difficult.

  Next, the acid addition step will be described in detail. The acid addition step is performed for the purpose of obtaining a reactive polycarboxylic acid compound (B) by introducing a carboxy group into the reactive epoxycarboxylate compound (A) obtained in the previous step as necessary. As a reason for introducing a carboxy group, for example, in applications where resist patterning or the like is required, the active energy ray non-irradiated part is given solubility in alkaline water, and adhesion to metals, inorganic substances, etc. is given. It is introduced with the purpose of. Specifically, a carboxyl group is introduced via an ester bond by addition reaction of a polybasic acid anhydride (d) to a hydroxyl group generated by a carboxylation reaction.

  As specific examples of the polybasic acid anhydride (d), for example, any compound having an acid anhydride structure in one molecule can be used. For example, it can be used in alkaline aqueous solution developability, heat resistance, and hydrolysis resistance. Excellent succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride Acid is particularly preferred.

  The reaction for adding the polybasic acid anhydride (d) can be performed by adding the polybasic acid anhydride (d) to the carboxylation reaction solution. The amount added should be changed as appropriate according to the application.

  However, when the reactive polycarboxylic acid compound (B) of the present invention is to be used as an alkali development resist, the reactive polycarboxylic acid compound (B) finally obtained from the polybasic acid anhydride (d) is used. ) Is preferably 30 to 120 mg · KOH / g, preferably 40 to 105 mg · KOH / g, based on JIS K5601-2-1: 1999. When the solid content acid value at this time is within this range, the aqueous alkaline solution developability of the resin composition of the present invention exhibits good developability. That is, good patternability and a wide control range for over-development are possible, and no excess acid anhydride remains.

  During the reaction, it is preferable to use a catalyst to promote the reaction. The amount of the catalyst used is the addition of the reactive epoxycarboxylate compound (A) and the polybasic acid anhydride (d), optionally a solvent or the like. It is 0.1-10 mass% with respect to the total amount of the reaction material. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, Examples include zirconium octoate.

  The acid addition reaction can be performed without a solvent or diluted with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent that does not react with the acid addition reaction. In addition, in the case of producing using a solvent in the carboxylation reaction that is the previous step, it may be subjected directly to the acid addition reaction that is the next step without removing the solvent, provided that both reactions are inert. it can. The preferred amount of solvent used should be adjusted as appropriate depending on the viscosity and intended use of the resin obtained, but preferably 90-30% by mass as the solid content, more preferably 80-50% by mass. Use.

  In addition, it can carry out in the single or mixed organic solvent of the reactive compound (C) etc. which are mentioned later. In this case, it can be directly used as a composition after the reaction.

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

  In this reaction, the end point is determined when the acid value of the reaction product is within a 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, cation-reactive other epoxy compounds, and vinyl compounds sensitive to both. Can be mentioned.

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

  Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, Examples include phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

  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, 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, hydrogen Ε-Caprola of bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, and neopent glycol hydroxybivalate Tone adduct di (meth) acrylate, poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, reaction product of dipentaerythritol and ε-caprolactone, 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) acrylate and its ethylene oxide adduct, etc. Is mentioned.

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

  Furthermore, as so-called reactive oligomers, urethane acrylate having a functional group capable of acting on active energy rays and a urethane bond in the same molecule, and similarly a functional group capable of acting on active energy rays and an ester bond in the same molecule. Examples thereof include polyester acrylate, epoxy acrylate derived from an epoxy resin, and epoxy acrylate having a functional group capable of acting on active energy rays in the same molecule, and a reactive oligomer in which these bonds are used in combination.

  The cation reactive monomer is not particularly limited as long as it is generally a compound having an epoxy group. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4, -epoxycyclohexanecarboxylate (“Union Carbide” SyraCure UVR-6110 "), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (such as" ELR-4206 "manufactured by Union Carbide), limonene dioxide (Daicel Chemical Industries) “Celoxide 3000”, etc.), allyl cyclohexylene dioxide, 3,4, -epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxy) Cyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate (such as “Syracure UVR-6128” manufactured by Union Carbide), bis (3,4 -Epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane and the like.

  Of these, the reactive compound (C) is most preferably an acrylate that is radically curable. In the case of the cation type, the carboxylic acid and the epoxy react with each other, so that a two-component mixed type is required.

