KR20140074189A - Actinic radiation hardenable resin composition and spacer for display device using the same, and protective layer of color filter - Google Patents

Abstract

The present invention provides a spacer for a spacer for a display device having excellent heat resistance, heat resistant transparency, surface smoothness, flexibility, and strength and to a color filter protective film. The present invention relates to an active energy ray hardened resin composition for a spacer or a color filter protective film for a display device. The active energy ray hardened resin composition comprises: a reactive polycarbonic acid compound (A); a reactive compound (B) other than the reactor polycarbonic acid compound (A); a photopolymerization initiator (C); and an organic solvent (D). The reactive polycarbonic compound (A) is obtained by making a reactant of an epoxy resin (a), a compound (b), and a compound (c) additionally react with anhydrous itaconic acid as a polybasic acid anhydride (d). The epoxy resin (a) has two or more epoxy groups in one molecule. The compound (b) has one or more polymerizable ethylene-type unsaturated groups and one or more carboxylic groups in one molecule. The compound (C) has two or more hydroxyl groups and one or more carboxylic groups in one molecule if needed.

Description

TECHNICAL FIELD [0001] The present invention relates to an active energy ray-curable resin composition, a spacer for a display element using the same, and a protective film for a color filter,

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

A resin composition comprising a binder polymer, a photopolymerizable monomer and a photopolymerization initiator has been used as a material for a display device. Description of the Related Art [0002] Recently, as a material used for display device materials (LCD, EL, PDP, FED (SED), rear projection display, electronic paper, A display device (LCD) is rapidly spreading. In general, in a color liquid crystal display device, a gap portion of about 1 to 10 mu m is formed by opposing an electrode substrate such as a color filter and a TFT substrate, a liquid crystal compound is filled in the gap portion, As shown in Fig.

The color filter includes a black matrix layer formed in a predetermined pattern so as to shield a boundary portion between pixels on a transparent substrate, and a black matrix layer formed on the transparent substrate in such a manner that red (R), green A protective film and a transparent electrode film are stacked in this order from the side close to the transparent substrate. An alignment film is formed on the inner surface side of the color filter and the electrode substrate facing the color filter. In order to uniformly and uniformly maintain the cell gap between the color filter and the electrode substrate, pores having a predetermined particle diameter as a spacer are dispersed or a pillar shape or a stripe shape having a height corresponding to the cell gap A spacer is formed. A color image is obtained by controlling the light transmittance of the liquid crystal layer behind each colored pixel in each color. Such a color filter is not limited to a color liquid crystal display device but is used for other display devices such as an EL and a rear projection display.

The colored layer, the protective film, and the spacer may be formed using a resin. The colored layer needs to be formed in a predetermined pattern for each pixel of each color. It is preferable that the protective film can cover only the region where the colored layer on the transparent substrate is formed in consideration of the adhesion and tightness of the seal portion. In addition, the spacer needs to be accurately formed in the formation region of the black matrix layer, that is, in the non-display region. Therefore, the colored layer, the protective film, and the columnar spacer are formed by using the curable resin which can easily confine the area to be cured by the photomask.

Further, when development is carried out using an organic solvent after exposing the coated surface of the curable resin in order to form a colored layer, a protective film or a columnar spacer, it is troublesome in terms of handling and waste solution treatment, , A curable resin is developed in which an acid group is introduced into a curable resin and developed with an aqueous alkaline solution after exposure. In these applications, a high temperature (200-260 占 폚 or higher) is applied at the time of formation of an orientation film and formation of a transparent electrode, so that it is required to have a very high heat resistance, and particularly excellent color resist and heat resistance coloring property in a spacer have.

Patent Document 1 uses a photosensitive resin produced by neutralizing an acid-modified epoxy acrylate of a cresol novolac epoxy resin with a primary amino compound as a polymer component of a photosensitive resin composition for a photo-spacer and a color filter. However, such a composition containing a salt of a primary amino compound or water is inferior in coatability and flatness, so that it can not be said that the compatibility with an apparatus such as a slit coater is sufficient.

In Patent Document 2, acid-modified epoxy acrylate of cresol novolak epoxy resin or phenol novolac epoxy resin is used as a polymer component of the photosensitive resin composition for a photo-spacer. However, there has been a problem that the radiation sensitivity and developability are inferior and the level is not sufficiently satisfactory.

Patent Document 3 discloses that a reaction product obtained by adding acrylic acid and dimethylol propionic acid to a cresol novolac epoxy resin as a polymer component of a protective film for a color filter or a resist ink composition for a flexible printed wiring board is subjected to caprolactone modification and further modified with tetrahydrophthalic anhydride One active energy ray-curable resin is used. The polymer component, which is the main component of the composition, is excellent in developability and flexibility, but has a problem that the elastic recovery rate required for the photo-spacer is inferior.

In Patent Document 4, a reactive polycarboxylic acid resin in which an anhydride of itaconic anhydride is added to an epoxy (meth) acrylate of a bisphenol-type epoxy resin or a reaction product of a bisphenol-type epoxy resin and itaconic acid and (meth) A reactive polycarboxylic acid resin modified with phthalic anhydride is used. However, there is a problem that it is not a level that can satisfy the elastic recovery rate required as the photo spacers.

On the other hand, Patent Documents 5 to 8 disclose an epoxy carboxylate compound and a resin composition containing the epoxy carboxylate compound.

Japanese Patent Application Laid-Open No. 2004-109752 Japanese Patent Application Laid-Open No. 2007-010885 Japanese Laid-Open Patent Publication No. 2004-300266 Japanese Patent Application Laid-Open No. 2004-067814 Japanese Patent Application Laid-Open No. 2009-046604 Japanese Laid-Open Patent Publication No. 2009-102501 Japanese Laid-Open Patent Publication No. 2009-120737 Japanese Patent Application Laid-Open No. 2009-275167

Disclosure of the Invention The present invention has been made to solve the problems of the prior art described above and to provide an active energy ray curable resin composition which is excellent in developability, And a filter protective film.

The inventors of the present invention have made intensive investigations to solve the above problems, and as a result, they found that a specific compound and a resin composition having a composition solve the above problems, and have reached the present invention.

That is,

(1) A photocurable resin composition which comprises 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 a reaction product of an epoxy resin (a) having at least two epoxy groups in one molecule and a compound (b) having at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in one molecule (A) obtained by reacting an anhydride of itaconic acid as a polybasic acid anhydride (d) with an active energy ray-curable resin composition for a display element spacer or a color filter protective film.

