TW201430045A - Active energy beam-curable resin composition and spacer for display device and/or color filter protective film using the same - Google Patents

Abstract

The invention provides a spacer for a display device and a color filter protective film having excellent thermal resistance, thermal resistant transparency, flatness, softness, and toughness. The invention provides the spacer for the display device or an active energy beam-curable resin composition for the color filter protective film, including a reactive polycarboxylic acid compound (A), reactive compound (B) besides the reactive polycarboxylic acid compound (A), a photopolymerization initiator (C) and an organic solvent (D); the reactive polycarboxylic acid compound (A) is obtained by allowing a reactant of an epoxy resin (a) having at least two or more epoxy groups among one molecule, and a compound (b) having one or more polymerizable ethylene unsaturated groups and one or more carboxyl groups, and a compound (c) having at least two or more hydroxyl groups and one or more carboxyl groups among one molecule based on needs to react with an itaconic anhydride serving as a polybasic anhydride (d).

Description

Active energy ray-curable resin composition and display element using the same Protective film with spacers and / or color filters

The present invention relates to an active energy ray-curable resin composition, a spacer for a display element, and/or a color filter protective film.

As the material for the display device, a resin composition containing a binder polymer, a photopolymerizable monomer, a photopolymerization initiator, or the like can be used. In recent years, it has been used as a material for display devices (for liquid crystal display (LCD), electro-luminescence (EL), plasma display panel (PDP), field emission display ( Field Emission Display, FED) (Surface-conduction Electron-emitter Display (SED)), back projection display, electronic paper, or digital camera, etc., especially for display elements, materials around display elements For example, a color liquid crystal display (LCD) has been rapidly popularized. In general, a color liquid crystal display device has a configuration in which a color filter is disposed opposite to an electrode substrate such as a thin film transistor (TFT) substrate, and a gap portion of about 1 μm to 10 μm is provided. The liquid crystal compound is filled in the gap portion, and the periphery thereof is sealed by a sealing material.

The color filter has a structure in which a layer is sequentially formed on the transparent substrate from the side close to the transparent substrate: a black matrix layer formed into a specific pattern in order to shield the boundary portion between the pixels, and is usually formed to form each pixel. A coloring layer, a protective film, and a transparent electrode film in which red (R), green (G), and blue (B) are arranged in a specific order. Further, an alignment film is provided on the inner surface side of the color filter and the electrode substrate opposed thereto. Further, in the gap portion, in order to fix and uniformly maintain the cell gap between the color filter and the electrode substrate, beads having a fixed particle diameter are dispersed as a spacer or formed to have a height corresponding to the cell gap. Columnar or striped spacers. Further, a color image is obtained by controlling the light transmittance of the liquid crystal layer located behind each of the pixels colored in each color. Such a color filter is not limited to a color liquid crystal display device, and can be used as an EL, a rear projection display or the like as another display device.

The colored layer, the protective film, and the spacer can be formed using a resin. The colored layer must be formed into a specific pattern on each pixel of each color. In consideration of the adhesion or sealing property of the sealing portion, it is preferable that the protective film can cover only the region on the transparent substrate where the colored layer is formed. In addition, the spacer must be accurately disposed in the formation region of the black matrix layer, that is, the non-display region. Therefore, a colored layer, a protective film, and a columnar spacer are formed using a curable resin which can easily define a region to be cured by a photomask.

In addition, in order to form a coloring layer, a protective film, or a columnar spacer, if an organic solvent is used for development after exposing the coated surface of the curable resin, the operation and waste liquid treatment are complicated, and the hydroxyl group is lacking. Stability, so developed in hard A curable resin which is introduced into an acidic resin and which is developed by an aqueous alkaline solution after exposure. In these applications, a high temperature (200 ° C - 260 ° C or higher) is applied during the formation of the alignment film and the formation of the transparent electrode, so that very high heat resistance is required, and particularly in a color resist, Among the separators, those having excellent heat resistance and coloring properties are required.

In Patent Document 1, as a polymer component of a photosensitive resin composition for a light spacer and a color filter, an acid-modified epoxy acrylate having a cresol novolak epoxy resin capable of using a primary amine compound is used. A photosensitive resin obtained by neutralizing an ester. However, in the composition containing the salt or water of such a primary amino group compound, the coatability and flatness are inferior, and the suitability of a device such as a slit coater is not sufficient.

In Patent Document 2, an acid-modified epoxy acrylate of a cresol novolac epoxy resin or a phenol novolak epoxy resin is used as a polymer component of the photosensitive resin composition for a light spacer. However, there is a problem that radiation sensitivity or developability is poor, and it is not a level that can be sufficiently satisfactory.

In Patent Document 3, as a protective component of a color filter or a polymer component of a resist ink composition for a flexible printed wiring board, an acrylic acid or a dimethylol group is added to a cresol novolak epoxy resin. The reactant obtained by propionic acid is modified with caprolactone, and then an active energy ray-curable resin obtained by modifying tetrahydrophthalic anhydride is used. The polymer component which is a main component of the composition is excellent in developability and flexibility, but there is a problem in that the elastic recovery ratio required as a photo spacer is poor.

Further, in Patent Document 4, a reactive polycarboxylic acid resin obtained by adding itaconic anhydride to an epoxy (meth) acrylate of a bisphenol epoxy resin, or A reactive polycarboxylic acid resin obtained by modifying tetrahydrophthalic anhydride with a reaction product of a bisphenol type epoxy resin and itaconic acid and (meth)acrylic acid. However, there is a problem that the elastic recovery rate required as a photo spacer is not a satisfactory level.

On the other hand, Patent Document 5 to Patent Document 8 describe an epoxy carboxylate compound and a resin composition containing the same.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-109752

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-010885

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-300266

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-067814

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2009-046604

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2009-102501

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2009-120737

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2009-275167

The present invention has been made in view of the above problems in the prior art, and an object of the present invention is to provide an active energy ray-curable resin composition which is excellent in developability, hardenability, and high-speed coating property, and heat resistance, heat-resistant transparency, flatness, flexibility, and A spacer for a display element excellent in toughness and a color filter protective film.

In order to solve the above problems, the inventors of the present invention conducted intensive studies and found that a resin composition having a specific compound and composition can solve the above problems. The present invention has thus been completed.

That is, the present invention is concerned

(1) An active energy ray-curable resin composition for a display element spacer or a color filter protective film, comprising: a reactive polycarboxylic acid compound (A), a reactive compound (B), a photopolymerization initiator (C) and an organic solvent (D); the reactive polycarboxylic acid compound (A) is an epoxy resin (a) having at least two or more epoxy groups in one molecule and having 1 in one molecule The reaction product of the polymerizable ethylenically unsaturated group and the one or more carboxyl group-containing compound (b) is further reacted with itaconic anhydride as the polybasic acid anhydride (d).

(2) An active energy ray-curable resin composition for a display element spacer or a color filter protective film comprising: a reactive polycarboxylic acid compound (A), a reactive polycarboxylic acid compound a reactive compound (B) other than (A), a photopolymerization initiator (C), and an organic solvent (D); and the reactive polycarboxylic acid compound (A) is one having at least two or more epoxy groups in one molecule. The epoxy resin (a) and the compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule, and a compound having at least two or more hydroxyl groups and one or more carboxyl groups in one molecule ( The reactant of c) is further reacted with itaconic anhydride as the polybasic acid anhydride (d).

(3) Further, a spacer for a display element is formed of the active energy ray-curable resin composition.

(4) Further, a color filter protective film formed of the above active energy ray-curable resin composition.

The resin composition of the present invention is excellent in developability, has high radiation sensitivity, and can provide a spacer for a display element and a color filter protective film which are excellent in heat resistance, heat-resistant transparency, flatness, flexibility, and toughness.

Hereinafter, the present invention will be described in detail.

