TW201333065A - Reactive carboxylate compound, active-energy-ray-curable resin composition utilizing the same and use of the same - Google Patents

Abstract

To provide a resin composition which can be cured with an active energy ray such as ultraviolet ray or the like and enables to produce a rigid film or a molding material. Disclosed is a reactive compound derived from a phenolic epoxy resin containing a specific structure in the molecule, a compound having both of at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in the molecule, and a compound having both of at least one hydroxyl group and at least one carboxyl group in the molecule. Also disclosed is a curable resin composition utilizing the reactive compound. A rigid cured article can be produced from the curable resin composition. The reactive compound has a good pigment-dispersing property.

Description

Reactive carboxylic acid ester compound, active energy ray-curable resin composition using the same, and use thereof

The present invention relates to a reactive epoxy carboxylate compound (A) and a reactive polycarboxylic acid compound (B) as an acid modifier thereof, which is in a molecule a phenol type epoxy resin (a) having a specific structure, and a compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in a molecule typified by acrylic acid or the like, and a molecule A compound obtained by reacting a compound (c) having one or more hydroxyl groups and one or more carboxyl groups. The reactive epoxy carboxylate compound (A) and the reactive polycarboxylic acid compound (B) have a good affinity for the pigment, and a toughened cured product can be obtained from the resin composition containing the above.

In order to make the mobile device compact and lighter or to increase the communication speed, the printed circuit board is required to have high precision and high density. Accordingly, the requirements for the solder resist of the coated circuit itself are also continuously improved. Compared with the previous requirements, the printed circuit board is required to further maintain heat resistance, thermal stability, and can enhance substrate adhesion, high insulation, and electroless plating. For the performance of gold, a material for forming a film having a tougher cured property is sought.

In order to cope with the demand for high performance of a solder resist, the industry has developed an epoxy resin containing a specific structure in a molecule, and a cured resin containing the resin or the like, or an acid-modified epoxy carboxylate resin thereof, is known.

Patent Document 1 or Patent Document 2 discloses, for example, a phenol aralkyl type epoxy resin (for example, NC-3000 series manufactured by Nippon Kasei Co., Ltd., NC-2000 series, etc.) as a basic skeleton. The acid-modified epoxy acrylate is generally known as a material which exhibits high toughness after hardening. Also, research has been conducted on the use of it as a solder resist.

Patent Document 3 discloses an acid-modified epoxy acrylate compound having a polycyclic hydrocarbon group-containing epoxy resin as a basic skeleton and a cured product thereof, and has a relatively high toughness after curing. In addition, the use of the solder resist is also disclosed. However, although the solder resist has relatively high reliability, it does not satisfy the performance that can satisfy higher reliability as required by the electronicization of transmission equipment and the like in recent years.

In addition, as an application of the acid-modified epoxy acrylate of the epoxy resin, it is attempted to disperse a coloring pigment such as carbon black in the like, and to apply it to a black matrix resist used in a liquid crystal display panel or the like.

Patent Document 4 and Patent Document 5 disclose that a coloring pigment such as carbon black is dispersed in an acid-modified epoxy acrylate having a phenol aralkyl type epoxy resin as a basic skeleton, and is used as a black matrix photoresist. Application examples.

Further, an attempt has been made to disperse a coloring 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 as a black matrix resist. (Patent Document 6)

However, in the case of a black matrix resist used in a liquid crystal display panel or the like, when a coloring pigment such as carbon black is blended at a high concentration, since the pigment is well dispersed in the resin by affinity with the resin, even if a high concentration of the pigment exists, It also shows good developability, and development of a pigment-free residue can be achieved. In this case, developability at a higher pigment concentration, that is, higher pigment dispersibility is sought. Although the prior acid-modified epoxy acrylates exhibit relatively good pigment dispersibility, there is a disadvantage that the pigment dispersion exhibits a pseudo-coagulation phenomenon resulting in poor stability.

On the other hand, a carboxylate compound obtained by reacting acrylic acid and a carboxylic acid compound having a hydroxyl group with a common epoxy resin is known, and is a material having a low acid value and excellent developability, and further Patent Document 7 It is disclosed that the compound has photoresist ink compatibility.

[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-140144

[Patent Document 2] Japanese Patent Laid-Open No. Hei 5-194708

[Patent Document 3] Japanese Patent Laid-Open No. Hei 5-214048

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2005-55814

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2003-183354

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2004-295084

[Patent Document 7] Japanese Patent Laid-Open No. Hei 6-324490

The above-mentioned hardened resin composition containing an epoxy resin having a specific structure in the molecule can obtain a relatively tough cured product, but it is required as a material for use in applications requiring extremely high reliability of a transmission device. Resistant to hardened physical properties such as substrate bending.

Further, in the use as a photoresist of a coloring system, in the case of a composition, it is required to have higher dispersibility to a coloring pigment, especially carbon black, and the like, and have good development even at a high pigment concentration. A characteristic acid-modified epoxy acrylate. At this time, a material having a relatively high molecular weight and having moderate developability is required. Further, it is necessary to obtain a color pigment dispersion resin composition which exhibits long-term storage stability without being observed in the pigment dispersion.

In order to solve the above problems, the inventors of the present invention have found that an epoxy resin having a specific structure in a molecule and a compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in the molecule, and a reactive epoxy carboxylate compound obtained by reacting a compound (c) having one or more hydroxyl groups and one or more carboxyl groups in one molecule, and further reacting the reactive epoxy carboxylate compound with a polybasic acid anhydride (d) The obtained reactive polycarboxylic acid compound has particularly excellent resin physical properties and resin physical properties as a cured product thereof.

Further, it has been found that the resin composition has particularly good affinity with the coloring pigment, and can be a photoresist material which has good developability even at a high pigment concentration.

In other words, the present invention relates to a reactive epoxy carboxylate compound (A) which is an epoxy resin (a) represented by the following formula (1) and which has one or more polymerizable one molecule. A compound (b) having an ethylenically unsaturated group and one or more carboxyl groups, and a compound (c) having one or more hydroxyl groups and one or more carboxyl groups in one molecule are obtained by reacting: (wherein R _{1 is the} same or different from each other, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms; and R ₂ represents a divalent polycyclic hydrocarbon group having 7 to 16 carbon atoms or a carbon number of 7 to 18; Aralkyl group; m represents an integer from 1 to 4, and n is an average value, indicating a positive number from 1 to 10.

The present invention further relates to an epoxy resin (a) which is a reactive epoxy carboxylate compound (A) of the formula (2): (wherein R _{3 is the} same or different from each other, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms; o represents an integer of 1 to 4, and p is an average value, and represents a positive number of 1 to 10).

The present invention further relates to an epoxy resin (a) which is a reactive epoxy carboxylate compound (A) of the formula (3): (wherein R _{4 is the} same or different from each other, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms; q represents an integer of 1 to 4, and r is an average value, and represents a positive number of 1 to 10).

The present invention further relates to an epoxy resin (a) which is a reactive epoxy carboxylate compound (A) of the formula (4): (wherein R _{5 is the} same or different from each other, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms; s represents an integer of 1 to 4, and t is an average value, indicating a positive number of 1 to 10).

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

Further, the present invention relates to an active energy ray-curable resin composition comprising the reactive carboxylic acid ester compound (A) and/or a reactive polycarboxylic acid compound (B).

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

The present invention further relates to an active energy ray-curable resin composition containing a coloring pigment.

The present invention further relates to an active energy ray-curable resin composition containing a photopolymerization initiator.

Further, the present invention relates to the active energy ray-curable resin composition which is a material for molding.

Further, the present invention relates to the active energy ray-curable resin composition which is a material for forming a film.

The present invention further relates to the above active energy ray-curable resin composition, which is a photoresist material composition.

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

The present invention further relates to an article which is covered by the above active energy ray-curable resin composition.

The active energy ray-curable resin composition containing the epoxy resin having a specific structure in the molecule of the present invention not only provides a toughened cured product, but also has excellent resin physical properties even in a state where the solvent is dried. The cured product obtained from the active energy ray-curable resin composition of the present invention can be suitably used as a material for forming a film which requires heat and mechanical toughness. As a particularly preferable use, a solder resist for a printed circuit board, an interlayer insulating material for a multilayer printed circuit board, a solder resist for a flexible printed circuit board, a plating resist, a photosensitive optical waveguide, etc., can be cited, and in particular, it can be used for higher requirements. In the use of special animals.