(B) a photopolymerization initiator (C) and an organic solvent (D) other than the reactive polycarboxylic acid compound (A) and the reactive polycarboxylic acid compound (A)

The reactive polycarboxylic acid compound (A) is obtained by reacting an epoxy resin (a) having at least two epoxy groups in one molecule with a compound (b) having at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in one molecule, (A) which is obtained by reacting a reaction product of a compound (c) having at least two hydroxyl groups and at least one carboxyl group in a molecule with an anhydride of itaconic acid as the polybasic acid anhydride (d) A spacer or a color filter protective film.

(3) a spacer for a display element formed from the active energy ray-curable resin composition.

(4) a color filter protective film formed from the active energy ray-curable resin composition.

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

(Mode for carrying out the invention)

Hereinafter, the present invention will be described in detail.

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

That is, by using a reactive polycarboxylic acid obtained by reacting a reactive epoxycarboxylate compound with an anhydride of itaconic acid as a polybasic acid and introducing a methacryl group into the side chain, the heat resistance is remarkably improved and the characteristics of the present invention are exhibited.

Specific examples of the epoxy resin (a) having at least two epoxy groups in one molecule in the present invention include phenol novolak type epoxy resin, cresol novolak type epoxy resin, trishydroxyphenyl methane type epoxy resin , Bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, biphenol-type epoxy resin, bisphenol-A novolac type epoxy resin, naphthalene skeleton-containing epoxy resin, glyoxyl type epoxy resin , Heterocyclic epoxy resins, and the like.

Examples of the phenol novolak type epoxy resin include EPICLON N-770 (manufactured by Dainippon Ink and Chemicals Inc.), DEN438 (manufactured by Dow Chemical Company), EPIKOTE 154 (manufactured by Emulsion Cell Epoxy Co., EPPN-201, RE-306 (manufactured by Nippon Kayaku Co., Ltd.), and the like. Examples of the cresol novolac epoxy resin include Epiclon N-695 (manufactured by Dainippon Ink and Chemicals Inc.), EOCN-102S, EOCN-103S and EOCN-104S (manufactured by Nippon Kayaku Co., (Manufactured by Kawasaki K.K.), and ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.).

Examples of the trishydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Co.), Epikote E1032H60 Manufactured by Kokusan Co., Ltd.). Examples of the dicyclopentadiene phenol type epoxy resin include epoxy resins such as XD-1000 (manufactured by Nippon Kayaku Co., Ltd.), Epiclon EXA-7200 (manufactured by Dainippon Ink and Chemicals Inc.), TACTIX-556 .

Examples of the bisphenol type epoxy resin include Epicote 828, Epikote 1001 (emulsifying cell epoxy), UVR-6410 (Union Carbide), DER-331 (Dow Chemical), YD-8125 Type epoxy resin, UVR-6490 (manufactured by Union Carbide Corp.), YDF-8170 (manufactured by Toto Chemical), NER-1202 and NER-1302 (manufactured by Nippon Kayaku Co., Ltd.) -7403, NER-7604 (manufactured by Nippon Kayaku Co., Ltd.), and the like.

Examples of the biphenol-type epoxy resin include biphenol type epoxy resins such as NC-3000 and NC-3000-H (manufactured by Nippon Kayaku Co., Ltd.), and bis-phenol type epoxy resins such as YX-4000 (manufactured by Emulsifying Cell Epoxy Co., Epoxy resin, YL-6121 (manufactured by Emulsifying Cell Epoxy Co., Ltd.), and the like. Examples of the bisphenol A novolak type epoxy resin include Epiclon N-880 (manufactured by Dainippon Ink and Chemicals Inc.) and Epikote E157S75 (manufactured by Emulsion Cell Epoxy Co., Ltd.).

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

Among them, phenol novolak type epoxy resin, cresol novolak type epoxy resin, biphenol type epoxy resin and the like are particularly preferable.

The compound (b) having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in one molecule in the present invention reacts to impart reactivity to an active energy ray. The ethylenic unsaturated group and the carboxyl group are not limited as long as they have one or more ethylenic unsaturated groups and carboxyl groups, respectively. These include monocarbonic acid compounds and polycarboxylic acid compounds.

Examples of the monocarboxylic acid compound having one carboxyl group per molecule include (meth) acrylic acid, crotonic acid,? -Cyanosinic acid, cinnamic acid, or a monoglycidyl compound containing a saturated or unsaturated dibasic acid and an unsaturated group . ≪ / RTI > Examples of the (meth) acrylic acids in the above include (meth) acrylic acid,? -Styryl acrylic acid,? -Furfuryl acrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride, (Meth) acrylate derivatives having a hydroxyl group, semi-esters which are a molar reactant, half-esters such as a sugar-molar reaction product of a saturated or unsaturated dibasic acid with a monoglycidyl (meth) And the like.

Examples of the polycarboxylic acid compound having two or more carboxyl groups in one molecule include (meth) acrylate derivatives having a plurality of hydroxyl groups in one molecule, half esters as a sugar mole reactant, and saturated or unsaturated dibasic acids and plural epoxy groups (Meth) acrylate derivative having a glycidyl (meth) acrylate group, and the like.

Of these, the reaction product of (meth) acrylic acid, (meth) acrylic acid and? -Caprolactone, or cinnamic acid from the viewpoint of sensitivity when the active energy ray-curable resin composition is used is most preferable. As the compound (b), it is preferable that the compound does not have a hydroxyl group.

The compound (c) having at least two hydroxyl groups and at least one carboxyl group in a molecule in the present invention reacts for the purpose of introducing a hydroxyl group into the carboxylate compound

Specific examples of the compound (c) having at least two hydroxyl groups and at least one carboxyl group in a molecule in the present invention include dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylol And polyhydroxy-containing monocarboxylic acids such as valeric acid and dimethylolcaproic acid. Particularly preferred examples include dimethylolpropionic acid and the like.

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

The ratio of the total amount of the epoxy resin (a) and the total amount of the carbonic acid of the compound (b) and the compound (c) in this reaction should be appropriately changed depending on the application. That is, when all the epoxy groups are carboxylated, the unreacted epoxy groups do not remain, so that the storage stability of the reactive epoxy carboxylate compound is high. In this case, only the reactivity due to the introduced double bond is used.