The reactive polycarboxylic acid compound (A) of the present invention is an epoxy resin (a) having at least two or more epoxy groups in one molecule and one or more polymerizable ethylenically unsaturated groups in one molecule. The reactive epoxy carboxylate compound (E) obtained by reacting the compound (b) having one or more carboxyl groups, and further reacted with itaconic anhydride as the polybasic acid anhydride (d); and/or having at least 2 in one molecule The epoxy group (a) having one or more epoxy groups and the compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule, and at least two or more hydroxyl groups in one molecule The reactive epoxy carboxylate compound (E') obtained by reacting the compound (c) having one or more carboxyl groups is further reacted with itaconic anhydride as the polybasic acid anhydride (d).

In other words, by reacting a reactive epoxy carboxylate compound with itaconic anhydride as a polybasic acid, a reactive polycarboxylic acid having a methacryl group introduced into the side chain is used, and the heat resistance is drastically Enhance and exert the features of the present invention.

Epoxy having at least two epoxy groups in one molecule of the present invention Specific examples of the resin (a) include a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a trishydroxyphenylmethane type epoxy resin, and a dicyclopentadiene phenol type epoxy resin. Bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, biphenol type epoxy resin, bisphenol-A novolak type epoxy resin, epoxy resin containing naphthalene skeleton, glyoxal type epoxy Resin, heterocyclic epoxy resin, etc.

Examples of the phenol novolac type epoxy resin include EPICLON N-770 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), DEN438 (manufactured by Dow Chemical Co., Ltd.), and Epikote. 154 (manufactured by Yuka Shell Epoxy Co., Ltd.), EPPN-201, RE-306 (manufactured by Nippon Kayaku Co., Ltd.), etc. Examples of the cresol novolac type epoxy resin include EPICLON N-695 (manufactured by Dainippon Ink Chemicals Co., Ltd.), EOCN-102S, EOCN-103S, and EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.). , UVR-6650 (manufactured by Union Carbide Co., Ltd.), ESCN-195 (manufactured by Sumitomo Chemical Industries Co., Ltd.), and the like.

Examples of the trihydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by The Dow Chemical Co., Ltd.), and Epikote E1032H60 ( Oiled shell epoxy (manufacturing) and so on. Examples of the dicyclopentadiene phenol type epoxy resin include XD-1000 (manufactured by Nippon Kayaku Co., Ltd.), EPICLON EXA-7200 (manufactured by Dainippon Ink Chemicals Co., Ltd.), and TACTIX-556 (Tao). Made by Chemical Company).

Examples of the bisphenol type epoxy resin include Epikote 828 and Epikote. 1001 (manufactured by Oiled Shell Epoxy Co., Ltd.), UVR-6410 (manufactured by Union Carbon Corporation), DER-331 (manufactured by The Dow Chemical Company), YD-8125 (manufactured by Dongdu Chemical Co., Ltd.), NER-1202, NER-1302 bisphenol-A type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.); UVR-6490 (manufactured by Union Carbon Compound Co., Ltd.), YDF-8170 (manufactured by Tohto Kasei Co., Ltd.), NER-7403, NER-7604 (Japan) A bisphenol-F type epoxy resin or the like is produced by a drug (stock).

Examples of the biphenol-type epoxy resin include a biphenol type epoxy resin such as NC-3000 and NC-3000-H (manufactured by Nippon Kayaku Co., Ltd.), and YX-4000 (oiled shell epoxy). Manufactured) a bis xylenol type epoxy resin, YL-6121 (manufactured by Oiled Shell Epoxy Co., Ltd.). Examples of the bisphenol A novolac type epoxy resin include EPICLON N-880 (manufactured by Dainippon Ink Chemicals Co., Ltd.), Epikote E157S75 (manufactured by Oiled Shell Epoxy Co., Ltd.), and the like.

Examples of the epoxy resin containing a naphthalene skeleton include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.) and EXA-4750 (manufactured by Dainippon Ink Chemicals Co., Ltd.). Examples of the glyoxal type epoxy resin include GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.). Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Chemical Industries Co., Ltd.). Examples of the heterocyclic epoxy resin include TEPIC (manufactured by Nissan Chemical Industries Co., Ltd.).

Among them, as a particularly preferable one, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a biphenol type epoxy resin, etc. are mentioned.

One or more polymerizable ethylenic unsaturated in one molecule of the present invention The compound (b) having a thiol group and one or more carboxyl groups is a reaction for imparting reactivity to an active energy ray. There is no limitation if one or more ethylenically unsaturated groups and carboxyl groups are present in the molecule. As such a compound, a monocarboxylic acid compound and a polycarboxylic acid compound are mentioned.

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-saturated acid. A reactant of a saturated mono-glycidyl compound. Examples of the (meth)acrylic acid in the above may, for example, be (meth)acrylic acid, β-styrylacrylic acid, β-mercaptoacrylic acid, (meth)acrylic acid dimer, or a saturated or unsaturated dibasic acid anhydride. a half ester of a molar reactant such as a (meth) acrylate derivative having one hydroxyl group in one molecule, a saturated or unsaturated dibasic acid, and a monoglycidyl (meth)acrylate derivative. Semi-esters of the molar reactants, and the like.

Further, examples of the polycarboxylic acid compound having two or more carboxyl groups in one molecule include a half ester of a molar reactant such as a (meth) acrylate derivative having a plurality of hydroxyl groups in one molecule, and may be saturated or A half ester of an equimolar reactant of an unsaturated dibasic acid and 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), those having no hydroxyl group in the compound are preferred.

In the present invention, at least two or more hydroxyl groups and one or more molecules are present in one molecule The compound (c) having a carboxyl group is a reaction for introducing a hydroxyl group into the carboxylate compound.

Specific examples of the compound (c) having at least two or more hydroxyl groups and one or more carboxyl groups in one molecule of the present invention include, for example, dimethylolpropionic acid, dimethylolbutanoic acid, and dimethylol group. A monocarboxylic acid containing a polyhydroxy group such as acetic acid, dimethylolbutanoic acid, dimethylolvaleric acid or dihydroxymethylhexanoic acid. As a particularly preferable one, dimethylolpropionic acid etc. are mentioned.

Among these, in consideration of the stability of the reaction between the epoxy resin (a), the compound (b) and the compound (c), it is preferred that the compound (b) and the compound (c) are monocarboxylic acids in combination. When the carboxylic acid and the polycarboxylic acid are used, the value of the total mole amount of the monocarboxylic acid/the total mole amount of the polycarboxylic acid is preferably 15 or more.

The ratio of the total amount of the carboxylic acid in the epoxy resin (a) and the compound (b) and the compound (c) in the reaction should be appropriately changed depending on the use. In other words, when all the epoxy groups are carboxylated, the storage stability of the reactive epoxy carboxylate compound is high in order to prevent the unreacted epoxy group from remaining. At this time, only the reactivity due to the introduced double bond is utilized.

On the other hand, by intentionally reducing the amount of the carboxylic acid compound to be supplied, the unreacted residual epoxy group remains, and the reactivity due to the introduced unsaturated bond or the residual epoxy group may be used in combination. The reaction, for example, a polymerization reaction or a thermal polymerization reaction due to a photocationic catalyst. However, at this time, attention should be paid to the storage and production conditions of the reactive epoxy carboxylate compound (E) or the reactive epoxy carboxylate compound (E').

When the reactive epoxy carboxylate compound (E) or the reactive epoxy carboxylate compound (E') in which no epoxy group remains, the compound (b) is equivalent to 1 equivalent of the epoxy resin (a). The total amount of the compound (c) is preferably from 90 equivalent% to 120 equivalent%. If the total is in this range, it can be produced under relatively stable conditions. When the total amount of the compound (b) and the compound (c) is more than the above range, the excess of the compound (b) and the compound (c) is excessive, which is not preferable.

Further, when the epoxy group is intentionally left, the total of the compound (b) and the compound (c) is preferably from 20 equivalent % to 90 equivalent % based on 1 equivalent of the epoxy resin (a). When it is out of this range, the reaction due to the epoxy group does not proceed more fully. At this time, sufficient attention must be paid to the gelation in the reaction or the temporal stability of the reactive epoxy carboxylate compound (E).

