CN108628099B - Colored photosensitive resin composition for red pixel, color filter and application thereof - Google Patents

Colored photosensitive resin composition for red pixel, color filter and application thereof Download PDF

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CN108628099B
CN108628099B CN201810201456.2A CN201810201456A CN108628099B CN 108628099 B CN108628099 B CN 108628099B CN 201810201456 A CN201810201456 A CN 201810201456A CN 108628099 B CN108628099 B CN 108628099B
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photosensitive resin
resin composition
colored photosensitive
chemical formula
red pixels
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CN108628099A (en
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尹贞玉
柳廷昊
李瑞桓
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Dongwoo Fine Chem Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

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  • Spectroscopy & Molecular Physics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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  • Optical Filters (AREA)

Abstract

The invention provides a colored photosensitive resin composition for a red pixel, a color filter formed by using the colored photosensitive resin composition for the red pixel and application thereof. The colored photosensitive resin composition for red pixels of the present invention has excellent adhesion and hardness, and can suppress development unevenness.

Description

Colored photosensitive resin composition for red pixel, color filter and application thereof
Technical Field
The present invention relates to a colored photosensitive resin composition for red pixels, a color filter, and an image display device, and more particularly, to a colored photosensitive resin composition for red pixels which has excellent adhesion and hardness and suppresses the occurrence of developed spots, a color filter formed using the colored photosensitive resin composition for red pixels, and an image display device including the color filter.
Background
Color filters are widely used in image pickup devices, liquid crystal display devices (LCDs), and the like, and their application range is expanding. Color filters are typically manufactured as follows: on the substrate on which the black matrix pattern is formed, a colored photosensitive resin composition containing pigments of respective colors corresponding to red, green and blue is uniformly applied, and then heated and dried, and the formed coating film is exposed and developed, and further heated and cured as necessary, and the above-described operations are repeated for each color to form pixels of respective colors.
Korean laid-open patent No. 10-2012 and 0112188 discloses a colored photosensitive resin composition for red pixels, which uses a benzimidazolone pigment having high brightness and contrast as a coloring material for red pixels.
However, in order to provide a high-quality color filter having high color reproducibility, development of a colored photosensitive resin composition for red pixels, which is excellent in adhesion and hardness and suppresses the occurrence of development unevenness, has been demanded.
Disclosure of Invention
Problems to be solved
An object of the present invention is to provide a colored photosensitive resin composition for red pixels, which has excellent adhesion and hardness and suppresses the occurrence of development patches.
Another object of the present invention is to provide a color filter formed using the colored photosensitive resin composition for red pixels.
Still another object of the present invention is to provide an image display device including the color filter.
Means for solving the problems
In one aspect, the present invention provides a colored photosensitive resin composition for a red pixel, including an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a colorant, and a solvent, wherein the photopolymerization initiator includes a compound represented by the following chemical formula 1, and the colorant includes a compound represented by the following chemical formula 2.
[ chemical formula 1]
Figure BDA0001594612710000021
[ chemical formula 2]
Figure BDA0001594612710000022
In the above-mentioned formula, the compound of formula,
R1～R3each independently of the others is hydrogen, halogen, C1-C20Alkyl, aryl, C1-C20Alkoxy, aralkyl, C1-C20Hydroxyalkyl of (C)2-C40Hydroxyalkoxyalkyl or C3-C20Cycloalkyl groups of (a);
R4～R10each independently is hydrogen, C1-C20Alkyl, aryl, C1-C20Alkoxy, aralkyl, C1-C20Hydroxyalkyl of (C)2-C40Hydroxyalkoxyalkyl of、C3-C20Cycloalkyl, amino, nitro, cyano or hydroxy;
p is 0 or 1.
In another aspect, the present invention provides a color filter formed using the colored photosensitive resin composition for red pixels.
In still another aspect, the present invention provides an image display device including the color filter.
Effects of the invention
The colored photosensitive resin composition for red pixels of the present invention contains an oxime ester fluorene-based photopolymerization initiator having a specific structure as a photopolymerization initiator and a brominated diketopyrrolopyrrole compound as a colorant, and thus has excellent adhesion and hardness and can suppress development mottle.
Detailed Description
The present invention will be described in more detail below.
One embodiment of the present invention relates to a colored photosensitive resin composition for red pixels, which includes an alkali-soluble resin (a), a photopolymerizable compound (B), a photopolymerization initiator (C), a colorant (D), and a solvent (E), wherein the photopolymerization initiator includes an oxime ester fluorene photopolymerization initiator having a specific structure, and the colorant includes a brominated diketopyrrolopyrrole compound.
Alkali soluble resin (A)
In one embodiment of the present invention, the alkali-soluble resin (a) may be used without limitation as long as it is soluble in an alkali developing solution used in a developing step. In order to dissolve in an alkali developing solution, it is a general method to introduce a carboxyl group into a resin and to provide an acid value. The alkali-soluble resin (a) can be produced by copolymerizing an ethylenically unsaturated monomer (a1) having a carboxyl group with another monomer (a3) copolymerizable with the above monomer, or by reacting an acid anhydride with a resin copolymer (a2) having a hydroxyl group to impart an acid value thereto.