Further, since the active energy ray-curable resin composition obtained has high affinity with a coloring pigment such as carbon black, it exhibits good pigment dispersibility even at a high pigment concentration, and exhibits high developability. And can maintain the pigment dispersion of the color pigment dispersion for a long period of time The state thus provides a resin composition capable of ensuring storage stability in a highly dispersed state. Therefore, as a particularly good use, it can be suitably used as a photoresist for color resists and color filters, especially a black matrix material.

The reactive epoxy carboxylic acid ester compound (A) of the present invention is a phenolic type having a characteristic skeleton represented by the following formula (1) in which a phenol epoxy group is bonded to a hydrocarbon group having a specific structure by imparting reactivity. The epoxy resin (a), the compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in the molecule, and one or more hydroxyl groups and one or more carboxyl groups in one molecule Compound (c) is obtained by reaction. That is, the ethylenically unsaturated group and the hydroxyl group are simultaneously introduced into the molecular chain by esterification of the epoxy carboxylic acid to exhibit the characteristics of the present invention:

The epoxy resin (a) represented by the formula (1) used in the present invention is characterized in that it contains a phenolic epoxy group and has a carbon number of 7 to 16 represented by R ₂ . A phenolic epoxy resin having a cyclic hydrocarbon group or a repeating skeleton of a hydrocarbon group having a carbon number of 7 to 18 and an aralkyl group.

In the above formula, R _{1 is the} same or different from each other, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms. Here, the halogen atom means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Further, the hydrocarbon group having a carbon number of 1 to 4 represents a methyl group, an ethyl group, a vinyl group, a n-propyl group, an isopropyl group, a propenyl group, a n-butyl group, an isobutyl group, a second butyl group, and a t-butyl group. a saturated and unsaturated hydrocarbon group such as a butenyl group.

R ₂ represents a divalent polycyclic hydrocarbon group having a carbon number of 7 to 16, or a aralkyl group having a carbon number of 7 to 18. Examples of the divalent polycyclic hydrocarbon group having a carbon number of 7 to 16 include a bicyclo[2,2,1]heptyl group, a bicyclo[2,2,2]octyl group, and an octahydrocyclopentylene group. Alkenediyl, decahydronaphthalenediyl, tetrahydrodicyclopentadienyldiyl, tetrahydrodicyclohexadienyldiyl. Among these, tetrahydrodicyclopentadienyldiyl can be preferably used.

Further, examples of the exoaralkyl group having a carbon number of 7 to 18 include a phenylene bismethylene group, a phenylene extended methyl group, a bisphenylene methylene group, and a phenyl diphenyl group. A group, a naphthyl bismethylene group, a bis-methylene group, a phenymethylene group, a bis-methylene group, and the like. Among these, phenylene bismethylene and phenylbismethylene may be preferably used.

Further, in the formula (1), m represents an integer of 1 to 4, and represents the number of functional groups introduced. n is an average value, which represents a positive number of 1 to 10, preferably 1 to 6. When the value of n is less than 10, preferably less than 6, the epoxy resin (a) is in a suitable viscosity range. In addition, the average value of n means the average repetition number, and can be calculated based on the measured value obtained by the gel permeation chromatography (GPC).

As the epoxy resin (a) used in the present invention, it is preferred to use an epoxy resin having a characteristic biphenyl skeleton represented by the following general formula (2):

In the above formula, R _{3 is the} same or different from each other, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms. The halogen atom means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Further, o represents an integer of 1 to 4, and p is an average value, and represents a positive number of 1 to 10, preferably 1 to 6. When the value of p is less than 10, preferably less than 6, the epoxy resin (a) is in a suitable viscosity range.

In the epoxy resin (a) represented by the formula (2), all of R ₃ is a hydrogen atom, and it is preferably obtained at low cost. Usually, it is commercially available as a NC-3000 series from Nippon Kayaku. In the NC-3000 series, all of R ₃ in the above formula are hydrogen atoms, and p is an average value, and each represents a positive number of 1 to 10. In the present invention, a suitable one can be appropriately selected among the grades of the series.

Further, as the epoxy resin (a) used in the present invention, it is preferred to use a phenol aralkyl type epoxy resin represented by the formula (3):

In the above formula, R _{4 is the} same or different from each other, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms. Further, q is a substitution number and represents an integer of 1 to 4, and r is an average value, and represents a positive number of 1 to 10, respectively.

In the epoxy resin represented by the formula (3), it is preferred that all of R ₄ is a hydrogen atom or a methyl group. The epoxy resin represented by the general formula (3) can be usually obtained as a NC-2000 series from a Japanese chemical. In the NC-2000 series, all of R ₄ in the above formula are hydrogen atoms, and r is an average value and is a positive number of 1 to 10. In the present invention, a suitable one can be appropriately selected among the grades of the series.

Further, as the epoxy resin (a) used in the present invention, an epoxy resin having a polycyclic hydrocarbon group represented by the general formula (4) is preferred:

In the above formula, R _{5 is the} same or different from each other, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms, s is a substitution number, and represents an integer of 1 to 4, and t is an average value, and represents 1 to 10 A positive number.

Among them, a compound in which all of R ₅ is a hydrogen atom or a compound in which all are a methyl group can be preferably obtained at low cost. R _{5 is} all a hydrogen atom, and t is an average value, and a compound representing a positive number of 1 to 10 can be obtained as a XD-1000 series from Nippon Chemical Co., Ltd. In the present invention, a suitable compound can be appropriately selected from the series of grades.

In the present invention, a compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule is used to cause a reaction to react with an active energy ray. These may, for example, be a monocarboxylic acid compound or a polycarboxylic acid compound.

Examples of the monocarboxylic acid compound having one carboxyl group in one molecule include (meth)acrylic acid or crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a saturated or unsaturated dibasic acid and a non-containing compound. A reactant of a saturated mono-glycidyl compound. In the above, examples of the acrylic acid include (meth)acrylic acid, β-styrylacrylic acid, β-mercaptoacrylic acid, (meth)acrylic acid dimer, and a saturated or unsaturated dibasic acid anhydride. a half ester of a molar reactant such as a hydroxyl group (meth) acrylate derivative in the molecule, which is a saturated or unsaturated dibasic acid and a (meth)acrylic acid monoglycidyl ester derivative. Semi-esters of the ear reactants, and the like.

Further, examples of the polycarboxylic acid compound having a plurality of carboxyl groups in one molecule include (meth)acrylate derivatives having a plurality of hydroxyl groups in one molecule, and dibasic acid anhydrides. A half ester of a molar reactant, a half ester of a saturated or unsaturated dibasic acid, and a molar reactant such as a glycidyl (meth)acrylate derivative having a plurality of epoxy groups.

In terms of sensitivity in the preparation of the active energy ray-curable resin composition, the most preferable ones are: (meth)acrylic acid, a reaction product of (meth)acrylic acid and ε-caprolactone, or cinnamic acid. .

As the compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule, it is preferred that the compound does not have a hydroxyl group.

In the present invention, the compound (c) having one or more hydroxyl groups and one or more carboxyl groups in one molecule is used for the reaction in which a hydroxyl group is introduced into the carboxylate compound. These include a compound having one hydroxyl group and one carboxyl group in one molecule, a compound having two or more hydroxyl groups and one carboxyl group in one molecule, and a compound having one or more hydroxyl groups and two or more carboxyl groups in one molecule.

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

Further, examples of the compound having two or more hydroxyl groups and one carboxyl group in one molecule include dihydroxymethylacetic 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 and the like.

Among these, in view of the effects of the present invention, those having two or more hydroxyl groups in one molecule are preferred. Further, in view of the stability of the carboxylic acid esterification reaction, it is preferred that one molecule contains one carboxyl group. Most preferably, one molecule has two hydroxyl groups and one carboxyl group. Particularly preferred are dimethylolpropionic acid and dimethylolbutanoic acid in view of the availability of raw materials.

As the compound (c) having one or more hydroxyl groups and one or more carboxyl groups in one molecule, it is preferred that the compound does not have a polymerizable ethylenically unsaturated group.

In the above, in view of the reaction stability of the above epoxy resin (a) and the two carboxylic acid compounds (b) and (c), it is preferred that (b) and (c) are monocarboxylic acids, and preferably. Even if the monocarboxylic acid is used together In the case of a polycarboxylic acid, the total mole amount of the monocarboxylic acid/the total mole amount of the polycarboxylic acid is also 15 or more.