With respect to the use ratio of the compound (b) to the compound (c), in the molar ratio with respect to the carboxylic acid, the compound (b): the compound (c) is preferably 100:0 to 5:95, and more preferably 100: Range of 0~40:60. When the amount of the compound (c) used is 0, it is a reactive epoxy carboxylate compound (E), and when the amount of the compound (c) used is more than 0, it is a reactive epoxy carboxylate compound (E'). When it is this range, the sensitivity to the active energy ray is good, and in order to react the reactive epoxy carboxylate compound (E) or the reactive epoxy carboxylic acid ester compound (E') with the polybasic acid anhydride (d), A sufficient hydroxyl group can be introduced.

The carboxylic acid esterification reaction can also be carried out by reacting without a solvent or 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 appropriately adjusted depending on the viscosity or use of the obtained resin, and is preferably 90 parts by mass to 30 parts by mass, more preferably 80 parts by mass to 50 parts by mass, based on the solid content. Solvent.

Specific examples thereof include an aromatic hydrocarbon solvent such as toluene, xylene, ethylbenzene or tetramethylbenzene, and an aliphatic hydrocarbon solvent such as hexane, octane or decane, and a mixture thereof. Petroleum ether, white gasoline, solvent naphtha, etc., ester solvent, ether solvent, ketone solvent, and the like.

Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate; cyclic esters such as γ-butyrolactone; ethylene glycol monomethyl ether acetate; and diethyl 2 Alcohol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate And monoalkylene glycol monoalkyl ether monoacetate such as butanediol monomethyl ether acetate or polyalkylene glycol monoalkyl ether monoacetate, dialkyl glutarate, amber A polycarboxylic acid alkyl ester such as a dialkyl acid ester or a dialkyl adipate.

Examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and triethylene glycol. A glycol ether such as methyl ether or triethylene glycol diethyl ether or a cyclic ether such as tetrahydrofuran.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone.

In addition, other reactive compounds (B), etc., which will be described later, may be used alone or in combination. It is carried out in an organic solvent. In this case, when it is used as a curable composition, it can be used as a composition as it is, and therefore it is preferable.

In the reaction, in order to promote the reaction, it is preferred to use a catalyst, and the total amount of the reactants relative to the reactants, that is, the epoxy resin (a), the carboxylic acid compound (b), the compound (c), and, if appropriate, other solvents. The amount of the catalyst used is 0.1 parts by mass to 10 parts by mass. The reaction temperature at this time is from 60 ° C to 150 ° C, and the reaction time is preferably from 5 hours to 60 hours. Specific examples of the usable catalyst include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethylammonium iodide. A known basic alkaline catalyst such as triphenylphosphine, triphenylsulfonium, methyltriphenylphosphonium hydrogenate, chromium octoate or zirconium octylate.

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

In the present reaction, the acid value of the sample is 5 mgKOH/g or less, preferably 3 mgKOH/g or less, as an end point, while appropriately sampling.

As a preferable molecular weight range of the reactive epoxy carboxylate compound (E) thus obtained, the polystyrene-converted mass average molecular weight obtained by Gel Permeation Chromatography (GPC) is 1,000 to 50,000. The range is preferably 2,000 to 30,000.

When the molecular weight of the reactive epoxy carboxylate compound (E) is less than the molecular weight, the toughness of the cured product is not sufficiently exhibited, and when the molecular weight is too large, the viscosity is high and coating is difficult.

Next, the acid addition step will be described in detail. The acid addition step is to introduce a carboxyl group into the reactive epoxy carboxylate compound (E) or the reactive epoxy carboxylate compound (E') obtained in the previous step to obtain a reactive polycarboxylic acid compound (A). And proceed. In other words, the carboxyl group generated by the carboxylic acid esterification reaction is subjected to an addition reaction with the polybasic acid anhydride (d) to introduce a carboxyl group via an ester bond.

When the polybasic acid anhydride (d) is a compound having a polymerizable ethylenically unsaturated group and an acid anhydride structure in the molecule, it can be used in its entirety, and it is particularly preferably an alkaline aqueous solution excellent in developability, heat resistance, hydrolysis resistance, and the like. Itaconic anhydride.

The reaction of adding 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 should be changed as appropriate depending on the application.

When the amount of the polybasic acid anhydride (d) to be added is, for example, when the reactive polycarboxylic acid compound (A) of the present invention is to be used as an alkali-developing resist, it is preferred to introduce the finally obtained reactive polycarboxylic acid compound. The solid component acid value of (A) (according to JIS K5601-2-1:1999) is 40 mg. KOH/g~120mg. KOH / g, more preferably 60mg. KOH/g~120mg. A calculated value of KOH/g of polybasic anhydride (d). When the solid content acid value at this time is in this range, the alkaline aqueous solution developability of the photosensitive resin composition of the present invention exhibits good developability. That is, the management of good patterning property and overdevelopment is also wide, and an excessive amount of acid anhydride does not remain.

In the reaction, in order to promote the reaction, it is preferred to use a catalyst, a reactive epoxy carboxylate compound (E) obtained from the reactant, that is, the epoxy compound (a) and the carboxylic acid compound (b), or a reactive epoxy carboxylate compound (E') obtained from the epoxy compound (a), the carboxylic acid compound (b) and the compound (c), and a polybasic acid anhydride (d), The total amount of the reactants added with another solvent depending on the case, and the amount of the catalyst used is 0.1 parts by mass to 10 parts by mass. The reaction temperature at this time is from 60 ° C to 150 ° C, and the reaction time is preferably from 5 hours to 60 hours. Specific examples of the usable catalyst include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethylammonium iodide. , triphenylphosphine, triphenylphosphonium hydrogen, methyl triphenyl hydrogen halide, chromium octoate, zirconium octoate and the like.

The acid addition reaction can also be carried out without a solvent or by dilution with a solvent. The solvent which can be used herein is not particularly limited as long as the acid addition reaction is an inert solvent. Further, when a solvent is used for the carboxylic acid esterification reaction as the preceding step, the acid addition reaction may be directly supplied to the next step without removing the solvent under the condition that the two reactions are inert. The solvent which can be used can be the same as that which can be used in the esterification reaction of a carboxylic acid.

The amount of the solvent to be used is appropriately adjusted depending on the viscosity or use of the obtained resin, and is preferably 90 parts by mass to 30 parts by mass, more preferably 80 parts by mass to 50 parts by mass, based on the solid content. .

Further, it can be carried out in the above-mentioned reactive compound (B) or the like alone or in a mixed organic solvent. In this case, when it is used as a curable composition, it can be used as a composition as it is, and therefore it is preferable.

Further, the thermal polymerization inhibitor or the like is preferably the same as those exemplified in the above-mentioned carboxylic acid esterification reaction.

This reaction is an end point of the time when the acid value of the reactant is within ±10% of the set acid value while appropriately sampling.

As a preferable molecular weight range of the reactive polycarboxylic acid compound (A), the polystyrene-converted mass average molecular weight obtained by GPC is in the range of 1,000 to 50,000, more preferably 2,000 to 30,000.

The reactive compound (B) which can be used in the present invention includes so-called reactions such as a radical reaction type acrylate, a cationic reaction type other epoxy compound, and a vinyl compound which reacts with the two. Sex oligomers. The reactive polycarboxylic acid compound (A) is not included in the reactive compound (B).

Examples of the radical-reactive acrylates include monofunctional (meth) acrylates, difunctional (meth) acrylates, trifunctional or higher (meth) acrylates, and polyester (meth) acrylates. A (meth)acrylic acid urethane oligomer, a polyester (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, or the like.

Examples of the monofunctional (meth) acrylate include acryloyl morpholine; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxy (meth) acrylate. a hydroxyl group-containing (meth) acrylate such as butyl ester; cyclohexane-1,4-dimethanol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, An aliphatic (meth) acrylate such as dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate or dicyclopentenyloxyethyl (meth)acrylate; benzene (meth)acrylate Oxyethyl ester, (poly)ethoxyphenyl (meth) acrylate, p-cumylphenoxyethyl (meth)acrylate, tribromophenoxyethyl (meth)acrylate, (methyl) Phenylthioethyl acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenylphenol (poly)ethoxy(meth)acrylate, phenylphenol (meth)acrylate An aromatic (meth) acrylate such as an ester.