On the other hand, by deliberately reducing the amount of the carbonic acid compound to leave the unreacted residual epoxy group, the reactivity by the introduced unsaturated bond and the reaction by the remaining epoxy group, for example, the polymerization reaction by the light- Can be used in combination. However, in this case, attention should be paid to the preservation of the reactive epoxy carboxylate compound (E) or the reactive epoxy carboxylate compound (E ') and examination of the production conditions.

The total amount of the compound (b) and the compound (c) is 1 equivalent of the epoxy resin (a) when the reactive epoxy carboxylate compound (E) or the reactive epoxy carboxylate compound (E ' Is preferably 90 to 120 equivalent%. Within this range, production under relatively stable conditions is possible. If the total amount of the compound (b) and the compound (c) is large, the excess amount of the compound (b) and the compound (c) remains undesirably.

When the epoxy group is intentionally left to remain, the total amount of the compound (b) and the compound (c) is preferably 20 to 90 equivalent% based on 1 equivalent of the epoxy resin (a). When deviating from this range, the reaction by the epoxy group does not proceed sufficiently. In this case, it is necessary to pay attention to the gelation during the reaction and the stability with time of the reactive epoxy carboxylate compound (E).

The ratio of the compound (b) to the compound (c) in the molar ratio to the carboxylic acid is 100: 0 to 5:95, Range is preferred. The reactive epoxy carboxylate compound (E) is used when the amount of the compound (c) is 0, and the reactive epoxy carboxylate compound (E ') when the amount of the compound (c) Within this range, the sensitivity to the active energy ray is good and a sufficient hydroxyl group can be introduced to react the reactive epoxy carboxylate compound (E) or the reactive epoxy carboxylate compound (E ') with the polybasic acid anhydride (d).

The carboxylation reaction may be carried out by reacting with a solvent or by diluting with a solvent. The solvent usable here is not particularly limited as long as it is an inert solvent for the carboxylation reaction.

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

Specific examples thereof include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane and decane; and mixtures thereof such as petroleum ether, white gasoline, solvent naphtha Etc., ester solvents, ether solvents, ketone solvents and the like.

Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate, cyclic esters such as? -Butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol mono Ethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, and butylene glycol monomethyl ether acetate, or polyalkylene glycol monoalkyl ether mono And polycarboxylic acid alkyl esters such as acetates, dialkyl glutarates, dialkyl succinates and dialkyl adipates.

Examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether, ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, Glycol ethers such as glycol diethyl ether, and cyclic ethers such as tetrahydrofuran.

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

In addition, it can be carried out in a single or mixed organic solvent such as other reactive compound (B) described below. In this case, when the composition is used as a curable composition, it is preferable because it can be directly used as a composition.

In the reaction, it is preferable to use a catalyst in order to accelerate the reaction. The amount of the catalyst to be used may vary depending on the reactants, namely, the epoxy resin (a), the carbonic acid compound (b), the compound (c) Is 0.1 to 10 parts by mass based on the total amount of the reactants. The reaction temperature at that time is 60 to 150 占 폚, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, And basic catalysts such as zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide and zirconium oxide.

As the thermal polymerization inhibitor, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenyl picrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4-hydroxytoluene and the like are used .

This reaction is defined as the end point when the acid value of the sample becomes 5 mgKOH / g or less, preferably 3 mgKOH / g or less, while appropriately sampling.

The preferred molecular weight range of the reactive epoxy carboxylate compound (E) thus obtained is in the range of 1,000 to 50,000, more preferably 2,000 to 30,000, in terms of polystyrene-equivalent weight average molecular weight in GPC.

If the molecular weight is smaller than the molecular weight, the hardness of the cured product is not sufficiently exhibited. If the molecular weight is too large, the viscosity becomes high and the coating becomes difficult.

Next, the process of the acid part will be described in detail. The acid part treatment is carried out for the purpose of obtaining a reactive polycarboxylic acid compound (A) by introducing a carboxyl group into the reactive epoxy carboxylate compound (E) or the reactive epoxy carboxylate compound (E ') obtained in the previous step . That is, the addition reaction of the polybasic acid anhydride (d) to the hydroxyl group generated by the carboxylation reaction introduces the carboxyl group through the ester bond.

As the polybasic acid anhydride (d), any compound having an ethylenically unsaturated group capable of polymerizing in the molecule and an acid anhydride structure can be used, and it is particularly preferable to use an itaconic anhydride having excellent alkaline aqueous solution developability, heat resistance and hydrolytic resistance.

The reaction of adding the polybasic acid anhydride (d) can be carried out by adding a polybasic acid anhydride (d) to the carboxylation reaction solution. The addition amount should be appropriately changed depending on the application.

When the reactive polycarboxylic acid compound (A) of the present invention is to be used as an alkali developing type resist, for example, the amount of the polybasic acid anhydride (d) to be added can be adjusted by adding the reactive polycarboxylic acid compound (d) (Based on JIS K5601-2-1: 1999) of 40 to 120 mg KOH / g, and more preferably 60 to 120 mg KOH / g. When the acid value of the solid at this time is within this range, the developability of the aqueous alkali solution of the photosensitive resin composition of the present invention is satisfactory. In other words, the patterning performance is good and the management of the (over) phenomenon is wide, and the excess acid anhydride does not remain.

In the reaction, it is preferable to use a catalyst in order to accelerate the reaction. The amount of the catalyst to be used is preferably in the range of 1 to 100 parts by weight per 100 parts by weight of the reactive epoxy carboxylate compound (E) obtained from the reaction product, namely, the epoxy compound (a) Is added to the total amount of the reactive epoxy compound (E ') obtained from the compound (a), the carboxylic acid compound (b) and the compound (c) and the polybasic acid anhydride (d) 10 parts by mass. The reaction temperature at that time is 60 to 150 占 폚, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, Boron, chromium octanoate, zirconium octanoate, and the like.

The reaction of the acid part can be carried out by reacting with a solvent or by diluting with a solvent. The solvent usable here is not particularly limited as long as the acid moiety is an inert solvent for the reaction. Further, in the case of the production using a solvent in the predominantly carboxylate formation reaction, the acid moiety directly as the next step may be directly supplied to the reaction without removing the solvent, provided that the reaction is inert to both reactions. The solvent which can be used is the same as that which can be used in the carboxylation reaction.

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

In addition, the reaction can be carried out in a single solvent or a mixed organic solvent such as the above-mentioned reactive compound (B). In this case, when the composition is used as a curable composition, it is preferable because it can be directly used as a composition.