The ratio of the total amount of the epoxy resin (a) to the carboxylic acid of the carboxylic acid compounds (b) and (c) in the reaction should be appropriately changed depending on the use. That is, in the case of esterifying all of the epoxy carboxylic acids, since the unreacted epoxy group does not remain, the storage stability of the reactive carboxylic acid ester compound is high. In this case, only the reactivity brought about by the introduced double bond will be utilized.

On the other hand, by reducing the amount of the carboxylic acid compounds (b) and (c), the unreacted remaining epoxy group is intentionally left, and the reactivity by the introduced unsaturated bond is utilized in combination. And a reaction caused by the remaining epoxy group, such as a polymerization reaction or a thermal polymerization reaction caused by a photocationic catalyst. However, in this case, care must be taken in preserving the reactive carboxylic acid ester compound and in studying the manufacturing conditions.

In the case of producing a reactive epoxy carboxylate compound (A) which does not have a reactive epoxy group, it is preferred that the carboxylic acid compound (b) is equivalent to 1 equivalent of the epoxy group of the above epoxy resin (a). The sum of (c) and (c) is 90 to 120 equivalent%. If it is within this range, it can be manufactured under relatively stable conditions. When the amount of the carboxylic acid compound to be added is more than this, the excess carboxylic acid compound (b) remains and is unsatisfactory.

Further, in the case where the epoxy group is intentionally left, it is preferred that the total of the carboxylic acid compounds (b) and (c) is 20 to 90 equivalent % based on 1 equivalent of the epoxy resin (a). When it is out of this range, the effect of the composite hardening is weakened. Of course, in this case, it is necessary to give sufficient attention to the gelation in the reaction and the stability over time of the carboxylate compound (A).

The ratio of the compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups to the compound (c) having one or more hydroxyl groups and one or more carboxyl groups in terms of the molar ratio of the carboxyl group ( b): (c) is preferably in the range of 9:1 to 1:9, more preferably in the range of 4:6 to 8:2. If it is within this range, it is possible to prevent the sensitivity from being lowered when (b) is too small, and it is possible to prevent the effect of (c) from being weakened when (c) is too small.

The carboxylic acid esterification reaction can be carried out in the absence of a solvent, or can be carried out by diluting with a solvent. The solvent which can be used herein is not particularly limited as long as it is a solvent inert to the carboxylic acid esterification reaction.

The amount of the solvent to be used is preferably adjusted depending on the viscosity or use of the obtained resin, and it is preferred to use a solvent in such a manner that the solid content is 90 to 30% by mass, more preferably 80 to 50% by mass.

Specific examples of the solvent that can be used as the solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene, and aliphatic hydrocarbon solvents such as hexane, octane, and decane. And petroleum ether, white gasoline, solvent petroleum brain, etc. as a mixture thereof.

Further, examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate; cyclic esters such as γ-butyrolactone; and ethylene glycol monomethyl ether acetate; Ethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether Mono or polyalkylene glycol monoalkyl ether monoacetate such as acid ester, butanediol monomethyl ether acetate; dialkyl glutarate, dialkyl succinate, dialkyl adipate And other polycarboxylic acid alkyl esters and the like.

Further, examples of the ether solvent include alkyl ethers such as diethyl ether and ethylbutyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and triethylene glycol. a glycol ether such as glyceryl ether or triethylene glycol diethyl ether; or a cyclic ether such as tetrahydrofuran.

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

In addition, the reaction can be carried out in a single or mixed organic solvent such as the reactive compound (C) other than (A) or (B) described later. In this case, it is preferred to use it as a composition when it is used as a hardening type composition.

In the reaction, it is preferred to use a catalyst for promoting the reaction, and the amount of the catalyst used is relative to the total amount of the reactants, that is, the above epoxy compound (a), compound (b), compound (c), and The total amount of the reactants to be added with a solvent or the like is 0.1 to 10% by mass. Reaction temperature at this time The degree is 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include triethylamine, dimethylbenzylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethyliodideamine, and the like. A known general alkaline catalyst such as phenylphosphine, triphenylsulfonium, methyltriphenylphosphonium, chromium octylate or zirconium octylate.

Further, as the thermal polymerization inhibitor, it is preferred to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenyl bitter, diphenylamine, 3,5- Di-tert-butyl-4-hydroxytoluene and the like.

In the present reaction, sampling is suitably carried out, and the acid value of the sample is 5 mgKOH/g or less, preferably 2 mgKOH/g or less, as an end point.

As a preferable molecular weight range of the reactive carboxylic acid ester compound (A) obtained in this manner, the polystyrene-equivalent weight average molecular weight of GPC is in the range of 1,000 to 30,000, more preferably 1,500 to 20,000.

When the molecular weight is less than the molecular weight, the toughness of the cured product cannot be sufficiently exhibited. When the molecular weight is larger than the molecular weight, the viscosity is increased and coating or the like is difficult.

Hereinafter, the reactive polycarboxylic acid compound (B) of the present invention obtained by an acid addition step will be described. The acid addition step is carried out to introduce a carboxyl group into the reactive carboxylic acid ester compound (A) obtained in the previous step as necessary to obtain a reactive polycarboxylic acid compound (B). The carboxyl group is introduced for the purpose of, for example, a pattern in which a photoresist is to be patterned, and the active energy ray non-irradiated portion is rendered soluble in alkaline water, and imparts adhesion to a metal or an inorganic material.

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

As a specific example of the polybasic acid anhydride (d), for example, a compound having an acid anhydride structure in one molecule can be used, and particularly preferred are succinic anhydrides and neighboring resins which are excellent in alkaline aqueous solution developability, heat resistance and hydrolysis resistance. Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methylhexahydroortylene Dicarboxylic anhydride, trimellitic anhydride, or maleic anhydride.

The addition of the polybasic acid anhydride (d) can be carried out by adding the polybasic acid anhydride (d) to the above carboxylic acid esterification reaction liquid. The amount of addition needs to be changed as appropriate depending on the application.

However, when the polycarboxylic acid compound (B) of the present invention is to be used as an alkali-developing type photoresist, it is preferred to introduce a polybasic acid anhydride (d) in an amount calculated as follows, i.e., to make the final The solid acid value (according to JIS K5601-2-1:1999) of the obtained reactive polycarboxylic acid compound (B) is 30 to 120 mg. KOH / g, more preferably 40 ~ 105 mg. Calculated value of KOH/g. When the acid value of the solid matter at this time is in this range, the alkaline aqueous solution developability of the active energy ray-curable resin composition of the present invention exhibits good developability. That is, the patterning property is good and the management range for overdevelopment is also wide, and no excess acid anhydride remains.

In the reaction, it is preferred to use a catalyst to promote the reaction. The amount of the catalyst used is relative to the total amount of the reactants, that is, relative to the epoxy compound (a), the carboxylic acid compound (b) and (c). The total amount of the obtained carboxylate compound (A), the polybasic acid anhydride (d), and a solvent or the like to be added as needed is 0.1 to 10% by mass. The reaction temperature at this 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 triethylamine, dimethylbenzylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethyliodideamine, and the like. Phenylphosphine, triphenylsulfonium, methyltriphenylphosphonium, chromium octoate, zirconium octoate, and the like.

The acid addition reaction can be carried out in the absence of a solvent, or can be carried out by diluting with a solvent. The solvent which can be used herein is not particularly limited as long as it is inert to the acid addition reaction. Specifically, the same ones as those exemplified in the carboxylic acid esterification reaction of the previous step can be used. When the carboxylic acid esterification reaction in the previous step is carried out using a solvent, it may be inert with respect to the two reactions, and the solvent may be directly removed to the next step, that is, the acid addition reaction. .

The amount of the solvent to be used is preferably adjusted depending on the viscosity or use of the obtained resin, and it is preferred to use the solvent in such a manner that the solid content is 90 to 30% by mass, and more preferably 80 to 50% by mass.

Other than this, it can be carried out in a single or mixed organic solvent such as the following reactive compound (C). In this case, it is preferred to use it as a composition when it is used as a hardening type composition.

Further, it is preferred that the thermal polymerization inhibitor or the like be the same as the above-described example of the above-mentioned carboxylic acid esterification reaction.

In the present reaction, sampling is appropriately performed, and the point at which the acid value of the reactant reaches a range of ±10% of the set acid value is taken as an end point.

