JP2009102501A - Novel epoxy carboxylate compound, its derivative, active energy ray-curable resin composition containing it and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition that is cured by an active energy ray or the like such as an ultraviolet ray or the like and is capable of producing a tough film or a molding material. <P>SOLUTION: An epoxy carboxylate compound produced by reacting an epoxy resin containing a polycyclic hydrocarbon group having a specific structure with a compound having both a polymerizable unsaturated group and a carboxyl group in a molecule and a compound having both a hydroxyl group and a carboxyl group in a molecule is provided. A polycarboxylic acid compound being an acid modified product of the epoxy carboxylate compound is provided. An active energy ray-curable resin composition containing the epoxy carboxylate compound and the acid modified product thereof is provided. A cured product of the active energy ray-curable resin composition is provided. The cured product has not only high reliability and toughness but also good pigment dispersibility. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an epoxy resin (a) having a polycyclic hydrocarbon group having a specific structure, a compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, and one molecule. An epoxycarboxylate compound (A) obtained by reacting a compound (c) having both a hydroxyl group and a carboxy group, a polycarboxylic acid compound (B) which is an acid-modified product thereof, an active energy ray-curable resin composition containing them, Moreover, it relates to the cured product. These epoxy carboxylate compound (A) and polycarboxylic acid compound (B) have good affinity for the pigment, and a tough cured product can be obtained from the resin composition containing them.

  Printed wiring boards are required to have higher precision and higher density in order to reduce the size and weight of portable devices and improve communication speed. With this, the demand for solder resist that covers the circuit itself of the wiring board is becoming increasingly sophisticated. Therefore, there is a demand for heat resistance and thermal stability that are higher than conventional requirements, as well as high reliability, that is, performance that can withstand high-temperature and high-humidity conditions and thermal shock.

Patent Document 1 describes an acid-modified epoxy acrylate compound having an epoxy resin having a polycyclic hydrocarbon group as a basic skeleton and a cured product thereof, and is also known to have relatively high toughness after curing. It has been. A solder resist using the same is also described.
Although this solder resist has a relatively high reliability, it does not satisfy the higher reliability required in recent years with the digitization of transportation equipment and the like.

  On the other hand, Patent Document 2 describes an epoxy carboxylate compound obtained by reacting a general epoxy resin with a carboxylic acid compound having acrylic acid and a hydroxyl group, and has excellent developability while having a low acid value. Further, it is described that this compound has resist ink suitability, but the performance is insufficient.

  Also known is an attempt to disperse a color pigment such as carbon black in an acid-modified epoxy acrylate compound having an epoxy resin having a polycyclic hydrocarbon group as a basic skeleton and to apply it to a black matrix resist used in a liquid crystal display panel or the like. ing. (Patent Document 3)

In this application, even when a coloring pigment such as carbon black is blended at a high concentration, the pigment is favorably dispersed with affinity to the resin, thereby exhibiting good developability and enabling development without pigment residue. Although these conventional acid-modified epoxy acrylates exhibit relatively good dispersibility, developability at a higher pigment concentration, that is, higher pigment dispersibility has been demanded. And when it was set as the pigment dispersion in order to acquire affinity with a favorable colored pigment, there existed a fault that the dispersion liquid aggregated pseudo | simulated and the storage stability of the dispersion liquid was not good.
Japanese Patent Laid-Open No. 5-214048 JP-A-6-324490 JP 2004-295094 A

Although the curable resin composition containing an epoxy resin having a polycyclic hydrocarbon group can obtain a relatively tough cured material, it is problematic for use in a material that requires extremely high reliability such as transportation equipment. There is.
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. At this time, it is necessary to have a relatively high molecular weight and appropriate developability.

In order to solve the above-mentioned problems, the present inventors have prepared a compound (b) having both an ethylenically unsaturated group polymerizable in one molecule and a carboxy group in an epoxy resin having a polycyclic hydrocarbon group having a specific structure. An epoxycarboxylate compound (A) obtained by reacting a compound (c) having both a hydroxyl group and a carboxy group in one molecule, and a polycarboxylic acid compound obtained by reacting it with a polybasic acid anhydride (d) It was found that (B) has particularly excellent resin properties.
Furthermore, it has been found that it has a particularly good affinity with colored pigments, and that the resulting composition can be a resist material having good developability even at a high pigment concentration.

［式中、Ｒは同一でも異なっていてもよく、水素原子、ハロゲン原子又は炭素数１〜４の炭化水素基を示し、ｎは平均値で１〜１０の正数を示す。］ That is, the present invention relates to an epoxy resin (a) represented by the following general formula (1), a compound (b) having both an ethylenically unsaturated group polymerizable in one molecule and a carboxy group, and a hydroxyl group in one molecule. The present invention relates to an epoxycarboxylate compound (A) obtained by reacting a compound (c) having a carboxy group.

[Wherein, R may be the same or different and each represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and n represents an average value of 1 to 10 positive numbers. ]

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

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

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

Furthermore, it is related with the hardened | cured material of said active energy ray hardening-type resin composition.
Furthermore, the present invention relates to an article overcoated with a cured product of the active energy ray-curable resin composition.

  The active energy ray-curable resin composition containing an epoxy resin having a polycyclic hydrocarbon group having a specific structure and / or an acid-modified compound thereof according to the present invention not only obtains a tough cured product but also only dries the solvent. Even in this state, it has excellent resin properties. In addition, a cured product obtained by curing the active energy ray-curable resin composition of the present invention with active energy rays such as ultraviolet rays has thermal and mechanical toughness, good storage stability, and high temperature and high temperature. It can be suitably used for a film-forming material having high reliability that can withstand moisture and cold shock.