The acid value of the alkali-soluble resin (A) is preferably 30 to 200 mgKOH/g. When the acid value of the alkali-soluble resin (a) is less than 30mgKOH/g, it is difficult to secure a sufficient development speed in the red pixel colored photosensitive resin composition, and when it exceeds 200mgKOH/g, the adhesion to the substrate is decreased, a short circuit of the pattern is likely to occur, the compatibility with the colorant is decreased, the colorant in the red pixel colored photosensitive resin composition is precipitated, or the storage stability of the red pixel colored photosensitive resin composition is decreased, and the viscosity is likely to increase.
Specific examples of the ethylenically unsaturated monomer having a carboxyl group (a1) include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and anhydrides of the above dicarboxylic acids; and mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω -carboxy polycaprolactone mono (meth) acrylate, and acrylic acid and methacrylic acid are preferred.
As a method of reacting an acid anhydride with the resin copolymer (a2) having a hydroxyl group to impart an acid value, there is a method of further reacting an acid anhydride with a hydroxy acrylate copolymer to impart an acid value, but the method is not limited thereto.
Representative examples of the above-mentioned hydroxy acrylates include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate.
In the production of the alkali-soluble resin (a), the other monomer (a3) copolymerizable with the ethylenically unsaturated monomer having a carboxyl group is exemplified below, but is not necessarily limited thereto:
aromatic vinyl compounds such as styrene, vinyltoluene, α -methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether;
n-substituted maleimide compounds such as N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide and N-p-methoxyphenylmaleimide;
alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate;
cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ] meth (acrylate)2,6]Alicyclic (meth) acrylates such as decan-8-yl ester, 2-dicyclopentanyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate;
aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;
unsaturated oxetane compounds such as 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane and 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like.
The monomers exemplified as the other copolymerizable monomer (a3) may be used alone or in combination of two or more.
The content of the alkali-soluble resin (a) may be 10 to 80% by weight, preferably 10 to 70% by weight, based on 100% by weight of the total solid content in the colored photosensitive resin composition for red pixels. When the content of the alkali-soluble resin (a) is in the above range, the solubility in a developer is sufficient, and a pattern can be easily formed.
Photopolymerizable compound (B)
In one embodiment of the present invention, the photopolymerizable compound (B) is a compound polymerizable by the action of the photopolymerization initiator (C) described below, and a monofunctional monomer, a difunctional monomer, or another polyfunctional monomer may be used, and preferably a polyfunctional monomer having two or more functionalities may be used.
Specific examples of the monofunctional monomer include, but are not limited to, nonylphenylcarbinol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone.
Specific examples of the bifunctional monomer include, but are not limited to, 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol a, and 3-methylpentanediol di (meth) acrylate.
Specific examples of the other polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and the like, but are not limited thereto.
The content of the photopolymerizable compound (B) may be 1 to 45% by weight, preferably 3 to 45% by weight, based on 100% by weight of the total solid content in the colored photosensitive resin composition for red pixels. When the content of the photopolymerizable compound (B) is in the above range, the intensity and smoothness of the pixel portion can be improved.
Photopolymerization initiator (C)
In one embodiment of the present invention, the photopolymerization initiator (C) contains an oxime ester fluorene photopolymerization initiator as a compound for initiating polymerization of the photopolymerizable compound (B). In particular, by including a photopolymerization initiator represented by the following chemical formula 1 as the oxime ester fluorene photopolymerization initiator, the colored photosensitive resin composition for red pixels can exhibit high resolution while improving patterning by increasing sensitivity and shortening exposure time.
[ chemical formula 1]
Figure BDA0001594612710000061
In the above-mentioned formula, the compound of formula,
R1～R3each independently of the others is hydrogen, halogen, C1-C20Alkyl, aryl, C1-C20Alkoxy, aralkyl, C1-C20Hydroxyalkyl of (C)2-C40Hydroxyalkoxyalkyl or C3-C20Cycloalkyl groups of (a);
R4～R10each independently is hydrogen, C1-C20Alkyl, aryl, C1-C20Alkoxy, aralkyl, C1-C20Hydroxyalkyl of (C)2-C40Hydroxyalkoxyalkyl of (C)3-C20Cycloalkyl, amino, nitro, cyano or hydroxy;
p is 0 or 1.
C used in the present specification1-C20The alkyl group in (b) is a straight or branched chain-type 1-valent hydrocarbon group having 1 to 20 carbon atoms, and includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and the like, but is not limited thereto.
Aryl as used in this specification includes all aromatic and heteroaromatic groups and their partially reduced derivatives. The aromatic group is a 5-to 15-membered monocyclic or fused cyclic group, and the heteroaromatic group is an aromatic group containing one or more of oxygen, sulfur, or nitrogen. Examples of the representative aryl groupExamples thereof include phenyl, naphthyl, pyridyl (pyridyl), furyl (furyl), thienyl (thiophenyl), indolyl (indolyl), quinolyl (quinolyl), imidazolinyl (imidazolinyl), and the like,
Figure BDA0001594612710000062
Oxazolyl (oxazolyl), thiazolyl (thiazolyl), tetrahydronaphthyl, and the like, but are not limited thereto.
C used in the present specification1-C20The alkoxy group (b) is a straight-chain or branched alkoxy group having 1 to 20 carbon atoms, and includes, but is not limited to, methoxy, ethoxy, n-propoxy, and the like.
