CN111679557B - Colored curable resin composition containing blue dye, color filter and image display device - Google Patents

Colored curable resin composition containing blue dye, color filter and image display device Download PDF

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CN111679557B
CN111679557B CN201911141519.0A CN201911141519A CN111679557B CN 111679557 B CN111679557 B CN 111679557B CN 201911141519 A CN201911141519 A CN 201911141519A CN 111679557 B CN111679557 B CN 111679557B
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parts
weight
chemical formula
resin composition
curable resin
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CN111679557A (en
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金兑昱
金一镐
尹秀珍
田浚豪
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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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • 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
    • 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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Structural Engineering (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Organic Chemistry (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)

Abstract

The invention provides a coloring curable resin composition containing blue dye, a color filter and an image display device. The colored curable resin composition containing a blue dye is characterized by comprising a colorant and an alkali-soluble resin, wherein the colorant comprises a blue dye represented by chemical formula 1, a violet dye represented by chemical formula 2 and a blue pigment, the alkali-soluble resin comprises a first resin containing a repeating unit represented by chemical formula 3 and having a glass transition temperature of 0 ℃ or higher and a second resin containing a repeating unit represented by chemical formula 4 and having a glass transition temperature of less than 0 ℃, the content of the blue dye represented by chemical formula 1 is 20 to 40 parts by weight relative to 100 parts by weight of the entire colorant, the content of the violet dye represented by chemical formula 2 is 5 to 25 parts by weight relative to 100 parts by weight of the entire colorant, and the content of the blue pigment is 40 to 60 parts by weight relative to 100 parts by weight of the entire colorant.

Description

Colored curable resin composition containing blue dye, color filter and image display device
Technical Field
The present invention relates to a colored curable resin composition containing a blue dye, and a color filter and an image display device manufactured using the colored curable resin composition.
Background
The color filter is a thin film type optical member capable of forming a fine pixel unit by extracting three colors of red, green and blue from white light, and the size of one pixel is several tens to several hundreds micrometers. Such a color filter has a structure in which a black matrix layer and a pixel portion are sequentially stacked, the black matrix layer being formed in a predetermined pattern on a transparent substrate so as to shield a boundary portion between pixels, and the pixel portion being arranged in a predetermined order with three primary colors of a plurality of colors (typically, red R, green G, and blue B) so as to form the pixels.
In general, color filters are manufactured by applying three or more colors onto a transparent substrate by a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method, or the like, and in recent years, a pigment dispersion method using a pigment dispersion type curable resin has become a mainstream.
A pigment dispersion method, which is one of methods for forming a color filter, is a method of forming a colored film by repeating a series of processes of applying a curable resin composition including an alkali-soluble resin including a colorant, a photopolymerization monomer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives onto a transparent substrate provided with a black matrix, exposing a pattern in a desired form, and then removing a non-exposed portion with a solvent and thermally curing the same, and is widely used in the manufacture of LCDs for mobile phones, notebook computers, monitors, TVs, and the like.
In recent years, in practical cases, a curable resin composition for color filters using a pigment dispersion method having various advantages is required to have excellent pattern characteristics, and high color reproduction rate and further improved performances such as improved residual film and line peeling due to reduced developability at the time of forming a pattern, and improved sensitivity, development speed, adhesion, and the like are required.
However, color reproduction is achieved by transmitting light irradiated from a light source through a color filter, and in this process, a part of the light is absorbed by the color filter to decrease light efficiency, and there is a fundamental limitation in that perfect color reproduction cannot be achieved due to pigment characteristics as the color filter.
Korean laid-open patent No. 10-2013-01111076 provides a colored resin composition having high reliability, which has excellent color characteristics such as contrast and also excellent resistance to heat and the like by containing a specific blue dye-based compound, a binder resin, a solvent, a curing agent and the like.
However, the above conventional techniques have a problem of poor reliability such as heat resistance and light resistance, and poor stability.
Prior art literature
Patent literature
Patent document 1: korean laid-open patent No. 2013-01111076 (2013.10.21.)
