KR20140115965A - Actinic radiation hardenable resin composition, and colored spacer for display device and black matrix using the same - Google Patents

Abstract

The present invention provides an active energy line curable resin composition having good developing properties, curing properties, and high speed coating properties, and a coloring spacer and/or a black matrix for a display device having good voltage maintenance ratio and adhesiveness. The active energy line curable resin composition for the coloring spacer and/or the black matrix for a display device, includes a reactive polycarbonic acid compound (A), a reactive compound (B), a photo polymerizable initiator (C), a black coloring agent (D), a dispersing agent (E) and an organic solvent (F). The reactive polycarbonic acid compound (A) is obtained by making a reactant of an epoxy resin having at least two epoxy groups in a molecule (a), a compound having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in a molecule (b), and a compound having at least two hydroxyl groups and at least one carboxyl group in a molecule as occasion demands (c), react with dibasic anhydride (d). The epoxy resin having at least two epoxy groups in a molecule (a) is an epoxy resin containing a naphthalene skeleton and/or a glyoxal type epoxy resin.

Description

TECHNICAL FIELD [0001] The present invention relates to an active energy ray-curable resin composition, a colored spacer for a display device using the same, and a black matrix,

The present invention relates to an active energy ray-curable resin composition, a coloring spacer for a display element and / or a black matrix.

In a color liquid crystal display (LCD), 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 and the periphery thereof is sealed with a sealing material Structure. In order to keep the cell gap between the color filter and the electrode substrate constant and uniformly, pores having a predetermined diameter as a spacer are dispersed, or pillar-shaped or stripe-shaped A spacer is formed.

The color filter is formed by laminating a black matrix layer, a colored layer, a protective film, and a transparent electrode film on the transparent substrate in this order from the side close to the transparent substrate. The black matrix layer is formed in a predetermined pattern so as to shield the boundary portion between the pixels. In order to form each pixel, the colored layer is usually arranged in a predetermined order of red, green, and blue. An alignment film is formed between the color filter and the electrode substrate facing the color filter. 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 all be formed using a resin. The coloring 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. Further, the position of the spacer needs to be accurately formed in the formation region of the black matrix layer. Therefore, a colored layer, a protective film, and a columnar spacer are formed by using a curable resin which can easily confine an area to be cured by a photomask, instead of a pearl-shaped gap in which the position of the spacer can not be fixed . This spacer is required to have mechanical strength and heat resistance capable of withstanding high temperature and high pressure in a panel sealing step after liquid crystal injection in manufacturing a display panel (Patent Document 1).

When exposure is performed on a coated surface of a curable resin to form a colored layer, a protective film, or columnar spacers and then development is carried out using an organic solvent, it is troublesome in terms of handling and waste solution treatment. In order to improve this point, a curable resin is used in which an acidic group is introduced into a curable resin and developed with an aqueous alkaline solution after exposure. Since the display device is produced at a high temperature (200-260 占 폚 or higher), very high heat resistance is required for the curable resin to be used. Particularly, display device materials used for color resists and spacers are required to have heat resistance.

As the photosensitive resin used for the spacer, an alkali-soluble photosensitive resin is used. This has the advantage that the amount of the carboxyl group and the amount of the radically polymerizable (meth) acryloyl group can be freely controlled. As such resins, various resin skeletons have been proposed.

In Patent Document 2, an acid-modified epoxy acrylate of a cresol novolak epoxy resin is used as a polymer component of a photosensitive resin composition for a black matrix. However, there is a problem that the radiation sensitivity and the voltage holding ratio (VHR) are inferior and the level is not sufficiently satisfactory.

On the other hand, Patent Documents 3 to 4 disclose an epoxy carboxylate compound and a resin composition containing the epoxy carboxylate compound.

Japanese Patent Application Laid-Open No. 2002-040440 Japanese Patent Application Laid-Open No. 11-084126 Japanese Patent Application Laid-Open No. 2009-046604 Japanese Patent Application Laid-Open No. 4-165358

An object of the present invention is to provide a colored spacer for a display element and a black matrix which are excellent in developability, curability and high-speed coating ability, and which have excellent voltage holding ratio and adhesion.

According to the present invention,

(1) A photocurable composition containing a reactive polycarboxylic acid compound (A), a reactive compound (B), a photopolymerization initiator (C), a black colorant (D), a dispersant (E) and an organic solvent (F)

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 Is reacted with a polybasic acid anhydride (d), wherein the reactive polycarboxylic acid compound (A)

Wherein the epoxy resin (a) having at least two epoxy groups in one molecule is a naphthalene skeleton-containing epoxy resin or a glyoxylated epoxy resin,

A coloring spacer for a display element or an active energy ray-curable resin composition for a black matrix.

(C), a black colorant (D), a dispersing agent (E), and an organic solvent (F), wherein 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 reactive polycarboxylic acid compound (A) 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 a polybasic acid anhydride (d)

Wherein the epoxy resin (a) having at least two epoxy groups in one molecule is a naphthalene skeleton-containing epoxy resin or a glyoxylated epoxy resin,

A coloring spacer for a display element or an active energy ray-curable resin composition for a black matrix.

(3) The resin composition, wherein the epoxy resin (a) having at least two epoxy groups in one molecule is a naphthalene skeleton-containing epoxy resin and a glyoxylated epoxy resin.

(4) The epoxy resin (a) having at least two epoxy groups in one molecule is a naphthalene skeleton-containing epoxy resin.

(5) The epoxy resin (a) having at least two epoxy groups in a molecule is a glyoxylic epoxy resin.

