CN116643456A - Colored curable resin composition, color filter manufactured by using the same, and display device - Google Patents

Colored curable resin composition, color filter manufactured by using the same, and display device Download PDF

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Publication number
CN116643456A
CN116643456A CN202310062460.6A CN202310062460A CN116643456A CN 116643456 A CN116643456 A CN 116643456A CN 202310062460 A CN202310062460 A CN 202310062460A CN 116643456 A CN116643456 A CN 116643456A
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group
pigment
curable resin
resin composition
colored curable
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尹秀珍
金一镐
田濬豪
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Dongwoo Fine Chem Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—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
    • 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
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Optical Filters (AREA)

Abstract

The present invention relates to a colored curable resin composition, a color filter including the same, and an image display device, wherein the colored curable resin composition includes a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant includes a compound represented by chemical formula 1 and at least one selected from the group consisting of a red pigment, a yellow pigment, a violet pigment, and a xanthene dye. The present invention can realize a wide color gamut even with a small amount of colorant, and thus has excellent brightness, solvent resistance, and UV ashing resistance, even with a low weight concentration (PWC) of colorant.

Description

Colored curable resin composition, color filter manufactured by using the same, and display device
Technical Field
The present invention relates to a colored curable resin composition, a color filter manufactured using the colored curable resin composition, and a display device including the color filter.
Background
Color filters are widely used in various display devices such as imaging devices, liquid crystal display devices (LCDs), and Organic Light Emitting Diodes (OLEDs), and their application range is rapidly expanding.
The color filter used in the display device is composed of a coloring pattern of three colors of Red (Red), green (Green), and Blue (Blue), or a coloring pattern of three colors of Yellow (Yellow), magenta (Magenta), and Cyan (Cyan).
Each colored pattern of the color filter is generally formed using a colored curable resin composition containing a colorant such as a pigment and/or a dye, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The colored pattern processing using the colored curable resin composition is generally performed by a photolithography process.
In recent years, the market demand for high-quality displays having a wide color gamut (color gamut) is growing, and therefore the content of the colorant contained in the color curable resin composition for manufacturing color filters has been continuously increasing. In addition, studies have been made to use colorants having better tinting strength, contrast, and reliability.
However, when the content of the colorant increases, not only the manufacturing cost is increased, but also the manufacturability and reliability problems may occur during the formation of the pattern with the colored curable resin composition.
In this regard, korean patent No. 10-1639073 discloses a technique related to a coloring composition for forming red pixels, which contains at least one pigment selected from the group consisting of c.i. pigment red 177, c.i. pigment red 242, and c.i. pigment orange 38 as a colorant, but the patent does not propose a countermeasure for solving the above-mentioned problems.
[ Prior Art literature ]
[ patent literature ]
(patent document 1) korean patent No. 10-1639073
Disclosure of Invention
Technical problem
The present application has been made to solve the above-mentioned problems of the prior art, and an object thereof is to provide a colored curable resin composition which is excellent in brightness, solvent resistance and photosensitivity even in the case where the weight concentration (PWC: pigment Weight Concentration) of a colorant is low, and which is excellent in reliability such as chemical resistance, UV ashing (ashing) resistance and the like.
Further, an object of the present application is to provide a color filter made using the colored curable resin composition and an image display device including the color filter.
However, the technical problems to be solved by the present application are not limited to the above technical problems, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.
Technical proposal
In order to achieve the above object, the present application provides a colored curable resin composition comprising a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant comprises a compound represented by chemical formula 1 and at least one selected from the group consisting of a red pigment, a yellow pigment, a violet pigment, and a xanthene dye.
Further, the present invention provides a color filter comprising a colored pattern made of the above colored curable resin composition.
Further, the present invention provides an image display device including the color filter.
Effects of the invention
The colored curable resin composition of the present invention has the following effects by containing the compound represented by chemical formula 1 as a colorant: a wide color gamut (wide color gamut) can be achieved even with a relatively low weight concentration (PWC) of colorant while having excellent brightness, solvent resistance, and UV ashing resistance.
Detailed Description
The present invention relates to a colored curable resin composition, a color filter produced using the same, and an image display device including the color filter, wherein the colored curable resin composition includes a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant includes a compound represented by chemical formula 1 and at least one selected from the group consisting of a red pigment, a yellow pigment, a violet pigment, and a xanthene-based dye. It was confirmed through experiments that the colored curable resin composition according to the present invention can achieve a wide color gamut even in the case of lowering the weight concentration of colorant (PWC) by using the azo compound represented by chemical formula 1 as a colorant, and has excellent solvent resistance and UV ashing resistance while improving the brightness of the colored curable resin composition, thereby completing the present invention.
The colored curable resin composition may be characterized as being used for forming a red pixel.
Hereinafter, each component constituting the colored curable resin composition of the present invention will be described in detail. However, the present invention is not limited to these components.
< colored curable resin composition >
Coloring agent
The colorant is characterized by comprising a compound represented by the following chemical formula 1 and at least one selected from the group consisting of red pigment, yellow pigment, violet pigment and xanthene-based dye, and may further comprise additional pigments, dyes and mixtures thereof as required within a range that does not affect the object of the present invention.
[ chemical formula 1]
A-L 1 -B (I)
In chemical formula 1, L 1 A is a group represented by formula (ph 1), A is a group represented by formula (ia), and B is a group represented by formula (ib).
(in the formula (ph 1), X 1 Monovalent hydrocarbon groups of 1 to 20 carbon atoms, -NH, which are hydrogen atoms and may have substituents 2 、-CONH 2 -COOH, -CN, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 4 carbon atoms or a halogen atom, wherein-CH is contained in the hydrocarbon group 2 -may be substituted by-O-, -CO-, or-NH-, and-ch=contained in the hydrocarbon group may be substituted by-n=;
n represents an integer of 0 to 4;
When n is an integer of 2 or more, a plurality of X' s 1 May be the same or different, and X is an integer of 2 or more in n 1 X bonded to adjacent carbon atoms when bonded to adjacent carbon atoms 1 Can be bonded to each other to form a ring;
* Represents the number of bonds with a, and represents the number of bonds with B. )
Regarding X 1 The hydrocarbon group of (2) may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may be a chain hydrocarbon group or an alicyclic hydrocarbon group. Furthermore, the alicyclic hydrocarbon group may be a monocyclic or polycyclic hydrocarbon group. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4.
(in the formula (ia) and the formula (ib), X 6 To X 9 Each independently represents a monovalent hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, wherein the hydrocarbon group contains-CH 2 -ch=contained in the hydrocarbon group may be substituted with-n=and-CH contained in the hydrocarbon group<Can be covered by-N<Alternatively, an oxygen atom, a nitrogen atom, a sulfur atom or a carbonyl group may be interposed between carbon atoms constituting the hydrocarbon group;
X 6 and X 7 Can be bonded to each other to form a ring X 8 And X 9 Can be bonded to each other to form a ring;
* Representation and L 1 The number of bonds between them. )
Regarding X 6 To X 9 Examples of monovalent hydrocarbon groups of (2) include: straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, eicosyl and the like; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, sec-butyl, tert-butyl, 1, 3-dimethylbutyl, 2-ethylbutyl and the like; such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl,Alicyclic hydrocarbon groups such as cyclooctyl and tricyclodecyl. The number of carbon atoms of the monovalent hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4.
When the monovalent hydrocarbon group is an alicyclic hydrocarbon group, the number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 12, more preferably 3 to 10, most preferably 3 to 8.