The thermal polymerization inhibitor and the like are preferably the same as those exemplified in the above carboxylation reaction.

This reaction is an end point with the acid value of the reactant being in the range of plus or minus 10% of the set acid value while appropriately sampling.

The preferred molecular weight range of the reactive polycarboxylic acid compound (A) is in the range of 1,000 to 50,000, more preferably 2,000 to 30,000, in terms of polystyrene equivalent weight average molecular weight in GPC.

Examples of the reactive compound (B) that can be used in the present invention include radical reactive type acrylates, other cationic reaction type epoxy compounds, and so-called reactive oligomers such as vinyl compounds sensitive to both . The reactive polycarboxylic acid compound (A) is not included in the reactive compound (B).

Examples of the radical reactive acrylate include monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional or more (meth) acrylate, polyester (meth) acrylate, urethane Acrylate oligomer, polyester (meth) acrylate oligomer, and epoxy (meth) acrylate oligomer.

As the monofunctional (meth) acrylate, for example, acryloylmorpholine; (Meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, (Meth) acrylates such as phenoxy (meth) acrylate, phenyl (poly) ethoxy (meth) acrylate, p-cumylphenoxy Ethyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, phenylthioethyl (meth) acrylate, 2-hydroxy- (Meth) acrylate such as methoxy (meth) acrylate, and phenylphenol epoxy (meth) acrylate.

Examples of the bifunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane (Meth) acrylate, bisphenol A (poly) ethoxydi (meth) acrylate, bisphenol A (poly) propoxydi (meth) acrylate, bisphenol F Di (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of (poly) ethylene glycol di (meth) acrylate hydroxypivalic acid neopentyl glycol (eg, KAYARAD manufactured by Nippon Kayaku Co., HX-220, HX-620, etc.).

Examples of trifunctional or higher polyfunctional (meth) acrylates include ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolooctane tri (meth) acrylate, trimethylolpropane polyethoxy tri Methylol such as trimethylolpropane (poly) propoxytri (meth) acrylate, trimethylolpropane (poly) ethoxy (poly) propoxytri (meth) acrylate; (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol polyethoxy tetra (meth) acrylate, pentaerythritol (poly) propoxy tetra Erythritol such as erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Tris [(meth) acryloyloxyethyl] isocyanurate, and caprolactone-modified tris [(meth) acryloyloxyethyl] isocyanurate; Succinic acid-modified pentaerythritol triacrylate, and succinic acid-modified dipentaerythritol pentaacrylates.

(Poly) ester (meth) acrylate oligomer include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, polyethylene glycol, 1-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl- Straight-chain or branched alkyl diols such as pentanediol, 2,4-diethyl-1,5-pentanediol and 2-butyl-2-ethyl-1,3-propanediol, (Poly) ester diol which is a reaction product of a diol compound such as bisphenol A (poly) ethoxydiol or bisphenol A (poly) propoxydiol with the dibasic acid or an anhydride thereof, (Meth) acrylic acid, and the like.

Examples of the urethane (meth) acrylate oligomer include diol compounds such as 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, Butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A polyethoxydiol, bisphenol A Or a reaction product of these diol compounds with dibasic acids or anhydrides thereof (for example, succinic acid, adipic acid, azelaic acid, dimeric acid, isophthalic acid, terephthalic acid, phthalic acid or anhydrides thereof) Ester diols, organic polyisocyanates (e.g., tetramethylene diisocyanate, hexa Chain saturated hydrocarbon isocyanates such as methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate , Cyclic saturated hydrocarbon isocyanates such as methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate and hydrogenated toluene diisocyanate, 2,4-tolylene diisocyanate, 1,3- Aromatic polyisocyanates such as 2,6-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, ) Is reacted, and then the hydroxyl group-containing (meth) acrylate is added There may be mentioned the reaction product and the like.

The epoxy (meth) acrylate oligomer is a carboxylate compound of a compound having an epoxy group and (meth) acrylic acid. Examples of the epoxy (meth) acrylate include phenol novolak type epoxy (meth) acrylate, cresol novolak type epoxy (meth) acrylate, trishydroxyphenyl methane type epoxy (meth) acrylate, dicyclopentadiene phenol type epoxy Containing epoxy (meth) acrylate, bisphenol A epoxy (meth) acrylate, bisphenol F epoxy (meth) acrylate, biphenol epoxy (Meth) acrylate, glyoxylated epoxy (meth) acrylate, and heterocyclic epoxy (meth) acrylate.

Examples of vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds. Examples of the vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of the styrene include styrene, methylstyrene, and ethylstyrene. Other examples of the vinyl compound include triallyl isocyanurate and trimethallyl isocyanurate.

The cationic reaction type monomer is not particularly limited as long as it is a compound having an epoxy group in general. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl- 4-epoxycyclohexane carboxylate (CYRACURE UVR-6110 manufactured by Union Carbide Co., Ltd.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (Such as "ELR-4206" manufactured by Union Carbide Corporation), limonene dioxide ("CELLOXIDE 3000" manufactured by Daicel Chemical Industries, Ltd.), allylcyclohexene dioxide, 3,4- Propylene oxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate , &Quot; Sara Cure UVR-6128 " manufactured by Kabard Co., Ltd.), bis (3,4- (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane, and the like can be given .

Of these, the reactive compound (B) is most preferably a monofunctional, bifunctional or trifunctional or more (meth) acrylate from the viewpoint of good polymerizability and improved strength of the resulting spacer or the like.

The reactive compound (B) of the present invention may be used alone or in combination of two or more. The use ratio of the reactive compound (B) in the composition is preferably 30 parts by mass to 250 parts by mass, more preferably 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) to be used is from 30 parts by mass to 250 parts by mass, the sensitivity of the composition, the heat resistance and the elastic properties of the resulting spacer for a display element and the like become better.

As the photopolymerization initiator (C) of the present invention, an active species capable of initiating polymerization of a reactive compound (B) other than the reactive polycarboxylic acid compound (A) and the reactive polycarboxylic acid compound (A) ≪ / RTI > Examples of such photopolymerization initiators (C) include O-acyloxime compounds, acetophenone compounds, and imidazole compounds.

Examples of the O-acyloxime compound include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octan- Benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol- -9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol- Oxazol-3-yl) -1- (O-acetyloxime), ethanone -1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol- 3-yl] -1- (O-acetyloxime) -9H-carbazol-3- And the like. Among these, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- Yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- { Methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred. These O-acyloxime compounds may be used alone or in combination of two or more.