(6) The present invention also relates to a colored spacer for a display element formed from the resin composition.

(7) The present invention also relates to a black matrix formed from the resin composition.

The composition of the present invention can provide a coloring spacer or black matrix for a display element that is excellent in developability, has high radiation sensitivity, and has excellent voltage holding ratio and adhesion.

(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 (G) obtained by reacting the epoxy resin (a) obtained by the reaction of the epoxy resin (b) (B) having at least one polymerizable ethylenic 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, with a reactive epoxy carboxylate compound (D ') in addition to the polybasic acid anhydride (G').

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 & Chemicals, Inc.), DEN438 (manufactured by Dow Chemical), EPICOTE 154 EPPN-201, and RE-306 (manufactured by Nippon Kayaku Co., Ltd.). Examples of the cresol novolak type 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., Ltd.) -6650 (manufactured by Dow Chemical Company), and ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.).

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

(Dow Chemical), DER-331 (manufactured by Dow Chemical Company), YD-3310 (manufactured by Dow Chemical Company), Epikote 821, Epikote 1001 (manufactured by Yucca Shell Epoxy Co., Ltd.) A epoxy resin, UVR-6490 (manufactured by Dow Chemical Company) such as NER-1202 and NER-1302 (manufactured by Nippon Kayaku Co., Ltd.), YDF- And bisphenol-F type epoxy resins such as NERC-8170 (manufactured by Shin-Nikka Epoxy Co., Ltd.), NER-7403 and NER-7604 (manufactured by Nippon Kayaku Co., Ltd.)

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.), YX-4000 (manufactured by Yucca Shell Epoxy Co., Ltd.) A non-ionolone type epoxy resin, and YL-6121 (manufactured by Yucca Shell Epoxy Co., Ltd.). 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 Yucca Shell Epoxy Co., Ltd.).

NC-7000, NC-7700 (manufactured by Nippon Kayaku Co., Ltd.) and EXA-4750 (manufactured by Dainippon Ink and Chemicals, Incorporated) available from the market as naphthalene skeleton- And the like. Glyoxal epoxy resins available from the market include, for example, GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.). Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Co., Ltd.). As the heterocyclic epoxy resin, for example, TEPIC (manufactured by Nissan Chemical Industries Co., Ltd.) and the like can be mentioned.

Among them, naphthalene skeleton-containing epoxy resin and glyoxyl-type epoxy resin are particularly preferable.

The compound (b) having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in the molecule in the present invention is used for imparting reactivity to the reactive polycarboxylic acid compound (A) with 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 equimolar reactants with saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives, And the like.

Examples of the polycarboxylic acid compound having two or more carboxyl groups in a molecule include semi-esters, which are acombination reaction products of saturated or unsaturated dibasic acid anhydrides and (meth) acrylate derivatives having a plurality of hydroxyl groups in one molecule, saturated or unsaturated And half esters, which are equimolar reactants with a dibasic acid and a glycidyl (meth) acrylate derivative having a plurality of epoxy groups.

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.

In the present invention, the compound (c) having at least two hydroxyl groups and at least one carboxyl group in a molecule is used for 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 include dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, dimethylol And polyhydroxy-containing monocarboxylic acids such as caproic acid. Particularly preferred is, for example, dimethylolpropionic acid.

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), the compound (b) and the carboxylic acid (c) in the reaction in this reaction should be appropriately changed depending on the application. That is, when all the epoxy groups are carboxylated, the storage stability of the reactive epoxy carboxylate compound is high since an unreacted epoxy group is not left. In this case, only the reactivity due to the introduced double bond is used.

On the other hand, by reducing the amount of the carbonic acid compound introduced, the unreacted epoxy groups are left, and the reactivity by the introduced unsaturated bonds and the reaction by the remaining epoxy groups, for example, the polymerization reaction by the light- As shown in FIG. However, in this case, attention must be paid to the preservation of the reactive epoxy carboxylate compound (G) or the reactive epoxy carboxylate compound (G ') and the examination of the production conditions.

The total amount of the compound (b) and the compound (c) in the case of producing the reactive epoxy carboxylate compound (G) or the reactive epoxy carboxylate compound (G ') in which no epoxy group is left, 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.

In the case of leaving an epoxy group, 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 additional epoxy group does not proceed sufficiently. In this case, it is necessary to pay enough attention to the gelation during the reaction and the stability over time of the reactive epoxy carboxylate compound (G).

The ratio of the compound (b) to the compound (c) is in the range of 100: 0 to 5:95, more preferably 100: 0 to 40:60 in terms of the molar ratio of the compound (b) . The reactive epoxy carboxylate compound (G) is used when the amount of the compound (c) is 0, and the reactive epoxy carboxylate compound (G ') when the amount of the compound (c) Within this range, the sensitivity to the active energy ray is good, and sufficient hydroxyl groups can be introduced to react the reactive epoxy carboxylate compound (G) or the reactive epoxy carboxylate compound (G ') with the polybasic acid anhydride (d).

The carboxylation reaction may be performed by diluting with a solvent or 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 and application of the resin to be obtained, 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 a reactive compound (B) described later. The use of the reactive compound (B) as a solvent is preferable because it can be used as it is as a composition of the present invention.

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 100 parts by mass of the total amount of reactants. The reaction temperature at that time is 60 to 150 캜, 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, and zirconium octanoate, and the like.

As the thermal polymerization inhibitor, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenyl picrylhydrazine, diphenylamine, 3,5-di-t-butyl- Is preferably used.