The hydrogen atom contained in the monovalent hydrocarbon group may be selected from aromatic hydrocarbon groups having 6 to 10 carbon atoms such as phenyl, halogen atoms such as fluorine atoms, hydroxyl groups, -CN, -SO 3 H、-SO 3 - And the like.
In addition, L 1 May be a group represented by the formula (ph 2).
(in the formula (ph 2), X 2 To X 5 Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -NH 2 、-CONH 2 -COOH, -CN, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms or a halogen atom;
X 2 And X 3 Between and X 4 And X 5 Can be mutually bonded to form a ring;
* Represents the number of bonds with a, and represents the number of bonds with B. )
The group represented by the formula (ia) and the group represented by the formula (ib) may each independently be any one of the groups represented by the formulas (t 1) to (t 5).
[ 6 ] A method for producing a polypeptide
(in the formulae (t 1) to (t 5), R 1 To R 16 Each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, a 3-membered ringHeterocyclyl of up to 10 membered ring, -CN, -OH or halogen atom;
* Representation and L 1 The number of bonds between them. )
With respect to R 1 To R 16 Examples of the monovalent saturated hydrocarbon groups of (a) may include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, and the like; alicyclic saturated hydrocarbon groups having 3 to 10 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and the like. The number of carbon atoms of the monovalent saturated hydrocarbon group is preferably 1 to 6, more preferably 1 to 4.
The hydrogen atom contained in the monovalent saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms such as a phenyl group, a halogen atom such as a fluorine atom, a hydroxyl group or the like.
With respect to R 1 To R 16 Examples of the aromatic hydrocarbon group of (a) may include phenyl, tolyl, xylyl, naphthyl and the like, and preferably phenyl, tolyl. In addition, examples of the substituent that the aromatic hydrocarbon group may have may include: halogen atoms such as fluorine atom, chlorine atom, iodine atom, bromine atom, etc.; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and the like; -OH; -SO 3 H；-SO 3 - ；-SO 2 NR 17 R 18 The method comprises the steps of carrying out a first treatment on the surface of the Alkylsulfonyl groups having 1 to 6 carbon atoms such as methanesulfonyl; alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, and the like.
R 17 Represents a halogen atom, -OH or-NH 2 Aliphatic saturated hydrocarbon groups having 1 to 10 carbon atoms as substituents or may have halogen atoms, -OH or-NH 2 Alicyclic hydrocarbon groups having 3 to 10 carbon atoms as substituents.
R 18 Represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.
With respect to R 1 To R 16 The heterocyclic group of (2) may be a phenyl group which may have a substituent or a heterocyclic group containing a benzene ring, and preferably may be a benzene group which may have a halogen atom A group or a benzimidazolinyl group.
The compound represented by chemical formula 1 may contain a counter ion as needed. The counter ion may be a cation containing an alkaline earth metal, preferably at least one selected from the group consisting of a magnesium cation, a calcium cation, a strontium cation, and a barium cation, more preferably a barium cation.
The content of the compound represented by chemical formula 1 may be 1 to 15 wt%, preferably 1.5 to 10 wt%, based on the total weight of the colorant. When the compound represented by chemical formula 1 satisfies the above content range, high brightness and a wide color gamut can be achieved while the content of the colorant in the colored curable resin composition can be reduced, so that reliability such as solvent resistance and UV ashing resistance is excellent, and therefore this is preferable.
The red pigment may contain at least one selected from the group consisting of c.i. pigment red 177, c.i. pigment red 179, c.i. pigment red 202, c.i. pigment red 242, c.i. pigment red 254 and c.i. pigment red 291, preferably at least one selected from the group consisting of c.i. pigment red 177, c.i. pigment red 202, c.i. pigment red 254 and c.i. pigment red 291.
The yellow pigment may include at least one selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 185, and c.i. pigment yellow 231, and preferably may be c.i. pigment yellow 139.
The violet pigment may contain at least one selected from the group consisting of c.i. pigment violet 19, c.i. pigment violet 23, and c.i. pigment violet 29, and preferably may be c.i. pigment violet 19.
The xanthene dye may include at least one selected from the group consisting of compounds represented by the following chemical formula 2.
[ chemical formula 2]
In the chemical formula 2, the chemical formula is shown in the drawing,
R 21 、R 22 、R 23 、R 24 、R 25 r is R 26 Each independently is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;
R 27 and R is 28 Each independently represents a hydrogen atom, -COOH, -COO - 、-SO 3 - 、-SO 3 H、-SO 3 Na、-COOCH 3 or-COOCH 2 CH 3 。
The additional pigment may use an organic pigment or an inorganic pigment commonly used in the art, and these may be used singly or in combination of two or more.
The organic pigment or inorganic pigment may use various pigments for printing inks, inkjet inks, etc., and specific examples thereof may include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, pyrenone (perinone) pigments, dioxazine pigments, anthraquinone pigments, bianthraquinone pigments, anthrapyrimidine pigments, anthanthrone (anthantone) pigments, indanthrone (indantthrone) pigments, flavanthrone (flavanthrone) pigments, pyranthrone (pyranthone) pigments, pyrrolopyrrole dione pigments, etc.
Examples of the inorganic pigment may include: metal compounds such as metal oxides, complex metal oxides, and metal complex salts; or carbon black, etc. Specifically, examples of the metal include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and the like. In particular, specific examples of the organic pigment and the inorganic pigment may include compounds classified as pigments in color index (published by The Society of Dyers and Colourists (institute of dyers, uk)), and more specific examples may include pigments of the following index (c.i.) numbers, but are not necessarily limited to these.
For example, c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71;
c.i. pigment blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64, and 76;
c.i. pigment green 7, 10, 15, 25, 36, 47, 58, 59, 62, and 63;
c.i. pigment brown 28;
c.i. pigment black 1 and 7, etc.
These pigments may be used singly or in combination of two or more.
The organic pigments of these pigments may be treated as follows: the surface treatment is performed using a pigment derivative into which an acidic group or a basic group is introduced as needed, the grafting treatment is performed on the pigment surface using a polymer or the like, the micronization treatment is performed by a sulfuric acid micronization method (micronization) or the like, or the cleaning treatment is performed using an organic solvent, water or the like for removing impurities, and the removal treatment of ionic impurities is performed by an ion exchange method or the like.
When a pigment is used as the colorant, a pigment having a uniform average particle diameter is preferably used. Examples of the method of making the particle diameter of the pigment uniform may include a method of performing dispersion treatment by containing a surfactant as a pigment dispersant, and the like, according to which a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained.
Examples of the pigment dispersant may include surfactants such as cationic, anionic, nonionic, amphoteric, and the like, which may be used singly or in combination of two or more kinds, respectively. The pigment dispersant may be contained in the form of an additive described later, and preferably an acrylic pigment dispersant, and a commercially available product thereof may be used with Disper byk-2001 and the like, but is not limited thereto.
The pigment dispersant is used in an amount of 1 part by weight or less, preferably 0.05 to 0.5 part by weight, relative to 1 part by weight of the colorant in the colored curable resin composition. When the amount of the pigment dispersant is in the above range based on the above, a pigment having a uniform average particle diameter can be obtained, and therefore the amount in the above range based on the above is preferable.
One or more additional dyes may be added without limitation as long as they have 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 alkaline developer, heat resistance, solvent resistance, and the like. The dye may be selected from acid dyes having an acid group such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamide of acid dyes, and derivatives thereof, and azo acid dyes, phthalocyanine acid dyes, and derivatives thereof. Examples of dyes may include compounds classified as dyes in the color index (published by The Society of Dyers and Colourists) and known dyes described in the dyeing notes (color company).