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

  The resin composition of the present invention contains 97 to 5% by mass of the reactive epoxycarboxylate compound (A) and / or the reactive polycarboxylic acid compound (B) in the composition, preferably 87 to 10% by mass, (A). , (B) 3 to 95% by mass of the reactive compound (C), more preferably 3 to 90% by mass. If necessary, other components may be contained up to about 70% by mass.

  The reactive epoxycarboxylate compound (A) or the reactive polycarboxylic acid compound (B) in the resin composition of the present invention can be appropriately used depending on the application. For example, the reactive epoxy carboxylate compound (A) is used in the case of the so-called solvent development type in which a pattern is formed by a printing method or unreacted sites are washed away by a solvent or the like without developing even in the same solder resist application. In the case of 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 application from the viewpoint that the alkaline water development type can easily form a fine pattern. Of course, there is no problem even if (A) and (B) are used in combination.

  The resin composition of the present invention is easily cured by active energy rays. 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, particle rays such as alpha rays, beta rays and electron rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.

The color pigment that can be used in the present invention is used to make the resin composition of the present invention a coloring material.
In the present invention, since the color pigment is well dispersed, the pigment concentration can be increased. Also in the case of development, since the dispersion is in a good state, the patterning characteristics are excellent, and the development residue in the development dissolution portion is small.

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

  In the present invention, the molding material refers to a material in which an uncured composition is put in a mold, or a mold is pressed against an uncured composition and an object is molded, and then a curing reaction is caused by active energy rays to be molded, or It refers to a material used for applications in which an uncured composition is irradiated with a focused light such as a laser to cause a curing reaction to be molded.

  Specific applications include a sheet formed into a flat shape, a sealing material for protecting the element, a so-called nanoimprint material that performs fine molding by pressing a "mold" that has been micro-processed into an uncured composition, Furthermore, particularly suitable applications include peripheral sealing materials such as light-emitting diodes and photoelectric conversion elements, which have particularly severe thermal requirements.

  In the present invention, the film forming material is used for the purpose of coating the surface of a substrate. Specific applications include gravure inks, flexo inks, silk screen inks, offset inks and other ink materials, hard coats, top coats, overprint varnishes, clear coats and other coating materials, laminating, optical disk and other various adhesives. Such materials include adhesive materials such as adhesives and adhesives, resist materials such as solder resists, etching resists, and resists for micromachines. Furthermore, a film-forming material is temporarily applied to a peelable substrate to form a film, and then a so-called dry film in which a film is formed by being bonded to the originally intended substrate also corresponds to the film-forming material. .

  Among these, the introduction of the carboxy group of the reactive polycarboxylic acid compound (B) increases the adhesion to the base material. Therefore, the reactive polycarboxylic acid for the reaction for coating the plastic base material or the metal base material. Taking advantage of the feature that the compound (B) is soluble in an alkaline 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 means that a film layer of the composition is formed on a substrate, and then an active energy ray such as ultraviolet rays is partially irradiated to utilize the physical difference between an irradiated part and an unirradiated part. Then try to draw. Specifically, the irradiated part or the unirradiated part is removed by some method, for example, by dissolving with a solvent or an alkaline solution, 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, for example, a solder resist material and an interlayer insulating material for a build-up method, and further, as an optical waveguide, a printed wiring board, an optoelectronic substrate, a light It is also used for electrical / electronic / optical substrates such as substrates.

  As a particularly suitable application, taking advantage of the property that a tough cured product can be obtained, making use of a permanent resist application such as a solder resist, and the property of good pigment dispersibility, printing inks, color filters, etc. The use of a color resist, particularly a black matrix resist is preferred.

  The resin composition of the present invention is particularly suitably used as a dry film application requiring mechanical strength before a curing reaction by energy rays. That is, since the balance of the hydroxyl group and epoxy group of the epoxy resin (a) used in the present invention is in a specific range, the reactive epoxy carboxylate compound (A) and the reactive polycarboxylic acid compound (B) of the present invention. Although it has a relatively high molecular weight, good developability can be exhibited.

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

  The cured product of the resin composition of the present invention refers to a product obtained by irradiating and curing the active energy ray on the resin composition of the present invention.

  In addition, for the purpose of adapting the resin composition of the present invention to various uses, other components can be added to the resin composition with an upper limit of 70% by mass. Examples of other components include a photopolymerization initiator, other additives, other color pigments, and a volatile solvent added for viscosity adjustment for the purpose of imparting coating suitability. Examples of other components that can be used are shown below.