Disclosure of Invention
Problems to be solved
The present invention is an invention for solving the above-described problems, and it is an object of the present invention to provide a blue dye-containing colored curable resin composition which contains a specific colorant and a specific alkali-soluble resin and is excellent in pattern angle, residue characteristics, film retention, chemical resistance, and mechanical properties, and in particular, can improve heat resistance, light resistance, reliability, and the like, and a color filter and an image display device produced using the colored curable resin composition.
Means for solving the problems
The present invention provides a colored curable resin composition containing a blue dye, which comprises a colorant and an alkali-soluble resin, wherein the colorant comprises a blue dye represented by the following chemical formula 1, a violet dye represented by the following chemical formula 2 and a blue pigment, the alkali-soluble resin comprises a first resin containing a repeating unit represented by the following chemical formula 3 and having a glass transition temperature of 0 ℃ or higher, and a second resin containing a repeating unit represented by the following chemical formula 4 and having a glass transition temperature of less than 0 ℃, the content of the blue dye represented by the following chemical formula 1 is 20 to 40 parts by weight relative to 100 parts by weight of the entire colorant, the content of the violet dye represented by the following chemical formula 2 is 5 to 25 parts by weight relative to 100 parts by weight of the entire colorant, and the content of the blue pigment is 40 to 60 parts by weight relative to 100 parts by weight of the entire colorant.
[ chemical formula 1]
In the above-mentioned chemical formula 1,
r1 to R4 each independently represent an amino group which may be substituted, a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, an alkyl group having 2 to 20 carbon atoms which may be substituted with an oxygen atom by a methylene group contained in the alkyl group, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, or a hydrogen atom,
r1 and R2 may be bonded to form a ring together with the nitrogen atom to which they are bonded, R3 and R4 may be bonded to form a ring together with the nitrogen atom to which they are bonded,
r5 to R12 each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom may be inserted between methylene groups constituting the alkyl group,
r6 and R10 may be bonded to each other, and can be formed with-NH- -O-, -S-or-SO 2 -，
In R1 to R4 and R5 to R12, adjacent methylene groups are not simultaneously substituted with oxygen atoms, and a terminal methylene group of an alkyl group is not substituted with an oxygen atom,
t1 represents an aromatic heterocycle which may have a substituent,
[Y] m- represents an m-valent anion containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus,
m represents an integer of 2 to 14,
[ chemical formula 2]
In the above-mentioned chemical formula 2,
r13 to R18 are each independently hydrogen or C1-C5 alkyl,
r19 and R20 are each independently hydrogen, COOH, COO - 、SO 3 - 、SO 3 H、SO 3 Na、COOCH 3 Or COOCH 2 CH 3 ，
[ chemical formula 3]
In the above-mentioned chemical formula 3,
r21 is hydrogen or methyl, and the catalyst is a catalyst,
r22 is a C1-C7 linear or branched alkyl group.
[ chemical formula 4]
In the above-mentioned chemical formula 4, a catalyst,
r23 is hydrogen or methyl, and the catalyst is a compound,
r24 is a C4-C40 linear or branched alkyl group,
wherein the above chemical formulas 3 and 4 are different from each other.
The present invention also provides a color filter comprising a cured product of the above colored curable resin composition containing a blue dye.
The present invention also provides an image display device including the color filter.
Effects of the invention
The colored curable resin composition containing a blue dye of the present invention contains a specific colorant and a specific alkali-soluble resin, and thus has advantages of excellent pattern angle, excellent residue characteristics, film retention, chemical resistance, and mechanical properties, and particularly, improved heat resistance, light resistance, and reliability.
The color filter and the image display device of the present invention, which contain the cured product of the colored curable resin composition containing a blue dye, have the advantages of excellent pattern angle, excellent chemical resistance and mechanical properties, in particular excellent heat resistance, light resistance and reliability.
Detailed Description
The present invention will be described in more detail below.
In the present invention, when it is noted that a certain member is "on" another member, it includes not only the case where the certain member is in contact with the other member but also the case where another member exists between the two members.