Specific examples of dyes as c.i. solvent dyes may include: ,
yellow dyes such as c.i. solvent yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, etc.;
red dyes such as c.i. solvent red 8, 45, 49, 122, 125, 130, etc.;
orange dyes such as c.i. solvents orange 2, 7, 11, 15, 26, 45, 56, 62, etc.;
blue dyes such as c.i. solvent blue 35, 37, 45, 59, 67;
green dyes such as c.i. solvents green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc.
In addition, specific examples as the c.i. acid dye may include:
yellow dyes such as c.i. acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
red dyes such as c.i. acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
Orange dyes such as c.i. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173, etc.;
blue dyes such as c.i. acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324:1, 335, 340;
violet dyes such as c.i. acid violet 6B, 7, 9, 17, 19, etc.;
green dyes such as c.i. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc.
In addition, specific examples as the c.i. direct dye may include:
yellow dyes such as c.i. direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
red dyes such as c.i. direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
Orange dyes such as c.i. direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
blue dyes such as c.i. direct blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
violet dyes such as c.i. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104, etc.;
green dyes such as c.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc.
Further, specific examples as c.i. mordant dyes may include:
yellow dyes such as c.i. mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, etc.;
Red dyes such as c.i. mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
orange dyes such as c.i. mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, etc.;
blue dyes such as c.i. mordant blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
violet dyes such as c.i. mordant violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58, etc.;
green dyes such as c.i. mordant green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, and the like.
The content of the colorant may be 1 to 15% by weight, preferably 1.5 to 10% by weight, based on the total weight of the colored curable resin composition. When the colorant satisfies this content range, the color density of the pixel is sufficient, while the solvent resistance and UV ashing resistance are excellent, so that this content range is preferable.
Adhesive resin
The binder resin is a component imparting solubility in an alkaline developer used in a development treatment process at the time of forming a pattern. The binder resin may be polymerized by containing an ethylenically unsaturated monomer having a carboxyl group.
The ethylenically unsaturated monomer having a carboxyl group is not particularly limited, and examples thereof may include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and the like; dicarboxylic acids such as fumaric acid, mesaconic acid, itaconic acid, and anhydrides thereof; and mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω -carboxyl polycaprolactone mono (meth) acrylate, and the like, acrylic acid and methacrylic acid are preferred. These may be used singly or in combination of two or more.
The binder resin according to the present invention may be polymerized by further comprising at least one other monomer copolymerizable with the above-mentioned monomers. Examples thereof may include: aromatic vinyl compounds such as styrene, vinyl toluene, methyl styrene, 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, p-vinylbenzyl glycidyl ether, and the like; 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, 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, tert-butyl (meth) acrylate, and the like; alicyclic (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, 2-dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and the like; aryl (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, and the like; unsaturated oxetane compounds such as 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like. These may be used singly or in combination of two or more.
In the present specification, (meth) acrylate means acrylate or methacrylate.
In addition, in order to secure the developability of the colored curable resin composition, the acid value of the binder resin is 20 to 200mgKOH/g, preferably 30 to 150mgKOH/g. When the acid value of the binder resin satisfies the above range, the color curable resin composition can ensure a sufficient development speed and improve adhesion to the substrate, and thus can prevent pattern short-circuiting, and therefore the acid value within the above range is preferable.
The weight average molecular weight (Mw) of the binder resin of the present invention may be 3000 to 30000, preferably 5000 to 25000. Further, the molecular weight distribution of the binder resin of the present invention, that is, the weight average molecular weight (Mw)/number average molecular weight (Mn)) with respect to the number average molecular weight may be 1.5 to 6.0, preferably 1.8 to 4.0, has an advantage of excellent developability when the binder resin satisfies the above-described ranges of weight average molecular weight and molecular weight distribution.
The content of the binder resin may be 0.5 to 20% by weight, preferably 1 to 15% by weight, based on the total weight of the colored curable resin composition. When the content of the binder resin is within the above range, the binder resin has sufficient solubility in the developing solution to be able to prevent the generation of residues and promote the formation of patterns, and thus the content within the above range is preferable.
Photopolymerizable compound
The photopolymerizable compound contained in the colored curable resin composition of the present invention is a polymerizable compound such as a living radical or an acid generated by a photopolymerization initiator described later under irradiation with light, and may be a compound polymerizable under the action of the photopolymerization initiator described later. Specifically, the photopolymerizable compound of the present invention may use a monofunctional monomer, a difunctional monomer, or a polyfunctional monomer, and preferably a polyfunctional monomer having two or more functions is used.
Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc., but are not limited thereto.
Specific examples of the difunctional monomer include 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, 3-methylpentanediol di (meth) acrylate, and the like, but are not limited thereto.
Specific examples of the polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, or dipentaerythritol hexa (meth) acrylate, but are not limited thereto.
The content of the photopolymerizable compound may be 1 to 10% by weight, preferably 2 to 5% by weight, based on the total weight of the colored curable resin composition of the present invention. When the content of the photopolymerizable compound is within the above range, there is an advantage that photosensitivity and developability are excellent.
Photopolymerization initiator
The photopolymerization initiator is a compound that generates radicals or the like capable of initiating polymerization of the above photopolymerizable compound by exposure to radiation such as visible light, ultraviolet light, deep ultraviolet light, electron beam, or X-ray.
The photopolymerization initiator is not particularly limited as long as it is generally used in the art, but may preferably contain an oxime compound, and more preferably contains at least one selected from the group consisting of a compound represented by the following chemical formula 3, a compound represented by the following chemical formula 4, and a compound represented by the following chemical formula 5.
[ chemical formula 3]
[ chemical formula 4]
[ chemical formula 5]
(in the chemical formulas 3 to 5,
R 31 to R 46 Each independently is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a hydroxyalkyl group having 1 to 12 carbon atoms, a hydroxyalkoxyalkyl group having 2 to 24 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, an aralkyl group, an amino group, a nitro group, a cyano group, or a hydroxyl group. )
The content of the oxime compound is not particularly limited as long as the oxime compound can exert its function, but the content thereof is preferably 5 to 100% by weight based on 100% by weight of the total amount of the photopolymerization initiator. When the content of the oxime compound is within the above range, brightness and photosensitivity can be further improved, and therefore, the content within the above range is preferable.
The photopolymerization initiator may contain, in addition to the oxime-type compound, other photopolymerization initiators commonly used in the art within a range that does not affect the object of the present invention, as long as it is capable of polymerizing the binder resin and the photopolymerizable compound.
Examples of the photopolymerization initiator generally used may include triazine compounds, acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, and the like.
Examples of the triazine-based compound may include 2,4, 6-trichloro-s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -s-triazine, 2- (3 ',4' -dimethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4 '-methoxynaphthyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl-4, 6-bis (trichloromethyl) -s-triazine, 2-biphenyl-4, 6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphthalen-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthalen-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2, 4-trichloromethyl (4' -methoxystyryl) -6-triazine, and the like.
Specific examples of acetophenone compounds may include 2,2' -diethoxyacetophenone, 2' -dibutoxyacetophenone, 2-hydroxy-2-methylpropaneketone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2' -dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one, and the like.
Examples of the benzophenone-type compounds may include benzophenone, benzoyl benzoic acid, methylbenzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4' -bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 4' -dimethylaminobenzophenone, 4' -dichlorobenzophenone, 3' -dimethyl-2-methoxybenzophenone, and the like.