  Examples of the radical photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloro Acetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxylcyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane- Acetophenones such as 1-one; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; 2,4-diethylthioxanthone, 2- Thioxanthones such as sopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone, etc. Benzophenones of the above; known general radical photopolymerization initiators such as phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide .

  As cationic photopolymerization initiators, Lewis acid diazonium salt, Lewis acid iodonium salt, Lewis acid sulfonium salt, Lewis acid phosphonium salt, other halides, triazine initiator, borate initiator, And other photoacid generators.

  Examples of the diazonium salt of Lewis acid include p-methoxyphenyldiazonium fluorophosphonate, N, N-diethylaminophenyldiazonium hexafluorophosphonate (Sun Shine SI-60L / SI-80L / SI-100L, etc., manufactured by Sanshin Chemical Industry Co., Ltd.) and the like. Examples of Lewis acid iodonium salts include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate. Examples of Lewis acid sulfonium salts include triphenylsulfonium hexafluorophosphonate (Cyracure UVI-6990 manufactured by Union Carbide). And triphenylsulfonium hexafluoroantimonate (such as Cyracure UVI-6974 manufactured by Union Carbide) Gerare, the phosphonium salt of a Lewis acid, triphenyl phosphonium hexafluoroantimonate, and the like.

  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). ) Etanone (Sandray 1000 manufactured by Sandoz), α, α, α-tribromomethylphenylsulfone (BMPS manufactured by Iron Chemical Co., Ltd.) 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 Panchi), 2, 4-trichloromethyl- (4′-methoxystyryl) -6-triazine (such as Triazine PMS manufactured by Panchim), 2,4-trichloromethyl- (pipronyl) -6-triazine (such as Triazine PP manufactured by Panchim), 2, 4-trichloromethyl- (4′-methoxynaphthyl) -6-triazine (such as Triazine B manufactured by Panchim), 2 [2 ′ (5 ″ -methylfuryl) ethylidene] -4,6-bis (trichloromethyl)- s-triazine (manufactured by Sanwa Chemical Co., Ltd.), 2 (2'- Lil ethylidene) -4,6-bis (trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd.).

Examples of the borate initiator include NK-3876 and NK-3881 manufactured by Nippon Senshoku Dye Co., Ltd. Other photoacid generators include 9-phenylacridine, 2,2′-bis (o-chlorophenyl)- 4,4 ′, 5,5′-tetraphenyl-1,2-biimidazole (such as biimidazole manufactured by Kurokin Kasei), 2,2-azobis (2-amino-propane) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) V50), 2,2-azobis [2- (imidazolin-2-yl) propane] dihydrochloride (VA044 manufactured by Wako Pure Chemical Industries, Ltd.), (η ⁵ -2-4-cyclopentadien-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) and the like.

  In addition, an azo initiator such as azobisisobutyronitrile, a peroxide radical initiator sensitive to heat such as benzoyl peroxide, and the like may be used in combination. Further, both radical and cationic initiators may be used in combination. One initiator can be used alone, or two or more initiators can be used in combination.

  Other additives include, for example, thermosetting catalysts such as melamine, thixotropy imparting agents such as Aerosil, silicone-based and fluorine-based leveling agents and antifoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, oxidation An inhibitor or the like can be used.

  Further, as other coloring materials, for example, those not intended for coloring, so-called extender pigments can be used. Examples include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay and the like.

  Other resins that are not reactive with active energy rays (so-called inert polymers), such as other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene Resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof can also be used. These are preferably used in the range of up to 40% by mass in the resin composition of the present invention.

  In particular, when the reactive polycarboxylic acid compound (B) is to be used for solder resist applications, it is preferable to use a known general epoxy resin as a resin that does not show reactivity to active energy rays. This is because the carboxy group derived from the reactive polycarboxylic acid compound (B) remains even after being reacted and cured by active energy rays, and as a result, the cured product is inferior in water resistance and hydrolyzability. By using an epoxy resin, the remaining carboxyl group is further carboxylated to form a stronger cross-linked structure.

  Depending on the purpose of use, for the purpose of adjusting the viscosity, a volatile solvent may be added to the resin composition in a range of 50% by mass, preferably 35% by mass.