Examples of the acetophenone compound include an? -Amino ketone compound and? -Hydroxy ketone compound.

Examples of the? -amino ketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- 1- (4-morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one .

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

Among these acetophenone compounds,? -Amino ketone compounds are preferable, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one are more preferred.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) 5'-tetraphenyl-1,2'-biimidazole, and the like. Of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis (2,4,6-trichlorophenyl) -4,4' (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2', 5'-tetraphenyl- - nonimidazole is more preferred.

As a photopolymerization initiator (C), a commercially available product may be used, and for example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (Irgacure 907, 2 - (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (Irgacure 379), ethanone- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02) (available from Chiba Specialty Chemicals).

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

The photopolymerization initiator (C) may be used in combination with the curing accelerator (F). Examples of curing accelerators which can be used in combination include triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethylbenzoate, dimethylaminoacetophenone, p- dimethylaminobenzoic acid isoamino ester, EPA Amines, and 2-mercaptobenzothiazole. The amount of these curing accelerators used is 0% by mass or more and 5% by mass or less when the solid content of the resin composition of the present invention is 100% by mass.

As the organic solvent (D), those in which each component is uniformly dissolved or dispersed and do not react with each component are suitably used. Examples of such organic solvents (D) include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and mixtures thereof such as petroleum ether, white gasoline, solvent naphtha, ester solvents, ether solvents and ketone solvents, For example, alcohols, ethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol monoalkyl ether acetates Lactic acid esters, aliphatic carboxylic acid esters, amides, 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 ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate and diethylene glycol monobutyl ether acetate; Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether; Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate and dipropylene glycol monobutyl ether acetate; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate and isoamyl lactate; Hydroxypropyl methacrylate, ethyl 3-methoxypropionate, ethyl 3-ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxyacetate, Methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl acetate, Aliphatic carboxylic acid esters such as butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate and ethyl pyruvate; Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide and N, N-dimethylacetamide; And ketones such as N-methylpyrrolidone and? -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 mass% or more and 35 mass% or less. By setting the solid content concentration of the composition within the above range, it is possible to effectively suppress the occurrence of unevenness in coating, improvement in coating property, improvement in uniformity of film thickness, and the like.

The viscosity of the composition at 25 占 폚 is 1.0 mPa 占 퐏 or more and 1,000 mPa 占 퐏 or less. It is preferably 2.0 mPa s or more and 100 mPa s or less. By setting the viscosity of the composition within the above range, it is possible to balance the viscosity to such an extent that the film thickness uniformity can be maintained, and even if coating unevenness occurs, spontaneous uniformity can be achieved.

Examples of the alkali-soluble resin (G) used in the photosensitive resin composition of the present invention include 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, etc. , A monomer having a phenolic hydroxyl group, a monomer having a sulfonic acid group, other monomers, and the above-mentioned monofunctional (meth) acrylate.

Specific examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro- naphthyl (meth) acrylate, (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 anhydrides having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, 3-methylphthalic anhydride, methyl-5-norbornene- Tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-yl-succinic anhydride and the like.

Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof.

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, p-hydroxystyrene and the like. And at least one hydrogen atom of these benzene rings may be substituted with an alkyl group such as methyl group, ethyl group or n-butyl group; An alkoxy group such as a methoxy group, an ethoxy group or an n-butoxy group; A halogen atom; A haloalkyl group in which at least one hydrogen atom of the alkyl group is substituted with a halogen atom; A nitro group; Cyano; Amide groups and the like.

Examples of the monomer having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, (meth) allylsulfonic acid, 2-hydroxy-3- (meth) allyloxypropanesulfonic acid, (meth) Sulfopropyl, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid and the like.

Examples of other monomers include hydrocarbon-based olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylates, (meth) acrylamides, Chloroolefins, and conjugated dienes. These compounds may contain a functional group, and examples of the functional group include a carbonyl group and an alkoxy group. In particular, (meth) acrylate esters and (meth) acrylamides are preferred because the spacer formed from the composition is excellent in heat resistance.

When the alkali-soluble resin (G) is copolymerized, it can be produced by radical polymerization of an unsaturated compound in a solvent in the presence of a polymerization initiator. The above-mentioned solvents may be used when they are prepared, and they may be used alone or in combination of two or more kinds.

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

In the polymerization reaction for producing the alkali-soluble resin (G), a molecular weight regulator can be used to adjust the molecular weight. Examples of the molecular weight regulator include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid; Azetidine derivatives such as dimethylzantogen sulfide and diisopropylzantogen disulfide; Terpinolene, alpha -methylstyrene dimer, and the like.

(E) having a reactive group such as a monomer having a phenolic hydroxyl group or a monomer having a sulfonic acid group such as a monomer having a hydroxyl group, an acid anhydride having an ethylenic double bond, a monomer having a carboxyl group, or a monomer having an epoxy group, As the compound (f) having a functional group capable of binding with a group and an ethylenic double bond, for example, the following combinations can be mentioned.

(1) For the monomer (e) having a hydroxyl group, an acid anhydride (f) having an ethylenic double bond,

(2) Compounds (f) having an isocyanate group and an ethylenic double bond for the monomer (e) having a hydroxyl group,

(3) Compounds (f) and (f) having a hydroxyl group-containing monomer (e) and having an acyl chloride group and an ethylenic double bond,

(4) The compound (f) having a hydroxyl group and an ethylenic double bond for the acid anhydride (e) having an ethylenic double bond,

(5) Compounds (f), (f) having an epoxy group and an ethylenic double bond for the monomer (e) having a carboxyl group,

(6) A 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-mentioned examples.

Specific examples of the compound having an isocyanate group and an ethylenic double bond include 2- (meth) acryloyloxyethyl isocyanate and 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate.

Specific examples of the compound having an acyl chloride group and an ethylenic double bond include (meth) acryloyl chloride.

Specific examples of the compound having a hydroxyl group and an ethylenic double bond include the above-mentioned monomers having a hydroxyl group.

Specific examples of the compound having an epoxy group and an ethylenic double bond include the above-mentioned monomers having an epoxy group.

Specific examples of the compound having a carboxyl group and an ethylenic double bond include the above-mentioned monomers having a carboxyl group.