The active energy ray-curable resin composition of the present invention contains an epoxy carboxylic acid ester compound (A) and/or a polycarboxylic acid compound (B). The epoxy carboxylic acid ester compound (A) and/or the polycarboxylic acid compound (B) are appropriately used in accordance with the use thereof. For example, in the case of a solder resist application, when a pattern is formed by a printing method without developing, or when a solvent-developing type such as a so-called solvent developing type is removed by a solvent or the like, an epoxy carboxylate compound (A) can be used. In the case of developing with alkaline water, the polycarboxylic acid compound (B) can be used. In general, a polycarboxylic acid compound (B) is often used in this application from the viewpoint of easily producing a fine pattern in an alkaline water developing type. Of course, the epoxy carboxylate compound (A) and the polycarboxylic acid compound (B) are not used in any case.

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

In the present invention, specific examples of the reactive compound (C) which can be used include a radical reaction type acrylate, a cationic reaction type other epoxy compound, and an ethylene compound which induces the two. Reactive oligomers.

Examples of the acrylates which can be used include monofunctional (meth)acrylates and polyfunctional (meth)acrylates, and examples thereof include epoxy acrylates, polyester acrylates, and urethane acrylates. Ester and the like.

Examples of the monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, and polyethylene glycol. (A Acrylate, polyethylene glycol (meth) acrylate monomethyl ether, phenyl ethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, (methyl) Benzyl acrylate, tetrahydrofurfuryl (meth) acrylate, and the like.

Examples of the polyfunctional (meth) acrylate include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and ruthenium. Alcohol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)propene Ethoxyethyl isomeric cyanurate, polypropylene glycol di(meth)acrylate, adipic acid epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol Ethylene oxide (meth) acrylate, bisphenol di(meth) acrylate, ε-caprolactone adduct of hydroxypivalic acid neopentyl glycol, di(meth) acrylate, dipentaerythritol and ε- Poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, trishydroxyethylpropane tri(meth)acrylate And its ethylene oxide adduct, pentaerythritol tri(meth)acrylate and its ethylene oxide adduct, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(methyl) Acrylate and ethylene oxide adducts.

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

Further, examples of the reactive oligomer include an urethane amide having a functional group capable of inducing an active energy ray and a urethane bond in the same molecule; a polyester acrylate capable of sensing a functional group and an ester bond of an active energy ray; and an epoxy acrylate derived from an epoxy resin and having a functional group capable of inducing an active energy ray in the same molecule; A reactive oligomer or the like using these bonds is used in combination.

Further, the cationically reactive monomer is usually not particularly limited as long as it is 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-epoxycyclohexylformate ("Cyracure UVR-6110", manufactured by Union Carbide, etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexyl Formate, cyclohexene ethylene dioxide ("ELR-4206" manufactured by Union Carbide, etc.), limonene dioxide ("Celloxide 3000" manufactured by Daicel Chemical Industry Co., Ltd., etc.), propylene oxide Cyclohexene, 3,4-epoxy-4-methylcyclohexyl-2-propene oxide, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) ring Hexyl-intermediate Alkane, bis(3,4-epoxycyclohexyl) adipate ("Cyracure UVR-6128" by Union Carbide, etc.), bis(3,4-epoxycyclohexylmethyl) adipate And bis(3,4-epoxycyclohexyl)ether, bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexyl)diethyloxane, and the like.

Among these, as the reactive compound (C), a radical-curable acrylate is preferable. In the case of a cationic type, since a carboxylic acid reacts with an epoxy group, it is necessary to prepare a two-liquid mixing type.

By mixing the carboxylic acid ester compound (A) of the present invention and/or the reactive polycarboxylic acid compound (B) and, if necessary, the reactive compound (C) other than (A) and (B), The active energy ray-curable resin composition of the present invention. In this case, other components may be appropriately added depending on the application.

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

The colored pigment which can be used in the present invention means a user who has made the active energy ray-curable resin composition of the present invention into a colored material. The industry speculates as follows, due to this Since the balance of the hydroxy group of the carboxylic acid ester compound (A) and the reactive polycarboxylic acid compound (B) used in the invention is within a specific range, it is possible to exhibit particularly excellent affinity for a pigment, that is, dispersibility. Although it is not clear about the mechanism, since the dispersion can be performed well, the pigment concentration can be made rich, and in the composition which must be developed, a good patterning property can be exhibited due to a better dispersion state. Further, since the developing residue of the developing and dissolving portion is also small, it is preferable.

Examples of the coloring pigment include organic pigments such as phthalocyanine, azo, and quinacridone, and inorganic pigments such as carbon black and titanium oxide. The dispersibility of these medium carbon blacks is higher and better.

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

Examples of the radical photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and the like; acetophenone, 2,2-diethoxy-2- Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methylphenyl-1-propanone, diethyl Acetophenones such as oxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propane; - anthracene such as ethyl hydrazine, 2-tert-butyl fluorene, 2-chloroindole, 2-pentyl hydrazine; 2,4-diethyl-9-oxygen sulphide 2-isopropyl-9-oxosulfur 2-chloro-9-oxosulfur Et--9-oxygen a ketal such as acetophenone dimethyl ketal or benzyl dimethyl ketal; benzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 4,4' - benzophenones such as bismethylaminobenzophenone; 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzhydrazide) A conventional radical type photoreaction initiator such as a phosphine oxide such as phenylphosphine oxide.

Further, examples of the cationic photopolymerization initiator include a diazonium salt of a Lewis acid, a phosphonium salt of a Lewis acid, a phosphonium salt of a Lewis acid, a phosphonium salt of a Lewis acid, and other halides. An initiator, a borate initiator, and other photoacid generators.

Examples of the diazonium salt of the Lewis acid include p-methoxyphenyldiazonium fluorophosphonate. N,N-diethylaminophenyldiazonium hexafluorophosphonate (San-Aid SI-60L/SI-80L/SI-100L manufactured by Sanshin Chemical Industry Co., Ltd.), etc.; as a Lewis acid Examples of the salt include diphenylphosphonium hexafluorophosphonate and diphenylsulfonium hexafluoroantimonate; and examples of the phosphonium salt of the Lewis acid include triphenylsulfonium hexafluorophosphonate (Cyracure manufactured by Union Carbide Co., Ltd.). For example, UVI-6990 or the like, triphenylsulfonium hexafluoroantimonate (Cyracure UVI-6974, manufactured by Union Carbide Co., Ltd.), etc.; and a phosphonium salt of a Lewis acid include triphenylsulfonium hexafluoroantimonate.

Examples of the other halides include 2,2,2-trichloro-[1-4'-(dimethylethyl)phenyl]ethanone (Tiigonal PI manufactured by AKZO Co., Ltd.), 2,2-two. Chloro-1-4-(phenoxyphenyl)ethanone (Sandray 1000 manufactured by Sandoz Co., Ltd.), α, α, α-tribromomethylphenyl hydrazine (BMPS manufactured by Seiko Chemical Co., Ltd., etc.), and the like. As three As an initiator, it can be exemplified by 2,4,6-tris(trichloromethyl)-three 2,4-trichloromethyl-(4'-methoxyphenyl)-6-three (Triazine A, etc. manufactured by Panchim, etc.), 2,4-trichloromethyl-(4'-methoxystyryl)-6-three (Triazine PMS manufactured by Panchim, etc.), 2,4-trichloromethyl-(piperidinyl)-6-three (Triazine PP manufactured by Panchim, etc.), 2,4-trichloromethyl-(4'-methoxynaphthyl)-6-three (Triazine B, etc. manufactured by Panchim), 2-[2'-(5"-methylfuranyl)ethylene]-4,6-bis(trichloromethyl)-all (made by Sanwa Chemical Co., etc.), 2-(2'-furylethylidene)-4,6-bis(trichloromethyl)-all three (made by Sanwa Chemical Co., Ltd.), etc.

Examples of the boric acid ester-based initiator include NK-3876 and NK-3881 which are produced by Japanese photosensitive pigments, and examples of other photoacid generators include 9-phenylacridine and 2,2'-bis ( O-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole (biimidazole manufactured by Heijin Chemical Co., Ltd.), 2,2-azobis(2-amino- Propane) dihydrochloride (V50, etc., manufactured by Wako Pure Chemical Industries, Ltd.), 2,2-azobis[2-(imidazolin-2-yl)propane] dihydrochloride (VA044, manufactured by Wako Pure Chemical Industries, Ltd.) ), [η-5-2-4-(cyclopentadecyl)(1,2,3,4,5,6,η)-(methylethyl)-benzene]iron(II)hexafluorophosphine Acid salt (Irgacure 261, manufactured by Ciba Geigy Co., Ltd.), bis(y5-cyclopentadienyl) bis[2,6-difluoro-3-(1H-pyrid-1-yl)phenyl]titanium (Ciba Geigy The company manufactures CGI-784, etc.).