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

The softening point and epoxy equivalent were measured under the following conditions.
1) Epoxy equivalent: Measured by a method according to JIS K 7236: 2001.
2) Softening point: measured by a method according to JIS K 7234: 1986 3) Acid value: measured by a method according to JIS K 0070: 1992 4) GPC measurement conditions are as follows.
Model: TOSOH HLC-8220GPC
Column: TSKGEL Super HZM-N
Eluent: THF (tetrahydrofuran); 0.35 ml per minute. 40 ° C
Detector: Differential refractometer Molecular weight standard: Polystyrene

Synthesis example 1
A flask equipped with a thermometer, condenser, and stirrer was charged with 316 parts of phenol and 158 parts of resorcin, and the temperature was raised to 100 ° C. Then, 201 parts of 4,4′-bischloromethylbiphenyl was added in portions over 2 hours. And further reacted at the same temperature for 5 hours. Thereafter, the temperature was raised to 160 ° C. and all 4,4′-bischloromethylbiphenyl was reacted. Meanwhile, HCl formed was distilled off by trapping with alkali. After completion of the reaction, 266 parts of phenol resin (P-1) was obtained by distilling off unreacted phenol and unreacted resorcin at 180 ° C. under reduced pressure using a rotary evaporator. The obtained phenol resin (P-1) has a hydroxyl group equivalent of 137 g / eq. The softening point was 94 ° C., the ICI viscosity was 470 mPa · s, and the dihydric phenol introduction ratio was 64%.

Synthesis example 2
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen while 266 parts of the phenol resin (P-1) obtained in Synthesis Example 1, 719 parts of epichlorohydrin, 72 parts of methanol, 21 parts of water And heated up to 75 ° C. Next, 83 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 75 ° C. for 75 minutes. After completion of the reaction, washing was performed, and excess solvent such as epichlorohydrin was distilled off from the organic layer under reduced pressure at 140 ° C. using a rotary evaporator. To the residue, 750 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 75 ° C. Under stirring, 52 parts of a 30% aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour. The organic layer was washed with water until the washing water became neutral, and the pressure was reduced at 180 ° C. using a rotary evaporator. A solvent such as methyl isobutyl ketone was distilled off to obtain 338 parts of an epoxy resin (EP1). The epoxy equivalent of the obtained epoxy resin (EP1) was 209 g / eq. The softening point was 71 ° C., the viscosity at 150 ° C. was 370 mPa · s, and the introduction ratio of the divalent glycidyl-substituted phenyl group was 68%.

Synthesis example 3
A flask equipped with a thermometer, condenser, and stirrer was charged with 316 parts of phenol and 126 parts of resorcin, and the temperature was raised to 100 ° C. Then, 201 parts of 4,4′-bischloromethylbiphenyl was added in portions over 2 hours. And further reacted at the same temperature for 5 hours. Thereafter, the temperature was raised to 160 ° C. and all 4,4′-bischloromethylbiphenyl was reacted. Meanwhile, HCl formed was distilled off by trapping with alkali. After completion of the reaction, 194 parts of phenol resin (P-2) was obtained by distilling off unreacted phenol and unreacted resorcin under reduced pressure at 180 ° C. using a rotary evaporator. The phenolic resin (P-2) obtained had a hydroxyl group equivalent of 141 g / eq. The softening point was 89 ° C., the ICI viscosity was 446 mPa · s, and the proportion of dihydric phenol introduced was 51%.

Synthesis example 4
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 282 parts of the phenol resin (P-2) obtained in Synthesis Example 3 while performing nitrogen purge, 719 parts of epichlorohydrin, 72 parts of methanol, 21 parts of water And heated up to 75 ° C. Next, 83 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 75 ° C. for 75 minutes. After completion of the reaction, washing was performed, and excess solvent such as epichlorohydrin was distilled off from the organic layer under reduced pressure at 140 ° C. using a rotary evaporator. To the residue, 750 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 75 ° C. Under stirring, 52 parts of a 30% aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour. The organic layer was washed with water until the washing water became neutral, and the pressure was reduced at 180 ° C. using a rotary evaporator. Below, 352 parts of an epoxy resin (EP2) was obtained by distilling off a solvent such as methyl isobutyl ketone. The epoxy equivalent of the obtained epoxy resin (EP2) was 215 g / eq. The softening point was 78 ° C., the viscosity at 150 ° C. was 410 mPa · s, and the introduction ratio of the divalent glycidyl-substituted phenyl group was 55%.