Examples of thioxanthone compounds may include thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2, 4-diethyl thioxanthone, 2, 4-diisopropyl thioxanthone, 2-chlorothioxanthone, and the like.
Examples of benzoin compounds may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.
The content of the photopolymerization initiator may be 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the total weight of the colored curable resin composition of the present invention. When the content of the photopolymerization initiator is within the above range, it is possible to sufficiently cause photopolymerization during exposure in the pattern forming process and prevent a decrease in light transmittance due to unreacted initiator remaining after photopolymerization.
Solvent(s)
In an embodiment of the present invention, the solvent is not particularly limited as long as the colored curable resin composition has a suitable viscosity and the solvent can easily dissolve the remaining components, and various organic solvents used in the field of colored curable resin compositions can be used.
Specific examples of the solvent may 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, ethylene glycol dibutyl ether, and the like; glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol dialkyl ethers such as propylene glycol monomethyl ether; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, and the like; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, and the like; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, and the like; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, and the like; esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like; cyclic esters such as gamma butyrolactone, and the like.
Among these solvents, from the viewpoint of coatability and drying properties, an organic solvent having a boiling point of 100 ℃ to 200 ℃ is preferable, alkylene glycol alkyl ether acetates, ketones, esters (for example, ethyl 3-ethoxypropionate or methyl 3-methoxypropionate) are more preferable, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like are more preferable.
These solvents may be used singly or in combination of two or more.
The content of the solvent may be 60 to 95% by weight, preferably 70 to 85% by weight, based on the total weight of the colored curable resin composition. When the content of the solvent is within the above-described content range, an effect of improving coating performance when coating with a coating apparatus (e.g., roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, etc.) is provided, and thus the above-described content range is preferable.
Additive agent
The additive may be selectively added as needed, and may contain, for example, at least one selected from the group consisting of other high molecular compounds, a curing agent, a surfactant, an adhesion promoter, an ultraviolet absorber, and an anticoagulant.
Specific examples of other polymer compounds may include: curable resins such as epoxy resins, maleimide resins, and the like; thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane, and the like.
Curing agents for deep curing and increasing mechanical strength, specific examples of the curing agents may include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds, and the like.
Specific examples of the epoxy compound in the curing agent may include bisphenol a type epoxy resin, hydrogenated bisphenol a type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, block type epoxy resin, other aromatic type epoxy resin, alicyclic type epoxy resin, glycidyl ester type resin, glycidyl amine type resin, or brominated derivatives of the above epoxy resin, aliphatic, alicyclic or aromatic epoxy compounds other than the epoxy resin and brominated derivatives thereof, butadiene (co) polymer epoxide, isoprene (co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like.
Specific examples of the oxetane compound in the curing agent may include carbonate dioxetane, xylene dioxetane, adipic acid dioxetane, terephthalic acid dioxetane and cyclohexanedicarboxylic acid dioxetane.
The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerizing an epoxy group of an epoxy compound and an oxetane skeleton of an oxetane compound together with the curing agent.
Examples of the curing aid compound may include polycarboxylic acids, polycarboxylic acid anhydrides, acid generators, and the like. As the polycarboxylic acid anhydride, commercially available ones as an epoxy resin curing agent can be used. Examples of commercial products may include Adeka Hardener EH-700 (manufactured by ADEKA industries, inc.), rikacid HH (manufactured by New Japan Chemical, inc.), MH-700 (manufactured by New Japan Chemical, inc.), and the like. The above-exemplified curing agents may be used singly or in combination of two or more.
The surfactant may be used to further improve film formation of the colored curable resin composition, and silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, amphoteric-based surfactants and the like may be preferably used.
Examples of the silicone-based surfactant as commercial products include commercial products DC3PA, DC7PA, SH-11PA, SH-21PA, SH-8400, etc. from Dow Corning Toray Silicone company, TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452, etc. from GE Toshiba Silicone company.
Examples of the fluorine-based surfactant as a commercially available product may include MEGAFAC F-470, F-471, F-475, F-482, F-489 and the like of Dainippon Ink and Chemicals company.
Further, examples of commercially available Products that can be used include KP (Shin-Etsu Chemical Co.), POLYFLOW (Kyoeisha Chemical Co.), EFTOP (Tokem Products Co.), MEGAFAC (Dainippon Ink and Chemicals Co.), flourad (Sumitomo 3M Co.), asahi guard, surflon (above, asahi Glass Co.), SOLSPERSE (Lubrisol Co.), EFKA (EFKA Chemicals Co.), PB821 (Ajinomoto Co.), and Disperbyk series (BYK-chemi Co.), etc.
The above exemplified surfactants may be used singly or in combination of two or more kinds, respectively.
The kind of the adhesion promoter is not particularly limited, and specific examples of the usable adhesion promoter may include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, and the like.
The kind of the ultraviolet absorber is not particularly limited, but specific examples that can be used include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone, and the like.
The type of anticoagulant is not particularly limited, and sodium polyacrylate and the like can be specifically used.
The above exemplified additives may be used singly or in combination of two or more thereof, respectively. The content of the additive may be generally 0.01 to 5% by weight, preferably 0.05 to 2% by weight, based on the total weight of the colored curable resin composition.
< method for producing colored curable resin composition >
The colored curable resin composition of the present invention can be prepared, for example, by the following method. The dye may be pre-dissolved in some or all of the solvent to prepare a solution. In addition, it is preferable that a pigment and a part or all of the solvent are mixed in advance and dispersed by using a bead mill or the like. At this time, a pigment dispersant is used as needed, and part or all of the binder resin may be blended. Further, the remaining binder resin, photopolymerizable compound and photopolymerization initiator, other components used as needed, and additional solvents as needed are further added to the obtained dispersion (hereinafter sometimes referred to as mill base) to a predetermined concentration to obtain a desired colored curable resin composition.
< color Filter >
Another aspect of the present invention relates to a color filter formed by manufacturing using the above colored curable resin composition. A color filter according to an embodiment of the present invention is characterized by including a colored pattern formed by applying the above colored curable resin composition on a substrate and exposing and developing in a predetermined pattern.
Hereinafter, a method for forming a pattern using the colored curable resin composition of the present invention will be described in detail.
The method of forming a pattern using the colored curable resin composition of the present invention may use a method known in the art, but generally includes a coating step, an exposure step, and a removal step. The colored curable resin composition of the present invention can be used as colored pixels (colored images) by forming a pattern by coating on a substrate, photo-curing and developing.
Specifically, the glass substrate is coated with no coating by spin coating, slit coating or the like in an appropriate method and in an amount of 500 to(angstrom) thickness the colored curable resin composition is coated on a SiNx (protective film) -coated glass substrate at a thickness of 2.0 μm to 3.4 μm. After the coating, light irradiation is performed to form a pattern required for the color filter. After the light irradiation, if the coating layer is treated with an alkaline developer, the non-irradiated portion of the coating layer is dissolved, thereby forming a pattern required for the color filter. By repeating this process according to the number of R, G and B colors required, a color filter having a desired pattern can be obtained. In addition, in the above-mentioned process, the developed image pattern is cured by reheating or by irradiation with actinic rays, etc. to thereby obtain This can further improve crack resistance, solvent resistance, and the like.
< display device >
An embodiment of the present invention relates to a display device including the above color filter.
The color filter of the present invention can be applied not only to a general Liquid Crystal Display (LCD) but also to various 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 Diode (OLED).