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

It is also preferable to blend a polymerization inhibitor. As the polymerization inhibitor, publicly known polymerization inhibitors 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, in the case of reacting a copolymer having a hydroxyl group 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, dibutyltin di (maleic acid monoester), dioctyltin dilaurate, dioctyltin di (maleic acid monoester), dibutyltin diacetate and the like .

When a copolymer having a hydroxyl group and a compound having an acyl chloride group and an ethylenic double bond are reacted, a basic catalyst may be used. Examples of the basic catalyst include triethylamine, pyridine, dimethylaniline, tetramethylurea, and the like.

The Mw of the alkali-soluble resin (G) is preferably from 2 × 10 ^{3 to} 1 × 10 ⁵ , more preferably from 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 of the present invention (the property of accurately forming a desired pattern shape) can be increased.

If necessary, the photosensitive resin composition of the present invention may contain a surfactant, a leveling agent, a defoaming agent, a filler, an ultraviolet absorber, a photostabilizer, an antioxidant, a polymerization inhibitor, a crosslinking agent, It is also possible to add them to the resin composition to impart the desired functionality to each. Examples of the photo stabilizer include hindered amine compounds, benzoate compounds, and the like as the photo stabilizer. Examples of the antistatic agent include a fluorine-based compound, a silicon-based compound, and an acrylic compound as the antifoaming agent, a benzotriazole- Examples of the antioxidant include phenol compounds. Examples of the polymerization inhibitor include methoquinone, methylhydroquinone, and hydroquinone. Examples of the crosslinking agent include polyisocyanates, melamine compounds, and the like.

In addition, as the resin stream (so-called inert polymer) which does not show reactivity with the active energy ray, for example, other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, Diallyl phthalate resins, styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified materials thereof. These are preferably used in a range of up to 40 parts by mass in the resin composition.

When the total amount of the component (A) + the component (B) + the component (C) + the component (D) is 100 parts by mass, the reactive energy ray curable resin composition of the present invention contains the reactive polycarboxylic acid compound (A) 1 to 9 parts by mass, preferably 1 to 9 parts by mass of the photopolymerization initiator (C), the organic solvent (D) 60 to 90 parts by mass, and preferably 65 to 85 parts by mass. If necessary, other components may be contained in an amount of 0 to 80 parts by mass.

≪ Method of forming display spacer and color filter protective film >

The spacer for a display element formed of the resin composition of the present invention is an aspect of the present invention. The method for forming the spacer for a display element,

(1) a step of coating 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,

(3) a step of developing the coating film irradiated with the radiation, and

(4) heating the developed coating film.

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, slit coating, and the like, followed by drying to form a photosensitive resin composition layer. As a 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, a gravure coater and a comma coater.

If necessary, heat is applied and dried (prebaking). The drying temperature is preferably 50 占 폚 or higher, more preferably 70 占 폚 or higher, and is preferably lower than 150 占 폚, and more preferably 120 占 폚 or lower. The drying time is preferably 30 seconds or more, more preferably 1 minute or more, and preferably 20 minutes or less, and further preferably 10 minutes or less.

Subsequently, the photosensitive resin composition layer is exposed with an active energy ray through a predetermined photomask. When the photosensitive resin composition of the present invention, even if the diameter of the mask opening 5~10㎛ degree (area 20~100㎛ ² or so), with high accuracy, that is, be formed from a range of diameter 6~12㎛ (area 30~120㎛ ²⁾ .

The active energy ray used for exposure is not particularly limited as long as it can cure the photosensitive resin composition of the present invention. The active energy ray-curable resin composition of the present invention is easily cured by an active energy ray. Specific examples of the active energy ray include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays and laser beams, particle beams such as alpha rays, beta rays and electron rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferable in view of the suitable use of the present invention. The exposure dose is not particularly limited, but is preferably 20 to 1,000 mJ / cm 2.

Subsequently, the unexposed portion is removed with a developing solution to perform development. Here, the developing solution used in the development may be an organic solvent, but it is preferable to use an aqueous alkali solution. Examples of the aqueous alkali solution that can be used as a developer include aqueous solutions of inorganic salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and the like; Hydroxytetramethylammonium, hydroxytetraethylammonium and the like can be mentioned. These may be used singly or in combination of two or more. In addition, a surfactant such as an anionic surfactant, a cationic surfactant, a positive surfactant or a nonionic surfactant, or a water-soluble organic solvent such as methanol or ethanol may be added. The concentration of the alkali in the aqueous alkali solution is preferably 0.1 to 5% by mass from the viewpoint of achieving adequate developability. As the developing method, there are a dip method, a shower method, a puddle method and a vibration immersion method, but a shower method is preferable. The temperature of the developing solution is preferably 25 to 40 占 폚. The developing time is appropriately determined depending on the film thickness and the solubility of the resist.

(Baking) may be carried out as necessary in order to further ensure curing. In the case of baking, the baking temperature is preferably 120 to 250 캜. The baking time varies depending on the type of the heating apparatus. For example, when the heating process is performed on the hot plate, the baking time is 5 minutes to 30 minutes. When the heating process is performed in the oven, the baking time can be 30 minutes to 90 minutes. A step baking method in which two or more heating steps are performed, or the like may be used.

The film thickness of the spacer thus formed is preferably 0.1 mu m to 8 mu m, more preferably 0.1 mu m to 6 mu m, and particularly preferably 0.1 mu m to 4 mu m.

The spacer formed in the above forming method is a spacer which has no coating unevenness, has a high degree of flatness, is flexible, and has a small plastic deformation. A liquid crystal display element, an organic EL display element, or the like.

The color filter protective film is preferably 0.5 mu m to 100 mu m, more preferably 1 mu m to 10 mu m.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise stated, in the examples, parts represent parts by mass.

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

1) Epoxy equivalent: Measured by the method according to JIS K7236: 2001.

2) Softening point: Measured by the method according to JIS K7234: 1986.

3) Acid value: Measured by the method according to JISK0070: 1992

Examples 1 to 20: Preparation of reactive polycarboxylic acid compound (A)

NC-2000 (Epoxy equivalent weight: 230 g / eq), EOCN-103S (manufactured by Nippon Kayaku Co., Ltd., (Abbreviated AA, Mw = 72) as the compound (b) was used as the base material amount in Table 1, and the amount of acrylic acid (abbreviated AA, Mw = , And dimethylolpropionic acid (abbreviated as DMPA, Mw = 134) as the compound (c). 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content became 80% by mass of the reaction liquid, and the reaction was carried out at 100 占 폚 for 24 hours to obtain a reactive epoxy carboxylate compound (E) solution. And a solid acid value (AV: mgKOH / g) of 5 or less was used as a reaction end point and proceeded to the next reaction. The acid value measurement was carried out in the reaction solution and converted to the acid value as a solid content.