  Suitably, for example, it can be 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, photosensitive optical waveguides and the like that require particularly high reliability. I can do it.

  Furthermore, it has a high affinity with colored pigments such as carbon black, and can exhibit good developability even at high pigment concentrations, and resist materials for color resists, color filters, especially black matrix materials, etc. Also, it can be suitably used.

The epoxy carboxylate compound (A) of the present invention comprises the compound (b) having both an ethylenically unsaturated group and a carboxyl group polymerizable in one molecule in the epoxy resin (a) represented by the above formula (1). It is obtained by reacting a compound (c) having both a hydroxyl group and a carboxy group in the molecule.
That is, the characteristics of the present invention are exhibited by simultaneously introducing an ethylenically unsaturated group and a hydroxyl group into the molecular chain of the epoxycarboxylate compound at an arbitrary ratio.

  The epoxy resin (a) used for the production of the epoxycarboxylate compound (A) of the present invention has the above general formula (1) [wherein R may be the same or different and each represents a hydrogen atom, a halogen atom or a carbon number. 1 to 4 hydrocarbon groups are shown, and n represents an average value of 1 to 10 positive numbers. ] The epoxy resin which has a polycyclic hydrocarbon group shown by this.

In R of the present invention, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In R of the present invention, examples of the hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, and a t-butyl group. It is done.

Among them, a compound in which all R is a hydrogen atom or a compound in which a methyl group is available is preferable because it is available at low cost.
Furthermore, the manufacturing method of the epoxy resin (a) shown by General formula (1) is described in patent document 3 grade | etc.,. Compounds in which R is all hydrogen atoms and n is a positive number of 1 to 10 on average are available as XD-1000 series from Nippon Kayaku Co., Ltd.
In the present invention, a compound suitable for the softening point grade may be appropriately selected from the XD-1000 series.

  The compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule used for the production of the epoxycarboxylate compound (A) of the present invention has a reactivity to active energy rays during curing. These are compounds used for imparting, and these include monocarboxylic acid compounds and polycarboxylic acid compounds.

Examples of monocarboxylic acid compounds containing one carboxy group in one molecule include (meth) acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, and saturated or unsaturated dibasic acid and unsaturated group-containing monocarboxylic acid compounds. The reaction material with a glycidyl compound is mentioned.
Examples of acrylic acids include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth) acrylic acid dimer, reaction product of (meth) acrylic acid and ε-caprolactone, Half-esters, saturated or unsaturated dibasic acid and monoglycidyl (meth) acrylate, which are equimolar reactants of a saturated or unsaturated dibasic acid anhydride and a (meth) acrylate derivative having one hydroxyl group in one molecule And half-esters which are equimolar reactants with derivatives.

  Examples of the polycarboxylic acid compound having a plurality of carboxy groups in one molecule include, for example, half esters which are equimolar reaction products of a (meth) acrylate derivative having a plurality of hydroxyl groups in one molecule and a dibasic acid anhydride, And half-esters which are equimolar reaction products of a saturated or unsaturated dibasic acid and a glycidyl (meth) acrylate derivative having a plurality of epoxy groups.

  Most preferably among these, (meth) acrylic acid, reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid in terms of sensitivity to active energy rays when an active energy ray-curable resin composition is used. Is mentioned.

  As the compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule used for the production of the epoxycarboxylate compound (A) of the present invention, those having no hydroxyl group in the compound are preferable. .

  The compound (c) having both a hydroxyl group and a carboxy group in one molecule used in the production of the epoxycarboxylate compound (A) of the present invention is a compound used for introducing a hydroxyl group into the epoxycarboxylate compound. A compound having one hydroxyl group and one carboxy group in one molecule, a compound having two or more hydroxyl groups and one carboxy group in one molecule, one or more hydroxyl groups and two or more carboxy groups in one molecule And the like.

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

Among these, a compound containing two or more hydroxyl groups in one molecule is preferable in consideration of the effect of the present invention. That is, it becomes easy to introduce a hydroxyl group in a larger proportion in one molecule of the epoxycarboxylate compound. Furthermore, a compound containing two or more carboxy groups per molecule tends to complicate the epoxycarboxylation reaction, and therefore a compound having one carboxy group is preferred.
Among them, those having two hydroxyl groups and one carboxyl group in one molecule are preferable, and dimethylolpropionic acid or dimethylolbutanoic acid is mentioned in consideration of easy availability of the compound.

  As the compound (c) having both a hydroxyl group and a carboxy group in one molecule used in the production of the epoxycarboxylate compound (A) of the present invention, a compound having no polymerizable ethylenically unsaturated group in the compound is used. preferable.

  Considering the stability of the reaction of the epoxy resin (a) with the carboxylic acid compound (b) and the carboxylic acid compound (c), the carboxylic acid compound (b) and the carboxylic acid compound (c) are monocarboxylic acids. When monocarboxylic 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 amount of carboxylic acid groups of the epoxy resin (a), the carboxylic acid compound (b), and the carboxylic acid compound (c) in the production of the epoxy carboxylate compound (A) of the present invention is appropriately changed according to the application. do it. That is, when all epoxy groups are carboxylated, unreacted epoxy groups do not remain, so that the storage stability as an epoxy carboxylate compound is high. In this case, only the reactivity due to the introduced unsaturated group is used.