In addition to having the color filters described above, the display device of the present invention includes a configuration known in the art.
In addition to the above-described color filter, the display device according to an embodiment of the present invention may further have a filter including a red pattern layer including red quantum dot particles, a green pattern layer including green quantum dot particles, and a blue pattern layer including blue quantum dot particles. In this case, the emission light of the light source applied to the image display device is not particularly limited, but in view of more excellent color gamut, a light source emitting blue light may be preferably used.
In addition to the above-described color filters, the display device according to an embodiment of the present invention may further have a color filter including only two color pattern layers of the red pattern layer, the green pattern layer, and the blue pattern layer. At this time, 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 of wavelengths exhibiting the remaining colors that are not included may be used. For example, in the case where only the red pattern layer and the green pattern layer are included, a light source emitting blue light may be used. At this time, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer allows blue light to be transmitted as it is to represent blue.
Hereinafter, the present invention will be described in more detail with reference to examples, but the embodiments of the present invention disclosed below are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the invention has been presented in the claims and even all changes that come within the meaning and range of equivalency of the claims are to be embraced therein. In the following examples and comparative examples, "%" and "parts" indicating contents are by mass unless otherwise specified.
< example >
Synthesis example: synthesis of azo Compound represented by chemical formula 1
Synthesis example 1: synthesis of colorant (A-1)
To 5.0 parts of 2, 5-dichloro-4-nitroaniline, 4.0 parts of water, 10 parts of acetic acid, 10 parts of methanol, 25 parts of 98% sulfuric acid were added and stirred. Ice cooling was performed, and then 2.0 parts of sodium nitrite dissolved in 3.0 parts of water to obtain an aqueous solution, which was added to the reaction solution and stirred for 2 hours, to obtain a diazonium salt-containing suspension. On the other hand, 15 parts of methanol was added to 3.0 parts of barbituric acid (. Alpha.) and then 100 parts of 25% aqueous sodium hydroxide solution was added under ice cooling and stirred. To this was added dropwise a suspension containing the diazonium salt described above. After the completion of the dropwise addition, stirring was carried out at room temperature for 1 hour to obtain an orange suspension. The orange solid obtained by filtration was dried under reduced pressure at 60℃to obtain a compound represented by formula (1).
[ chemical 31 ]
Subsequently, 97 parts of water, 4.1 parts of sodium hydrogencarbonate and 3.8 parts of sodium sulfide hydrate were added to 8.4 parts of the compound represented by formula (1), and stirred at 85℃for 2 hours. The reaction solution was cooled to room temperature, then neutralized to pH6 with 35% hydrochloric acid and precipitated to obtain a solid. The obtained solid was washed with water and filtered, and the red solid thus obtained was dried under reduced pressure at 60 ℃ to obtain 6.3 parts of the compound represented by formula (2).
Subsequently, 20 parts of water, 6.7 parts of acetic acid and 33 parts of 98% sulfuric acid were added to 2.1 parts of the compound represented by formula (2), followed by stirring. The reaction mixture was ice cooled and then 0.6 parts of sodium nitrite was dissolved in 3.3 parts of water. The aqueous solution was added to the reaction solution and stirred for 2 hours to obtain a suspension containing diazonium salt. On the other hand, 0.8 part of methanol was added to 0.8 part of barbituric acid (. Beta.) and then 15 parts of 25% aqueous sodium hydroxide solution was added under ice-cooling and stirred. To this was added dropwise a suspension containing the diazonium salt described above. After the end of the addition, stirring was further carried out at room temperature for 1 hour to give a red suspension. The suspension was washed by filtration, and the thus-obtained solid was dried under reduced pressure at 60℃to obtain 1.7 parts (yield: 57%) of an azo compound represented by the formula (A-1).
Ionization mode = ESI: m/z=453.0 [ m-H ]] -
[ chemical formula 33 ]
Synthesis example 2: synthesis of colorant (A-2)
0.4 part (yield 15%) of a compound represented by the formula (A-2) was obtained in the same manner as in Synthesis example 1, except that 3.0 parts of barbituric acid (α) was replaced with 5.1 parts of 1, 3-dicyclohexylbarbituric acid (α) and 0.8 parts of barbituric acid (β) was replaced with 0.7 parts of 1, 3-dicyclohexylbarbituric acid (β).
Ionization mode = ESI: m/z=783.4 [ m+h ]] +
Synthesis example 3: synthesis of colorant (A-3)
3.9 parts (yield 66%) of a compound represented by the formula (A-3) was obtained by the same method as in Synthesis example 1 except that 3.0 parts of barbituric acid (α) was replaced with 1.8 parts of 3-cyano-1-butyl-6-hydroxy-4-methyl-2-pyridone (α) and 0.8 part of barbituric acid (β) was replaced with 1.4 parts of 3-cyano-1-butyl-6-hydroxy-4-methyl-2-pyridone (β).
Ionization mode = ESI: m/z=609.2 [ m-H] -
[ 35 ]
Synthesis example 4: synthesis of colorant (A-4)
0.8 part (yield 53%) of a compound represented by the formula (A-4) was obtained in the same manner as in Synthesis example 1 except that 3.0 parts of barbituric acid (α) was replaced with 4.2 parts of 3-methyl-1-phenyl-5-pyrazolone (α) and 0.8 parts of barbituric acid (β) was replaced with 0.5 parts of 3-methyl-1-phenyl-5-pyrazolone (β).
Ionization mode = ESI: m/z=547.2 [ m+h ]] +
Synthesis example 5: synthesis of colorant (A-5)
1.2 parts (yield 58%) of a compound represented by the formula (A-5) was obtained in the same manner as in Synthesis example 1 except that 3.0 parts of barbituric acid (α) was replaced with 4.9 parts of 3-methyl-1- (4-sulfophenyl) -2-pyrazolin-5-one (α) and 0.8 parts of barbituric acid (β) was replaced with 0.7 parts of 3-methyl-1- (4-sulfophenyl) -2-pyrazolin-5-one (β).
Ionization mode = ESI: m/z=705.0 [ m-H ]] +
[ FORMS 37 ]
Synthesis example 6: synthesis of colorant (A-6)
1.9 parts (yield 56%) of a compound represented by the formula (A-6) was obtained in the same manner as in Synthesis example 1 except that 0.8 part of barbituric acid (. Beta.) was replaced with 1.2 parts of 3-cyano-1-butyl-6-hydroxy-4-methyl-2-pyridone.
Ionization mode = ESI: m/z=533.0 [ m+h ]] +
Synthesis example 7: synthesis of colorant (A-7)
1.5 parts (yield: 54%) of a compound represented by the formula (A-7) was obtained in the same manner as in Synthesis example 1 except that 0.8 part of barbituric acid (. Beta.) was replaced with 1.0 part of 3-methyl-1-phenyl-5-pyrazolone.
Ionization mode = ESI: m/z=499.1 [ m-H ]] -
[ chemical formula 39 ]
Synthesis example 8: synthesis of colorant (A-8)
1.2 parts (yield: 37%) of a compound represented by the formula (A-8) was obtained in the same manner as in Synthesis example 1 except that 0.8 part of barbituric acid (. Beta.) was replaced with 0.5 part of 3-methyl-1- (4-sulfophenyl) -2-pyrazolin-5-one.