Synthesis example 5
A flask equipped with a thermometer, a condenser, and a stirrer was charged with 316 parts of phenol and 179 parts of resorcin, heated to 100 ° C., and then 201 parts of 4,4′-bischloromethylbiphenyl was added in portions over 2 hours. And further reacted at the same temperature for 5 hours. Thereafter, the temperature was raised to 160 ° C. and all 4,4′-bischloromethylbiphenyl was reacted. Meanwhile, HCl formed was distilled off by trapping with alkali. After completion of the reaction, 300 parts of phenol resin (P-3) was obtained by distilling off unreacted phenol and unreacted resorcin at 180 ° C. under reduced pressure using a rotary evaporator. The obtained phenol resin (P-3) has a hydroxyl group equivalent of 127 g / eq. The softening point was 112 ° C., the ICI viscosity was 2.0 Pa · s, and the dihydric phenol introduction ratio was 70%.

Synthesis Example 6
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen, and 254 parts of the phenol resin (P-3) obtained in Synthesis Example 5; 719 parts of epichlorohydrin; 72 parts of methanol; 21 parts of water And heated up to 75 ° C. Next, 83 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 75 ° C. for 75 minutes. After completion of the reaction, washing was performed, and excess solvent such as epichlorohydrin was distilled off from the organic layer under reduced pressure at 140 ° C. using a rotary evaporator. To the residue, 750 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 75 ° C. Under stirring, 52 parts of a 30% aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour. The organic layer was washed with water until the washing water became neutral, and the pressure was reduced at 180 ° C. using a rotary evaporator. 312 parts of epoxy resins (EP3) were obtained by distilling off solvents, such as methyl isobutyl ketone below. The epoxy equivalent of the obtained epoxy resin (EP3) was 194 g / eq. The softening point was 91 ° C., the viscosity at 150 ° C. was 1.2 Pa · s, and the introduction ratio of the divalent glycidyl-substituted phenyl group was 74%.

Example 1 Synthesis of Reactive Epoxy Carboxylate Compound (A) As epoxy resin (a), the epoxy resins obtained in Synthesis Example 2, Synthesis Example 4 and Synthesis Example 6 were used in the amounts shown in Table 1 as compound (b). Acrylic acid (abbreviation AA, Mw = 72) was added in the amount shown in Table 1, and dimethanolpropionic acid (abbreviation DMPA, Mw = 134) was added in Table 1 as the compound (c). 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent are added so as to be 80% by mass of the solid content of the reaction solution, reacted at 100 ° C. for 24 hours, and a reactive epoxycarboxylate compound (A) solution Got. The reaction end point was determined by solid content acid value (AV), and the measured values are shown in Table 1. The acid value was measured with a reaction solution and converted into an acid value as a solid content.

Comparative Example 1-1: Synthesis of reactive epoxycarboxylate compound to be compared NC-3000H (manufactured by Nippon Kayaku Co., Ltd., softening point 70 ° C., epoxy equivalent 288 g / eq.) 288 g, AA as compound (b) DMPA was added in the amount shown in Table 1 as the compound (c). 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added to a solid content of 80% by mass and reacted at 100 ° C. for 24 hours to obtain a reactive epoxycarboxylate compound solution. The reaction end point was determined by solid content acid value (AV), and the measured values are shown in Table 1. The acid value was measured with a reaction solution and converted into an acid value as a solid content.

Comparative Example 1-2: Synthesis of reactive epoxycarboxylate compound to be compared 200 g of cresol novolac type epoxy resin EOCN-103S (manufactured by Nippon Kayaku Co., Ltd., softening point 80 ° C., epoxy equivalent 200 g / eq.), Compound ( The amount of AA described in Table 1 was added as b), and the amount of DMPA described in Table 1 was added as compound (c). 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added to a solid content of 80% by mass and reacted at 100 ° C. for 24 hours to obtain a reactive epoxycarboxylate compound solution. The reaction end point was determined by solid content acid value (AV), and the measured values are shown in Table 1. The acid value was measured with a reaction solution and converted into an acid value as a solid content.

注）ＡＡ量のモル比はエポキシ樹脂（ａ）に対するＡＡ（ｂ）モル比である。
ＤＭＰＡ量のモル比はエポキシ樹脂（ａ）に対するＤＭＰＡ（ｃ）モル比である。

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

Example 2 Synthesis of Reactive Polycarboxylic Acid Compound (B) Tetrahydrophthalic anhydride (abbreviated as polybasic acid anhydride (d) was added to each of the reactive epoxycarboxylate compound (A) solutions obtained in Example 1. Reactive polycarboxylic acid compound by adding propylene glycol monomethyl ether monoacetate so that the solid content in the reaction solution is 65% by mass with the amount of THPA) listed in Table 2 and a solvent, and heating to 100 ° C. (B) A solution was obtained.