The end point of this reaction is a time point at which 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 (G) thus obtained is in the range of 1,000 to 50,000, more preferably 2,000 to 30,000 in mass average molecular weight in terms of polystyrene 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 acid addition step 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 (G) or the reactive epoxy carboxylate compound (G ') 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 specific examples of the polybasic acid anhydride (d), any compound having an acid anhydride structure in the molecule can be used. However, it is preferable to use an acid anhydride such as anhydrous succinic acid, anhydrous phthalic acid, tetrahydrophthalic anhydride , Hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride are particularly preferred.

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 is appropriately changed depending on the use.

When the reactive polycarboxylic acid compound (A) 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 (A) (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 in this range, the developability of the aqueous alkali solution of the composition of the present invention is satisfactory. That is, good patterning performance and management of the phenomenon are easy, and excess acid anhydride does not remain.

In the reaction, it is preferable to use a catalyst in order to accelerate the reaction, and the amount of the catalyst to be used may be appropriately selected in accordance with the amount of the reactive epoxy carboxylate compound (G) or the reactive epoxy carboxylate compound (G ') and the polybasic acid anhydride And 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the reactants added with the solvent and other components. The reaction temperature at that time is 60 to 150 캜, 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 it is an inert solvent for the reaction. Further, in the case where a solvent is used in the predominantly carboxylate formation reaction, an acid moiety, which is the next step directly, may be directly provided to the reaction without excluding the solvent, provided that the solvent is inert to both reactions. The solvent that can be used is the same as that available in the carboxylation reaction.

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

In addition, it can be carried out in a single solvent or a mixed organic solvent such as the 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.

The reaction is carried out by appropriately sampling while the acid value of the reactant is in the range of plus or minus 10% of the set acid value.

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

As the reactive compound (B) usable in the present invention, there may be mentioned reactive oligomers such as radical reaction type acrylates, other cationic reaction type epoxy compounds, and vinyl compounds which are responsive to both of them . 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) acrylates of ε-caprolactone adducts of glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, hydroxypivalic neopentyl glycol (eg, Nippon Kayaku ), KAYARAD HX-220, HX-620, etc.).

Examples of trifunctional or more polyfunctional (meth) acrylates include ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolooctane tri (meth) acrylate, trimethylolpropane Methylol such as trimethylolpropane tri (meth) acrylate, trimethylol propane (poly) propoxy tri (meth) acrylate, trimethylol propane (poly) ethoxy (poly) propoxy tri (meth) acrylate; (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol (poly) ethoxytetra (meth) acrylate, pentaerythritol Erythritol such as dipentaerythritol 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, Propylene glycol, and the like, glycols such as 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1-pentanediol, 2,4-diethyl-1,5-pentanediol and 2-butyl-2-ethyl-1,3-propanediol; and alicyclic diols such as cyclohexane- (Poly) ethoxy diol, or a reaction product of a diol compound such as bisphenol A (poly) propoxy diol and the above dibasic acid or an anhydride thereof, A reaction product of ester diol with (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 (e.g., succinic acid, adipic acid, azelaic acid, dimeric acid, isophthalic acid, terephthalic acid, phthalic acid or anhydrides thereof) Diols, organic polyisocyanates (e.g., tetramethylene diisocyanate, hexamer Chain saturated hydrocarbon isocyanates such as isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornadiisocyanate, 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 diisocyanates such as 2,6-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, Polyisocyanate), and then reacting the hydroxyl group-containing (meth) acrylate It may be added to the reaction 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- Epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, limonene dioxide, allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexanecarboxylate, 3,4- Propylene oxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexylmethyl) Diethylsiloxane, and the like.

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

The reactive compound (B) may be used alone or in combination of two or more. The proportion of the reactive compound (B) in the composition of the present invention 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) Do. When the amount of the reactive compound (B) to be used is 30 parts by mass to 250 parts by mass, the sensitivity of the composition of the present invention, heat resistance and elastic properties such as color spacers for display devices obtained are better.

The photopolymerization initiator (C) is a component that generates an active species capable of initiating polymerization of the reactive polycarboxylic acid compound (A) and the reactive compound (B) in response to an active energy ray. 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- , 1- [4- (phenylthio) -1,2-octanedione 2- (O-benzoyl acetyl oxime)], etc. . 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- (Phenylthio) -1,2-octanedione 2- (O-benzoyl acetyl oxime)] is preferable. 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 the photopolymerization initiator (C), a commercially available product may be used, and examples thereof include 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) , 2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyl acetyl oxime) 3-yl] -1- (O-acetyloxime).

The amount of the photopolymerization initiator (C) to be used in the composition of the present invention is 1% by mass or more and 20% by mass or less, preferably 1% by mass or more and 15% by mass or less when the solid content of the composition of the present invention is 100% Or less.

The photopolymerization initiator (C) may also be used in combination with the curing accelerator (H). Examples of the curing accelerator which can be used in combination include triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethylbenzoate, dimethylaminoacetophenone, p- dimethylaminobenzoic acid isoamino ester, Aminobenzoic acid ester (KAYACURE EPA, manufactured by Nippon Kayaku Co., Ltd.), and hydrogen donors such as 2-mercaptobenzothiazole. The amount of these curing accelerators to be used is 0% by mass or more and 5% by mass or less when the solid content of the composition of the present invention is 100% by mass.

As the black colorant (D), a black colorant may be used alone, or a mixture of red, green and blue. These coloring materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, it is preferable to disperse the pigment in an average particle size of 1 μm or less, preferably 0.5 μm or less.