Subsequently, propylene glycol monomethyl ether monoacetate was added to the reactive epoxycarboxylate compound (E) solution in such a manner that the amount of itaconic anhydride (abbreviation: IA) as the polybasic acid anhydride (d) After heating at 100 DEG C, the acid part was reacted to obtain a solution of the reactive polycarboxylic acid compound (A). The solid acid value (AV: mgKOH / g) is shown in Table 1.

Comparative Examples 1-1 to 1-6: Preparation of comparative reactive polycarboxylic acid compound

NC-2000 (epoxy equivalent weight 230 g / eq, manufactured by Nippon Kayaku Co., Ltd.), EOCN-103S (epoxy equivalent weight 200 g / eq, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight 288 g / , EPPN-201 (epoxy equivalent 190 g / eq, manufactured by Nippon Kayaku Co., Ltd.), EPOMIK R140P (manufactured by Mitsui Chemicals, Inc., epoxy equivalent 186 g / eq) 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content became 80% by mass of the reaction solution and reacted at 100 ° C for 24 hours to obtain a carboxylate compound solution . And a solid acid value (AV: mgKOH / g) of 5 mgKOH / g or less as a reaction end point.

Subsequently, propylene glycol monomethyl ether monoacetate was added to the reactive epoxy carboxylate compound solution so that the polybasic acid anhydride, tetrahydrophthalic anhydride (abbreviated as THPA) as the solvent and 65 mass parts of the solid content as the solvent were added, and heated to 100 ° C Then, the acid part was reacted to obtain a comparative reactive polycarboxylic acid compound solution. The solid acid value (AV: mgKOH / g) is shown in Table 1.

Comparative Example 1-7: Preparation of comparative reactive polycarboxylic acid compound

186 g of an epoxy equivalent of 186 g / eq, manufactured by Mitsui Chemicals, Inc.), 36 g of acrylic acid, 33 g of itaconic acid, 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent were added to a bisphenol A type epoxy resin The solid content was added to 80% by mass of the reaction solution, and the reaction was carried out at 100 占 폚 for 24 hours. Subsequently, 96 g of tetrahydrophthalic anhydride (abbreviated as THPA) as a polybasic acid anhydride and propylene glycol monomethyl ether monoacetate were added so as to have a solid content of 65 parts by mass as a solvent. After heating to 100 캜, To obtain a solution of a polycarboxylic acid compound. The solid acid value (AV: mgKOH / g) was 100 mgKOH / g.

Details of each component used in Examples and Comparative Examples are shown.

≪ Reactive Compound (B) >

B-1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

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

≪ Photopolymerization initiator (C) >

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

C-2: 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (Irgacure 379, Chiba Specialty Chemicals)

C-3: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime) (Irgacure OXE02, Ciba Specialty ㆍ Chemicals

≪ Organic solvent (D) >

PGMEA: Propylene glycol monomethyl ether acetate

DEGDM: diethylene glycol dimethyl ether

≪ Other optional components >

≪ Synthesis of alkali-soluble resin (G) >

[Synthesis Example 1]

7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methyl ethyl ether were placed in a flask equipped with a stirrer, a cooling tube and a stirrer. Subsequently, 5 parts by mass of styrene, 16 parts by mass of methacrylic acid, 34 parts by mass of dicyclopentyl methacrylate, 40 parts by mass of glycidyl methacrylate, and 3 parts by mass of? -Methylstyrene dimer were charged and replaced with nitrogen. , 5 parts by mass of 3-butadiene was added, and stirring was started gently. The temperature of the solution was raised to 70 캜, and this temperature was maintained (maintained) for 5 hours to obtain a polymer solution containing the copolymer [G-1]. The solid concentration of the obtained polymer solution was 33.1%, and the mass average molecular weight of the polymer was 10,000.

≪ Surfactant (H) >

H-1: Fluorine-based surfactant (Ftergent FTX-218, Neos)

H-2: Silicone surfactant (Dow Corning Silicone Co., Ltd., SH8400FLUID)

≪ Crosslinking agent (I) >

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

<Preparation of the composition of the present invention>

[Example 2-1]

100 parts by mass of (B-1) as the reactive compound (B), 100 parts by mass of the reactive compound (B), and 100 parts by mass of the reactive polycarboxylic acid compound (A) were added to a solution containing 100 parts by mass (solid content) 10 parts by mass of (C-3) as an initiator (C-3) and PGMEA and DEGDM as organic solvents were added so as to have a desired solid content concentration and 0.3 part by mass of (H-1) as a surfactant (H) ) Was filtered through a 0.2 mu m membrane filter to prepare the composition (S-1). The values of the organic solvents in Table 2 are mass ratios of PGMEA and DEGDM.

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

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 except that kinds and blending amounts of the respective components were changed as shown in Table 1 It was prepared. The values of the organic solvents in Table 2 are mass ratios of PGMEA and DEGDM.

<Evaluation>

The compositions of Examples 2-1 to 2-35 and Comparative Examples 2-1 to 2-9 and the spacers formed from the coatings were evaluated as follows. The evaluation results are shown in Tables 3 and 4.

(Viscosity)

Viscosity (mPa 占 퐏) of each composition at 25 占 폚 was measured using an E-type viscometer (TV-200, manufactured by Toki Sangyo Co., Ltd.).

(Solid concentration)

0.3 g of the composition was poured into an aluminum plate, about 1 g of diethylene glycol dimethyl ether was added, and the mixture was dried on a hot plate at 175 DEG C for 60 minutes. From the mass before and after drying, the solid content concentration (mass% ).

(Appearance of coating film)

The composition was coated on a 100 x 100 mm chromium-deposited glass using a slit die coater (Rikadai Co., Ltd.), dried under reduced pressure to 0.5 Torr, and then prebaked on a hot plate at 100 캜 for 2 minutes, And further exposed at an exposure amount of 200 mJ / cm &lt; 2 &gt; to form a film having a film thickness of 4 mu m from the upper surface of the chromium film-forming glass. Under the sodium lamp, the appearance of the coating film was visually observed. At this time, the stripe unevenness (unevenness of one or a plurality of straight lines formed in the coating direction or in the direction crossing the stripes) in the entire coating film, irregular irregularities (cloud irregularities), pin irregularities Shape dirt) was investigated. (Poor) "and" x (bad) "when it is apparent that the above-mentioned unevenness is almost invisible.