Comparative Example 2: Synthesis of Reactive Polycarboxylic Acid Compound THPA was listed in Table 2 as a polybasic acid anhydride (d) in the reactive epoxycarboxylate compound solution obtained in Comparative Examples 1-1 and 1-2. Further, propylene glycol monomethyl ether monoacetate was added as a solvent so that the solid content was 65% by mass, and the mixture was heated to 100 ° C. for acid addition reaction to obtain a reactive polycarboxylic acid compound solution.

Example 3 and Comparative Example 3: Preparation of composition for hard coat 20 g of the reactive epoxycarboxylate compound (A) synthesized in Example 1 and Comparative Example 1, and a radical curable type monomer as the other reactive compound (C) Dipentaerythritol hexaacrylate (6.0 g) as a body and 1.5 g of Irgacure 184 as an ultraviolet reactive initiator were added and dissolved by heating. Further, this was coated on a polycarbonate plate with a hand applicator so as to have a film thickness of 20 μm at the time of drying, and the solvent was dried in an electric oven at 80 ° C. for 30 minutes. After drying, a multilayer material was obtained by irradiating and curing ultraviolet rays with an irradiation dose of 1000 mJ using an ultraviolet vertical exposure apparatus (Oak Seisakusho) equipped with a high-pressure mercury lamp. The hardness of the coating film of this multilayer material was measured according to JIS K5600-5-4: 1999, and an impact resistance test was performed according to ISO6272-1: 2002.

○：傷、はがれなし。△：僅かに傷あり、×：剥がれた

○: No scratch or peeling. Δ: Slightly scratched, ×: Peeled

  As is apparent from the above results, the hardness and impact resistance of the examples were improved as compared with Comparative Examples 3-1 and 3-2. The reason for this is considered to be that the crosslinking density is improved by the structure A in the epoxy resin (a) represented by the general formula (1).

Example 4 and Comparative Example 4: Preparation of dry film type resist composition 56.73 g of the reactive polycarboxylic acid compound (B) obtained in Example 2 and Comparative Example 2 and DPCA as the other reactive compound (C) -60 (trade name: polyfunctional acrylate manufactured by Nippon Kayaku Co., Ltd.), 2.92 g of Irgacure 907 (manufactured by BASF) as a photopolymerization initiator and Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) 0.58 g, NC-3000H (Nippon Kayaku Co., Ltd.) 17.54 g as a curing component, 0.73 g melamine as a thermosetting catalyst, and 5.67 g propylene glycol monomethyl ether monoacetate as a concentration adjusting solvent Then, the mixture was kneaded with a bead mill and uniformly dispersed to obtain a resist resin composition. The obtained composition was 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., and a resin layer having a thickness of 20 μm was formed. A polyethylene film serving as a protective film was pasted on the resin layer to obtain a dry film. The obtained dry film was applied to a polyimide printed circuit board (copper circuit thickness: 12 μm, polyimide film thickness: 25 μm) using a heating roll at a temperature of 80 ° C., and a resin layer was attached to the entire surface of the substrate while peeling off the protective film. The (A) and (B) mixed products used in Example 4-4 are the same as those shown in Example 1-2 as the reactive epoxycarboxylate compound (A), and the reactive polycarboxylic acid compound ( B) What was shown in Example 2-2 was mixed at a solution mass of 50:50.

Next, in order to estimate the mask on which the circuit pattern was drawn and sensitivity using an ultraviolet exposure apparatus (Oak Manufacturing Co., Ltd., model HMW-680GW), Kodak Step Tablet No. 2 was irradiated with ultraviolet rays of 500 mJ / cm ² . Then, the film on a dry film was peeled and the peeling state was confirmed. Thereafter, spray development was performed with a 1% aqueous sodium carbonate solution to remove the resin on the non-irradiated part of the ultraviolet rays. After washing with water and drying, the printed circuit board was subjected to a heat curing reaction in a hot air drier at 150 ° C. for 60 minutes to obtain a cured film.

<Sensitivity evaluation>
Sensitivity was determined by how many density portions remained in the exposed portion that passed through the step tablet during development. The higher the number of steps (value), the higher sensitivity is determined in the dark part of the tablet (unit: step).