  On the other hand, by reducing the charged amount of the carboxylic acid compound and leaving an unreacted epoxy group, the reactivity due to the introduced unsaturated group and the reactivity due to the residual epoxy group can be used in combination, that is, depending on the photocationic catalyst. A polymerization reaction or a thermal polymerization reaction can be used. In this case, however, attention must be paid to the storage and production conditions of the epoxycarboxylate compound.

  When producing an epoxy carboxylate compound (A) that does not leave an epoxy group, the total amount of carboxy groups of the carboxylic acid compound (b) and the carboxylic acid compound (c) is 90 to 120 equivalents relative to 1 equivalent of the epoxy resin (a). % Is preferred. Within this range, it is possible to manufacture under relatively stable conditions. When the amount of the carboxylic acid compound is larger than this, an excess of the carboxylic acid compound remains in an unreacted state, which is not preferable.

  Moreover, when leaving an epoxy group, it is preferable that the sum total of the carboxy group of a carboxylic acid compound (b) and a carboxylic acid compound (c) is 20-90 equivalent% with respect to 1 equivalent of the said epoxy resin (a). . Of course, in this case, sufficient attention must be paid to the gelation during production and the temporal stability of the epoxycarboxylate compound (A). In the case of less than 20 equivalent%, the effect of combined curing due to the introduced ethylenically unsaturated group and the remaining epoxy group becomes low.

  In the production of the epoxycarboxylate compound (A) of the present invention, the use ratio of the compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group and the compound (c) having both a hydroxyl group and a carboxy group depends on the purpose of use. The molar ratio of carboxylic acid compound (b): carboxylic acid compound (c) is preferably about 9: 1 to 1: 9, more preferably 4: 6 to 8: 2. If it is this range, the fall of the reactivity of an ethylenically unsaturated group when there are too few carboxylic acid compounds (b) can be prevented, and the carboxylic acid compound (c) when there are too few carboxylic acid compounds (c). ) Can be prevented from becoming dilute.

This epoxycarboxylation reaction can be carried out without solvent or diluted with a solvent. The solvent is not particularly limited as long as it does not affect the epoxycarboxylation reaction.
What is necessary is just to adjust the usage-amount of a solvent suitably with the viscosity and usage of resin to obtain, Preferably it is 90 to 30 weight% as solid content, More preferably, it may be used so that it may become 80 to 50 weight%.
Although the solvent is illustrated below, in the present invention, these may be mixed and used.

  Examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane, and decane, and mixtures thereof such as petroleum ether, white gasoline, Solvent naphtha etc. are mentioned.

  The solvent may be an ester solvent such as alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether monoacetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoacetate. Mono- or polyalkylene glycol monoalkyl ether monoacetates such as ethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, butylene glycol monomethyl ether monoacetate, dialkyl glutarate , Dialkyl succinate, dialkyl adipate, etc. Carboxylic acid alkyl esters.

  The solvent may be an ether solvent, for example, 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, triethylene Examples include glycol ethers such as glycol diethyl ether and cyclic ethers such as tetrahydrofuran.

  The solvent may be a ketone solvent, and examples thereof include acetone, methyl ethyl ketone, cyclohexanone, isophorone and the like.

  Furthermore, it can also carry out in the single or mixed solvent chosen from reactive compounds (C) other than the epoxy carboxylate (A) of the postscript, and a polycarboxylic acid compound (B) instead of this solvent. In this case, it is preferable because it can be used as it is when used as a curable composition.

In the epoxy carboxylation reaction, a catalyst is preferably used to promote the reaction. When the catalyst is used, the amount used is about 0.1 to 10% by weight based on the total amount of the reactants. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours.
Examples of the catalyst include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, and zirconium octoate. A basic catalyst etc. are mentioned.

  The use of a thermal polymerization inhibitor is preferred. Examples of the thermal polymerization inhibitor include hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, and 3,5-di-tert-butyl-4. -Hydroxy toluene etc. are mentioned.

  The end point of this epoxycarboxylation reaction is the time when the acid value of the reaction product becomes 5 mgKOH / g or less, preferably 2 mgKOH / g or less, while sampling appropriately.

As a preferable molecular weight range of the epoxycarboxylate compound (A) thus obtained, the polystyrene-equivalent weight average molecular weight in GPC (gel filtration chromatography) is in the range of 1,000 to 30,000, more preferably 1,500. To 20,000.
When the molecular weight is smaller than this, the toughness of the cured product is not sufficiently exhibited. When the molecular weight is larger than this, the viscosity becomes high and coating or the like becomes difficult.

Next, the polycarboxylic acid (B) of the present invention will be described. The polycarboxylic acid (B) is obtained by reacting the epoxycarboxylate compound (A) with a polybasic acid anhydride (d).
Reasons for introducing a carboxyl group by this acid addition step include, for example, imparting solubility in alkaline water to an active energy ray non-irradiated part in applications where resist patterning or the like is required, and to metals, inorganic substances, etc. For example, imparting adhesiveness.
In this acid addition step, a polybasic acid anhydride (d) is reacted with a hydroxyl group of an epoxycarboxylate compound to introduce a carboxyl group via an ester bond.

  As the polybasic acid anhydride (d), for example, any compound having a cyclic acid anhydride structure in one molecule can be used, but it is excellent in alkaline aqueous solution developability, heat resistance, hydrolysis resistance and the like. Succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride preferable.

  The reaction for adding the polybasic acid anhydride (d) can be performed by adding the polybasic acid anhydride (d) to the solution of the epoxycarboxylate compound. What is necessary is just to change suitably the addition amount according to a use.