(Flatness)

The film thickness of the coating film on the chromium film-formed glass produced as described above was measured using a needle contact type measuring instrument (SURFCOM, manufactured by Tokyo Seimitsu Co., Ltd.). The film thickness uniformity was measured by measuring the film thickness at nine measurement points and calculated by the following formula. (50, 10), (50, 20), (50), and (50) are obtained when the short axis direction of the substrate is X and the long axis direction is Y, 30, 50, 40, 50, 50, 50, 60, 50, 70, 50, 80, When the film thickness uniformity is 2% or less, it can be judged that the film thickness uniformity is good.

Film thickness uniformity (%) = {FT (X, Y) max-FT (X, Y) min}

(X, Y) max is a maximum value among the film thicknesses at nine measurement points, FT (X, Y) min is a minimum value among the film thicknesses at nine measurement points, FT ) avg. is the average value of the film thickness at nine measurement points.

(High-speed coating property)

Alkali glass substrate of 100 mm x 100 mm using a slit coater and the coating liquid was ejected from the nozzle so that the distance between the base and the nozzle was 150 mu m and the film thickness after exposure was 2.5 mu m , And the moving speed of the nozzle was varied in a range of 120 mm / sec. To 200 mm / sec. To obtain a maximum speed at which no streak-shaped unevenness due to liquid depletion occurred. At this time, 180 mm / sec. It is possible to judge that it is possible to cope with high-speed coating.

(Radiation sensitivity)

The composition was coated on a 100 mm x 100 mm ITO sputtered glass substrate by spin coating and then prebaked on a hot plate at 90 캜 for 3 minutes to form a coating film having a thickness of 3.5 탆. Subsequently, the resulting coating film was exposed to light using an ultraviolet exposure apparatus (OAK Manufacturing Co., Ltd., model HMW-680GW) with a photomask having a circular pattern with a diameter of 12 mu m formed as an opening. Thereafter, the resist film was developed with a 0.05 mass% aqueous solution of potassium hydroxide at 25 ° C for 60 seconds, washed with pure water for 1 minute, and further baked in an oven at 230 ° C for 30 minutes to form a spacer made of a patterned film. At this time, the minimum exposure amount at which the residual film ratio after post-baking (film thickness of post-baking film × 100 / film thickness after post-baking) was 90% or more was examined. When the value is 55 mJ / cm 2 or less, the sensitivity is good.

In addition, the surface of the substrate was visually observed to confirm the presence or absence of the residue. The evaluation criteria are as follows.

○ ... No residue.

△ ... Residue is negligible.

× ... There is a lot of residue.

(Compression performance)

A spacer having a columnar pattern was formed on the substrate in the same manner as in the evaluation of the radiation sensitivity except that the exposure dose was an exposure dose corresponding to the sensitivity determined by the evaluation of the radiation sensitivity. At that time, the diameter of the photomask interposed at the time of exposure was changed so that the diameter of the pattern bottom portion after the post-baking became 20 占 퐉. This spacer was subjected to a compressive test at a load of 50 mN using a flat compactor having a shape of 50 mu m square using a micro compression tester (FisherScope H100C, manufactured by Fisher Instruments Co., Ltd.), and the compression displacement amount And the recovery rate (%) was calculated from the amount of displacement when the load of 50 mN was removed and the amount of displacement when the load of 50 mN was removed. At this time, when the recovery rate is not less than 70% and the displacement when the load of 50 mN is not less than 0.15 탆, it can be said that the spacer has a compression performance with both a high recovery rate and flexibility.

(Total light transmittance)

Coated on a 50 mm x 50 mm non-alkali glass substrate using a spin coater, dried under reduced pressure to 0.5 Torr, and then prebaked on a hot plate at 100 캜 for 2 minutes to form a coating film. Further, an exposure amount of 200 mJ / To form a film having a film thickness of 4 탆. The evaluation substrate having the cured coating film was measured using a haze meter (TC-H3DPK, manufactured by Denso Corporation).

(Heat resistance)

The cured coating film was measured using TG / DTA (TG / DTA6200, manufactured by SII Co., Ltd.). And the rate of change in mass after storage at 250 DEG C for 1 hour was described. The smaller the rate of change, the better the heat resistance.

(Heat resistance transparency)

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

As apparent from the above results, the active energy ray-curable compositions containing the reactive polycarboxylic acid compound (A) of the present invention in Examples 2-1 to 2-35 were excellent in the properties It has become clear that the composition is superior in developability, curability and high-speed coating ability, and excellent in heat resistance, heat-resistant transparency, flatness, flexibility and toughness.

The active energy ray curable composition of the present invention can form a spacer for a display element and a color filter protective film which are excellent in developability, curability and high-speed coating ability and excellent in heat resistance, heat resistance transparency, flatness, flexibility and toughness. 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 element, or a color filter protective film.

Claims (4)

(B), a photopolymerization initiator (C) and an organic solvent (D) other than the reactive polycarboxylic acid compound (A) and the reactive polycarboxylic acid compound (A)
The reactive polycarboxylic acid compound (A) is a reaction product of an epoxy resin (a) having at least two epoxy groups in one molecule and a compound (b) having at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in one molecule (A) obtained by further reacting itaconic anhydride as a polybasic acid anhydride (d) in the presence of a polyfunctional isocyanate compound (b) or an active energy ray-curable resin composition for a color filter protective film. (B), a photopolymerization initiator (C) and an organic solvent (D) other than the reactive polycarboxylic acid compound (A) and the reactive polycarboxylic acid compound (A)
The reactive polycarboxylic acid compound (A) is obtained by reacting an epoxy resin (a) having at least two epoxy groups in one molecule with a compound (b) having at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in one molecule, (A) which is obtained by reacting a reaction product of a compound (c) having at least two hydroxyl groups and at least one carboxyl group in a molecule with an anhydride of itaconic acid as the polybasic acid anhydride (d) Spacer or color filter protective film. A spacer for a display element formed from the active energy ray-curable resin composition according to claim 1 or 2. A color filter protective film formed from the active energy ray-curable resin composition according to claim 1 or 2.