In addition, an azo initiator such as azobisisobutyronitrile or benzoyl peroxide may be used in combination. A peroxide-based radical initiator such as ruthenium. Further, a radical initiator or a cationic initiator may be used in combination. The initiator may be used singly or in combination of two or more.

In addition, in order to apply the active energy ray-curable resin composition of the present invention to various uses, an additional component having an upper limit of 70% by mass may be added to the resin composition. Examples of the other components include other additives, a pigment material, a coloring material, and a volatile solvent added to adjust the viscosity to impart coating suitability and the like. The other ingredients that can be used are exemplified below.

As other additives, for example, a thermosetting catalyst such as melamine, a thixotropic imparting agent such as Aerosil, a polyfluorene-based or fluorine-based leveling agent or an antifoaming agent, hydroquinone or hydroquinone monomethyl ether can be used. Such as polymerization inhibitors, stabilizers, antioxidants and the like.

Further, as another pigment material, for example, a so-called filler pigment may be used without a purpose of coloring. For example, talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, vermiculite, clay, etc. are mentioned.

In addition, resins which do not exhibit reactivity to active energy rays (so-called inert polymers), such as other epoxy resins, phenol resins, amine ester resins, polyester resins, ketone-based formaldehyde resins, cresol resins, may also be used. , xylene resin, diallyl phthalate resin, styrene resin, guanamine resin, natural and synthetic rubber, acrylic resin, polyolefin resin, and the like. These resins are preferably used in the range of 40% by mass.

In particular, when the reactive polycarboxylic acid compound (B) is to be used for a solder resist application, it is preferred to use a conventional epoxy resin which is known as a resin which does not exhibit reactivity to an active energy ray. This is because the carboxyl group derived from (B) remains after the reaction and hardening by the active energy ray, and as a result, the water resistance or the hydrolysis property of the cured product is deteriorated. Therefore, the remaining carboxyl group is further carboxylated by using an epoxy resin to form a stronger crosslinked structure.

Further, a volatile solvent may be added to the range of 50% by mass, more preferably 35% by mass, for the purpose of adjusting the viscosity, depending on the purpose of use.

The present invention is an active energy ray-curable resin composition as a material for molding, a material for forming a film, or a composition for a photoresist.

In the present invention, the material for molding refers to a member in which an uncured composition is placed in a mold, or a mold is pressed to form an object, and then an active energy ray is used to cause a hardening reaction to be formed; or in an unhardened combination. A material used for applications in which a material such as a laser is irradiated with a focus light such as a laser to cause a hardening reaction.

As a specific use, the following preferable uses are used: a sheet formed into a flat shape, a sealing material for protecting the element, and a micromolded "die" pressed against the uncured composition to perform fine molding. The nanocompression molding material, in particular, a peripheral sealing material such as a light-emitting diode or a photoelectric conversion element which is strict in terms of heat.

In the present invention, the material for forming a film is used to cover the surface of the substrate. As specific applications, ink materials such as gravure ink, letterpress ink, screen ink, and plate ink, coating materials such as hard coat, overcoat, overprint varnish, and clear coat, various adhesives for lamination and optical disc, A resist material such as an adhesive, a resist material such as a solder resist, an etch resist, or a micro-mechanical photoresist is equivalent thereto. In addition, after the film formation material is temporarily applied to the release substrate, the film is bonded to the original target substrate, and the so-called ruthenium film which forms the film also corresponds to the film formation material.

Since the carboxyl group of the reactive polycarboxylic acid compound (B) is introduced to improve the adhesion to the substrate, it is preferably used for coating a plastic substrate or a metal substrate.

Further, it is also preferable to use the unreacted reactive polycarboxylic acid compound (B) to be soluble in an alkaline aqueous solution, and to use it as an alkaline water developing type resist material composition.

In the present invention, the photoresist composition refers to a film layer on which a composition is formed on a substrate, and then partially irradiates an active energy ray such as an ultraviolet ray, and is characterized by a difference in physical properties between the illuminating portion and the non-irradiated portion. Active energy ray-sensitive composition. Specifically, it refers to a composition which is used for the purpose of removing the irradiated portion or the unirradiated portion by a method such as dissolution with a solvent or the like, an alkaline solution, or the like.

The active energy ray-curable resin composition of the present invention can be easily hardened by an active energy ray. Here, specific examples of the active energy ray include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, and thunder rays, and particle beams such as α rays, β rays, and electron beams. Preferred light sources, such as ultraviolet light, lightning rays, visible light or electron beams, are preferred in view of the preferred use of the present invention.

The active energy ray-curable resin composition of the present invention can be applied to various materials that can be patterned, for example, particularly used as a solder resist material, an interlayer insulating material for a build-up method, and further, can be used as an optical waveguide. In electrical, electronic, optical substrates, etc., such as printed circuit boards, optoelectronic substrates or optical substrates.

As a particularly good use, it can make full use of its properties to obtain tough and hardened materials, and it can be used for permanent photoresist applications such as solder resists, and to make full use of its pigment dispersibility characteristics for printing inks and color filters. For color resists such as light sheets, it is particularly preferable to use the photoresist for black matrices.

In addition to this, it can also be used particularly preferably for decidual film applications which require mechanical strength for the hardening reaction using active energy ray. That is, since the balance of the hydroxyl group and the epoxy group of the above epoxy resin (a) used in the present invention is within a specific range, although the reactive carboxylate compound of the present invention has a relatively high molecular weight, Play a good developability.

The method of forming the film is not particularly limited, and any of the following methods may be employed: a gravure printing method such as a gravure, a letterpress printing method such as a letterpress, a stencil printing method such as a screen, a lithographic printing method such as a plate, a roll coating, a knife coating, and a die coating. Various coating methods such as curtain coating and spin coating.

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

The article covered by the active energy ray-curable resin composition of the present invention means that the active energy ray-curable resin composition of the present invention is formed on a suitable substrate. The layer is partially irradiated with an active energy ray such as an ultraviolet ray to obtain a hardened layer formed on the substrate. In this case, the cured product of the resin composition may be an article in which the film hardened layer is uniformly formed on the substrate, and the article may be formed by forming a film hardened layer by a resist pattern, and is not particularly limited.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples. Further, in the examples, unless otherwise specified, the parts represent parts by mass.

The softening point, epoxy equivalent, and the like were measured under the following conditions.

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

2) Softening point: Measurement was carried out in accordance with the method according to JIS K 7234:1986.

3) Acid value: It was measured in accordance with the method according to JIS K 0070:1992.

4) The measurement conditions of GPC are as follows.

Equipment type: TOSOH HLC-8220GPC

Column: TSKGEL Super HZM-N

Dissolved solution: THF (tetrahydrofuran); 0.35 ml per minute, 40 ° C

Detector: differential refractometer

Molecular weight standard: polystyrene

Reference Example 1: Preparation of Carboxylate Compound (A) of Epoxy Resin represented by General Formula (2)

288 g of NC-3000H (manufactured by Nippon Kayaku Co., Ltd., softening point of 70 ° C, epoxy equivalent of 288 g/eq, and all of R ₃ shown in the general formula (2) are hydrogen An atom, p is an average value, and is an acrylic acid (abbreviated as AA, Mw=) as a compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in the molecule described in Table 1 72) The dimethylolpropionic acid (abbreviated as DMPA, Mw = 134) which is a compound (c) having one or more hydroxyl groups and one or more carboxyl groups in the molecule described in Table 1. The input equivalent ratio of each AA and DMPA to the epoxy group is described in terms of molar ratio.

Add 3 g of triphenylphosphine as a catalyst, and add propylene glycol monomethyl ether as a solvent The acetate was reacted at 100 ° C for 24 hours so that the solid content became 80% by mass to obtain a solution of the carboxylate compound (A) of the present invention.

The reaction end point was determined by the solid acid value (AV; mgKOH/g), and the measured values are shown in Table 1. The acid value is measured in the reaction solution and then converted to the acid value of the solid.