  However, when the polycarboxylic acid compound (B) of the present invention is used as an alkali development resist, the polybasic acid anhydride (d) is converted into the solid content acid value (JIS K5601- 2-1: According to 1999) is preferably 30 to 120 mg · KOH / g, more preferably 40 to 100 mg · KOH / g. When the solid content acid value is within this range, the alkaline aqueous solution developability of the active energy ray-curable resin composition of the present invention exhibits good performance. That is, good patternability and a wide control range for over-development are possible, and no excess acid anhydride remains.

  In the acid addition reaction, it is preferable to use a catalyst for promoting the reaction, and the amount of the catalyst used is about 0.1 to 10% by weight based on the total amount of the reactants. The reaction temperature is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Examples of the catalyst include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, zirconium octoate and the like. Can be mentioned.

  This acid addition reaction can be reacted without solvent or diluted with a solvent. The solvent is not particularly limited as long as it does not affect the acid addition reaction. Further, when a solvent is used in the epoxy carboxylation reaction as the previous step, it can be directly subjected to an acid addition reaction without removing the solvent, provided that the acid addition reaction is not affected.

What is necessary is just to adjust the usage-amount of a solvent suitably with the viscosity and usage of resin to obtain, Preferably it is 90 to 30 weight% as solid content, More preferably, it may be used so that it may become 80 to 50 weight%.
Examples of the solvent include the solvents described as solvents that can be used in the epoxy carboxylate-forming step.

  The use of a thermal polymerization inhibitor is preferred, and examples of the thermal polymerization inhibitor include the same thermal polymerization inhibitors as those used in the epoxy carboxylation reaction.

  The end point of this acid addition reaction is determined when the acid value of the reaction product is in the range of plus or minus 10% of the set acid value while sampling appropriately.

  The active energy ray-curable resin composition of the present invention contains an epoxy carboxylate compound (A) and / or a polycarboxylic acid compound (B). The epoxy carboxylate compound (A) and / or the polycarboxylic acid compound (B) can be properly used depending on the application. For example, in the case of a solder resist application, when a pattern is formed by a printing method without development, or in the case of a so-called solvent development type in which an unreacted site is washed away by a solvent, the epoxy carboxylate compound (A) is used. In the case of developing with alkaline water, the polycarboxylic acid compound (B) may be used. In general, the polycarboxylic acid compound (B) is often used for this purpose from the viewpoint that the alkaline water development type can easily form a fine pattern. Of course, there is no problem even if they are used together.

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

  Examples of the reactive compound (C) include epoxy compounds other than the cation-reactive epoxy resin (a), radical-reactive acrylates, and vinyl compounds that are sensitive to both.

  Epoxy compounds other than the cation-reactive epoxy resin (a) are not particularly limited. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3, 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (such as “Syracure UVR-6110” manufactured by Union Carbide Co., Ltd.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene Dioxide (such as “ELR-4206” manufactured by Union Carbide Corporation), limonene dioxide (such as “Celoxide 3000” manufactured by Daicel Chemical Industries, Ltd.), allylcyclohexene dioxide 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4- Epoxycyclohexyl) adipate (such as “Syracure UVR-6128” manufactured by Union Carbide Corp.), bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4 And epoxy cyclohexyl methyl) ether and bis (3,4-epoxy cyclohexyl) diethyl siloxane.

  Examples of radical reaction type acrylates include monofunctional (meth) acrylates; polyfunctional (meth) acrylates; urethane acrylates, polyester acrylates, epoxy acrylates of epoxy compounds other than epoxy resin (a), etc. And other oligomers.

  Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate monomethyl Examples include ether, 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, hydrogenated Ε-Capro of bisphenol ethylene oxide di (meth) acrylate, bisphenol di (meth) acrylate, neopentyl glycol hydroxybivalate Di (meth) acrylate of kuton adduct, poly (meth) acrylate of reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly (meth) acrylate, trimethylolpropane tri (meth) acrylate, triethylolpropane tri ( And (meth) acrylate or its ethylene oxide adduct, pentaerythritol tri (meth) acrylate or its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate or its ethylene oxide adduct, etc. .

  Furthermore, urethane acrylates having both functional groups reactive to active energy rays and urethane bonds in the same molecule, polyester acrylates having functional groups reactive to active energy rays and ester bonds in the same molecule, epoxy resins Examples include epoxy acrylates derived from epoxy compounds other than (a) and having functional groups reactive to active energy rays in the same molecule, and reactive oligomers having these combined in the same molecule. It is done.

  Examples of the vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds.

Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and the like.
Examples of styrenes include styrene, methyl styrene, and ethyl styrene.
Examples of other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

  Of these, the reactive compound (C) is preferably a radical reaction type acrylate. In the case of a cation-reactive compound, it is necessary to use a two-component mixed type in order to avoid a reaction between an epoxy group and a carboxy group.

  The reactive compound (C) other than the epoxycarboxylate compound (A) and the polycarboxylic acid compound (B) is mixed with the (A) and / or the polycarboxylic acid compound (B) of the present invention as necessary. The active energy ray-curable resin composition of the present invention can be obtained. In this case, other components may be appropriately added depending on the use of the composition.

  The active energy ray-curable resin composition of the present invention contains 97 to 5% by weight, preferably 87 to 10% by weight, of epoxy carboxylate compound (A) and / or polycarboxylic acid compound (B) in the composition. The reactive compound (C) other than the carboxylate compound (A) and the polycarboxylic acid compound (B) is contained in an amount of 3 to 95% by weight, preferably 3 to 80% by weight. If necessary, other components may be included up to about 70% by weight.