Ionization mode = ESI: m/z=579.0 [ m-H ]
[ 40 ]
Synthesis example 9: synthesis of colorant (A-9)
In the same manner as in Synthesis example 2 except that 0.7 part of 1, 3-dicyclohexylbarbituric acid (. Beta.) was replaced with 0.2 part of 3-methyl-1-phenyl-5-pyrazolone, 0.3 part (yield: 31%) of a compound represented by the formula (A-9) was obtained.
Ionization mode = ESI: m/z=664.0 [ m] -
Synthesis example 10: synthesis of colorant (A-10)
35 parts (yield: 73%) of a compound represented by the formula (A-10) was obtained in the same manner as in Synthesis example 4, except that 4.2 parts of 3-methyl-1-phenyl-5-pyrazolone (. Alpha.) was replaced with 18 parts of 3-methyl-1- (4-sulfophenyl) -2-pyrazolin-5-one.
Ionization mode = ESI: m/z=625.1 [ m-H ]] -
Synthesis example 11: synthesis of colorant (A-11)
15 parts of chloroform and 0.4 part of N, N-dimethylformamide were added to 1.5 parts of the azo compound represented by the formula (A-10) with stirring, and 0.6 part of thionyl chloride was added dropwise while maintaining the temperature below 20 ℃. After the end of the dropwise addition, the temperature was raised to 50 ℃, the reaction was allowed to proceed for 3 hours at the same temperature, and then cooled to 20 ℃. After cooling, a mixture of 0.5 part of 2-methylcyclohexylamine and 1.9 parts of triethylamine was added dropwise while keeping the reaction solution at 20℃or lower with stirring. Then, the reaction was allowed to react at the same temperature for 5 hours. Subsequently, the solvent was removed from the obtained reaction mixture by an evaporator, and then a small amount of methanol was added and vigorously stirred. This mixture was added dropwise to 45 parts of a 20% aqueous sodium chloride solution while stirring, whereby crystals were precipitated. The precipitated crystals were washed with water and dried under reduced pressure at 60℃to give 1.2 parts (yield: 74%) of the compound represented by the formula (A-11).
Ionization mode = ESI: m/z=720.2 [ m-H ]] -
Synthesis example 12: synthesis of colorant (A-12)
In the same manner as in Synthesis example 11 except that 0.5 part of 2-methylcyclohexylamine was replaced with 2.1 parts of 3, 5-di-t-butylaniline, 0.8 part (yield 58%) of the compound represented by the formula (A-12) was obtained.
Ionization mode = ESI: m/z=813.2 [ m] -
Synthesis example 13: synthesis of colorant (A-13)
1.2 parts (yield: 74%) of a compound represented by the formula (A-13) was obtained in the same manner as in Synthesis example 11 except that 0.5 part of 2-methylcyclohexylamine was replaced with 1.3 parts of aniline.
Ionization mode = ESI: m/z=701.1 [ m ]] -
Synthesis example 14: synthesis of colorant (A-14)
In the same manner as in Synthesis example 11 except that 0.5 part of 2-methylcyclohexylamine was replaced with 1.8 parts of 1-adamantanamine, 0.9 part (yield: 59%) of a compound represented by the formula (A-14) was obtained.
Ionization mode = ESI: m/z=759.2 [ m] -
Synthesis example 15: coloring agent (A-15)Is synthesized by (a)
In the same manner as in Synthesis example 11 except that 0.5 part of 2-methylcyclohexylamine was replaced with 1.2 parts of 1, 3-dimethylbutylamine, 0.9 part (yield 62%) of a compound represented by formula (A-15) was obtained.
Ionization mode = ESI: m/z=709.2 [ m ] ] -
Synthesis example 16: synthesis of colorant (A-16)
To 0.5 part of the azo compound represented by the formula (A-10), 60 parts of water and 60 parts of N, N-dimethylformamide were added and stirred, followed by 1.2 parts of barium acetate. The temperature was raised to 60 ℃ and allowed to react at the same temperature for 2 hours, then cooled to 20 ℃. After cooling, the reaction solution was filtered and washed with methanol, and then dried under reduced pressure at 60℃to obtain 0.4 part (yield 76%) of the compound represented by the formula (A-16).
Synthesis example 17: synthesis of colorant (A-17)
0.4 part (yield 28%) of a compound represented by the formula (A-17) was obtained in the same manner as in Synthesis example 11 except that 1.5 parts of the azo compound represented by the formula (A-10) was replaced with 12 parts of the azo compound represented by the formula (A-5), 0.4 part of N, N-dimethylformamide was replaced with 0.3 part, 0.6 part of thionyl chloride was replaced with 9.4 parts, 0.5 part of 2-methylcyclohexylamine was replaced with 2.3 parts, and 1.9 parts of triethylamine was replaced with 5.3 parts.
Ionization mode = ESI: m/z=895.2 [ m-H] -
Synthesis example 18: synthesis of colorant (A-18)
3.2 parts (yield 65%) of a compound represented by the formula (A-18) was obtained in the same manner as in Synthesis example 7 except that 5.0 parts of 2, 5-dichloro-4-nitroaniline was replaced with 3.0 parts of 2-methyl-4-nitroaniline.
Ionization mode = ESI: m/z=445.2 [ m-H] -
Synthesis example 19: synthesis of colorant (A-19)
4.0 parts (yield 90%) of a compound represented by formula (A-19) was obtained in the same manner as in Synthesis example 10 except that 5.0 parts of 2, 5-dichloro-4-nitroaniline was replaced with 6.0 parts of 2-methyl-4-nitroaniline.
Ionization mode = ESI: m/z=571.2 [ m-H] -
Synthesis example 20: synthesis of colorant (A-20)
0.3 part (yield 20%) of a compound represented by the formula (A-20) was obtained in the same manner as in Synthesis example 11 except that 1.5 parts of the azo compound represented by the formula (A-10) was replaced with 1.5 parts of the azo compound represented by the formula (A-19).
Ionization mode = ESI: m/z=666.3 [ m-H ]] -
Synthesis example 21: synthesis of colorant (A-21)
1.3 parts (yield: 40%) of a compound represented by the formula (A-21) was obtained in the same manner as in Synthesis example 4 except that 5.0 parts of 2, 5-dichloro-4-nitroaniline was replaced with 3.0 parts of 2-chloro-4-nitroaniline.
Ionization mode = ESI: m/z=513.3 [ m+h] +
Synthesis example 22: synthesis of colorant (A-22)
0.3 part (yield 21%) of a compound represented by formula (A-22) was obtained in the same manner as in Synthesis example 4 except that 5.0 parts of 2, 5-dichloro-4-nitroaniline was replaced with 3 parts of 2, 6-dichloro-4-nitroaniline.
Ionization mode = ESI: m/z=545.3 [ m-H ]] -
Synthesis example 23: synthesis of colorant (A-23)
2.4 parts (yield: 73%) of a compound represented by formula (A-23) was obtained in the same manner as in Synthesis example 4 except that 5.0 parts of 2, 5-dichloro-4-nitroaniline was replaced with 2.0 parts of 4-nitroaniline.
Ionization mode = ESI: m/z=479.5 [ m+h ]] +
Synthesis example 24: synthesis of colorant (A-24)
0.3 part (yield: 15%) of a compound represented by formula (A-24) was obtained in the same manner as in Synthesis example 4 except that 5.0 parts of 2, 5-dichloro-4-nitroaniline was replaced with 1.0 part of 2, 5-dimethoxy-4-nitroaniline.