Reference Example 2: Preparation of Carboxylate Compound (A) of Epoxy Resin represented by General Formula (3)

230 g of NC-2000 (manufactured by Nippon Kayaku Co., Ltd., softening point of 60 ° C, epoxy equivalent of 230 g/eq, and all of R ₄ shown in the general formula (3) are hydrogen. The atom and r are the average values, and the amount of the acrylic acid as the compound (b) and the dimethylolpropionic acid as the compound (c) in the amounts shown in Table 1 are shown in Table 1. The input equivalent ratio of each AA and DMPA to the epoxy group is described in terms of molar ratio.

3 g of triphenylphosphine as a catalyst was added, and propylene glycol monomethyl ether monoacetate as a solvent was added to make the solid matter 80% by mass of the reaction liquid, and reacted at 100 ° C for 24 hours to obtain a carboxylate compound. (A) solution.

The reaction end point was determined by the solid acid value (AV; mgKOH/g), and the measured values are shown in Table 1. The acid value is measured in the reaction solution and then converted to the acid value of the solid.

Reference Example 3: Production of epoxy carboxylic acid ester compound (A) of epoxy resin represented by general formula (4)

250 g of XD-1000 (manufactured by Nippon Chemical Co., Ltd., softening point of 70 ° C, epoxy equivalent of 250 g/eq, and all of R ₅ shown in the general formula (4) are hydrogen. The atom, t is an average value, is 3), the acrylic acid as the compound (b) and the dimethylolpropionic acid as the compound (c) described in Table 1. The input equivalent ratio of each AA and DMPA to the epoxy group is described in terms of molar ratio.

Using 3 g of triphenylphosphine as a catalyst, and adding propylene glycol monomethyl ether monoacetate as a solvent to have a solid content of 80% by mass, and reacting at 100 ° C for 24 hours to obtain an epoxy carboxylate compound ( A) Solution.

The reaction end point was determined by the solid acid value (AV; mgKOH/g), and the measured values are shown in Table 1. The acid value is measured in the reaction solution and then converted to the acid value of the solid.

Example 1: Preparation of Comparative Carboxylate Compound

Add NC-3000H 288 g, 72 g (mole ratio: 1.0) of acrylic acid as the compound (b), 3 g of triphenylphosphine as a catalyst, and add propylene glycol monomethyl ether monoacetate as a solvent to make The solid content was 80% by mass, and the reaction was carried out at 100 ° C for 24 hours to obtain a carboxylate compound solution.

The reaction end point was determined by the solid acid value (AV; mgKOH/g), and the measured values are shown in Table 1. The acid value is measured in the reaction solution and then converted to the acid value of the solid.

Example 2: Preparation of comparative carboxylic acid ester compound

230 g of NC-2000, 72 g of acrylic acid (mole ratio: 1.0) as the compound (b), 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent were added thereto. The solid matter was 80% by mass of the reaction liquid, and reacted at 100 ° C for 24 hours to obtain a carboxylate compound solution.

The reaction end point was determined by the solid acid value (AV; mgKOH/g), and the measured values are shown in Table 1. The acid value is measured in the reaction solution and then converted to the acid value of the solid.

Example 3: Preparation of comparative epoxy carboxylate compound

Addition of propylene glycol monomethyl ether monoacetate as a solvent to XD-1000 250 g, 72 g of acrylic acid as compound (b) (mole ratio: 1.0), and 3 g of triphenylphosphine as a catalyst The solid content was 80% by mass, and the reaction was carried out at 100 ° C for 24 hours to obtain a solution of an epoxy carboxylate compound.

The reaction end point was determined by the solid acid value (AV; mgKOH/g), and the measured values are shown in Table 1. The acid value is determined in the reaction solution and then converted into the acid of the solid. value.

Comparative Example 4-1: Preparation of comparative carboxylic acid ester compound

Adding cresol novolac type epoxy resin EOCN-103S (manufactured by Nippon Kayaku Co., Ltd., softening point: 80 ° C, epoxy equivalent: 200 g / eq) 200 g, as one or more polymerizable ethylenic unsaturation in the molecule 36 g (molar ratio: 0.5) of acrylic acid having one or more carboxyl groups and (b), dimethylolpropionic acid (67 g) as a compound (c) having one or more hydroxyl groups and one or more carboxyl groups in the molecule Ear ratio: 0.5).

3 g of triphenylphosphine as a catalyst was added, and propylene glycol monomethyl ether monoacetate as a solvent was added to make the solid content 80% by mass, and reacted at 100 ° C for 24 hours to obtain a comparative carboxylic acid ester compound solution. .

The reaction end point was determined by the solid acid value (AV; mgKOH/g), and the measured values are shown in Table 1. The acid value is measured in the reaction solution and then converted to the acid value of the solid.

Comparative Example 4-2: Preparation of comparative carboxylic acid ester compound

Adding cresol novolac type epoxy resin jER-1002 (manufactured by Nippon Epoxy Co., Ltd., epoxy equivalent: 400 g/eq) 200 g, as (b) acrylic acid 18 g (mole ratio: 0.5), as a compound (c) dimethylolpropionic acid 34 g (mole ratio: 0.5).

3 g of triphenylphosphine as a catalyst was added, and propylene glycol monomethyl ether monoacetate as a solvent was added to make the solid matter 80% by mass of the reaction liquid, and reacted at 100 ° C for 24 hours to obtain a comparative carboxylic acid. Ester compound solution.

The reaction end point was determined by the solid acid value (AV; mgKOH/g), and the measured values are shown in Table 1. The acid value is measured in the reaction solution and then converted to the acid value of the solid.

[Table 1] Reference Examples 1, 2, 3, Examples 1, 2, 3 and Comparative Example 4: Preparation of epoxy carboxylate compound (A)

Test Example 1: Preservation stability of epoxy carboxylate compound (A)

The epoxy carboxylate compound solutions obtained in Reference Example 1 and Example 1 were stored in a freezer compartment at minus 5 ° C, and the time until crystals were produced was compared and shown in Table 2.

From the above results, it is clear that the storage stability of the resin solution is improved as the compound (c) having one or more hydroxyl groups and one or more carboxyl groups in the molecule is introduced.

Reference Example 4: Reactive Polycarboxylic Compound (B) of Epoxy Resin represented by General Formula (2) preparation

To 299 g of the carboxylic acid ester compound (A) solution obtained as Reference Examples 1-1, 1-2, and 1-3, respectively, the tetrahydro-o-benzene as the polybasic acid anhydride (d) was added in the amount shown in Table 3. Diacetic anhydride (abbreviated as THPA), and propylene glycol monomethyl ether monoacetate as a solvent is added to make the solid matter 65% by mass, and heated to 100 ° C to carry out an acid addition reaction to obtain a reactive polycarboxylic acid compound of the present invention. (B) Solution (Reference Examples 4-1, 4-2, 4-3, 4-4). The solid acid value (mgKOH/g) is shown in Table 3.

Reference Example 5: Preparation of Reactive Polycarboxylic Compound (B) of Epoxy Resin represented by General Formula (3)

In the 299 g of the carboxylate compound (A) solution obtained as Reference Examples 2-1, 2-2, 2-3, and 2-4, the amount described in Table 3 was added as the polybasic acid anhydride (d). Tetrahydrophthalic anhydride, and adding propylene glycol monomethyl ether monoacetate as a solvent to make the solid matter 65% by mass of the reaction liquid, heating to 100 ° C, and performing an acid addition reaction for 3 hours to obtain the present invention A reactive polycarboxylic acid compound (B) solution (Reference Examples 5-1, 5-2, 5-3, 5-4, 5-5). The solid acid value (mgKOH/g) is shown in Table 3.

Reference Example 6: Production of Polycarboxylic Acid Compound (B) of Epoxy Resin represented by General Formula (4)

In 299 g of the epoxy carboxylic acid ester compound (A) solution obtained as Reference Examples 3-1, 3-2, and 3-3, the amount of tetrahydrogen as the polybasic acid anhydride (d) described in Table 3 was added. Phthalic anhydride, and propylene glycol monomethyl ether monoacetate as a solvent is added to make the solid content 65% by mass, and the acid addition reaction is carried out by heating to 100 ° C to obtain a polycarboxylic acid compound (B) solution (Reference example) 6-1, 6-2, 6-3, 6-4). The solid acid value (mgKOH/g) is shown in Table 3.

Example 5: Preparation of comparative reactive polycarboxylic acid compound

To 299 g of the carboxylic acid ester compound solution obtained in Example 1, tetrahydrophthalic anhydride as a polybasic acid anhydride (d) was added in the amount described in Table 3, and propylene glycol monomethyl ether as a solvent was added. The acetate was subjected to an acid addition reaction by heating the solid content to 65% by mass to obtain a reactive polycarboxylic acid compound solution (Examples 5-1 and 5-2). Solid acid The value (mgKOH/g) is shown in Table 3.