  The active energy ray-curable resin composition of the present invention may further contain a color pigment, and the color pigment is used for using the resin composition of the present invention as a coloring material. When the epoxy carboxylate compound (A) or polycarboxylic acid compound (B) used in the active energy ray-curable resin composition of the present invention has a particularly excellent affinity for the pigment, that is, dispersibility. Inferred. As a result of good dispersibility, the pigment concentration can be increased. Further, in a composition that requires development, dispersibility is more suitable, good patterning characteristics are exhibited, and there are few development residues in the development-dissolved part, which is also suitable.

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

The present invention is an active energy ray-curable resin composition that is a molding material, a film-forming material, or a resist material composition.
In the present invention, the molding material is an uncured composition put into a mold, or an object is molded by pressing the mold and then molded by causing a curing reaction with active energy rays, or an uncured composition. It refers to a material used for applications in which a focus reaction such as laser is irradiated to cause a curing reaction to be molded. That is, a so-called nanoimprint material, especially a heat imprinting material, which is formed by pressing a flatly formed sheet, a sealing material for protecting the element, a “mold” finely processed into an uncured composition Examples of suitable applications include peripheral sealing materials such as light-emitting diodes and photoelectric conversion elements that are severely demanding.

In the present invention, the film forming material is used for the purpose of coating the surface of a substrate. That is, ink materials such as gravure ink, flexo ink, silk screen ink, offset ink; coating materials such as hard coat, top coat, overprint varnish, clear coat; various adhesives for laminating, optical disks, adhesives, etc. Adhesive materials; resist materials such as solder resist, etching resist, and micromachine resist. Furthermore, after the film-forming material is temporarily applied to a peelable substrate and formed into a film, the so-called dry film is also used for forming a film in the present invention. Applicable to the material.
Among these, since the adhesiveness to a base material increases with the carboxy group of a polycarboxylic acid compound (B), the use for coat | covering a plastic base material or a metal base material is preferable.

In the present invention, the resist material composition is formed by forming a film layer of the composition on a substrate, and then partially irradiating active energy rays such as ultraviolet rays, and the physical difference between irradiated and unirradiated parts. This refers to an active energy ray-sensitive composition that is intended to be drawn using. That is, it is a composition that draws by removing the irradiated or unirradiated portion by dissolving the irradiated portion or unirradiated portion with some method such as a solvent or an alkaline solution.
In particular, the active energy ray-curable resin composition containing the polycarboxylic acid compound (B) of the present invention is excellent as an alkaline water developing resist composition by taking advantage of its solubility in an alkaline aqueous solution.

The active energy ray-curable resin composition for resists of the present invention can be applied to various materials that can be patterned, and is useful, for example, as a solder resist material, an interlayer insulating material for a buildup method, and as an optical waveguide. It can also be used for printed wiring boards, electrical / electronic / optical substrates such as optoelectronic substrates and optical substrates.
Above all, it is used for permanent resists such as solder resists by making use of the characteristics that can obtain toughened cured products, and it is used for color resists such as printing inks and color filters, especially for black matrix, making use of the characteristics that pigment dispersibility is good. The use of resist is preferred.

Further, it is also suitably used for dry films in which mechanical strength before the curing reaction by active energy rays is required and developability is also required. That is, the active energy ray-curable resin composition of the present invention can exhibit good developability despite the epoxy carboxylate compound (A) having a relatively high molecular weight due to the epoxy resin (a). .
There are no particular restrictions on the method for forming the film, 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, a die coater, Various coating methods such as curtain coater and spin coater can be arbitrarily adopted.

  The active energy ray-curable resin composition of the present invention can be easily cured by irradiation with active energy rays, and the resulting cured product is also included in the present invention. Examples of 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. Although what is necessary is just to select suitably by a use, among these, an ultraviolet-ray, a laser beam, visible light, or an electron beam is preferable.

  As described above, as other components that may contain the upper limit of 70% by weight in the active energy ray-curable resin composition of the present invention, in addition to the coloring material, a photopolymerization initiator and other additives And volatile solvents added for viscosity adjustment for the purpose of imparting coating suitability.

  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, 2,2- Diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methylphenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio ) Acetophenones such as phenyl] -2-morpholino-propan-1-one; ant such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone Quinones; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide Benzophenones such as 4,4′-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, etc. A radical type photoinitiator is mentioned.

  As cationic photopolymerization initiators, Lewis acid diazonium salts, Lewis acid iodonium salts, Lewis acid sulfonium salts, Lewis acid phosphonium salts, other halides, triazine initiators, borate initiators and Other photoacid generators can be mentioned.

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.), etc. Is mentioned.
Examples of the iodonium salt of Lewis acid include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate.

Examples of the sulfonium salt of Lewis acid include triphenylsulfonium hexafluorophosphonate (such as Cyracure UVI-6990 manufactured by Union Carbide), triphenylsulfonium hexafluoroantimonate (such as Cyracure UVI-6974 manufactured by Union Carbide), and the like. .
Examples of the phosphonium salt of Lewis acid include triphenylphosphonium hexafluoroantimonate.

Examples of the halide include 2,2,2-trichloro-1- [4 ′-(dimethylethyl) phenyl] ethanone (Trigonal PI, etc., manufactured by AKZO), 2,2-dichloro-1- [4- (phenoxy Phenyl)] ethanone (Sandray 1000, etc. 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 (Triazine PMS, etc., manufactured by Panchim), 2,4-trichloromethyl- (4′-methoxynaphthyl) -6-triazine (manufactured by Panchi, Triazine) B), 2- [2 ′-(5 ″ -methylfuryl) ethylidene] -4,6-bis (trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd.), 2- (2′-furyl) And ethylidene) -4,6-bis (trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd.).