<Developability evaluation>
The developability was evaluated based on the time until the pattern shape portion was completely developed, that is, the so-called break time when developing the exposed portion that passed through the pattern mask (unit: second).

<Curability evaluation>
The evaluation of curability was shown by the pencil hardness of the cured film after heating at 150 ° C. The evaluation method was based on JIS K5600-5-4: 1999.

<Folding resistance evaluation>
The polyimide printed circuit board on which the cured film of the resist was formed was folded in a mountain with the cured film side up, and the bent portion was rubbed with fingers. The bent portion was returned to its original position, and the resist film was observed with a magnifying glass.
○: No crack Δ: Slight crack is observed ×: Peel

  As is apparent from the above results, the resin composition of the present invention has high hardness and high folding resistance. Also, it has good developability and sensitivity as a resist.

Example 5 and Comparative Example 5: Evaluation of Flame Retardancy 10.0 g of the resin composition of the present invention and comparative example prepared in Example 4 and Comparative Example 4, phosphorus-based reactive flame retardant (FRM-1000 Nippon Kayaku ( 0.5 g) was mixed and stirred. The composition was applied to a polyimide film having a film 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. The resin layer was irradiated with ultraviolet rays of 500 mJ / cm ² using an ultraviolet exposure device (Oak Manufacturing Co., Ltd., model HMW-680GW). After irradiation, the resin layer was subjected to a heat curing reaction for 60 minutes in a hot air dryer at 150 ° C. to obtain a cured film. The obtained cured film was cut out together with the polyimide base film in a strip shape having a length of 20 cm and a width of 2 cm. The cut out film was suspended vertically and lit with a lighter from the lower end to evaluate flame retardancy (Table 5).
○: Ignite but extinguish before burning.
X: It burns out completely.
In order to compare with folding resistance, the data of Example 4 and Comparative Example 4 are also described for reference. Evaluation and evaluation results are in accordance with Example 4 and Comparative Example 4.

  From the above results, it became clear that the reactive polycarboxylic acid compound (B) of the present invention is a material having both flame retardancy and folding resistance.

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

  As apparent from the above results, the coating film obtained from the resin composition containing the reactive polycarboxylic acid compound (B) obtained in Example 2 has a gloss value even when the content of the color pigment is large. There was no change. On the other hand, the gloss of the reactive polycarboxylic acid compound of Comparative Example 2-1 decreased as the content of the color pigment increased. The reactive polycarboxylic acid compound of Comparative Example 2-2 has a low gloss value and a low content dispersibility even when the content of the color pigment is small. The pigment dispersibility of the reactive polycarboxylic acid compound (B) of the present invention is excellent without depending on the content of the color pigment.

  The resin composition of the present invention is a material having both curability, flexibility, toughness, and flame retardancy, hard coat materials, resist materials that require flexibility for alkali development, and good pigment dispersibility. Indicates the application to use. In particular, active energy ray-curable printing inks, color resists, and materials suitable for resists such as pigment dispersibility and developability are 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 polymerizable in one molecule, and, if necessary, a hydroxyl group and A reactive epoxycarboxylate compound (A) obtained by reacting a compound (c) having a carboxy group.

(In the formula, each A is independently either (i) or (ii), and the molar ratio of (i) and (ii) is (i) / (ii) = 1-3. G is Represents a glycidyl group, where n is an average value of the number of repetitions and is a positive number of 0 <n ≦ 5.) The reactive epoxycarboxylate compound (A) according to claim 1, wherein (i) is (i) represented by the 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). A resin composition comprising the reactive epoxycarboxylate compound (A) according to claim 1 or 2 and / or the reactive polycarboxylic acid compound (B) according to claim 3. The resin composition according to claim 4, comprising a reactive compound (C) other than the reactive epoxycarboxylate compound (A) and the reactive polycarboxylic acid compound (B). The resin composition according to claim 4 or 5, comprising a photopolymerization initiator. The resin composition according to any one of claims 4 to 6, comprising a color pigment. The resin composition according to any one of claims 4 to 7, which is a molding material. The resin composition according to claim 4, wherein the resin composition is a film forming material. The resin composition according to any one of claims 4 to 7, which is a resist material. The hardened | cured material of the resin composition as described in any one of Claims 4 thru | or 10. An article overcoated with the cured product according to claim 11.