Example 6: Preparation of a comparative polycarboxylic acid compound for comparison

To 299 g of the carboxylate compound solution obtained in Example 2, tetrahydrophthalic anhydride as a polybasic acid anhydride (d) was added in an amount described in Table 3, and propylene glycol monomethyl ether as a solvent was added. The acetate was heated to 100 ° C in a solid content of 65% by mass of the reaction liquid, and an acid addition reaction was carried out for 3 hours to obtain a reactive polycarboxylic acid compound solution (Examples 6-1 and 6-2). The solid acid value (mgKOH/g) is shown in Table 3.

Example 7: Preparation of a comparative reactive polycarboxylic acid compound

To 299 g of the epoxy carboxylate compound solution obtained in Example 3, tetrahydrophthalic anhydride as a polybasic acid anhydride (d) was added in the amount shown in Table 3, and propylene glycol monomethyl as a solvent was added. The ether monoacetate was subjected to an acid addition reaction by heating the solid content to 65% by mass to obtain a polycarboxylic acid compound solution (Examples 7-1 and 7-2). The solid acid value (mgKOH/g) is shown in Table 3.

Comparative Example 8: Preparation of comparative reactive polycarboxylic acid compound

To 299 g of the epoxy carboxylic acid ester compound solution obtained in Comparative Examples 4-1 and 4-2, tetrahydrophthalic anhydride as a polybasic acid anhydride (d) described in Table 3 was added and added. The propylene glycol monomethyl ether monoacetate as a solvent was subjected to an acid addition reaction by heating to 100 ° C to obtain a polycarboxylic acid compound solution (Comparative Examples 8-1, 8-2, 8-3). ). The solid acid value (mgKOH/g) is shown in Table 3.

Reference Examples 7, 8, 9, Examples 9, 10, and 11 and Comparative Example 12: Preparation of a hard coating composition and a cured product thereof, and hardness evaluation test and impact evaluation test thereof

20 g of the reactive carboxylate compound (A) prepared in Reference Examples 1, 2, and 3, and Examples 1, 2, and 3 and Comparative Example 4, as the monomer of the radical hardening type (C) 4 g of pentaerythritol hexaacrylate and Irgacure 184 1.5 g as an ultraviolet reactive type initiator were dissolved by heating. (In Reference Examples 7-4, 8-4, and 9-4, UVI-6990 1.0 g was additionally added as a cationic initiator.)

Further, the film was applied to a polycarbonate plate by a manual applicator so as to have a film thickness of 20 μm at the time of drying, and dried in an electric oven at 80 ° C for 30 minutes. After drying, an ultraviolet ray vertical exposure apparatus (manufactured by ORC Manufacturing Co., Ltd.) equipped with a high-pressure mercury lamp was used, and ultraviolet rays having an irradiation line amount of 1000 mJ were irradiated and hardened to obtain a multilayer material.

The hardness of the coating film of the multilayer material was measured in accordance with JIS K 5600-5-4:1999 (Test Example 2), and the impact test (Test Example 3) was carried out in accordance with ISO 6272-1:2002, and The thermal shock test (Test Example 4) was carried out in JIS K 5600-7-4:1999. Each of the prepared test samples (Reference Examples 7 to 9, Examples 9 to 11 and Comparative Example 12) and each evaluation test result (Test Examples 2 to 4) are shown in Table 4.

From the above results, it is clear that the reference examples 7, 8, and 9 are compared with the examples 9, 10, and 11 in which all of the epoxy groups are acrylated without using a compound (c) having both a hydroxyl group and a carboxyl group in one molecule. The prepared hard coating material has improved impact resistance. The reason that the impact resistance is improved is that the density of the double bond is moderately decreased with the introduction of the compound (c), and The introduction of a hydroxyl group brings about a favorable influence by the loose crosslinked structure formed by hydrogen bonding.

Further, in Comparative Examples 12-1 and 12-2 derived from a general difunctional epoxy resin, the hardenability was greatly deteriorated, and the impact resistance was low.

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

The reactive polycarboxylic acid compound (B) obtained in Reference Examples 4, 5, and 6, Examples 5, 6, and 7 and Comparative Example 8 (54.44 g) and HX-220 (trade name) as another reactive compound (C) were added. ; a bisacrylate monomer manufactured by Nippon Kayaku Co., Ltd.) 3.54 g, Irgacure-907 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, 4.72 g, and Kayacure DETX-S (Japanese) Manufactured by a drug (stock) 0.47 g, GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.) 14.83 g as a hardening component, 1.05 g of melamine as a thermosetting catalyst, and methyl ethyl ketone 20.95 as a concentration adjusting solvent g, kneaded using a bead mill to uniformly disperse it to obtain a photoresist resin composition.

Using a bar coater #20, the resulting composition was uniformly coated on a polyethylene terephthalate film as a support film, and passed through a hot air drying oven at a temperature of 70 ° C to form a resin having a thickness of 20 μm. After the layer, a polyethylene film as an overcoat film was attached to the resin layer to obtain a ruthenium film. The outer layer of the obtained ruthenium film was peeled off while using the heating roll at a temperature of 80 ° C, and the resin layer was attached to the polyimide substrate (thickness of the copper circuit: 12 μm; thickness of the polyimide film: 25 Μm) on the entire substrate surface.

Further, the mixture of the so-called (A) and (B) used in Reference Examples 10-5, 11-6, and 12-5 means a ratio of 50:50 by weight of the solution, and the reference examples are respectively used. The acid-modified carboxylic acid ester compound (A) prepared in 1-1, 2-1, or 3-1, which is equivalent to the one prepared in Reference Example 4-1, 5-1, or 6-1 The polycarboxylic acid compound (B) of the oxygen resin is mixed.

Then, an ultraviolet exposure apparatus (ORC Manufacturing Co., Ltd.; model: HMW-680GW) was used, and a photomask having a circuit pattern was drawn, and a stage exposure meter No. 2 manufactured by Kodak was used to irradiate 500 mJ/cm for evaluation of sensitivity. ² ultraviolet rays. Thereafter, the film on the enamel film was peeled off, and the peeled state was confirmed. Thereafter, spray development was carried out using a 1% sodium carbonate aqueous solution to remove the resin in the ultraviolet non-irradiated portion. After washing with water, the printed substrate was subjected to a heat-hardening reaction for 60 minutes in a hot air dryer at 150 ° C to obtain a cured film.

The test was carried out by the evaluation method shown below (Test Examples 5 to 10), whereby the ruthenium film type resistive films obtained in Reference Examples 10, 11, 12, Examples 13, 14, 15 and Comparative Example 16 were evaluated. performance. The evaluation test results of the respective cured films are shown in Table 5.

Test Example 5: Evaluation of folding endurance

The polyimide printed circuit board on which the cured film of the photoresist is formed is mountain-folded so that the cured film side is positioned upward, and the bent portion is sufficiently folded by fingers. The bent portion was restored, and the photoresist film was observed with a magnifying glass.

Evaluation criteria: ○: no cracking; △: a few cracks were observed; ×: peeling occurred

Test Example 6: Evaluation of thermal shock resistance

A thermal shock test was performed on the polyimide substrate on which the resistive cured film was formed in the range of -65 to 120 °C. The test method is based on JIS C5012-9.1:1993. After the test, the peeling test was carried out using a cellophane tape (registered trademark).

Evaluation criteria: ○: no peeling; △: slight peeling was observed; ×: peeling occurred

Test Example 7: Evaluation of high temperature moisture resistance

The polyimide substrate on which the photoresist of the photoresist was formed was placed in an autoclave at 120 ° C for 1 hour. The substrate was taken out, air-dried at room temperature, and then subjected to a peeling test using a cellophane tape (registered trademark).

Evaluation criteria: ○: no peeling; △: slight peeling was observed; ×: peeling occurred

Test Example 8: Sensitivity evaluation

The sensitivity is determined based on the concentration portion remaining in the exposure portion of the stage exposure meter at the time of development to the first stage. When the number of stages (value) is large, it is determined that there is a high sensitivity (unit: level) in the rich portion of the exposure table.

Test Example 9: Developmentability evaluation

The developability is evaluated based on the time until the pattern-shaped portion is completely developed when the exposure portion of the transmission pattern mask is developed, that is, the development time (unit: second).