Examples of the difunctional (meth) acrylate include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol. Di(meth)acrylate, tricyclodecane dimethanol (meth) acrylate, bisphenol A (poly) ethoxy di(meth) acrylate, bisphenol A (poly) propoxy bis (a) Acrylate, bisphenol F (poly) ethoxy di(meth) acrylate, ethylene glycol di(meth) acrylate, (poly) ethylene glycol di(meth) acrylate neopentyl glycol Di(meth)acrylate of ε-caprolactone adduct of hydroxypivalate (for example, manufactured by Nippon Kayaku Co., Ltd., KAYARAD HX-220, KAYARAD HX-620, etc.).

Examples of the trifunctional or higher polyfunctional (meth) acrylate include di(trimethylolpropane)tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, and trimethylol. Octane tri(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acrylate, trimethylolpropane (poly)propoxy tri(meth)acrylate, trimethylol Hydroxymethyl groups such as propane (poly)ethoxy (poly) propoxy tri(meth) acrylate; pentaerythritol tri(meth) acrylate, pentaerythritol polyethoxy tetra (meth) acrylate, pentaerythritol ( Poly)propoxytetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate Ester and other erythritols; tris[(methyl) propylene methoxyethyl] isocyanurate, caprolactone modified trisuccinate [[meth) propylene oxiranyl ethyl] Ester, etc.; succinic acid modified pentaerythritol triacrylate, succinic acid modified dipentaerythritol pentaacrylate.

Examples of the (poly)ester (meth) acrylate oligomer include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol. a glycol such as pentanediol, polyethylene glycol or (poly)propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl a linear or branched alkyl glycol such as 1,3-propanediol, an alicyclic alkyl glycol such as cyclohexane-1,4-dimethanol, bisphenol A (poly)ethoxy glycol, Or a diol compound such as bisphenol A (poly)propoxy diol, a reaction product of the above dibasic acid or its anhydride, that is, a (poly) ester diol, followed by a reaction product with (meth)acrylic acid.

Examples of the (meth)acrylic acid urethane oligomer include a diol compound (for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 4). -butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl 1,2-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4- Dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A polyethoxy diol, bisphenol A polypropoxy diol, etc.) or these diol compounds and dibasic acids or anhydrides thereof (eg succinic acid, hexamethylene) The reactant of acid, azelaic acid, dimer acid, isophthalic acid, terephthalic acid, phthalic acid or anhydride of these acids, ie, a polyester diol, and an organic polyisocyanate (for example, tetramethylene) Chain-like saturated hydrocarbon isocyanate such as diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate or 2,4,4-trimethylhexamethylene diisocyanate, Ketone diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylene a cyclic saturated hydrocarbon isocyanate such as bis(4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate or hydrogenated toluene diisocyanate, 2,4-methylphenylene diisocyanate, 1, 3-xylene Aromatic compounds such as diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate, 1,5-naphthalene diisocyanate The polyisocyanate is reacted, followed by addition of a reaction product containing a hydroxyl group-containing (meth) acrylate.

The epoxy (meth) acrylate oligomer is a carboxylic acid ester compound of a compound having an epoxy group and (meth)acrylic acid. For example, a phenol novolak type epoxy (meth)acrylate, a cresol novolak type epoxy (meth)acrylate, a trihydroxyphenylmethane type epoxy (meth)acrylate, a dicyclopentylene Epphenol type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, biphenol type epoxy (meth) acrylate, Bisphenol-A novolak type epoxy (meth) acrylate, epoxy (meth) acrylate containing naphthalene skeleton, glyoxal type epoxy (meth) acrylate, heterocyclic epoxy (methyl ) Acrylate and the like.

Examples of the vinyl compound 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, the cationically reactive monomer is 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-epoxy cyclohexylmethyl 3 , 4-epoxycyclohexane carboxylate ("Cyracure UVR-6110" manufactured by Union Carbon Co., Ltd.), 3,4-epoxycyclohexylethyl 3,4-epoxycyclohexane carboxylate, ethylene oxide cyclohexene ("ELR-4206" manufactured by Union Carbon Corporation, etc.), limonene dioxide ("Celloxide 3000" manufactured by Daicel Chemical Industry Co., Ltd., etc.), Diallyl allyl cyclohexene, 3,4-epoxy-4-methylcyclohexyl-2-epoxypropane, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4 - epoxy) cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl) adipate ("Cyracure UVR-6128" manufactured by Union Carbon Corporation), adipic acid bis (3, 4-epoxycyclohexylmethyl)ester, bis(3,4-epoxycyclohexyl)ether, bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexyl) Diethyl decane and the like.

Among these, the reactive compound (B) is preferably a monofunctional, difunctional or trifunctional or higher (meth)acrylate, from the viewpoint of improving polymerizability and improving the strength of the obtained separator.

The reactive compound (B) of the present invention may be used singly or in combination of two or more. The use ratio of the reactive compound (B) in the composition is preferably from 30 parts by mass to 250 parts by mass, more preferably from 50 parts by mass to 200 parts by mass, per 100 parts by mass of the reactive polycarboxylic acid compound (A). . When the amount of the reactive compound (B) used is from 30 parts by mass to 250 parts by mass, the heat resistance and elastic properties of the composition, the obtained spacer for a display element, and the like are further improved.

The photopolymerization initiator (C) of the present invention reacts with an active energy ray to produce a reactive compound other than the reactive polycarboxylic acid compound (A) and the reactive polycarboxylic acid compound (A). The component of the active species at the beginning of the polymerization of B). Examples of such a photopolymerization initiator (C) include an O-indenyl hydrazine compound, an acetophenone compound, and a biimidazole compound.

As the O-indenyl ruthenium compound, for example, ethyl ketone-1-[9-ethyl-6-(2-methylbenzomethyl)-9H-carbazol-3-yl]-1-(O) can be mentioned. -Ethyl hydrazide), 1-[9-ethyl-6-benzylidene-9H-carbazol-3-yl]-octane-1-one oxime-O-acetate, 1-[9 -ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-n-butyl -6-(2-ethylbenzylidenyl)-9H-indazol-3-yl]-ethane-1-one oxime-O-benzoate, ethyl ketone-1-[9-ethyl- 6-(2-Methyl-4-tetrahydrofuranylbenzylidene)-9H-indazol-3-yl]-1-(O-acetamidoxime), ethyl ketone-1-[9-ethyl- 6-(2-Methyl-4-tetrahydropyranylbenzylidene)-9H-indazol-3-yl]-1-(O-acetamidopurine), ethyl ketone-1-[9- Ethyl-6-(2-methyl-5-tetrahydrofuranylbenzylidene)-9H-indazol-3-yl]-1-(O-ethylindenyl), ethyl ketone-1-[9- Ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidenyl}-9H-indazol-3-yl] -1-(O-Ethyl hydrazine) and the like. Among these, ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-ethylindenyl) is preferred. Ethylketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-1-(O-acetamidine) Ketone) or ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzimidazole }}-9H-carbazol-3-yl]-1-(O-ethylindenyl). These O-indenyl ruthenium compounds may be used singly or in combination of two or more.

Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.

Examples of the α-amino ketone compound include 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one and 2-dimethylamine. 2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthiobenzene) Benzyl-2-morpholinylpropan-1-one and the like.

Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1-(4-isopropylphenyl)-2-hydroxy-2-methyl. Propane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, and the like.

Among these acetophenone compounds, an α-amino ketone compound is preferred, and 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1- is more preferred. Ketone or 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one.