In the present invention, when a certain component is "included" in the present invention, unless otherwise stated, it means that other components may be further included, and that other components are not excluded.
< coloring curable resin composition containing blue dye >
The present invention relates to a colored curable resin composition containing a blue dye, which contains a colorant containing a blue dye represented by the following chemical formula 1, a violet dye represented by the following chemical formula 2, and a blue pigment, and an alkali-soluble resin containing a first resin having a glass transition temperature of 0 ℃ or higher and containing a repeating unit represented by the following chemical formula 3, and a second resin having a repeating unit represented by the following chemical formula 4 and having a glass transition temperature of less than 0 ℃, wherein the content of the blue dye represented by the following chemical formula 1 is 20 to 40 parts by weight relative to 100 parts by weight of the entire colorant, the content of the violet dye represented by the following chemical formula 2 is 5 to 25 parts by weight relative to 100 parts by weight of the entire colorant, and the content of the blue pigment is 40 to 60 parts by weight relative to 100 parts by weight of the entire colorant.
[ chemical formula 1]
In the above-mentioned chemical formula 1,
r1 to R4 each independently represent an amino group which may be substituted, a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, an alkyl group having 2 to 20 carbon atoms which may be substituted with an oxygen atom by a methylene group contained in the alkyl group, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, or a hydrogen atom,
r1 and R2 may be bonded to form a ring together with the nitrogen atom to which they are bonded, R3 and R4 may be bonded to form a ring together with the nitrogen atom to which they are bonded,
r5 to R12 each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom may be inserted between methylene groups constituting the alkyl group,
r6 and R10 may be bonded to each other, and can be formed with-NH- -O-, -S-or-SO 2 -，
In R1 to R4 and R5 to R12, adjacent methylene groups are not simultaneously substituted with oxygen atoms, and a terminal methylene group of an alkyl group is not substituted with an oxygen atom,
t1 represents an aromatic heterocycle which may have a substituent,
[Y] m- represents an m-valent anion containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus,
m represents an integer of 2 to 14,
[ chemical formula 2]
In the above-mentioned chemical formula 2,
r13 to R18 are each independently hydrogen or C1-C5 alkyl,
r19 and R20 are each independently hydrogen, COOH, COO - 、SO 3 - 、SO 3 H、SO 3 Na、COOCH 3 Or COOCH 2 CH 3 ，
[ chemical formula 3]
In the above-mentioned chemical formula 3,
r21 is hydrogen or methyl, and the catalyst is a catalyst,
r22 is a C1-C7 linear or branched alkyl group.
[ chemical formula 4]
In the above-mentioned chemical formula 4, a catalyst,
r23 is hydrogen or methyl, and the catalyst is a compound,
r24 is a C4-C40 linear or branched alkyl group,
wherein the above chemical formulas 3 and 4 are different from each other.
Coloring agent
The colored curable resin composition containing a blue dye of the present invention contains a colorant containing a blue dye represented by the following chemical formula 1, a violet dye represented by the following chemical formula 2, and a blue pigment. The blue dye-containing colored curable resin composition of the present invention contains the above-described colorant, and therefore has advantages such as heat resistance, light resistance, and reliability, which are disadvantages of the colored curable resin compositions using conventional dyes, can be significantly improved.
In the colorant of the present invention, the content of the blue dye represented by the following chemical formula 1 is 20 to 40 parts by weight based on 100 parts by weight of the entire colorant. Since the content of the blue dye represented by the above chemical formula 1 is within the above range, a colored curable resin composition containing a blue dye having excellent brightness and contrast and excellent reliability can be provided even if the content of the coloring material is low.