The aralkyl group (aralkyl group) used in the present specification means a complex group in which an aryl group (aromatic hydrocarbon group) is substituted on a carbon of an alkyl group, and includes, for example, a benzyl group, a phenethyl group, and the like, but is not limited thereto.
C used in the present specification1-C20The hydroxyalkyl group in (b) is a linear or branched hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, and includes, for example, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group and the like, but is not limited thereto.
C used in the present specification2-C40The hydroxyalkoxyalkyl group in (1) is a complex group in which an alkyl group having 1 to 20 carbon atoms is substituted with an alkoxy group, and the alkoxy group is a linear or branched alkoxy group having 1 to 20 carbon atoms, which is substituted with a hydroxyl group, and includes, for example, a hydroxymethoxymethyl group, a hydroxyethoxymethyl group, a hydroxymethoxyethyl group, and the like, but is not limited thereto.
C used in the present specification3-C20The cycloalkyl group in (b) is a monocyclic or fused ring-shaped hydrocarbon group having 3 to 20 carbon atoms, and includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like, but is not limited thereto.
In one embodiment of the present invention, R1～R3Each independently is hydrogen, C1-C6Alkyl or phenyl of R4～R10Each independently hydrogen or nitro, and p may be 0.
In one embodiment of the present invention, R1～R3Each independently is hydrogen or C1-C6Alkyl of R4～R10P may be 1 for hydrogen.
For example, the photopolymerization initiator represented by the above chemical formula 1 in which p is 0 includes the following compounds.
Figure BDA0001594612710000071
Furthermore, the method is simple. For example, the photopolymerization initiator represented by the above chemical formula 1 in which p is 1 may be the following compounds.
Figure BDA0001594612710000081
In one embodiment of the present invention, the photopolymerization initiator (C) may further include one or more compounds selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, biimidazole-based compounds, oxime-based compounds, and thioxanthone-based compounds in addition to the photopolymerization initiator represented by the chemical formula 1.
The content of the photopolymerization initiator (C) may be 0.1 to 30% by weight, specifically 0.1 to 10% by weight, based on 100% by weight of the total solid content in the colored photosensitive resin composition for red pixels. When the content of the photopolymerization initiator is within the above range, it is possible to prevent the short circuit of the pattern in the developing step due to the decrease in sensitivity, and it is possible to prevent the wrinkle formation and the decrease in the physical properties of the coating film due to the excessive crosslinking reaction due to the excessive reaction.
Colorant (D)
In one embodiment of the present invention, the colorant (D) contains a brominated diketopyrrolopyrrole compound represented by the following chemical formula 2 as a pigment.
[ chemical formula 2]
Figure BDA0001594612710000091
The colorant (D) may further include a compound represented by the following chemical formula 3 and c.i. pigment red 177 as a pigment.
[ chemical formula 3]
Figure BDA0001594612710000092
The compound represented by chemical formula 2 and the compound represented by chemical formula 3 may be used by synthesizing them as they are or by purchasing them in a commercially available form. As a commercially available product of the compound represented by the above chemical formula 2, there is a product of Pasteur
Figure BDA0001594612710000093
Red S3620 CF is a commercially available product of the compound represented by chemical formula 3, which is c.i. pigment Red 254.
The compound represented by chemical formula 2 and the compound represented by chemical formula 3 may be included in a weight ratio of 1:9 to 9: 1.
The content of the compound represented by chemical formula 2 may be 5 to 60% by weight with respect to 100% by weight of the total colorant, the content of the compound represented by chemical formula 3 may be 5 to 60% by weight with respect to 100% by weight of the total colorant, and the content of the c.i. pigment red 177 may be 5 to 70% by weight with respect to 100% by weight of the total colorant.
When the contents of the compound represented by chemical formula 2, the compound represented by chemical formula 3, and the c.i. pigment red 177 are respectively less than the above ranges, the coloring power may be decreased, and when the contents exceed the above ranges, the pattern formation may become difficult to cause the decrease in the adhesion power.
If the contents of the compound represented by chemical formula 2, the compound represented by chemical formula 3, and c.i. pigment red 177 respectively satisfy the above content ranges, a decrease in adhesion force can be prevented, and reliability can be increased.
The colorant may further include other pigments in addition to the compound represented by chemical formula 2, the compound represented by chemical formula 3, and c.i. pigment red 177.
The pigment may be an organic pigment or an inorganic pigment generally used in the art. The pigment may be subjected to the following treatment as necessary: rosin treatment; surface treatment with a pigment derivative or the like having an acidic group or a basic group introduced thereto; a graft treatment of the pigment surface with a polymer compound or the like; micronization treatment by sulfuric acid micronization method; washing treatment with an organic solvent or water for removing impurities; or removal treatment of ionic impurities by an ion exchange method or the like.
Specific examples of the organic pigment include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, and perylene pigments
Figure BDA0001594612710000101
Oxazine pigments, anthraquinone pigments, dianthraquinone-based pigments, anthrapyrimidine pigments, anthanthrone (anthanthrone) pigments, indanthrone (indanthrone) pigments, flavanthrone pigments, pyranthrone (pyranthrone) pigments, diketopyrrolopyrrole pigments, and the like.
Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specifically include oxides or complex metal oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony.
In particular, as The organic pigment and The inorganic pigment, specifically, compounds classified as pigments in color index (published by The society of Dyers and Colourists), more specifically, pigments numbered by The following color index (c.i.) are mentioned, but not limited thereto, and they may be used alone or in combination of two or more kinds.