Test Example 10: Evaluation of hardenability

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

From the above results, it is clear that the photoresist composition of the present invention can obtain a cured product having a relatively high hardness and has good developability and sensitivity as a photoresist. Further, it has high folding endurance in the case of Reference Examples 10 and 11. Further, in Reference Example 12, it has high cold shock resistance and high temperature moisture resistance. The photoresist composition of the comparative example and the cured product thereof did not show good evaluation results in terms of folding endurance, thermal shock resistance, developability, and sensitivity, and could not satisfy the performance as a ruthenium film resist material.

Reference Example 13, Example 17 and Comparative Example 18: Preparation of Flame Retardant Resin and Comparative Resin

9.5 g of the photoresist composition prepared in Reference Example 10-2, Example 13-1 and Comparative Example 16-1, and 0.5 g of a phosphate ester flame retardant (SP-703H manufactured by Shikoku Chemicals Co., Ltd.) were mixed and stirred. A hardened resin composition was obtained. The composition was applied to a polyimide film having a film thickness of 25 μm by a bar coater #20, and passed through a hot air drying oven at a temperature of 70 ° C to form a resin layer having a thickness of about 15 μm. Ultraviolet rays of 500 mJ/cm ^{2 were} irradiated using an ultraviolet exposure apparatus (ORC Manufacturing Co., Ltd.; model: HMW-680GW). After the irradiation, the printed substrate was subjected to a heat curing reaction for 60 minutes in a hot air dryer at 150 ° C to obtain a cured film (Reference Example 13, Example 17, and Comparative Example 18, respectively).

Test Example 11: Evaluation of flame retardancy

The cured film obtained in Reference Example 13, Example 17, and Comparative Example 18 was cut together with a polyimide film to form a strip having a length of 20 cm and a width of 2 cm. Vertically cut the film Straight suspension, ignited from the lower end with an igniter to evaluate flame retardancy. In order to compare the flame retardancy and the folding endurance, the folding endurance test data of Reference Example 10-2, Example 13-1, and Comparative Example 16-1 are collectively described in Table 6 below for reference.

From the above results, it is clear that the carboxylic acid ester compound of the reference example is a material which can simultaneously have flame retardancy and folding resistance.

Reference Examples 14, 15, 16, Examples 19, 20, 21 and Comparative Example 22: Preparation of Colored Pigment Dispersion Resin

20 g of the reactive polycarboxylic acid compound (B) obtained in Reference Examples 4, 5, 6, Examples 5, 6, and 9 and Comparative Example 8, DPHA (trade name; Japan) as another reactive compound (C) 5.0 g of an acrylate monomer manufactured by a chemical (stock), 10 g of propylene glycol monomethyl ether acetate as an organic solvent, and 10 g of Mitsubishi carbon black MA-100 as a coloring pigment were mixed and stirred. 35 g of glass beads were placed therein and dispersed by a paint shaker for 1 hour.

The dispersion after completion of the dispersion was applied onto a polyethylene terephthalate film by a bar coater #2, and dried in a warm air dryer at 80 ° C for 10 minutes to obtain each carbon black dispersion resin.

Test Example 12: Evaluation of pigment dispersibility

The carbon black dispersion resin obtained in Reference Examples 14, 15, 16, Examples 19, 20, 21 and Comparative Example 22 was used using a 60° reflection gloss meter (1G-331 gloss meter manufactured by Horiba, Ltd.). The gloss of the surface of the coating film was measured to evaluate the dispersibility of carbon black. At this time, the higher gloss indicates that the pigment dispersibility is good. The results are shown in Table 7.

From the above results, it was confirmed that the dispersibility of the pigment of the reactive polycarboxylic acid compound (B) of the reference example was improved. According to the difference between the polycarboxylic acid and the example, the pigment dispersing action is considered to be due to the addition of an epoxy resin and a specific structure in the basic skeleton of the molecule. The difference in effect produced by the compound (c).

Reference Example 17, Example 23, and Comparative Example 24: Preparation of Colored Pigment Dispersion Resin

20 g of the reactive polycarboxylic acid compound (B) obtained in Reference Example 4-2, Example 5-1 and Comparative Example 8-1, and DPHA (trade name; Nipponization) as another reactive compound (C) 5.0 g of acrylate monomer manufactured by the drug (stock), 10 g of propylene glycol monomethyl ether acetate as an organic solvent, and 10 g of Mitsubishi carbon black MA-100 as a coloring pigment were mixed and stirred. 35 g of glass beads were placed therein and dispersed by a paint shaker for 1 hour. The obtained carbon black dispersion resin liquid was collected in a sample bottle to obtain a color pigment dispersion liquid.

Test Example 13: Evaluation of storage stability of coloring pigment dispersion

The color pigment dispersion liquid prepared in Reference Example 17, Example 23, and Comparative Example 24 was allowed to stand at 40 ° C for 2 weeks, and the state of the dispersion liquid was visually evaluated. The results are shown in Table 8.

According to the above results, it is clear that the color pigment dispersion liquid of the reference example does not cause separation of the dispersion liquid and remains uniform even after two weeks at 40 ° C. On the other hand, in Example 23, a transparent layer (varnish floating matter) appeared in the upper layer, and the dispersed state was unstable. In Comparative Example 24, the colored pigment was precipitated, and it did not become uniform even when stirred.

According to the above results, it is clear that in the reactive polycarboxylic acid compound (B) of the present invention, one or more polymerizable vinyl groups are introduced into the molecule by the epoxy resin (a) having a specific structure as a basic skeleton. a compound (b) having an unsaturated group and one or more carboxyl groups, and a molecule The compound (c) having one or more hydroxyl groups and one or more carboxyl groups can enhance the dispersibility of the pigment and improve the storage stability of the pigment dispersion.

[Industrial availability]

The active energy ray-curable resin of the present invention is exemplified as a hard coat material, an alkali developable film, and a flexible material as a material having both curability, flexibility, toughness, and flame retardancy. The active energy ray-curable resin of the present invention can be used as, for example, an active energy ray-curable printing ink, a color resist, and especially as a pigment dispersion, in order to be a necessary photoresist material and to exert a good pigment dispersibility. It is particularly suitable for use in a color resist for LCD (liquid crystal display), especially a black matrix or the like, as a resistive material such as a property and developability.

Claims (14)

A reactive epoxy carboxylate compound obtained by using the epoxy resin (a) represented by the formula (1) and one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule The compound (b) is reacted to obtain: (wherein R _{1 is the} same or different from each other, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms; and R ₂ represents a divalent polycyclic hydrocarbon group having 7 to 16 carbon atoms or a carbon number of 7 to 18; An aralkyl group; m represents an integer from 1 to 4, and n is an average value, indicating a positive number from 1 to 10. The reactive epoxy carboxylate compound of claim 1, wherein the epoxy resin (a) is of the formula (2): (wherein R _{3 is the} same or different from each other, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms; o represents an integer of 1 to 4, and p is an average value, and represents a positive number of 1 to 10). The reactive epoxy carboxylate compound of claim 1, wherein the epoxy resin (a) is of the formula (3): (wherein R _{4 is the} same or different from each other, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms; q represents an integer of 1 to 4, and r is an average value, and represents a positive number of 1 to 10). The reactive epoxy carboxylate compound of claim 1, wherein the epoxy resin (a) is of the formula (4): (wherein R _{5 is the} same or different from each other, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms; s represents an integer of 1 to 4, and t is an average value, and represents a positive number of 1 to 10). A reactive polycarboxylic acid compound obtained by reacting the reactive carboxylic acid ester compound (A) according to any one of claims 1 to 4 with a polybasic acid anhydride (d). An active energy ray-curable resin composition, which comprises the reactive carboxylate compound (A) according to any one of claims 1 to 4, and/or the reactive polycarboxylate according to claim 5 Acid compound (B). The active energy ray-curable resin composition of claim 6, which further contains a reactive compound (C) other than (A) and (B). The active energy ray-curable resin composition of claim 6, which further contains a coloring pigment. The active energy ray-curable resin composition of claim 6, which further contains a photopolymerization initiator. The active energy ray-curable resin composition of claim 6, which is a material for molding. The active energy ray-curable resin composition of claim 6, which is a material for forming a film. The active energy ray-curable resin composition of claim 6, which is a photoresist material composition. A cured product which is a cured product of the active energy ray-curable resin composition of claim 6. An article which is covered by an active energy ray-curable resin composition as claimed in claim 6.