As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'- can be mentioned. Biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4- Dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4 ',5,5'-tetraphenyl-1,2'-biimidazole. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2) is preferred. ,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis(2,4,6-trichlorophenyl)- 4,4',5,5'-tetraphenyl-1,2'-biimidazole, more preferably 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5 '-Tetraphenyl-1,2'-biimidazole.

As the photopolymerization initiator (C), a commercially available product can be used, and, for example, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one (Irgacure 907) can be mentioned. , 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)-butan-1-one (Irgacure 379), ethyl ketone-1-[ 9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-acetamidofluorene) (Irgacure OXE02) (above is Ciba Refinery (Ciba) Specialty Chemicals)).

In the photosensitive resin composition of the present invention, when the solid content of the resin composition of the present invention is 100% by mass, the amount of the component (C) used is 1 The mass% or more and 20% by mass or less are preferably 1% by mass or more and 10% by mass or less.

Further, the photopolymerization initiator (C) may be used in combination with the hardening accelerator (F). Examples of the hardening accelerator which can be used together include triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethyl benzoate, dimethylaminoacetophenone, p-dimethylamine. An amine such as isobutyl benzoate, an amine such as KAYACURE EPA (4-methylaminobenzoate, manufactured by Nippon Kayaku Co., Ltd.), or a hydrogen donor such as 2-mercaptobenzothiazole. When the solid content of the resin composition of the present invention is 100% by mass, the amount of the curing accelerator used is 0% by mass or more and 5% by mass or less.

As the organic solvent (D), it is preferred to use a compound which uniformly dissolves or disperses each constituent component and does not react with each constituent component. Examples of such an organic solvent (D) include an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, and petroleum ether, white gasoline, solvent naphtha, etc. as a mixture of these, an ester solvent, an ether solvent, and a ketone. Examples of the solvent and the like include alcohols, ethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, and diethylene glycol monoalkyl ether acetates. Dipropylene glycol monoalkyl ethers, dipropylene glycol monoalkyl ether acetates, lactic acid esters, aliphatic carboxylic acid esters, guanamines, ketones, and the like. These may be used alone or in combination of two or more.

Examples of the organic solvent (D) include alcohols such as benzyl alcohol; ethylene glycol monoalkyl groups such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Ethers; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and other propylene glycol monoalkyl ethers; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and other diethylene glycol monoalkane Ether ether; diethylene glycol monomethyl ether acetate, diethylene glycol Diethylene glycol monoalkyl ether acetate such as monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate; dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether Dipropylene glycol monoalkyl ethers such as dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether; dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol single Dipropylene glycol monoalkyl ether acetate such as butyl ether acetate; methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, lactic acid Lactic acid esters such as isoamyl ester; ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutanoate, ethyl ethoxyacetate, 3-methoxy Methyl propyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl acetate 3-methoxybutyl acrylate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetate, ethyl acetate , methyl pyruvate, ethyl pyruvate, etc. Aliphatic carboxylic acid esters; amides such as N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide; N a ketone such as methylpyrrolidone or γ-butyrolactone. These may be used alone or in combination of two or more.

The solid content concentration of the composition is 10% by mass or more and 40% by mass or less. The solid content concentration of the composition is preferably 15% by mass or more and 35% by mass or less. When the solid content concentration of the composition is in the above range, the coating property is improved, the film thickness uniformity is improved, and the occurrence of coating unevenness can be effectively suppressed.

The viscosity at 25 ° C of the composition was 1.0 mPa. Above s, 1,000mPa. s below. Preferably it is 2.0 mPa. Above s, 100mPa. s below. By the group The viscosity at 25 ° C of the product is in the above range, and the uniformity of the film thickness can be maintained in a balanced manner, and even if coating unevenness occurs, the viscosity which is spontaneously uniform can be achieved.

The alkali-soluble resin (G) used as a photosensitive resin composition of the present invention can be, for example, a monomer having a hydroxyl group, an acid anhydride having an ethylenic double bond, a monomer having a carboxyl group, and having an epoxy group. A monomer such as a monomer, a monomer having a phenolic hydroxyl group, a monomer having a sulfonic acid group, another monomer, and the above monofunctional (meth)acrylate are copolymerized and produced.

Specific examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (methyl). 4-hydroxybutyl acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, neopentyl glycol mono(methyl) Acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether , 2-hydroxyethyl allyl ether, N-hydroxymethyl (meth) acrylamide, N, N-bis(hydroxymethyl) (meth) acrylamide, and the like.

Specific examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, 3-methylphthalic anhydride, and methyl-5- Norbornene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-butene -1-yl-succinic anhydride and the like.

Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, and antibutene. Acid, cinnamic acid, or a salt of these.

Specific examples of the monomer having an epoxy group include glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl acrylate.

Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene. Further, a monomer in which one or more hydrogen atoms of the benzene ring are substituted by the following groups: an alkyl group such as a methyl group, an ethyl group or a n-butyl group; a methoxy group, an ethoxy group, a n-butoxy group or the like; An alkoxy group; a halogen atom; a haloalkyl group in which one or more hydrogen atoms of the alkyl group are substituted into a halogen atom; a nitro group; a cyano group; an anthranyl group.

Examples of the monomer having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, (meth)allylsulfonic acid, and 2-hydroxy-3-(methyl)allyloxypropanesulfonic acid. (meth)acrylic acid-2-sulfonate (sulfo)ethyl ester, (meth)acrylic acid-2-sulfopropyl propyl ester, 2-hydroxy-3-(methyl)acryloxypropane sulfonic acid, 2 -(Methyl) acrylamide-2-methylpropanesulfonic acid and the like.

Examples of the other monomer include hydrocarbon olefins, vinyl ethers, isopropylene ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylates, and (meth) propylene oxime. An amine, an aromatic vinyl compound, a chloroolefin, or a conjugated diene. These compounds may also contain a functional group, and examples of the functional group include a carbonyl group, an alkoxy group and the like. In particular, since the separator formed of the composition is excellent in heat resistance, it is preferably a (meth) acrylate or a (meth) acrylamide.

When the alkali-soluble resin (G) is copolymerized, it can be produced by radical polymerization of an unsaturated compound in the presence of a polymerization initiator in a solvent. Made. In the production, the above solvents may be used, and they may be used singly or in combination of two or more.

As the polymerization initiator used in the polymerization for producing the alkali-soluble resin (G), those known as radical polymerization initiators can be generally used. Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-(2,4-dimethylvaleronitrile), and 2, An azo compound such as 2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile); benzamidine peroxide, laurel peroxide, t-butyl peroxypivalate, An organic peroxide such as 1,1'-bis-(t-butylperoxy)cyclohexane and hydrogen peroxide. When a peroxide is used as a radical polymerization initiator, a peroxide can be used together with a reducing agent as a redox type initiator.

In the polymerization reaction for producing the alkali-soluble resin (G), a molecular weight modifier may be used in order to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tri-dodecyl mercaptan, and mercapto group. Mercaptans such as acetic acid; xanthogenates such as dimethyl xanthogen sulfide, diisopropyl xanthate disulfide; terpinolene, α-methylbenzene Ethylene dimer, etc.

The monomer having a sulfonic acid group has a reaction with respect to a monomer having a hydroxyl group, an acid anhydride having an ethylenic double bond, a monomer having a carboxyl group, a monomer having an epoxy group, or the like having a phenolic hydroxyl group. The compound (f) having a functional group capable of bonding to the above reactive group and an ethylenic double bond, and the following combinations are exemplified.

(1) an acid anhydride (f) having an ethylenic double bond with respect to the monomer (e) having a hydroxyl group; (2) having an isocyanate group and an ethylenic group with respect to the monomer (e) having a hydroxyl group a compound (f) of a bond; (3) a compound (f) having a fluorenyl group and an ethylenic double bond with respect to the monomer (e) having a hydroxyl group; (4) an acid anhydride having an ethylenic double bond ( e) a compound (f) having a hydroxyl group and an ethylenic double bond; (5) a compound (f) having an epoxy group and an ethylenic double bond with respect to the monomer (e) having a carboxyl group; (6) The compound (f) having a carboxyl group and an ethylenic double bond with respect to the monomer (e) having an epoxy group.