C.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 180, 192, 208, 215, 216, 224, 242, 255 and 264
The pigment may be a yellow pigment together with the red pigment, and specifically, a yellow pigment numbered by the following color index (c.i.).
Pigment yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185
C.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71
The above pigments may be used each alone or in combination of two or more.
The pigment is preferably a pigment dispersion liquid in which the particle diameter is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of performing a dispersion treatment by adding a pigment dispersant, and a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained by this method.
Specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, zwitterionic, polyester and polyamine surfactants, and these may be used alone or in combination of two or more.
The pigment dispersant is added for the purpose of disaggregation and maintenance of stability of the pigment, and any pigment dispersant generally used in the art can be used without limitation.
An acrylate-based dispersant (hereinafter, referred to as an acrylic dispersant) containing Butyl Methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA) is preferably contained. In this case, the acrylic dispersant is preferably manufactured by the activity control method disclosed in Korean laid-open patent No. 2004-0014311, and examples of commercially available acrylic dispersants manufactured by the activity control method include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150.
The above-exemplified acrylic dispersants may be used each alone or in combination of two or more.
The pigment dispersant may be a resin type pigment dispersant other than the acrylic dispersant. Examples of the other resin-type pigment dispersants include known resin-type pigment dispersants, and particularly oil-based dispersants such as polyurethanes, polycarboxylates represented by polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphates, esters of hydroxyl-containing polycarboxylic acids and modified products thereof, or amides or salts thereof formed by reaction of polyesters having free (free) carboxyl groups with poly (lower alkylene imine); water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinyl pyrrolidone; a polyester; a modified polyacrylate; ethylene oxide/propylene oxide adducts; and phosphoric acid esters and the like. As a commercial product of the above resin type dispersant, for example, a cationic resin dispersant is available under the trade name of BYK chemical: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, and DISPER BYK-184; trade name of BASF (BASF) corporation: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; trade name of Lubrizol (lubriun) corporation: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; trade name of Chuanjian refining company: HINACT T-6000, HINACT T-7000, HINACT T-8000; trade name of ajinomoto corporation: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; trade name of Kyoeisha chemical Co: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc. The resin type pigment dispersants other than the above-mentioned acrylic dispersant may be used alone or in combination of two or more kinds, or may be used in combination with the acrylic dispersant.
The amount of the pigment dispersant used may be 5 to 60 parts by weight, and more preferably 15 to 50 parts by weight, based on 100 parts by weight of the pigment used. If the content of the pigment dispersant exceeds 60 parts by weight on the above basis, the viscosity may be increased, and in the case of less than 5 parts by weight, the micronization of the pigment may be difficult, or a problem of gelation after dispersion may be caused.
In one embodiment of the present invention, the colorant (D) may further contain one or more dyes.
The dye may be used without limitation as long as it has solubility in an organic solvent. It is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility in an alkali developing solution, solvent resistance, and stability with time.
As the dye, an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye with a nitrogen-containing compound, a sulfonamide of an acid dye, or a derivative thereof can be used, and in addition thereto, an azo-based, xanthene-based, phthalocyanine-based acid dye, or a derivative thereof can be selected.
Preferably, The above-mentioned dye may be a compound classified as a dye in The color index (published by The society of Dyers and Colourists) or a known dye described in a dyeing manual (Dyers).
The content of the colorant (D) may be 1 to 60% by weight, preferably 5 to 50% by weight, based on 100% by weight of the total solid content in the colored photosensitive resin composition for red pixels. When the content of the colorant (D) is in the above range, the color density of the pixel is sufficient even if a thin film is formed, and the releasability of the non-pixel portion is not reduced at the time of development, and therefore residue is not easily generated, which is preferable.
In the present invention, the solid component means a component remaining in addition to the solvent.
Solvent (E)
In one embodiment of the present invention, the solvent (E) is not particularly limited as long as it is effective in dissolving other components contained in the colored photosensitive resin composition for red pixels, and a solvent used in a general colored photosensitive resin composition can be used, and ethers, acetates, aromatic hydrocarbons, ketones, alcohols, esters, and the like are particularly preferable.
Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; propylene glycol monomethyl ether, and the like.
Examples of the acetates include methyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, 3-methoxy-1-butyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1, 3-butanediol diacetate, diethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, ethylene glycol diacetate, Diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, and the like.
Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.
Examples of the ketones include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.
Examples of the alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, and 4-hydroxy-4-methyl-2-pentanone.
Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and γ -butyrolactone.
The solvents mentioned above may be used either individually or in combination of two or more.
From the viewpoint of coating properties and drying properties, the solvent preferably used is an organic solvent having a boiling point of 100 to 200 ℃, and examples thereof include alkylene glycol alkyl ether acetates, alkylene glycol monoalkyl ethers, ketones, and esters, and more preferably include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate.
The content of the solvent (E) may be 60 to 90% by weight based on 100% by weight of the entire colored photosensitive resin composition for red pixels. If the content of the solvent is within the above range, the coating properties may be improved when the coating is performed by a coating apparatus such as a roll coater, a spin coater, a slit coater (also referred to as a die coater), or a spray coater.
Additive (F)
The colored photosensitive resin composition for red pixels of the present invention may further contain additives such as other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-coagulants, if necessary.
Specific examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.