Examples of the usable coloring materials for preparing the black coloring material include Victorian pure blue (42595), aramin O (41000), catylon brillant flavin (basic 13), rhodamine 6 GCP (45160), rhodamine B (45170) , Sopranin OK 70: 100 (50240), Eliogluxin X (42080), No.120 / Rionol Yellow 21090, Rionol Yellow GRO 21090, Shimura First Yellow 8GF (21105), Benzidine Yellow 4T 540D (21095), Shimura First Red 4015 (12355), Lionol Red 7B4401 (15850), Fastgene Blue TGR-L (74160), Rionol Blue SM (26150), Rionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), and the like (and the numbers in parentheses indicate color index (CI)).

In addition, C.I. As a number, for example, C.I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. green pigment 7, C.I. Brown pigments 23, 25, 26, and the like.

Examples of the black color material which can be used alone include carbon black, acetylene black, lamp black, black black, graphite, iron black, aniline black, cyanine black and titanium black.

Of these, carbon black is preferable from the viewpoint of light shading ratio and image characteristics. Examples of the carbon black include the following carbon blacks. MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45 , # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B.

Printex3, Printex3, Printex30, Printex30, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, PrintexA, PrintexL, PrintexG, PrintexP, PrintexU, PrintexV, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250 , SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, ColorBlackFW1, ColorBlackFW2, ColorBlackFW2V, ColorBlackFW18, ColorBlackFW18, ColorBlackFW200, ColorBlackS160, ColorBlackS170, and the like.

Monarch 160, Monarch 180, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, , VULCANXC72R, and ELFTEX-8.

Manufactured by Columbian Chemicals Company, RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U , RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000, and the like.

Examples of other black pigments include titanium black, aniline black, iron oxide black pigments, and organic pigments of three colors of red, green and blue, and can be used as a black pigment.

As the pigment, barium sulfate, lead sulfate, titanium oxide, yellow lead, spinach, chromium oxide and the like may be used.

A plurality of these pigments may be used in combination. For example, to adjust the chromaticity, a green pigment and a yellow pigment may be used together as a pigment, or a blue pigment and a purple pigment may be used in combination.

The average particle diameter of these pigments is usually 1 占 퐉, preferably 0.5 占 퐉 or less, and more preferably 0.25 占 퐉 or less. Examples of the dyes usable as the coloring material include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

As the azo dye, for example, C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Modern Red 7, C.I. Modern Yellow 5, C.I. Modern Black 7 and so on.

As the anthraquinone-based dye, for example, C.I. Bat Blue 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, C.I. Disperse Blue 60 and the like.

In addition, as phthalocyanine dyes, for example, C.I. Pad Blue 5 or the like, as quinone imine dye, for example, C.I. Basic Blue 3, C.I. Basic Blue 9 and the like, and quinoline dyes such as C.I. Solvent Yellow 33, C.I. Acid Yellow 3, C.I. Disperse Yellow 64, and the like, as nitro dyes, for example, C.I. Acid Yellow 1, C.I. Acid Orange 3, C.I. Disperse Yellow 42 and the like.

The amount of the component (D) to be used in the composition of the present invention is 1% by mass or more and 70% by mass or less, preferably 10% by mass or more and 70% by mass or less when the solid content of the composition of the present invention is 100% Or less. If the content of the black coloring material (D) is too small, the film thickness against the color density becomes excessively large, which adversely affects the gap control at the time of forming the liquid crystal cell. On the contrary, if the content of the black color material (D) is too large, sufficient image forming properties may not be obtained.

In the present invention, it is essential that the dispersing agent (E) be contained because fine dispersion of the black coloring material (D) and stabilization of the dispersing state are important.

The dispersant (E) is preferably a polymer dispersant having a functional group. Further, from the viewpoint of dispersion stability, functional groups such as a carboxyl group, a phosphoric acid group, a sulfonic acid group and a salt thereof, a primary, secondary, tertiary amino group, quaternary ammonium salt, nitrogen containing hetero ring such as pyridine, pyrimidine, Is used.

Examples of the dispersant (E) include a urethane dispersant, an acrylic dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, an aliphatic modified polyester dispersant Specific examples thereof include, but are not limited to, EFKA (manufactured by EFKA), Disperbyk (manufactured by BICKEMISA), DISPARLON (manufactured by Cuslimokasei), SOLSPERSE (Manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyowa Chemical Industry Co., Ltd.) and AJISPER (manufactured by Ajinomoto Fine Techno Co., Ltd.) . These may be used singly or in a mixture of two or more kinds.

The mass average molecular weight of these dispersants (E) in terms of polystyrene by GPC is 700 or more, preferably 1000 or more, 100,000 or less, and preferably 50,000 or less.

The dispersant (E) is particularly preferable in view of adhesiveness and linearity, having a urethane-based and acrylic-based polymer dispersant having a functional group. Examples of the urethane-based and acrylic-based polymer dispersing agents include Disperbyk 160 to 166 series, Disperbyk 2000, and the like (both manufactured by Bigmix).

Examples of the pigment derivative include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrone, And derivatives such as triphene, perylene, perinone, diketopyrrolopyrrole, and dioxazine, among which quinophthalone is preferable. Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, etc. directly in the pigment skeleton or with an alkyl group, an aryl group, And is preferably a sulfonic acid group. These substituents may be substituted by plural substituents in one pigment skeleton. Specific examples of the pigment derivative include a sulfonic acid derivative of phthalocyanine, a sulfonic acid derivative of quinophthalone, an anthraquinone sulfonic acid derivative, a quinacridone sulfonic acid derivative, a diketopyrrolopyrrole sulfonic acid derivative, and a dioxazine sulfonic acid derivative. These may be used singly or in a mixture of two or more kinds. As the dispersant, it is preferable to use a polymer dispersant and a pigment derivative in combination.