Specific examples of the acid anhydride having an ethylenic double bond include the above examples.

Specific examples of the compound having an isocyanato group and an ethylenic double bond include 2-(methyl)propenyloxyethyl isocyanate and 1,1-(bis(meth)acrylic acid isocyanate.醯oxymethyl)ethyl ester and the like.

Specific examples of the compound having a fluorenyl chloride group and an ethylenic double bond include (meth) acrylonitrile.

Specific examples of the compound having a hydroxyl group and an ethylenic double bond include an example of the above monomer having a hydroxyl group.

Specific examples of the compound having an epoxy group and an ethylenic double bond can be listed An example of the above monomer having an epoxy group.

Specific examples of the compound having a carboxyl group and an ethylenic double bond include an example of the above monomer having a carboxyl group.

When the copolymer is reacted with the compound (f) having a functional group capable of bonding with a reactive group and an ethylenic double bond, as the solvent used for the reaction, a solvent exemplified in the synthesis of the above copolymer can be used. .

Further, it is preferred to formulate a polymerization inhibitor. As the polymerization inhibitor, a publicly known polymerization inhibitor can be used, and specific examples thereof include 2,6-di-t-butyl-p-cresol.

In addition, a catalyst or a neutralizing agent may be added. For example, when a copolymer having a hydroxyl group is reacted with a compound having an isocyanate group and an ethylenic double bond, a tin compound or the like can be used. Examples of the tin compound include dibutyltin dilaurate, dibutylbis(maleic acid monoester)tin, dioctyltin dilaurate, and dioctyldi(maleate monoester). Tin, dibutyl diacetate, and the like.

When a copolymer having a hydroxyl group is reacted with a compound having a fluorenyl chloride group and an ethylenic double bond, a basic catalyst can be used. Examples of the basic catalyst include triethylamine, pyridine, dimethylaniline, and tetramethylurea.

The Mw of the alkali-soluble resin (G) is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ³ to 5 × 10 ⁴ . By setting the Mw of the alkali-soluble resin (G) to 2 × 10 ³ to 1 × 10 ⁵ , the radiation sensitivity and developability of the composition (characteristics of accurately forming a desired pattern shape) can be improved.

Further, the photosensitive resin composition of the present invention may also contain a surfactant, a leveling agent, an antifoaming agent, a filler, an ultraviolet absorber, a photostabilizer, or An antioxidant, a polymerization inhibitor, a crosslinking agent, a adhesion aid, a pigment, a dye, or the like is added to the photosensitive resin composition of the present invention to impart the desired functional properties. Examples of the leveling agent and the antifoaming agent include a fluorine compound, an anthrone compound, and an acrylic compound. Examples of the ultraviolet absorber include a benzotriazole compound, a benzophenone compound, and a triazine. Examples of the light stabilizer include a hindered amine compound and a benzoate compound. Examples of the antioxidant include a phenol compound and the like. Examples of the polymerization inhibitor include p-methoxy group. Examples of the phenol (methoquinone), methyl hydroquinone, hydroquinone, and the like include a polyisocyanate or a melamine compound.

Further, as the resin (so-called inert polymer) which does not exhibit reactivity to the active energy ray, for example, other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde can also be used. Resins, cresol resins, xylene resins, diallyl phthalate resins, styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modifications of these. These are preferably used in the range of up to 40 parts by mass in the resin composition.

In the active energy ray-curable resin composition of the present invention, when the total of the component (A) + the component (B) + the component (C) + the component (D) is 100 parts by mass, the composition contains a reactive polycarboxylic acid. The sum of the compound (A) and the other reactive compound (B) is 1 part by mass to 39 parts by mass, more preferably 9 parts by mass to 34 parts by mass, and the photopolymerization initiator (C) is 1 part by mass to 17 parts by mass. It is preferably 1 part by mass to 9 parts by mass, and the organic solvent (D) is 60 parts by mass to 90 parts by mass, preferably 65 parts by mass to 85 parts by mass. Other components may be included in an amount of from 0 parts by mass to 80 parts by mass as needed.

<Method for Forming Display Spacer and Color Filter Protective Film>

The spacer for a display element formed of the resin composition of the present invention is one embodiment of the present invention. The method for forming a spacer for a display element includes: (1) a step of applying the composition on a substrate to form a coating film; (2) a step of irradiating at least a part of the coating film with radiation; and (3) irradiating the composition. a step of developing the coating film of the radiation; and (4) a step of heating the coating film developed as described above.

A method of forming a photo spacer and/or a color filter protective film by photolithography using the active energy ray-curable resin composition of the present invention will be briefly described. The active energy ray-curable resin composition of the present invention is uniformly applied onto a substrate by a known method such as roll coating, spin coating, spray coating or slit coating, and dried to form a photosensitive resin composition layer. As the coating device, a known coating device can be used, and examples thereof include a spin coater, an air-knife coater, a roll coater, a bar coater, a curtain coater, and a gravure coat. Cloth machine and comma coater, etc.

Heat it as needed (pre-bake). The drying temperature is preferably 50 ° C or more, more preferably 70 ° C or more, and is preferably less than 150 ° C, more preferably 120 ° C or less. The drying time is preferably 30 seconds or longer, more preferably 1 minute or longer, and is preferably 20 minutes or shorter, more preferably 10 minutes or shorter.

Then, exposure of the photosensitive resin composition layer is performed by an active energy ray through a specific photomask. In the case of the photosensitive resin composition of the present invention, the opening of the mask having a diameter of about 5 μm to 10 μm (area of about 20 μm ² to 100 μm ² ) can be excellent in precision, that is, a diameter of 6 μm to 12 μm (area). It is formed in the range of 30 μm ² to 120 μm ² ).

The active energy ray used for the exposure is not particularly limited as long as the photosensitive resin composition of the present invention can be cured. The active energy ray-curable resin composition of the present invention is easily cured 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 laser rays, and particle beams such as α rays, β rays, and electron beams. In view of the preferred use of the present invention, these are preferably ultraviolet rays, laser rays, visible rays, or electron beams. The amount of exposure is not particularly limited, but is preferably 20 mJ/cm ² to 1,000 mJ/cm ² .

Then, the unexposed portion is removed by the developer and developed. Here, as the developer for development, an organic solvent can be used, and an alkaline aqueous solution is preferably used. Examples of the alkaline aqueous solution usable as the developing solution include aqueous solutions of inorganic salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydrogencarbonate; hydroxytetramethylammonium, hydroxytetraethylammonium, and the like. An aqueous solution of an organic salt. These may be used alone or in combination of two or more. Further, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a surfactant such as a nonionic surfactant, or a water-soluble solution such as methanol or ethanol may be added. Use as an organic solvent. The concentration of the alkali in the alkaline aqueous solution is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. As the developing method, there are a dipping method, a shower method, a puddle method, and a vibration dipping method, and a shower method is preferred. It is preferably used at a temperature of the developer of from 25 ° C to 40 ° C. The development time depends on the film thickness or the solubility of the resist. Determined appropriately.

In order to perform hardening more reliably, heating (baking) may be performed as needed. When baking is performed, as baking temperature, it is preferable that it is 120-250 degreeC. The baking time varies depending on the type of the heating device. For example, when the heating step is performed on the hot plate, it can be set to 5 minutes to 30 minutes, and when the heating step is performed in the oven, it can be set to 30 minutes to 90 minutes. A step-by-step baking method or the like which performs two or more heating steps may also be used.

The film thickness of the spacer formed as described above is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, particularly preferably 0.1 μm to 4 μm.

The spacer formed in this forming method is a spacer which is free from coating unevenness, has high flatness, and is soft and plastically deformed. It can be preferably used for a display element such as a liquid crystal display element or an organic EL display element.

The color filter protective film is preferably from 0.5 μm to 100 μm, more preferably from 1 μm to 10 μm.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited. In the examples, the parts represent parts by mass unless otherwise specified.