The curing agent is used for achieving deep curing and improving mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds, and the like.
Specific examples of the epoxy compound in the curing agent include bisphenol a type epoxy resins, hydrogenated bisphenol a type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol F type epoxy resins, novolac type epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester type resins, glycidyl amine type resins, or brominated derivatives of such epoxy resins, aliphatic, alicyclic, or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co) polymer epoxides, isoprene (co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, triglycidyl isocyanurate, and the like.
Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexane dicarboxylic acid bisoxetane, and the like.
The curing agents exemplified above may be used alone or in combination of two or more.
The curing agent may be used in combination with a co-curing compound capable of ring-opening polymerizing an epoxy group of the epoxy compound or an oxetane skeleton of the oxetane compound together with the curing agent. Examples of the curing assistant compound include polycarboxylic acids, polycarboxylic acid anhydrides, and acid generators. The polycarboxylic acid anhydride may be a commercially available epoxy resin curing agent. Specific examples of the epoxy resin curing agent include ADEKA HARDENER EH-700 (trade name, manufactured by ADEKA industries, Ltd.), RIKACID HH (trade name, manufactured by Nissian Chemicals Co., Ltd.), MH-700 (trade name, manufactured by Nissian Chemicals Co., Ltd.), and the like.
The surfactant may be used for further improving the film formability of the photosensitive resin composition, and a fluorine-based surfactant, a silicone-based surfactant, or the like may be preferably used.
Examples of the silicone surfactants include commercially available silicone surfactants such as DC3PA, DC7PA, SH11PA, SH21PA and SH8400 available from Dow Corning Tokyo Silicones, TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 available from GE Toshiba Silicones. Examples of the above-mentioned fluorine-based surfactants include MEGAFAC F-470, F-471, F-475, F-482 and F-489, which are commercially available from Dainippon ink chemical industries, Ltd. The above-exemplified surfactants may be used each alone or in combination of two or more.
Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like. The adhesion promoters exemplified above may be used each alone or in combination of two or more. The content of the adhesion promoter may be usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on 100% by weight of the total solid content in the colored photosensitive resin composition for red pixels.
Specific examples of the antioxidant include 2,2' -thiobis (4-methyl-6-tert-butylphenol), 2, 6-di-tert-butyl-4-methylphenol and the like.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.
Specific examples of the anti-gelling agent include sodium polyacrylate and the like.
The colored photosensitive resin composition for red pixels according to one embodiment of the present invention can be produced, for example, by the following method.
First, the pigment in the colorant (D) is mixed with the solvent (E) and dispersed by a bead mill or the like until the average particle diameter of the pigment becomes 0.2 μm or less. In this case, the pigment dispersant, a part or the whole of the alkali-soluble resin (a), or the dye may be dissolved or dispersed by mixing with the solvent (E) as needed. The colored photosensitive resin composition of the present invention can be produced by further adding the remaining alkali-soluble resin (a), photopolymerization initiator (C), photopolymerizable compound (B), and additive (F), and if necessary, solvent (E) to the above mixed dispersion liquid so as to achieve a predetermined concentration.
One embodiment of the present invention relates to a color filter formed using the colored photosensitive resin composition for red pixels. The color filter according to an embodiment of the present invention is characterized by including a colored layer formed by applying the colored photosensitive resin composition for red pixels on a substrate, and then exposing and developing the composition in a predetermined pattern.
Hereinafter, a method for forming a pattern using the colored photosensitive resin composition for red pixels of the present invention will be described in detail.
The method for forming a pattern using the colored photosensitive resin composition for red pixels of the present invention may employ a method known in the art, and generally includes a coating step, an exposure step, and a removal step. The colored photosensitive resin composition for red pixels of the present invention is applied to a substrate, and photocured and developed to form a pattern, thereby being used as a colored pixel (colored image).
The coating step is a step of coating the colored photosensitive resin composition for red pixels of the present invention on a substrate (generally, though not limited thereto, glass or a silicon wafer) or a photosensitive resin composition layer formed in advance, and predrying the coated film to remove volatile components such as a solvent and obtain a smooth coated film. In this case, the thickness of the coating film is preferably 1 to 3 μm.
The exposure step is a step of irradiating a specific region with ultraviolet light through a mask to cure the specific region so as to obtain a target pattern from the coating film. In this case, in order to uniformly irradiate the entire exposure portion with parallel light and accurately align the Mask with the substrate, it is preferable to use a Mask Aligner (Mask Aligner), a Stepper (Stepper), or the like.
The removal step is a step of bringing the coating film, which has been cured by irradiation with ultraviolet rays, into contact with an aqueous alkali solution to dissolve and develop the non-exposed region, thereby obtaining a target pattern. After the development, the resultant may be dried at 140 to 200 ℃ for 10 to 60 minutes, particularly at about 150 ℃ as required.
As the developer used for the above-mentioned development, any known developer in the art can be used without limitation, and an aqueous solution containing an alkali compound and a surfactant can be generally used.
The above-mentioned basic compound may be an inorganic or organic basic compound. Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, diammonium hydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, and the like. Specific examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. These inorganic and organic basic compounds may be used each alone or in combination of two or more. The content of the alkali compound in the developer may be 0.01 to 10% by weight, preferably 0.03 to 5% by weight.