Examples of the baud rate initiator include NK-3876 and NK-3881 manufactured by Nippon Photosensitive Dye.
Examples of other photoacid generators include 9-phenylacridine, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2-biimidazole (black). Biimidazole manufactured by Kasei Chemical Co., Ltd.), 2,2-azobis (2-amino-propane) dihydrochloride (V50 manufactured by Wako Pure Chemical Industries, Ltd.), 2,2-azobis [2- (imidazolin-2-yl) propane] dihydro Chloride (VA044 manufactured by Wako Pure Chemical Industries, Ltd.), [eta-5-2-4- (cyclopentadecyl) (1,2,3,4,5,6, eta)-(methylethyl) -benzene] iron ( II) Hexafluorophosphonate (Irgacure 261, etc. manufactured by Ciba Geigy), bis (eta-5-cyclopentadienyl) bis [2,6-difluoro-3- (1H-py-1-yl) Eniru] titanium (Ciba Geigy Corp. CGI-784, etc.), and the like.

Further, 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 photopolymerization initiators may be used in combination. A photoinitiator can also be used individually by 1 type and can also be used in combination of 2 or more types.

  Other additives include, for example, thermosetting catalysts such as melamine, thixotropic agents such as aerosil, silicone-based, fluorine-based leveling agents and antifoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, An antioxidant etc. can be used.

  As other pigment materials, for example, extender pigments that are not intended for coloring can also be used. Examples of extender pigments include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, and clay.

  In addition, as other additives, resins that do not react with active energy rays (so-called inert polymers), for example, epoxy resins other than the above, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylenes Resins, diallyl phthalate resins, styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof can also be used. When these are included in the active energy ray-curable resin composition of the present invention, the content in the composition is preferably in the range of up to 40% by weight.

  In particular, when the polycarboxylic acid compound (B) is used as a solder resist application, it is preferable to use an epoxy resin for the purpose of eliminating a carboxy group remaining after curing and development and obtaining a stronger cured film. . In this case, a carboxyl group derived from the polycarboxylic acid compound (B) remains even after being reacted and cured by active energy rays, and the cured product may be inferior in water resistance or hydrolyzability. In such a case, a stronger cross-linked structure can be formed by causing an epoxy carboxylation reaction with a remaining carboxy group by using an epoxy resin.

  In order to adjust the viscosity according to the purpose of use, a volatile solvent may be added to the active energy ray-curable resin composition in a range of 50% by weight, more preferably up to 35% by weight.

  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 weight 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 / min 40 ° C
Detector: Differential refractometer Molecular weight standard: Polystyrene

  Example 1: Production of epoxycarboxylate compound (A)

XD-1000 as an epoxy resin (a) (Nippon Kayaku Co., Ltd., softening point 70 ° C., epoxy equivalent 250 g / eq, R in the general formula (1) are all hydrogen atoms, n is 3 on average) As a compound (b) having both an ethylenically unsaturated group polymerizable in one molecule and a carboxy group, acrylic acid (abbreviation AA, Mw = 72) is listed in Table 1, and hydroxyl group and carboxy in one molecule. As the compound (c) having both groups, dimethanolpropionic acid (abbreviation DMPA, Mw = 134) was mixed in the amounts shown in Table 1.
Using 3 g of triphenylphosphine as a catalyst, propylene glycol monomethyl ether monoacetate as a solvent was added so as to have a solid content of 80%, and reacted at 100 ° C. for 24 hours to obtain an epoxy carboxylate compound (A) 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 1-1: Preparation of Epoxy Carboxylate Compound to be Compared 250 g of XD-1000 (manufactured by Nippon Kayaku Co., Ltd., softening point 70 ° C., epoxy equivalent 250 g / eq), an ethylenic polymer that can be polymerized in one molecule Acrylic acid having both a saturated group and a carboxy group (abbreviation AA, Mw = 72) described in Table 1, added to 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent to a solid content of 80% And reacted at 100 ° C. for 24 hours to obtain an 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: Preparation of epoxy carboxylate 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)) in one molecule Acrylic acid having a polymerizable ethylenically unsaturated group and a carboxy group (abbreviation AA, Mw = 72) in the amount shown in Table 1, dimethanolpropionic acid having both a hydroxyl group and a carboxy group in one molecule (abbreviation DMPA, Mw = 134) were mixed in the amounts shown in Table 1.
3 g of triphenylphosphine was added as a catalyst, and propylene glycol monomethyl ether monoacetate was added as a solvent to a solid content of 80% and reacted at 100 ° C. for 24 hours to obtain an epoxycarboxylate compound solution.

  The reaction end point was determined by the solid content acid value (AV; mgKOH / g), 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.

Table 1: Example of epoxy carboxylate compound of Example 1 and Comparative Example 1 Epoxy resin AA amount DMPA amount Solid content acid value
(Molar ratio) (Molar ratio)
Example 1-1 XD-1000 14 (0.2) 107 (0.8) 2.4
Example 1-2 XD-1000 36 (0.5) 67 (0.5) 2.1
Example 1-3 XD-1000 58 (0.8) 27 (0.2) 2.8
Example 1-4 XD-1000 22 (0.3) 27 (0.2) 0.9

Comparative Example 1-1 XD-1000 72 (1.0) 0 (0.0) 2.5
Comparative Example 1-2 EOCN-104S 36 (0.5) 67 (0.5) 2.2

Example 2 Production of Polycarboxylic Acid Compound (B) Polybasic acid anhydride (c) was added to 299 g of the epoxycarboxylate compound (A) solution obtained as each of Examples 1-1, 1-2, and 1-3. Polytetrahydrophthalic anhydride (abbreviated as THPA) in Table 2 and propylene glycol monomethyl ether monoacetate as a solvent so that the solid content is 65% by weight and heated to 100 ° C. for acid addition reaction A compound (B) solution was obtained. The solid content acid value (mgKOH / g) is shown in Table 2.