Ionization mode = ESI: m/z=537.2 [ m-H] -
Preparation example: preparation of azo Compound Dispersion and colorant Dispersion
< preparation example 1: azo Compound Dispersion (a 1-1) >
4.5 parts of the compound represented by the formula (A-1) obtained in Synthesis example 1-1, 5.7 parts of a dispersing agent (BYKLPN-6919 manufactured by BYK Co.) in terms of solid content, a dispersion resin (a copolymer of 30 parts by weight of methacrylic acid and 70 parts by weight of benzyl methacrylate, an acid value of 80mgKOH/g, a weight average molecular weight of 11000) in terms of solid content, 9.9 parts of propylene glycol monomethyl ether acetate 74.3 parts, and 5.0 parts of diacetone alcohol were mixed, and then 300 parts of 0.2mm zirconia beads were added and mixed and dispersed to obtain an azo compound dispersion (a 1-1).
Preparation example 2: azo compound Dispersion (a 1-2)>
An azo compound dispersion (a 1-2) was obtained in the same manner as in production example 1, except that the compound represented by the formula (A-1) was replaced with the compound represented by the formula (A-3) obtained in synthesis example 3.
Preparation example 3: azo compound Dispersion (a 1-3)>
An azo compound dispersion (a 1-3) was obtained in the same manner as in production example 1, except that the compound represented by the formula (A-1) was replaced with the compound represented by the formula (A-4) obtained in production example 4.
Preparation example 4: azo compound Dispersion (a 1-4)>
An azo compound dispersion (a 1-4) was obtained in the same manner as in production example 1, except that the compound represented by the formula (A-1) was replaced with the compound represented by the formula (A-6) obtained in synthesis example 6.
Preparation example 5: azo compound Dispersion (a 1-5)>
An azo compound dispersion (a 1-5) was obtained in the same manner as in production example 1, except that the compound represented by the formula (A-1) was replaced with the compound represented by the formula (A-7) obtained in synthesis example 7.
Preparation example 6: azo compound Dispersion (a 1-6)>
An azo compound dispersion (a 1-6) was obtained in the same manner as in production example 1, except that the compound represented by the formula (A-1) was replaced with the compound represented by the formula (A-8) obtained in synthesis example 8.
Preparation example 7: azo compound Dispersion (a 1-7)>
An azo compound dispersion (a 1-7) was obtained in the same manner as in production example 1, except that the compound represented by the formula (A-1) was replaced with the compound represented by the formula (A-9) obtained in production example 9.
Preparation example 8: azo compound Dispersion (a 1-8)>
An azo compound dispersion (a 1-8) was obtained in the same manner as in production example 1, except that the compound represented by the formula (A-1) was replaced with the compound represented by the formula (A-10) obtained in production example 10.
Preparation example 9: azo compound Dispersion (a 1-9)>
An azo compound dispersion (a 1-9) was obtained in the same manner as in production example 1, except that the compound represented by the formula (A-1) was replaced with the compound represented by the formula (A-13) obtained in synthesis example 13.
Preparation example 10: azo compound Dispersion (a 1-10)>
An azo compound dispersion (a 1-10) was obtained in the same manner as in production example 1, except that the compound represented by the formula (A-1) was replaced with the compound represented by the formula (A-18) obtained in production example 18.
Preparation example 11: azo compound Dispersion (a 1-11)>
An azo compound dispersion (a 1-11) was obtained in the same manner as in production example 1, except that the compound represented by the formula (A-1) was replaced with the compound represented by the formula (A-20) obtained in synthesis example 20.
Preparation example 12: azo compound Dispersion (a 1-12)>
An azo compound dispersion (a 1-12) was obtained in the same manner as in production example 1, except that the compound represented by the formula (A-1) was replaced with the compound represented by the formula (A-22) obtained in production example 22.
Preparation example 13: yellow colorant dispersion (a 2)
A yellow colorant dispersion (a 2) was obtained in the same manner as in production example 1, except that the compound represented by the formula (A-1) was replaced with C.I. pigment yellow 139.
Preparation example 14: red colorant dispersion (a 3)
A red colorant dispersion (a 3) was obtained in the same manner as in production example 1, except that the compound represented by the formula (A-1) was replaced with C.I. pigment Red 254.
Preparation example 15: red colorant dispersion (a 4)
A red colorant dispersion (a 4) was obtained in the same manner as in production example 1, except that the compound represented by the formula (A-1) was replaced with C.I. pigment Red 291.
Preparation example 16: red colorant dispersion (a 5)
A red colorant dispersion (a 5) was obtained in the same manner as in production example 1, except that the compound represented by the formula (A-1) was replaced with C.I. pigment Red 177.
Preparation example 17: red colorant dispersion (a 6)
A red colorant dispersion (a 6) was obtained in the same manner as in production example 1, except that the compound represented by the formula (A-1) was replaced with C.I. pigment Red 202.
Preparation example 18: purple colorant dispersion (a 7)
A violet colorant dispersion (a 7) was obtained in the same manner as in production example 1, except that the compound represented by the formula (A-1) was replaced with C.I. pigment violet 19.
Examples 1 to 20 and comparative examples 1 to 6: preparation of colored curable resin composition
Colored curable resin compositions were prepared according to the compositions and contents of tables 1 and 2 below.
TABLE 1
TABLE 2
(A) Coloring agent
(a 1-1 to a 1-12): azo compound dispersions according to preparation examples 1 to 12
(a2) The method comprises the following steps Yellow colorant Dispersion according to preparation example 13
(a3) The method comprises the following steps Red colorant dispersion according to preparation example 14
(a4) The method comprises the following steps Red colorant dispersion according to preparation example 15
(a5) The method comprises the following steps Red colorant dispersion according to preparation example 16
(a6) The method comprises the following steps Red colorant dispersion according to preparation example 17
(a7) The method comprises the following steps Purple colorant dispersion according to preparation 18
(a8) The method comprises the following steps Xanthylium (xanthylium) salts, 3-dipropylamino, 6-diethylamino, 9- (2-sulfophenyl) -, intramolecular salts; dyes of chemical formula 2
(B) Binder resin: copolymers of methacrylic acid and benzyl methacrylate (acid value 100mgKOH/g, weight average molecular weight based on polystyrene 20000)
(C) Photopolymerizable compound: a9550 (Shin Nakamura Co.)
(D) Photopolymerization initiator: OXE-02 (BASF corporation)
(E-1) additive 1: organosilicon surfactant (SH-8400)
(E-2) additive 2: adhesion promoter (3-methacryloxypropyl trimethoxysilane)
(F) Solvent: propylene glycol monomethyl ether acetate
Experimental example
1. Color filter fabrication
The colored curable resin compositions according to examples and comparative examples were coated on a 5×5cm glass substrate and dried, and then bar-coated to a thickness of 2.5 μm. Subsequently, the resultant was dried in an oven at 100℃for 3 minutes to remove the solvent, then exposed to light with a cumulative light amount of 40mJ at a distance of 300 μm from the photomask and 313nm wavelength of the FUSION lamp, and then taken out after being immersed in an aqueous KOH solution at pH14 for 1 minute, taken out after being immersed in distilled water again for 1 minute, and put in an oven at 230℃to bake for 20 minutes, thereby manufacturing a color filter.
2. Evaluation of brightness
The color filter manufactured as above was mounted on a spectrophotometer (CM-3700d,Konica Minolta Sensing product, ltd.) and the transmitted chromaticity in the X, Y, Z coordinate axis was measured at 2 ° of the C light source, and the Y value at this time was used as the luminance. The brightness of the color filters according to the remaining examples and comparative examples was calculated as a relative value (%) with respect to the brightness of the color filters manufactured using the colored curable resin composition of comparative example 1 as a standard (100%), and the results are shown in tables 3 and 4 below.