The surfactant may be one selected from the group consisting of nonionic surfactants, anionic surfactants and cationic surfactants, or a mixture thereof. Specific examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene derivatives, ethylene oxide/propylene oxide block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, fatty acid glycerides, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, and the like. Specific examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleyl sulfate, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, and alkylaryl sulfonate salts such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate. Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. The above surfactants may be used singly or in combination of two or more. The content of the surfactant in the developer may be usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1 to 5% by weight.
One embodiment of the present invention relates to an image display device including the color filter.
The color filter of the present invention can be applied not only to a general liquid crystal display device (LCD) but also to various image display devices such as an electroluminescence display device (EL), a plasma display device (PDP), a field emission display device (FED), and an organic light emitting element (OLED).
The image display device of the present invention includes a configuration known in the art, in addition to the color filter.
The image display device according to one embodiment of the present invention may further include a color filter including a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles, in addition to the color filter. In this case, although the light emitted from the light source applied to the image display device is not particularly limited, it is preferable to use a light source that emits blue light in terms of more excellent color reproducibility.
The image display device according to an embodiment of the present invention may further include a color filter including only two color pattern layers of a red pattern layer, a green pattern layer, and a blue pattern layer, in addition to the color filter. In this case, the color filter further includes a transparent pattern layer containing no quantum dot particles. In the case of a pattern layer having only two colors, a light source that emits light having a wavelength of the remaining color that is not included may be used. For example, in the case of including only a red pattern layer and a green pattern layer, a light source emitting blue light may be used. In this case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer directly transmits blue light to show blue color.
The present invention will be described in more detail below with reference to examples, comparative examples and experimental examples. These examples, comparative examples and experimental examples are only for illustrating the present invention, and it is obvious to those skilled in the art that the scope of the present invention is not limited thereto.
Synthesis example 1 Synthesis of photopolymerization initiator (C-1)
Reaction 1.
5.0g of 2-nitrofluorene was dissolved in 100ml of anhydrous nitrobenzene, 6.31g of anhydrous aluminum chloride was added, then the reaction was heated to 45 ℃ and a solution of acetyl chloride 2.79g dissolved in 30ml of anhydrous nitrobenzene was slowly added over 30 minutes, and the reaction was heated to 65 ℃ and stirred for 1 hour. Then, the reaction mixture was cooled to room temperature, 70ml of distilled water was added thereto, and the mixture was stirred for about 30 minutes, and then the resultant was filtered. The resulting solid product was dispersed in 50ml of diethyl ether, stirred at room temperature for 30 minutes, filtered and dried to obtain 5.08g of a pale yellow reaction product, 1(1- (9, 9-H-7-nitrofluoren-2-yl) -ethanone).
Reaction 2.
1.5g of reactant 1(1- (9, 9-H-7-nitrofluoren-2-yl) -ethanone) was dispersed in 30ml of ethanol, 0.49g of hydroxylamine hydrochloride and 0.58g of sodium acetate were added, and then the reaction solution was slowly warmed and stirred under reflux for 2 hours. The reaction mixture was cooled to room temperature, 20ml of distilled water was added thereto, the mixture was stirred for about 30 minutes, and the obtained solid product was filtered, washed with distilled water several times, and dried to obtain 1.38g of light gray reactant 2(1- (9, 9-H-7-nitrofluoren-2-yl) -ethanone oxime).
Reaction 3.
1.20g of reactant 2(1- (9, 9-H-7-nitrofluoren-2-yl) -ethanone oxime) was dispersed in 50ml of ethyl acetate, and 0.69g of anhydrous acetic acid was added, and then the reaction solution was slowly warmed and stirred under reflux for 3 hours. The reaction mixture was cooled to room temperature, washed with 20ml of a saturated aqueous sodium bicarbonate solution and 20ml of distilled water in this order, and the recovered organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled under reduced pressure, and the resultant product was recrystallized from 20ml of methanol to obtain 1.22g of a pale yellow initiator C-1(1- (9, 9-H-7-nitrofluoren-2-yl) -ethanone oxime-O-acetate).
Synthesis example 2 Synthesis of photopolymerization initiator (C-2)
Reaction 1.
200.0g of fluorene, 268.8g of potassium hydroxide and 19.9g of potassium iodide were dissolved in 1L of anhydrous dimethyl sulfoxide under a nitrogen atmosphere, the reaction mixture was maintained at 15 ℃, 283.3g of bromoethane was slowly added over 2 hours, and the reaction mixture was stirred at 15 ℃ for 1 hour. Then, 2L of distilled water was added to the reaction mixture and stirred for 30 minutes, and then the product was extracted with 2L of dichloromethane, the extracted organic layer was washed 2 times with 2L of distilled water, the recovered organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled under reduced pressure, and the obtained product was fractionally distilled under reduced pressure to obtain 248.6g of a pale yellow reaction product 1(9, 9-diethyl-9H-fluorene) as a high-viscosity liquid.
Reaction 2.
100.5g of reactant 1(9, 9-diethyl-9H-fluorene) was dissolved in 1L of dichloromethane, and after the reactant was cooled to-5 ℃, 72.3g of aluminum chloride was slowly added, and then 50.1g of propionyl chloride diluted in 50ml of dichloromethane was slowly added over 2 hours while preventing the temperature of the reactant from rising, and the reactant was stirred at-5 ℃ for 1 hour. Then, the reaction product was poured slowly into 1L of ice water and stirred for 30 minutes to separate an organic layer, and then the organic layer was washed with 500ml of distilled water, the recovered organic layer was distilled under reduced pressure, and the obtained product was purified by silica gel column chromatography (developing solvent; ethyl acetate: n-hexane ═ 1:4), whereby 75.8g of reactant 2(1- (9, 9-diethyl-9H-fluoren-2-yl) -1-propanone) was obtained as a pale yellow solid.