The amount of the dispersant (E) to be used in the composition of the present invention is 1% by mass or more and 50% by mass or less, preferably 5% by mass or more and 30% by mass or less when the solid content of the composition of the present invention is 100% to be. When the content of the dispersant (E) is too small, sufficient dispersibility can not be obtained. When the content of the dispersant (E) is excessively large, the proportion of other components is decreased, and the color density, sensitivity and film formability are deteriorated.

As the organic solvent (F), it is suitably used that each constituent component is uniformly dissolved or dispersed and does not react with each constituent component. Examples of such organic solvents (F) 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 (F) 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 of the present invention is 5 mass% or more and 40 mass% or less. The solid content concentration of the composition of the present invention is preferably 10% by mass or more and 35% by mass or less. By setting the solid content concentration of the composition of the present invention within the above range, it is possible to improve the coating property and the film thickness uniformity, thereby effectively suppressing the occurrence of nonuniform coating.

The viscosity of the composition of the present invention 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 占 퐏 or more and 100 mPa 占 퐏 or less. By setting the viscosity of the composition of the present invention within the above-mentioned range, it is possible to balance the viscosity to such an extent that evenness of coating can be spontaneously even if coating unevenness occurs, while maintaining the uniformity of the film thickness.

In the composition of the present invention, an alkali-soluble resin (J) (except for the reactive polycarboxylic acid compound (A)) may be used if necessary. Examples of the alkali-soluble resin (J) include monomers having a phenolic hydroxyl group, monomers having a sulfonic acid group, such as monomers having a hydroxyl group, acid anhydrides having an ethylenic double bond, monomers having a carboxyl group and monomers having an epoxy 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 anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, 3-methylphthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride , Anhydrous 3,4,5,6-tetrahydrophthalic acid, anhydrous cis-1,2,3,6-tetrahydrophthalic acid, and 2-butene-1-yl-anhydrous succinic acid.

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. Particularly, in order to improve the heat resistance of the spacer, (meth) acrylic acid esters and (meth) acrylamides are preferable.

When the alkali-soluble resin (J) 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 at the time of production, or they may be used alone or in combination of two or more.

As the polymerization initiator used in the polymerization reaction for producing the alkali-soluble resin (J), 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 the radical polymerization initiator, the peroxide may be used in combination with a reducing agent to form a rydax type initiator.

In the polymerization reaction for producing the alkali-soluble resin (J), 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; Azotigens such as dimethylzantogen disulfide 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 to a reactive 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) For the monomer (e) having a hydroxyl group, a compound (f) having an isocyanate group and an ethylenic double bond,

(3) For the monomer (e) having a hydroxyl group, a compound (f) having an acyl chloride group and an ethylenic double bond,

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

(5) Compounds (f) and (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 for the monomer (e) having an epoxy group.

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.

Further, in the polymerization reaction for producing the alkali-soluble resin (J), it is preferable to add 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 molecular weight (Mw) of the alkali-soluble resin (J) 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 (J) 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.

The composition of the present invention may further contain additives such as a surfactant, a leveling agent, a defoaming agent, a filler, an ultraviolet absorber, a photostabilizer, an antioxidant, a polymerization inhibitor, a crosslinking agent, So that it is possible to give each of the functions of interest. Examples of the photostabilizer include a hindered amine compound, a benzoate compound, and the like as a light stabilizer, a fluorine compound, a silicon compound, an acrylic compound and the like as the antifoaming agent, a benzotriazole compound, a benzophenone compound and a triazine compound as the antifoaming agent, 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 resin, phenol resin, urethane resin, polyester resin, ketone formaldehyde resin, cresol resin, Allyl phthalate resins, styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products 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) + the component (E) + the component (F) is 100 parts by mass, the reactive polycarboxylic acid compound 1 to 30 parts by mass, preferably 1 to 27 parts by mass, of the reactive compound (A), 1 to 31 parts by mass, more preferably 1 to 27 parts by mass, the photopolymerization initiator (C) Preferably 0.1 to 20 parts by mass, and more preferably 0.3 to 12 parts by mass of the dispersant (E), 0.1 to 6 parts by mass of the colorant (D), 0.1 to 28 parts by mass, preferably 0.5 to 28 parts by mass of the black coloring material (F) of 60 to 95 parts by mass, preferably 65 to 90 parts by mass. Other components may be contained in an amount of 0 to 80 parts by mass, if necessary.

≪ Method of forming black matrix and coloring spacer for display element >

The black matrix formed by the composition of the present invention and the coloring spacer for a display element are aspects of the present invention. The method for forming the black matrix and the coloring spacer for a display element includes:

(1) a step of coating the composition of the present invention 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 composition of the present invention will be briefly described. The composition of the present invention is uniformly applied to 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.

After applying the composition of the present invention, it is dried by heat (pre-baking) if necessary. 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 composition layer is exposed with an active energy ray via a predetermined photomask. If the composition of the present invention, the diameter of the mask opening, even 5~10㎛ degree (area 20~100㎛ ² or so), with high accuracy, that can be formed within 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 composition of the present invention. The composition of the present invention is readily cured by an active energy beam. 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, and development is performed. 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 alone or in combination of two or more. In addition, a surfactant such as an anionic surfactant, a cationic surfactant, a amphoteric surfactant or a nonionic surfactant, or a water-soluble organic solvent such as methanol or ethanol may be added and used It is possible. 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. When baking is performed, the baking temperature is usually 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 black matrix thus formed is preferably 0.2 to 20 占 퐉, more preferably 0.5 to 10 占 퐉, and particularly preferably 0.8 to 5 占 퐉.