Comparative Example 2: Preparation of polycarboxylic acid compound To 299 g of the epoxycarboxylate compound solution obtained in Comparative Examples 1-1 and 1-2, tetrahydrophthalic anhydride (abbreviated as THPA), which is a polybasic acid anhydride, is listed in Table 2. Propylene glycol monomethyl ether monoacetate was added as an amount and a solvent so that the solid content was 65% by weight, and the mixture was heated to 100 ° C. to cause an acid addition reaction to obtain a polycarboxylic acid compound solution. The solid content acid value (mgKOH / g) is shown in Table 2.

Table 2: Examples of reactive polycarboxylic acid compounds of Example 2 and Comparative Example 2 Compound (A) (b) / (c) THPA amount Solid content acid value Example 2-1 Example 1-1 0.2 / 0.8 66g 81
Example 2-2 Example 1-2 0.5 / 0.5 66 g 82
Example 2-3 Example 1-3 0.8 / 0.2 66g 80
Example 2-4 Example 1-2 0.5 / 0.5 29g 41

Comparative Example 2-1 Comparative Example 1-1 1.0 / 0.0 66 g 81
Comparative Example 2-2 Comparative Example 1-2 0.5 / 0.5 66 g 80
Comparative Example 2-3 Comparative Example 1-1 1.0 / 0.0 29 g 40

Example 3 and Comparative Example 3: Preparation of composition for hard coat 20 g of epoxycarboxylate compound synthesized in Example 1 and Comparative Example 1, 4 g of dipentaerythritol hexaacrylate which is a radical curable reactive compound, UV reactive type As a photopolymerization initiator, 1.5 g of Irgacure 184 was dissolved by heating. (In Example 3-4, 1.0 g of UVI-6990 was additionally added as a cationic photopolymerization initiator.)
Subsequently, it coated on the polycarbonate board with the hand applicator so that it might become the film thickness of 20 micrometers at the time of drying, and solvent drying was implemented in 80 degreeC for 30 minutes. After drying, an ultraviolet ray exposure apparatus (Oak Seisakusho) equipped with a high-pressure mercury lamp was irradiated with an ultraviolet ray with an irradiation dose of 1000 mJ and cured to obtain a film-formed product.

The hardness of the coating film of this formed product was measured according to JIS K5600-5-4: 1999, and a test for thermal shock resistance was further measured according to JIS K5600-7-4: 1999.
○: No scratch or peeling △: Slightly scratched ×: Peeled

Table 4 Composition examples for hard coat of Example 3 and Comparative Example 3 Compound (A) (b) / (c) Pencil hardness Cold resistance to thermal shock Example 3-1 Example 1-1 0.2 / 0.8 HB ○
Example 3-2 Example 1-2 0.5 / 0.5 2H ○
Example 3-3 Example 1-3 0.8 / 0.2 3H Δ
Example 3-4 Example 1-4 0.3 / 0.2 3H ○

Comparative Example 3-1 Comparative Example 1-1 1.0 / 0.0 3H ×
Comparative Example 3-2 Comparative Example 1-2 0.5 / 0.5 H ×

  As is clear from the above results, Comparative Example 1-1 in which all the epoxy groups were converted to an epoxy acrylate without using the compound (c) having both a hydroxyl group and a carboxy group in one molecule, an epoxy represented by the general formula (1) Compared to Comparative Example 1-2, which was derived using a cresol novolac type epoxy resin instead of the resin (a), the epoxy carboxylate compound of the present invention had improved thermal shock resistance. The reason for this improvement is considered to be that the density of unsaturated groups was moderately lowered with the introduction of the compound (c), and that the moderately crosslinked structure due to hydrogen bonding had a positive effect with the introduction of the hydroxyl group. .

Example 4 and Comparative Example 4: Dried Film Type Resist Composition 54.44 g of each of the polycarboxylic acid compounds obtained in Examples 2-1 to 2-4 or Comparative Examples 2-1 to 2-3, and a reactive compound (C) 3.54 g of HX-220 (trade name: manufactured by Nippon Kayaku Co., Ltd.) and 4.72 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator. And Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.), 0.47 g of GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.) as a curing component, 1.05 g of melamine as a thermosetting catalyst and concentration 20.95 g of methyl ethyl ketone was added as an adjusting solvent, 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 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 attached to a polyimide printed circuit board (copper circuit thickness: 12 μm, polyimide film thickness: 25 μm) while the protective film was peeled off using a heating roll at a temperature of 80 ° C., and the resin layer was attached to the entire surface of the substrate.
In addition, (A) and (B) mixed goods used in Example 4-5 are what was manufactured in Example 1-1 as an epoxy carboxylate compound (A), and implemented as a polycarboxylic acid compound (B). What was manufactured in Example 2-1 was mixed with a solution weight of 50:50.

Next, in order to estimate the mask on which the circuit pattern was drawn and the 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 . Thereafter, the film on the dry film was peeled off and the peeled state was confirmed. Thereafter, spray development was performed with a 1% sodium carbonate aqueous solution to remove the resin in the non-irradiated part. After washing with water and drying, the printed circuit board was subjected to a heat curing reaction in a hot air dryer at 150 ° C. for 60 minutes to obtain a cured film.