Reaction 3.
44.5g of reactant 2(1- (9, 9-diethyl-9H-fluoren-2-yl) -1-propanone) was dissolved in 900ml of Tetrahydrofuran (THF), and the solution was added to 1, 4-bis
Figure BDA0001594612710000191
150ml of 4N HCl of an alkane and 24.7g of isobutyl nitrite and the reaction was stirred at 25 ℃ for 6 hours. Then, adding to the reaction solutionAfter separating the organic layer by adding 500ml of ethyl acetate and stirring for 30 minutes, the organic layer was washed with 600ml of distilled water, and the recovered organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled under reduced pressure, and the obtained solid product was recrystallized using 300ml of a mixed solvent of ethyl acetate: hexane (1:6) and then dried to obtain 27.5g of reactant 3(1- (9, 9-diethyl-9H-fluoren-2-yl) -1, 2-propanedione-2-oxime) as a pale gray solid.
Reaction 4.
After the reactant 3(1- (9, 9-diethyl-9H-fluoren-2-yl) -1, 2-propanedione-2-oxime) was dissolved in 1L of N-methyl-2-pyrrolidone (NMP) under a nitrogen atmosphere and the reactant was maintained at-5 ℃, 35.4g of triethylamine was added and the reaction solution was stirred for 30 minutes, and then a solution of 27.5g of acetyl chloride dissolved in 75ml of N-methyl-2-pyrrolidone was slowly added over 30 minutes and stirred for 30 minutes while preventing the temperature of the reactant from rising. Then, 1L of distilled water was slowly poured into the reaction mixture and stirred for 30 minutes to separate an organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained solid product was recrystallized from ethanol 1L and then dried to obtain 93.7g of initiator C-2(1- (9, 9-diethyl-9H-fluoren-2-yl) -1, 2-propanedione-2-oxime-O-acetate) as a pale gray solid.
Production example 1: production of colorant Dispersion liquid D-1
A mixed solution containing 40 parts by weight of c.i. pigment red 254 represented by chemical formula 3 as a pigment, 24 parts by weight (about 10.8 parts by weight in terms of solid content) of BYK2001 (DISPERBYK: Bike (BYK)) as a dispersant, and 136 parts by weight of propylene glycol methyl ether acetate as a solvent was mixed and dispersed for 12 hours by a bead mill to produce a colorant dispersion D-1.
Production example 2: production of colorant Dispersion D-2
A pigment containing brominated diketopyrrolopyrrole represented by chemical formula 2 (of BASF corporation) was prepared using a bead mill
Figure BDA0001594612710000201
Red S3620 CF)40 parts by weight, BYK2001 (DISPERBYK: a mixed solution of 24 parts by weight (solid content concentration: 45.1% by weight) (about 10.8 parts by weight in terms of solid content) of BYK corporation and 136 parts by weight of propylene glycol methyl ether acetate as a solvent was mixed and dispersed for 12 hours to produce a colorant dispersion liquid D-2.
Production example 3: production of colorant Dispersion D-3
A mixed solution containing 40 parts by weight of c.i. pigment red 177 as a pigment, 24 parts by weight (about 10.8 parts by weight in terms of solid content) of BYK2001 (DISPERBYK: BYK (BYK)) as a dispersant, and 136 parts by weight of propylene glycol methyl ether acetate as a solvent was mixed and dispersed for 12 hours by a bead mill to produce a colorant dispersion D-3.
Examples 1 to 8 and comparative examples 1 to 8: production of colored photosensitive resin composition for red pixel
The respective components were mixed in accordance with the composition shown in Table 1 below to prepare a colored photosensitive resin composition for red pixels (unit: wt%).
[ Table 1]
Figure BDA0001594612710000211
Alkali-soluble resin (a): SPCY-1L (Showa electrician Co., Ltd.)
Photopolymerizable compound (B): a9550 (New Zhongcun Co., Ltd.)
Photopolymerization initiator (C)
C-1: photopolymerization initiator of Synthesis example 1
C-2: photopolymerization initiator of Synthesis example 2
C-3: i-369 (Basfu)
C-4: OXE-01 (Basff)
Colorant Dispersion liquid (D)
D-1: preparation example 1 colorant Dispersion
D-2: colorant Dispersion liquid of production example 2
D-3: colorant Dispersion liquid of production example 3
Solvent (E): propylene glycol monomethyl ether acetate
Additive (F): organosilicon surfactant SH8400 (Dow Kangning Dongli organosilicon Co., Ltd.)
Experimental example 1
Color filters were produced using the colored photosensitive resin compositions for red pixels produced in the above examples and comparative examples as follows, and the adhesion, development unevenness, and film strength at this time were measured by the following methods, and the results are shown in table 2 below.