The thickness of the colored spacer 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.

(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 following examples, parts denote parts by weight.

The softening point, epoxy equivalent, acid value and NMR 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.

4) < 13 > C-NMR:

Measuring device: VARIAN NMR system 400 MHz

Solvent: Heavy chloroform

Synthesis Example 1-1

168 parts by mass of 2,6-bis (hydroxymethyl) -p-cresol (1.0 mole) and 1008 parts by mass of? -Naphthol (7.0 mole) were charged into a glass container equipped with a thermometer, a reflux condenser and a stirrer, And 1,500 mL of methyl isobutyl ketone were added, and the mixture was stirred at room temperature under a nitrogen atmosphere. 1.7 parts by mass of p-toluenesulfonic acid (1.0% by mass based on 2,6-bis (hydroxymethyl) -p-cresol) was slowly added so that the temperature of the liquid did not exceed 50 占 폚. After the addition, the mixture was warmed to 50 ° C on an oil bath and allowed to react for 2 hours. Then, 500 mL of methyl isobutyl ketone was added, and the mixture was transferred to a separating funnel. The water was washed with water until the washing water exhibited neutrality, and the organic layer was concentrated under reduced pressure to obtain 370 parts by mass of pale yellow viscous material. The softening temperature (JIS K 2425 ring method) was 112 ° C and the hydroxyl equivalent (g / mol) was 138.

Subsequently, 138 parts by mass of the obtained pale yellow viscous substance and 460 parts by mass of epichlorohydrin were introduced into a 1 L reactor provided in a thermometer, a stirring apparatus, a dropping funnel and a distilled water separating apparatus, and nitrogen replacement was carried out. Subsequently, 85 parts by mass of a 48 mass% aqueous sodium hydroxide solution was added dropwise over 5 hours. The epoxidized water is continuously removed from the reaction system by azeotropic distillation with epichlorohydrin in water of water and aqueous sodium hydroxide solution under the conditions of a reaction temperature of 60 ° C and a pressure of 100 to 150 mmHg, Back. Subsequently, the excess unreacted epichlorohydrin was recovered under reduced pressure, and then 500 mL of methyl isobutyl ketone was added thereto, and the mixture was washed until 100 mL of water became neutral. The methyl isobutyl ketone layer was concentrated under reduced pressure to obtain 170 parts by mass of a solid yellow epoxy resin product (EP1).

The product had an epoxy equivalent (g / mol) of 213 at a softening temperature (JIS K2425) of 75 占 폚. As a result of GPC analysis of this product, the compositional ratio of the epoxy resin of the formula (1) was 57 mass%. M ⁺ 588 was obtained by mass spectrum (FAB-MS) of the epoxy resin product, and it was confirmed that the component having the following structure was the main component.

Synthesis Example 1-2

168 parts by mass of 2,6-bis (hydroxymethyl) -p-cresol (1.0 mole) and 1008 parts by mass of? -Naphthol (7.0 mole) were charged into a glass container equipped with a thermometer, a reflux condenser and a stirrer, And 1,500 mL of methyl isobutyl ketone were added, and the mixture was stirred at room temperature under a nitrogen atmosphere. 1.7 parts by mass of p-toluenesulfonic acid (1.0% by mass based on 2,6-bis (hydroxymethyl) -p-cresol) was added slowly so that the temperature of the liquid did not exceed 50 占 폚. After the addition, the mixture was warmed to 80 DEG C in an oil bath and allowed to react for 2 hours, 500 mL of methyl isobutyl ketone was added, and the mixture was transferred to a separating funnel and then water-filtered. After washing with water until the washing water exhibited neutrality, the organic layer was concentrated under reduced pressure to obtain 371 parts of a yellow solid. The softening temperature (JIS K2425 ring method) was 113 占 폚, and the hydroxyl equivalent (g / mol) was 138.

Subsequently, 138 parts by mass of the yellow solid (hydroxyl equivalent (g / mol) 138) and 460 parts by mass of epichlorohydrin were fed into a 1 L reactor equipped with a thermometer, a stirring device, a dropping funnel and a distilled water separator, , And 85 mass parts of a 48 mass% sodium hydroxide aqueous solution was added dropwise over 5 hours. The dropping was continuously removed from the reaction system by azeotropic distillation with water and epichlorohydrin in aqueous sodium hydroxide solution under the conditions of a reaction temperature of 60 ° C and a pressure of 100 to 150 mmHg, and the epichlorohydrin was returned to the system. Subsequently, the excess unreacted epichlorohydrin was recovered under reduced pressure, and then 500 mL of methyl isobutyl ketone was added thereto, and the mixture was washed until 100 mL of water became neutral. The methyl isobutyl ketone layer was concentrated under reduced pressure to obtain 169 parts by mass of an epoxy resin product (EP2) as a pale yellow solid. This product had a softening temperature of 76 占 폚 and an epoxy equivalent (g / mol) of 214. The compositional ratio of the epoxy resin of the formula (2) in the product was 55% by mass and the mass spectrum (FAB-MS) was M ⁺ 588.