Evaluation of cold thermal shock resistance A thermal shock test was performed on a polyimide printed board on which a cured resist film was formed in the range of −65 to 120 ° C. The test method was based on JIS C5012-9.1: 1993. After completion of the test, a peel test using cellophane tape (registered trademark) was performed.
○: No peeling Δ: Slight peeling is observed ×: Peeling

Evaluation of high temperature and humidity resistance A polyimide printed circuit board on which a cured resist film was formed was placed in an autoclave at 120 ° C. for 1 hour. The substrate was taken out, allowed to air dry at room temperature, and then subjected to a peeling test using cellophane tape (registered trademark).
○: No peeling Δ: Slight peeling is observed ×: Peeling

Sensitivity evaluation Sensitivity was determined based on 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).

Evaluation of developability The developability was evaluated based on the so-called break time (unit: second) until the pattern shape portion was completely developed when developing the exposed portion that passed through the pattern mask.

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

Table 5 Dried film resist examples of Example 4 and Comparative Example 4 Compound (B) Cold shock Impact resistance Sensitivity Developability Curability Example 4-1 Example 2-1 ○ ○ 4 22 2H
Example 4-2 Example 2-2 ○ ○ 8 31 3H
Example 4-3 Example 2-3 Δ ○ 9 49 3H
Example 4-4 Example 2-4 ○ ○ 10 50 3H
Example 4-5 Example 1-1 ○ ○ 7 35 2H
Example 2-1

Comparative Example 4-1 Comparative Example 2-1 × Δ 7 50 3H
Comparative Example 4-2 Comparative Example 2-2 × × 9 45 3H
Comparative Example 4-3 Comparative Example 2-3 × Δ Development impossible 3H

  As is apparent from the above results, the resist composition in the present invention has high cold thermal shock resistance and high temperature and humidity resistance. Moreover, it has good developability and sensitivity as a resist.

Example 5 and Comparative Example 5: Pigment dispersibility 20 g of the polycarboxylic acid compound obtained in Example 2 or Comparative Example 2 and DPHA (trade name: Nippon Kayaku Co., Ltd. acrylate) as the reactive compound (C) Monomer) 5.0 g, 10 g of propylene glycol monomethyl ether acetate as an organic solvent, and 10 g of Mitsubishi Carbon Black MA-100 as a color pigment were mixed and stirred. 35 g of glass beads were put there and dispersed for 1 hour with a paint shaker.
The dispersion after completion of the 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), and the dispersibility of carbon black was evaluated. At this time, a higher gloss indicates better pigment dispersibility.

Table 7 Examples of pigment dispersibility of Example 5 and Comparative Example 5 Compound (B) (b) / (c) Glossy Example 6-1 Example 2-1 0.2 / 0.8 45
Example 6-2 Example 2-2 0.5 / 0.5 62
Example 6-3 Example 2-3 0.8 / 0.2 48
Example 6-4 Example 2-4 0.5 / 0.5 59

Comparative Example 6-1 Comparative Example 2-1 1.0 / 0.0 30
Comparative Example 6-2 Comparative Example 2-2 0.5 / 0.5 17
Comparative Example 6-3 Comparative Example 2-4 1.0 / 0.0 25

  As is clear from the above results, the compound (b) having both an ethylenically unsaturated group polymerizable in one molecule and a carboxy group to the epoxy resin (a) which is the basic skeleton of the reactive polycarboxylic acid in the present invention, and It has been clarified that the dispersibility of the pigment is improved by reacting the compound (c) having both a hydroxyl group and a carboxy group in one molecule.

  The active energy ray-curable composition of the present invention and the cured product thereof are hard coat materials and resist materials that require flexibility capable of alkali development as materials having both curability, flexibility, toughness, and flame retardancy. Suitable for applications exhibiting good pigment dispersibility, for example, active energy ray-curable printing inks, color resists, especially color resists for LCDs as materials having both resist dispersibility and developability, etc. In particular, it can be particularly suitably used for a black matrix or the like.

Claims (11)

The epoxy resin (a) represented by the following general formula (1) has a compound (b) having both an ethylenically unsaturated group polymerizable in one molecule and a carboxy group, and a compound having both a hydroxyl group and a carboxy group in one molecule ( An epoxycarboxylate compound (A) obtained by reacting c).

[Wherein, R may be the same or different and each represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and n represents an average value of 1 to 10 positive numbers. ] The polycarboxylic acid compound (B) obtained by making a polybasic acid anhydride (d) react with the epoxycarboxylate compound (A) of Claim 1. An active energy ray-curable resin composition comprising the epoxycarboxylate compound (A) according to claim 1 and / or the polycarboxylic acid compound (B) according to claim 2. The active energy ray-curable resin composition according to claim 3, further comprising a reactive compound (C) other than the epoxycarboxylate compound (A) and the polycarboxylic acid compound (B). Furthermore, the active energy ray hardening-type resin composition of Claim 3 or 4 containing a photoinitiator. Furthermore, the active energy ray hardening-type resin composition of any one of Claims 3-5 containing a coloring pigment. The active energy ray-curable resin composition according to any one of claims 3 to 6, which is a molding material. The active energy ray-curable resin composition according to any one of claims 3 to 6, which is a film-forming material. The active energy ray-curable resin composition according to any one of claims 3 to 6, which is a resist material composition. Hardened | cured material of the active energy ray hardening-type resin composition as described in any one of Claims 3-9. An article overcoated with a cured product of the active energy ray-curable resin composition according to claim 8.