3. Calculation of colorant concentration
The colorant concentrations of the colored curable resin compositions according to examples and comparative examples manufactured as described above were calculated. The colorant concentrations of the colored curable resin compositions according to the remaining examples and comparative examples were calculated as relative values (%) by comparison with the colorant concentrations of the colored curable resin composition of comparative example 1 as a standard (100%), the lower the numerical value, the better the physical properties. The results are shown in tables 3 and 4 below.
4. Evaluation of solvent resistance
The color filter manufactured as above was cut into 3X 3cm and then immersed in 14.6ml of NMP (N-methyl-2-pyrrolidone) solution at 80℃for 40 minutes. Subsequently, absorbance of the impregnation liquid was measured using a UV-Vis spectrometer and solvent resistance was evaluated according to the following evaluation criteria, the results of which are shown in tables 3 and 4 below.
< evaluation criteria for solvent resistance >
O: the absorbance is below 2
Delta: absorbance of more than 2 and less than 4
X: absorbance of greater than 4
UV ashing resistance evaluation
The color filter manufactured as above was irradiated with 2000mW/cm using an ultraviolet ozone cleaning device (UV-312, manufactured by the company of technovision) 3 Ultraviolet rays of (2) and calculating a color difference DeltaEab before and after ultraviolet irradiation using the following equation 1 * Then, UV ashing resistance was evaluated according to the following evaluation criteria, and the results thereof are shown in tables 3 and 4 below.
[ mathematics 1]
ΔEab * ＝(ΔL * ) 2 +(Δa * ) 2 +(Δb * ) 2 ] 1/2
< evaluation criteria for UV ashing resistance >
○：ΔEab * =less than 5
X：ΔEab * =5 or more
TABLE 3
/>
TABLE 4
Referring to the results of tables 3 and 4, it can be confirmed that in the case of using the color filters manufactured using the colored curable resin compositions of examples 1 to 20 containing the compound represented by chemical formula 1 of the present invention, not only excellent brightness but also reliability such as solvent resistance and UV ashing resistance are also excellent.
In contrast, in the case of comparative examples 1 to 6 containing no compound represented by chemical formula 1 of the present invention, it can be confirmed that the luminance is generally decreased. In addition, it was confirmed that reliability such as solvent resistance and UV ashing resistance was significantly lowered, particularly in the case of comparative examples 1 to 4.

Claims (13)

1. A colored curable resin composition comprising a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,
wherein the colorant comprises at least one selected from the group consisting of a red pigment, a yellow pigment, a violet pigment, and a xanthene dye, represented by the following chemical formula 1:
[ chemical formula 1]
A-L 1 -B (I)
In the chemical formula 1, L 1 A is a group represented by the following formula (ph 1), A is a group represented by the following formula (ia), B is a group represented by the following formula (ib),
in formula (ph 1), X 1 Represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -NH 2 、-CONH 2 -COOH, -CN, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 4 carbon atoms or a halogen atom, wherein-CH is contained in the hydrocarbon group 2 -may be substituted by-O-, -CO-, or-NH-, and-ch=contained in the hydrocarbon group may be substituted by-n=;
n represents an integer of 0 to 4, and when n is an integer of 2 or more, a plurality of X' s 1 May be the same or different, and X is an integer of 2 or more in n 1 X bonded to adjacent carbon atoms when bonded to adjacent carbon atoms 1 Can be bonded to each other to form a ring;
* Represents the number of bonds with a, represents the number of bonds with B,
in the formula (ia) and the formula (ib), X 6 To X 9 Each independently represents a monovalent hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, wherein the hydrocarbon group contains-CH 2 -ch=contained in the hydrocarbon group may be substituted with-n=and-ch=contained in the hydrocarbon group may be substituted with-O-, -CO-, or-NH- <Can be covered by-N<Alternatively, an oxygen atom, a nitrogen atom, a sulfur atom or a carbonyl group may be interposed between carbon atoms constituting the hydrocarbon group;
X 6 and X 7 Can be bonded to each other to form a ring X 8 And X 9 Can be bonded to each other to form a ring;
* Representation and L 1 The number of bonds between them.
2. The colored curable resin composition according to claim 1, wherein the L 1 Is a group represented by the following chemical formula (ph 2):
in formula (ph 2), X 2 To X 5 Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -NH 2 、-CONH 2 -COOH, -CN, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms or a halogen atom;
X 2 and X 3 Between and X 4 And X 5 Can be mutually bonded to form a ring;
* Represents the number of bonds with a, and represents the number of bonds with B.
3. The colored curable resin composition according to claim 1, wherein the content of the compound represented by the chemical formula 1 is 10 to 70% by weight based on the total weight of the colorant.
4. The colored curable resin composition according to claim 1, wherein the red pigment comprises at least one selected from the group consisting of c.i. pigment red 177, c.i. pigment red 179, c.i. pigment red 202, c.i. pigment red 242, c.i. pigment red 254, and c.i. pigment red 291.
5. The colored curable resin composition according to claim 1, wherein the yellow pigment comprises at least one selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 185, and c.i. pigment yellow 231.
6. The colored curable resin composition according to claim 1, wherein the violet pigment comprises at least one selected from the group consisting of c.i. pigment violet 19, c.i. pigment violet 23, and c.i. pigment violet 29.
7. The colored curable resin composition of claim 1 wherein said xanthene-based dye comprises at least one selected from the group consisting of compounds represented by the following chemical formula 2:
[ chemical formula 2]
In the chemical formula 2 described above, the chemical formula,
R 21 、R 22 、R 23 、R 24 、R 25 r is R 26 Each independently is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;
R 27 and R is 28 Each independently represents a hydrogen atom, -COOH, -COO - 、-SO 3 - 、-SO 3 H、-SO 3 Na、-COOCH 3 or-COOCH 2 CH 3 。
8. The colored curable resin composition according to claim 1, wherein the photopolymerization initiator comprises an oxime compound.
9. The colored curable resin composition according to claim 8, wherein the oxime-based compound comprises at least one selected from the group consisting of a compound represented by the following chemical formula 3, a compound represented by the following chemical formula 4, and a compound represented by the following chemical formula 5:
[ chemical formula 3]
[ chemical formula 4]
[ chemical formula 5]
In the chemical formulas 3 to 5,
R 31 to R 46 Each independently is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a hydroxyalkyl group having 1 to 12 carbon atoms, a hydroxyalkoxyalkyl group having 2 to 24 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, an aralkyl group, an amino group, a nitro group, a cyano group, or a hydroxyl group.
10. The colored curable resin composition according to claim 1, wherein the colored curable resin composition is used for forming red pixels.
11. The colored curable resin composition according to claim 1, wherein the colored curable resin composition comprises,
the colorant is present in an amount of 1 to 15 weight percent;
the content of the binder resin is 0.5 to 20 wt%;
the content of the photopolymerizable compound is 1 to 10 wt%;
the content of the photopolymerization initiator is 0.1 to 10% by weight; and is also provided with
The solvent is contained in an amount of 60 to 95% by weight.
12. A color filter comprising a colored pattern made of the colored curable resin composition according to any one of claims 1 to 11.
13. An image display device comprising the color filter of claim 12.
CN202310062460.6A 2022-02-24 2023-01-20 Colored curable resin composition, color filter manufactured by using the same, and display device Pending CN116643456A (en)

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