Synthesis Example 1-3

A glass container equipped with a thermometer, a reflux condenser and a stirrer was purged with nitrogen while nitrogen purge was carried out, and a naphthol-cresol novolac resin (naphthol: 70% by mass, 160 parts by mass of? -Naphthol in naphthol (5% by mass: softening point 110 占 폚), 370 parts by mass of epichlorohydrin (4 molar equivalents vs. phenol resin) and 37 parts by mass of dimethylsulfoxide were dissolved, The temperature was raised to 40 to 45 占 폚. Subsequently, 41 parts by mass of flaky sodium hydroxide was added in portions over 90 minutes, and then further reacted at 40 DEG C for 2 hours and at 70 DEG C for 1 hour. After completion of the reaction, water was washed with 500 parts by mass of water, and excess solvent such as epichlorohydrin was distilled off from the oil layer using a rotary evaporator under reduced pressure. 500 parts by mass of methyl isobutyl ketone was added to the residue, and the temperature was raised to 70 占 폚. 10 parts by mass of an aqueous solution of 30% by mass of sodium hydroxide was added under stirring, and the reaction was carried out for 1 hour. Thereafter, water washing was carried out until the washing water in the oil layer became neutral. From the resulting solution, methyl isobutyl Butyl ketone and the like were distilled off to obtain 196 parts by mass of an epoxy resin (EP3).

This product had a softening temperature of 93 캜, an epoxy equivalent (g / ㏖) of 233, and a melt viscosity (ICI melt viscosity cone # 1) at 150 캜 of 1.3 Pa · s. Further, in 13 C-NMR, the ratio of the total amount of the peak area of 74 to 76 ppm and the total amount of the peak area of 68 to 71 ppm was 64:36.

Synthesis Examples 2-1 to 2-8: Preparation of reactive polycarboxylic acid compound (A)

The epoxy resin (a) obtained in Synthesis Examples 1-1 to 1-3 and the epoxy resin or GTR-1800 (epoxy equivalent weight: 170 g / eq, manufactured by Nippon Kayaku Co., Ltd.) (Parts) in Table 1, and dimethylolpropionic acid (abbreviated as DMPA, Mw = 134) as the compound (c) were added to the base material (parts) in Table 1 as acrylic acid (abbreviated AA, Mw = 72) . 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 the reaction was carried out at 100 占 폚 for 24 hours to obtain a reactive epoxy carboxylate compound (G) solution. And a solid acid value (AV: mgKOH / g) of 5 mgKOH / g or less as a reaction end point. The acid value measurement was carried out by measuring the reaction solution and calculating the acid value as a solid content.

Subsequently, the amount (parts by weight) of tetrahydrophthalic anhydride (abbreviated as THPA) as the polybasic acid anhydride (d) in the reactive epoxy carboxylate compound (G) solution and the propylene Glycol monomethyl ether monoacetate was added, and the mixture was heated to 100 캜, and then the acid part 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 Synthesis Examples 2-1 to 2-2: Preparation of comparative reactive polycarboxylic acid compound

An epoxy equivalent weight of 288 g / eq) or EOCN-103S (epoxy equivalent weight of 200 g / eq, manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin (a) (Parts) in Table 1, 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solids content became 80% by mass of the reaction solution , And reacted at 100 DEG 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, to the reactive epoxy carboxylate compound solution, tetrahydrophthalic anhydride (abbreviated as THPA) was added as the polybasic acid anhydride (d) in the amount shown in Table 1 and propylene glycol monomethyl (meth) acrylate After adding ether monoacetate, the mixture was heated to 100 占 폚, and then the acid moiety was reacted to obtain a comparative reactive polycarboxylic acid compound solution. The solid acid value (AV: mgKOH / g) is shown in Table 1.

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.)

≪ Photopolymerization initiator (C) >

C-1: 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoylacetyloxime)] (Irgacure OXE01,

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

≪ Organic solvent (F) >

PGMEA: Propylene glycol monomethyl ether acetate

DEGDM: diethylene glycol dimethyl ether

≪ Synthesis of Pigment Dispersion (I) >

20.0 parts by mass of carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation) as a black color material, 6.0 parts by mass of Ajisper-PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as a dispersant, and 74 parts by mass of PGMEA as an organic solvent , And mixed and dispersed in a bead mill for 12 hours to obtain a pigment dispersion (I-1).

≪ Other optional components >

≪ Synthesis of alkali-soluble resin (J) >

[Synthesis Example 3]

7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methyl ethyl ether were fed into 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 dicyclopentanyl 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 1,3-butadiene was added, and stirring was started gently. The temperature of the solution was raised to 70 캜 and the temperature was maintained (maintained) for 5 hours to obtain a polymer solution containing the copolymer [J-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 (K) >

K-1: fluorine-based surfactant (Ftergent FTX-218, Neos)

K-2: Silicone surfactant (SH8400FLUID manufactured by Toray Dow Corning)

≪ Crosslinking agent (L) >

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

<Preparation of the composition of the present invention>

[Example 1-1]

8 parts by mass of (B-1) as a reactive compound (B), 80 parts by mass of a polyfunctional (meth) acrylate compound as a reactive polycarboxylic acid compound (A) , 8 parts by mass of (C-2) as the initiator (C), 54 parts by mass (solid content) of the pigment dispersion (I-1) as the pigment dispersion (I-1), PGMEA and DEGDM as the organic solvents were added so as to have the desired solid concentration, And 0.05 parts by mass of (K-1) as the component (K) were mixed to prepare the composition (S-1) of the present invention. The values of the organic solvents in Table 2 are mass ratios of PGMEA and DEGDM.

[Examples 1-2 to 1-16 and Comparative Examples 1-1 to 1-3]

The compositions of Examples 1-2 to 1-16 and Comparative Examples 1-1 to 1-3 were prepared in the same manner as in Example 1-1 except that the 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 1-1 to 1-16 and Comparative Examples 1-1 to 1-3 and the black matrix formed of the coating film were evaluated as described below. The evaluation results are shown in Table 3.