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

1) Epoxy equivalent: It was measured by the method according to JIS K7236:2001.

2) Softening point: Measurement was carried out by the method according to JIS K7234:1986.

3) Acid value: It was measured by the method according to JIS K0070:1992.

Example 1 to Example 1-20: Reactive Polycarboxylic Acid Compound (A) preparation

The amount of NC-3000H (manufactured by Nippon Chemical Co., Ltd., epoxy equivalent: 288 g/eq) and NC-2000 (manufactured by Nippon Chemical Co., Ltd., epoxy equivalent: 230 g/eq) were added in the amounts shown in Table 1. EOCN-103S (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 200 g/eq), EPPN-201 (manufactured by Nippon Chemical Co., Ltd., epoxy equivalent: 190 g/eq) as epoxy resin (a), Acetic acid (abbreviated as AA and Mw=72) in the amount described in Table 1 was added as the compound (b), and dimethylolpropionic acid (abbreviated as DMPA, Mw=134) in the amounts described in Table 1 was added as a compound ( c). 3 g of triphenylphosphine was added as a catalyst, and propylene glycol monomethyl ether monoacetate was added as a solvent in a solid content of 80% by mass of the reaction liquid, and the reaction was carried out at 100 ° C for 24 hours to obtain a reactive epoxy carboxyl group. Acidate compound (E) solution. The solid content acid value (AV: mgKOH/g) was set to 5 or less as the reaction end point, and the next reaction was carried out. The acid value was measured by a reaction solution and converted into an acid value as a solid component.

Then, in the reactive epoxy carboxylate compound (E) solution, the amount of itaconic anhydride (abbreviated as IA) shown in Table 1 was added as the polybasic acid anhydride (d), and the solid content was 65 parts by mass. Propylene glycol monomethyl ether monoacetate was added as a solvent, and after heating to 100 ° C, an acid addition reaction was carried out to obtain a solution of the reactive polycarboxylic acid compound (A). The solid component acid value (AV: mgKOH/g) is shown in Table 1.

Comparative Example 1-1 to Comparative Example 1-6: Preparation of Comparative Reactive Polycarboxylic Acid Compound

The amount of NC-3000H (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g/eq), NC-2000 (manufactured by Nippon Kayaku Co., Ltd., Epoxy) was added in the amount shown in Table 1. Amount: 230g/eq), EOCN-103S (manufactured by Nippon Chemical Co., Ltd., epoxy equivalent: 200g/eq), EPPN-201 (manufactured by Nippon Chemical Co., Ltd., epoxy equivalent: 190g/eq), EPOMIK R140P (manufactured by Mitsui Chemicals Co., Ltd., epoxy equivalent: 186 g/eq), adding acrylic acid in the amount described in Table 1 as the compound (b), adding 3 g of triphenylphosphine as a catalyst, and reacting as a solid component Propylene glycol monomethyl ether monoacetate was added as a solvent in an amount of 80% by mass of the liquid, and the mixture was reacted at 100 ° C for 24 hours to obtain a carboxylate compound solution. The solid content acid value (AV: mgKOH/g) was set to 5 mgKOH/g or less, and the reaction was carried out, and the next reaction was carried out.

Then, tetrahydrophthalic anhydride (abbreviated as THPA) in the amount shown in Table 1 was added as a polybasic acid anhydride in the reactive epoxy carboxylate compound solution, and propylene glycol was added so that the solid content was 65 parts by mass. Monomethyl ether monoacetate was used as a solvent, and after heating to 100 ° C, an acid addition reaction was carried out to obtain a comparative reactive polycarboxylic acid compound solution. The solid content acid value (AV: mgKOH/g) is shown in Table 1.

Comparative Example 1-7: Preparation of Comparative Reactive Polycarboxylic Acid Compounds

Add bisphenol A type epoxy resin EPOMIK R140P (manufactured by Mitsui Chemicals Co., Ltd., epoxy equivalent: 186g/eq) 186g, acrylic acid 36g, itaconic acid 33g, and add triphenylphosphine 3g as catalyst to solid content Propylene glycol monomethyl ether monoacetate was added as a solvent to 80% by mass of the reaction liquid, and the reaction was carried out at 100 ° C for 24 hours. Then, 96 g of tetrahydrophthalic anhydride (abbreviated as THPA) was added as a polybasic acid anhydride, and propylene glycol monomethyl ether monoacetate was added as a solvent so that the solid content was 65 parts by mass, and the mixture was heated to 100 ° C to carry out acid addition. The reaction was carried out to obtain a comparative reactive polycarboxylic acid compound solution. The solid component acid value (AV: mgKOH/g) is 100 mgKOH/g.

The details of each component used in the examples and comparative examples are shown.

<Reactive Compound (B)>

B-1: mixing of dipentaerythritol hexaacrylate with dipentaerythritol pentaacrylate (KAYARAD DPHA, manufactured by Nippon Chemical Co., Ltd.)

B-2: Polyfunctional urethane-based compound (KAYARAD DPHA-40H, manufactured by Nippon Kayaku Co., Ltd.)

<Photopolymerization initiator (C)>

C-1: 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one (Irgacure 907, Ciba Specialty Chemicals)

C-2: 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)-butan-1-one (Irgacure 379, Ciba refined) the company)

C-3: Ethyl-1-(9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-ethylindenyl) (Irgacure OXE02) , Ciba Precision Chemical Company)

<Organic solvent (D)>

PGMEA: propylene glycol monomethyl ether acetate

DEGDM: Diethylene glycol dimethyl ether

<Other optional ingredients>

<Synthesis of alkali-soluble resin (G)>

[Synthesis Example 1]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methyl ether were charged. Then, 5 parts by mass of styrene, 16 parts by mass of methacrylic acid, 34 parts by mass of dicyclopentanyl methacrylate, 40 parts by mass of glycidyl methacrylate, and 3 parts by mass of α-methylstyrene dimer were carried out. After nitrogen substitution, 5 parts by mass of 1,3-butadiene was introduced, and stirring was started slowly. The temperature of the solution was raised to 70 ° C and the temperature was maintained for 5 hours. A polymer solution containing the copolymer [G-1] was obtained. The obtained polymer solution had a solid content concentration of 33.1%, and the polymer had a mass average molecular weight of 10,000.

<Interacting Agent (H)>

H-1: Fluorine-based surfactant (NEOS, FTERGENT FTX-218)

H-2: Anthrone-based surfactant (Dow Corning Toray Silicone, SH8400FLUID)

<Crosslinking agent (I)>

I-1: cresol novolac type epoxy resin EOCN-103S (manufactured by Nippon Kayaku Co., Ltd.)

<Preparation of the composition>

[Example 2-1]

In the solution containing the amount of the reaction product obtained in Example 1-1 corresponding to 100 parts by mass (solid content) as the reactive polycarboxylic acid compound (A), (B-1) 100 parts by mass was added as a reactive property. Compound (B), 10 parts by mass of (C-3) was added as a photopolymerization initiator (C), and PGMEA and DEGDM were added as an organic solvent so as to have a desired solid content concentration, and (H-1)0.3 mass was mixed. This fraction was prepared as a surfactant (H) by filtration through a membrane-filter having a pore size of 0.2 μm to prepare the composition (S-1). In addition, the value of the organic solvent in Table 2 is the mass ratio of PGMEA to DEGDM.

[Example 2-2 to Example 2-35 and Comparative Example 2-1 to Comparative Example 2-9]

The types and the blending amounts of the respective components are set as described in Table 1, and The compositions of Examples 2-2 to 2-35 and Comparative Examples 2-1 to 2-9 were prepared in the same manner as in Example 2-1. In addition, the value of the organic solvent in Table 2 is the mass ratio of PGMEA to DEGDM.

<evaluation>

The composition of Example 2-1 to Example 2-35 and Comparative Example 2-1 to Comparative Example 2-9 and the separator formed of the coating film thereof were subjected to the following evaluations. The evaluation results are shown in Tables 3 and 4.

(viscosity)

The viscosity (mPa.s) of each composition at 25 ° C was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., TV-200).