< production of color Filter >
After the colored photosensitive resin composition for red pixels was coated on a glass substrate by a spin coating method, the glass substrate was placed on a hot plate and maintained at a temperature of 100 ℃ for 3 minutes to form a color layer film. Next, a test photomask having a line/space pattern of 1 to 50 μm is placed, and ultraviolet rays are irradiated to the test photomask at a distance of 250 μm. In this case, a 1kW high pressure mercury lamp containing g, h and i lines was used as the ultraviolet light source at a rate of 50mJ/cm2The illumination of (2) is performed without using a special optical filter. The color layer film irradiated with ultraviolet rays was immersed in a KOH aqueous solution developing solution having a ph of 10.5 for 2 minutes to be developed. The glass substrate on which the developed color layer film was formed was washed with distilled water, then dried in a nitrogen atmosphere, and heated in a heating oven at 200 ℃ for 1 hour for thermosetting, thereby manufacturing a color filter.
(1) Adhesion Property
The resulting pattern was observed with an optical microscope, and the degree of peeling of the 20 μm pattern was evaluated according to the following evaluation criteria.
< evaluation criteria >
O: no peeling off on the pattern
And (delta): peeling 1 to 4 pieces of the pattern
X: peeling off more than 5 pieces on the pattern
(2) Developing stripes
The pixel portions obtained after the development step were observed under an Na lamp, and the number of patterns without development unevenness was counted and evaluated according to the following evaluation criteria.
< evaluation criteria >
O: the number of the developed streaky pattern is 4 or more
And (delta): 1-3 patterns without developing stripes
X: pattern free of developed mottle
(3) Hardness of
The hardness of the coating film (heat-cured film) was measured in accordance with the test method of JIS-K-5400. When a load of 9.8N was applied to the heat-cured film using a pencil hardness tester, the highest hardness at which no defects were generated in the coating film was set as the hardness. The pencil used as a control was "Mitsubishi HI-UNI".
< evaluation criteria >
Very good: over 6H
○：4H～5H
△：2H～3H
X: 1H or less
[ Table 2]
Adhesion Property Developing stripes Hardness of
Comparative example 1 △ X △
Comparative example 2 △ X △
Comparative example 3 △ X ○
Comparative example 4 X X X
Comparative example 5 △ △ ○
Comparative example 6 X △ △
Comparative example 7 △ △ ○
Comparative example 8 X △ △
Example 1 ○ ○ ◎
Practice ofExample 2 ○ ○ ◎
Example 3 ○ ○ ◎
Example 4 ○ ○ ◎
Example 5 ○ ○ ◎
Example 6 ○ ○ ◎
Example 7 ○ ○ ◎
Example 8 ○ ○ ◎
As shown in table 2, it was confirmed that the colored photosensitive resin compositions for red pixels of examples 1 to 8, which contain the oxime ester fluorene based photopolymerization initiator having a specific structure of the present invention and contain the brominated diketopyrrolopyrrole compound as a colorant, are more excellent in adhesion and hardness and can suppress the occurrence of development unevenness than the colored photosensitive resin compositions for red pixels of comparative examples 1 to 8, which do not contain any one of the oxime ester fluorene based photopolymerization initiator and the brominated diketopyrrolopyrrole compound having a specific structure.
While certain aspects of the present invention have been described in detail, it will be apparent to those skilled in the art that such specific techniques are merely preferred embodiments, and the scope of the present invention is not limited thereto. Those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above-described matters.
Accordingly, the actual scope of the invention is defined by the appended claims and equivalents thereof.

Claims (7)

1. A colored photosensitive resin composition for red pixels, comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a colorant and a solvent,
the photopolymerization initiator includes a compound represented by the following chemical formula 1,
the colorant comprises a compound represented by the following chemical formula 2, a compound represented by the following chemical formula 3, and c.i. pigment red 177,
chemical formula 1
Figure FDA0002969483050000011
Chemical formula 2
Figure FDA0002969483050000012
Chemical formula 3
Figure FDA0002969483050000013
In the formula, the compound is shown in the specification,
R1～R3each independently of the others is hydrogen, halogen, C1-C20Alkyl, aryl, C1-C20Alkoxy, aralkyl, C1-C20Hydroxyalkyl of (C)2-C40Hydroxyalkoxyalkyl or C3-C20Cycloalkyl groups of (a);
R4～R10each independently is hydrogen, C1-C20Alkyl, aryl, C1-C20Alkoxy, aralkyl, C1-C20Hydroxyalkyl of (C)2-C40Hydroxyalkoxyalkyl of (C)3-C20Cycloalkyl, amino, nitro, cyano or hydroxy;
p is 0 or 1.
2. The colored photosensitive resin composition for red pixels according to claim 1, R1～R3Each independently is hydrogen, C1-C6Alkyl or phenyl of R4～R10Each independently hydrogen or nitro, and p is 0.
3. The colored photosensitive resin composition for red pixels according to claim 1, R1～R3Each independently is hydrogen or C1-C6Alkyl of R4～R10Is hydrogen and p is 1.
4. The colored photosensitive resin composition for red pixels according to claim 1, wherein the content of the photopolymerization initiator is 0.1 to 30% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition for red pixels.
5. The colored photosensitive resin composition for red pixels according to claim 1, wherein the content of the compound represented by the chemical formula 2 is 5 to 60% by weight based on 100% by weight of the total colorant.
6. A color filter formed by using the colored photosensitive resin composition for red pixels according to any one of claims 1 to 5.
7. An image display device comprising the color filter according to claim 6.
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