(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)

About 0.3 g of the composition was poured into an aluminum plate and about 1 g of diethylene glycol dimethyl ether was added and dried on a hot plate at 175 ° C for 60 minutes to give a solid content The concentration (mass%) was obtained.

(Appearance of coating film)

The composition was coated on a 100 mm x 100 mm non-alkali glass substrate using a slit die coater (Technomachine, Lihua Dai Co., Ltd.), dried under reduced pressure to 0.5 Torr, Baked to form a film having a film thickness of 4 mu m from the upper surface of the chromium film-forming glass by further exposure at an exposure amount of 200 mJ / cm &lt; 2 &gt;. 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.

(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 the range of 120 mm / sec to 200 mm / sec to obtain the maximum velocity at which no striped irregularity due to liquid depletion (film thickness non-uniformity) occurred. At this time, 150 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 (Okusay Sakusho, model HMW-680GW) via a photomask having a circular pattern with a diameter of 12 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 investigated. When this value is 100 mJ / cm 2 or less, the sensitivity can be said to be good.

Further, the surface of the substrate was observed with naked eyes 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.

(Adhesion)

The minimum pattern size of the developable resist at an exposure dose to faithfully reproduce a mask pattern of 20 mu m was observed with a microscope. The magnification of the microscope is 200 times. The evaluation criteria are as follows.

○ ... When the minimum pattern dimension is 10 mu m or less

× ... When the minimum pattern dimension exceeds 10 mu m

(Measurement of impurity forcible extraction treatment and voltage holding ratio [VHR] by ITO method)

As a electrode, a glass substrate (100 mm x 100 mm) on which an ITO electrode was formed was cleaned according to a regular method. Next, the composition was coated on the ITO electrode of the glass substrate by spin coating, pre-baked at 90 DEG C for 3 minutes, and exposed to light of 100 mJ / cm &lt; 2 &gt; Followed by spraying with 0.05% KOH aqueous solution for 60 seconds and then post baking at 230 캜 for 30 minutes to form a 1.5 탆 thick black matrix layer on the ITO electrode. On the other hand, as a counter electrode, a glass substrate (100 mm x 100 mm) on which an ITO electrode was formed was prepared and cleaned according to a regular method.

A liquid crystal (MLC-6846-000 manufactured by Merck Japan Co., Ltd.) was injected between the electrodes, and the injection port was sealed to produce a liquid crystal cell for measurement. The liquid crystal used had a voltage holding ratio of 98% or more as measured under the following conditions of voltage holding ratio measurement in the liquid crystal cell for measurement in the state before the impurity forced extraction treatment.

Each of the liquid crystal cells for measurement prepared above was subjected to heat treatment (left in an oven at 105 ° C for 2.5 hours), and the black matrix layer was subjected to impurity forced extraction treatment. Next, the measurement liquid crystal cell subjected to the impurity forcible extraction treatment as described above was returned to room temperature, and a voltage holding ratio was measured by applying a voltage between the electrode and the counter electrode under the following conditions. If this value is more than 95%, the voltage conservation rate is good. For the measurement of the voltage holding ratio, a voltage holding ratio measuring system VHR-6254 (manufactured by Toyo Technica Co., Ltd.) was used.

(Voltage holding ratio measurement condition)

· Distance between the electrode and the counter electrode: 5 to 15 μm

· Applied voltage pulse amplitude: 5V

· Applied voltage pulse frequency: 60㎐

· Applied voltage pulse width: 20 μsec

As is apparent from the above results, the active energy ray curable composition containing the reactive polycarboxylic acid compound (A) obtained from the naphthalene skeleton-containing epoxy resin or the glyoxal epoxy resin of Examples 1-1 to 1-16, Compared with the compositions of Comparative Examples 1-1 to 1-3 which do not contain the reactive polycarboxylic acid compound (A) obtained from the skeletal epoxy resin or the glyoxylic epoxy resin, the developability, curability and high-speed coating property are good , Voltage holding ratio, and adhesion.

The composition of the present invention can form a colored spacer for a display element and a black matrix which are excellent in developability, curability and high-speed coating property, and excellent in voltage holding ratio and adhesion. Therefore, the composition is suitable as a material for forming a color spacer and a black matrix for a display element such as a liquid crystal display element, an organic EL element, and the like.

Claims (4)

(A), a reactive compound (B), a photopolymerization initiator (C), a black colorant (D), a dispersant (E) and an organic solvent (F)
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 Is reacted with a polybasic acid anhydride (d), wherein the reactive polycarboxylic acid compound (A)
Wherein the epoxy resin (a) having at least two epoxy groups in a molecule is a naphthalene skeleton-containing epoxy resin or a glyoxylated epoxy resin, or a naphthalene skeleton-containing epoxy resin and a glyoxylated epoxy resin.
A coloring spacer for a display element or an active energy ray curable resin composition for a black matrix. (A), a reactive compound (B), a photopolymerization initiator (C), a black colorant (D), a dispersant (E) and an organic solvent (F)
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 reactive polycarboxylic acid compound (A) 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 a polybasic acid anhydride (d)
Wherein the epoxy resin (a) having at least two epoxy groups in a molecule is a naphthalene skeleton-containing epoxy resin or a glyoxylated epoxy resin, or a naphthalene skeleton-containing epoxy resin and a glyoxylated epoxy resin.
A coloring spacer for a display element or an active energy ray curable resin composition for a black matrix. A colored spacer for a display element formed from the active energy ray-curable resin composition according to any one of claims 1 to 3. A black matrix formed from the active energy ray-curable resin composition according to claim 1 or 2.