(solid content concentration)

0.3 g of the composition was placed in an aluminum dish, and about 1 g of diethylene glycol dimethyl ether was added, and then dried and cured on a hot plate at 175 ° C for 60 minutes, and the mass of the composition was determined from the mass before and after drying. Solid content concentration (% by mass).

(appearance of the film)

This composition was applied onto a 100 mm × 100 mm chromium film-forming glass by a slit die coater (manufactured by a precision machine (Techno Machine), physical and chemical mold), dried under reduced pressure to 0.5 Torr, and heated. The plate was prebaked at 100 ° C for 2 minutes to form a coating film, which was then exposed to an exposure amount of 200 mJ/cm ² to form a film having a film thickness of 4 μm from the upper surface of the chromium film-forming glass. The appearance of the coating film was observed by naked eyes under a sodium lamp. At this time, the uneven streaks of the entire coating film (unevenness of one or more straight lines which can be formed in the coating direction or the direction intersecting therewith), unevenness of mist (uneven cloudiness), and pin (pin) were investigated. The occurrence of uneven marks (dot unevenness that can be formed on the substrate support pins). The situation where the unevenness is hardly seen is judged as "○ (good)", and it is judged as "△ (slightly bad)" when a slight unevenness is seen, and it is judged that the unevenness is clearly seen as "× (bad)".

(flatness)

The film thickness of the coating film on the chromium film-forming glass produced as described above was measured using a needle contact type measuring machine (manufactured by Tokyo Seiko Co., Ltd., Surfcom). The film thickness uniformity was measured by the film thickness of nine measurement points, and was calculated according to the following formula. When the number of the short-axis directions of the substrate is X and the long-axis direction is Y, (X[mm], Y[mm]) is (50, 10), (50, 20), (50). 30), (50, 40), (50, 50), (50, 60), (50, 70), (50, 80), (50, 90). When the film thickness uniformity is 2% or less, the film thickness uniformity can be judged to be good.

Film thickness uniformity (%) = {FT (X, Y) max - FT (X, Y) min} × 100 / {2 × FT (X, Y) avg.}

In the above formula, FT(X, Y)max is the maximum value among the film thicknesses of the nine measurement points, and FT(X, Y)min is the minimum value among the film thicknesses of the nine measurement points, FT(X, Y) Avg. is the average value of the film thicknesses of the nine measurement points.

(High speed coating property)

Coating on a 100 mm × 100 mm alkali-free glass substrate using a slit coater, and as a coating condition, the distance from the nozzle to the nozzle was 150 μm, and the film thickness after the exposure was 2.5 μm. In the coating liquid, the moving speed of the nozzle is changed within a range of 120 mm/sec. to 200 mm/sec., and it is determined that no liquid leakage occurs. The maximum speed of streaky unevenness. At this time, when streaky unevenness does not occur at a speed of 180 mm/sec or more, it can be judged that high-speed coating can be handled.

(radiation sensitivity)

The composition was coated on a 100 mm × 100 mm Indium Tin Oxide (ITO) sputtered glass substrate by spin coating, and then prebaked on a hot plate at 90 ° C for 3 minutes. This formed a coating film having a film thickness of 3.5 μm. Then, on the obtained coating film, exposure was carried out by using a UV exposure apparatus (ORC MANUFACTURING (model), model HMW-680GW) through a mask which formed a circular pattern having a diameter of 12 μm as an opening. Then, it was developed by a 0.05% by mass aqueous potassium hydroxide solution at 25 ° C for 60 seconds, and then washed with pure water for 1 minute, followed by post-bake for 30 minutes in an oven at 230 ° C. This forms a spacer comprising a patterned film. At this time, the residual film rate after the post-baking (the film thickness after the post-baking film × 100 / the film thickness after the exposure (before post-baking)) was 90% or more, and the value was taken as the minimum exposure amount. Sensitivity. When the value is 55 mJ/cm ² or less, it can be said that the sensitivity is good.

Further, the presence or absence of the residue was confirmed by visually observing the upper surface of the substrate. The evaluation criteria are as follows.

○... no residue.

△... There is a small amount of residue.

×... There are many residues.

(compression performance)

The exposure amount is set to correspond to the feeling determined by the evaluation of the above-described radiation sensitivity Other than this, the operation was performed in the same manner as the evaluation of the radiation sensitivity, and a spacer including a columnar pattern was formed on the substrate. At this time, the diameter of the reticle that passed through the exposure was changed so that the diameter of the bottom of the pattern after baking was 20 μm. The spacer was subjected to a compression test using a 50 μm angular flat head using a 50 μm angular flat head using a micro compression tester (Fischerscope H100C, manufactured by Fischer Instruments) to measure the amount of compression displacement. The recovery rate (%) was calculated from the displacement amount at the load of 50 mN and the displacement amount at the time of removing the load of 50 mN. In this case, when the recovery ratio is 70% or more and the displacement at a load of 50 mN is 0.15 μm or more, it can be said that it has a separator having high compression performance and high flexibility.

(total light transmittance)

Coating on a 50 mm × 50 mm alkali-free glass substrate using a spin coater, drying under reduced pressure to 0.5 Torr, and prebaking at 100 ° C for 2 minutes on a hot plate to form a coating film, followed by 200 mJ/ The exposure amount of cm ² was exposed, whereby a film having a film thickness of 4 μm was formed. The evaluation substrate having the above-mentioned cured coating film was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., TC-H3DPK).

(heat resistance)

The hardened coating film was measured using a Thermo Gravimetric/Differential Thermal Analysis (TG/DTA) (Seiko Instruments Inc., SII), TG/DTA6200. The mass change rate after holding at 250 ° C for 1 hour is described. The smaller the rate of change, the better the heat resistance.

(heat resistant transparency)

The evaluation substrate having the above-mentioned cured coating film was subjected to heat treatment at 250 ° C for 1 hr, and the transmittance of light having a wavelength of 400 nm and 540 nm was measured using a spectrophotometer (manufactured by Hitachi, Ltd., U-3310).

From the above results, it is understood that the active energy ray-curable composition containing the reactive polycarboxylic acid compound (A) of the present invention in Examples 2-1 to 2-35, and Comparative Example 2-1 to Comparative Example The composition of 2-9 is excellent in developability, hardenability, and high-speed coating property, and is excellent in heat resistance, heat-resistant transparency, flatness, flexibility, and toughness.

[Industrial availability]

The active energy ray-curable composition of the present invention is excellent in developability, curability, and high-speed coating property, and can form a spacer for a display element and a color filter which are excellent in heat resistance, heat-resistant transparency, flatness, flexibility, and toughness. Light film protective film. Therefore, the composition is suitable as a material for forming a spacer for a display element such as a liquid crystal display element, an organic EL, or the like, and a color filter protective film.

Claims (4)

An active energy ray-curable resin composition for a display element spacer or a color filter protective film containing a reactive polycarboxylic acid compound (A) or a reactive polycarboxylic acid compound (A) Reactive compound (B), photopolymerization initiator (C), and organic solvent (D); reactive polycarboxylic acid compound (A) is an epoxy resin having at least two epoxy groups in one molecule ( a) A reaction product of the compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule, and further reacted with itaconic anhydride as the polybasic acid anhydride (d). An active energy ray-curable resin composition for a display element spacer or a color filter protective film containing a reactive polycarboxylic acid compound (A) or a reactive polycarboxylic acid compound (A) Reactive compound (B), photopolymerization initiator (C), and organic solvent (D); reactive polycarboxylic acid compound (A) is an epoxy resin having at least two epoxy groups in one molecule ( a) a reaction with a compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule, and a compound (c) having at least two or more hydroxyl groups and one or more carboxyl groups in one molecule The product is further reacted with itaconic anhydride as the polybasic acid anhydride (d). A spacer for a display element which is formed of an active energy ray-curable resin composition as described in claim 1 or 2. A color filter protective film formed of the active energy ray-curable resin composition as described in claim 1 or 2.