[ chemical formula 1]
In the above-mentioned chemical formula 1,
r1 to R4 each independently represent an amino group which may be substituted, a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, an alkyl group having 2 to 20 carbon atoms which may be substituted with an oxygen atom by a methylene group contained in the alkyl group, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, or a hydrogen atom,
r1 and R2 may be bonded to form a ring together with the nitrogen atom to which they are bonded, R3 and R4 may be bonded to form a ring together with the nitrogen atom to which they are bonded,
r5 to R12 each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom may be inserted between methylene groups constituting the alkyl group,
r6 and R10 may be bonded to each other, and can be formed with-NH- -O-, -S-or-SO 2 -，
In R1 to R4 and R5 to R12, adjacent methylene groups are not simultaneously substituted with oxygen atoms, and a terminal methylene group of an alkyl group is not substituted with an oxygen atom,
t1 represents an aromatic heterocycle which may have a substituent,
[Y] m- represents an m-valent anion containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus,
m represents an integer of 2 to 14.
The alkyl group may be a straight-chain or branched alkyl group, and may include, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a n-octyl group, a n-decyl group, and the like.
Further, as the above aralkyl group, benzyl, chlorobenzyl, α -methylbenzyl, α -dimethylbenzyl, phenylethyl, phenylvinyl and the like can be included.
The content of the blue dye represented by the chemical formula 1 may be preferably 20 to 35 parts by weight, more preferably 25 to 35 parts by weight, based on 100 parts by weight of the entire colorant, and in this case, the effect is preferably maximized.
In the colored curable resin composition containing a blue dye of the present invention, the content of the xanthene-based violet dye represented by the following chemical formula 2 is 5 to 25 parts by weight based on 100 parts by weight of the entire colorant, and thus the color density of the pixel is excellent and the decrease in heat resistance can be suppressed.
[ chemical formula 2]
In the above-mentioned chemical formula 2,
r13 to R18 are each independently hydrogen or C1-C5 alkyl,
r19 and R20 are each independently hydrogen, COOH, COO - 、SO 3 - 、SO 3 H、SO 3 Na、COOCH 3 Or COOCH 2 CH 3 。
The xanthene dye can be used directly or by synthesis. Specifically, the xanthene dye may be xanthene Salts, 3, 6-bis [ (2, 6-dimethylphenyl) propylamino]9- (2-sulfophenyl) -, an intramolecular salt (manufactured by Sumitomo chemical Co., ltd.), and the like, but is not limited thereto.
The content of the violet dye represented by the chemical formula 2 may be preferably 5 to 20 parts by weight, more preferably 10 to 20 parts by weight, based on 100 parts by weight of the entire colorant, and in this case, the effect is preferably maximized.
In the colored curable resin composition containing a blue dye of the present invention, the content of the blue pigment may be 40 to 60 parts by weight, preferably 45 to 60 parts by weight, and more preferably 48 to 60 parts by weight, based on 100 parts by weight of the entire colorant. Since the content of the blue pigment is within the above range, the color density of the pixel is excellent, and the occurrence of residue can be suppressed.
The blue pigment may be selected from one or more blue pigments commonly used in conventional curable resin compositions for coloring color filters, and may include copper phthalocyanine blue pigments. Examples of the copper phthalocyanine blue pigment include a compound classified as a pigment in the color index (published by the institute of dyeing (The Society of Dyers and Colourists)). As more specific examples, epsilon-ketophthalocyanine (c.i. pigment blue (color index pigment blue) 15:6, 15:1, 15:2, 15:3, 15:4) can be mentioned.
The blue pigment may be used together with a pigment dispersant, but is not limited thereto. Specifically, the pigment, or the pigment dispersion composition containing the pigment and the pigment dispersant can be produced and used together with the dye.
Specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine and other surfactants, which may be used alone or in combination of two or more.
Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.
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 nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene derivatives other than polyoxyethylene alkyl aryl ethers, ethylene oxide/propylene oxide block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.
Further, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethylene imines, and the like can be mentioned.
The pigment dispersant preferably contains an acrylic ester dispersant (hereinafter, acrylic ester dispersant) containing Butyl Methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Examples of the commercial products of the acrylic acid ester-based dispersants include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150, and the acrylic acid ester-based dispersants may be used alone or in combination of two or more.
The pigment dispersant may be a resin type pigment dispersant other than an acrylic dispersant. Examples of the other resin-type pigment dispersants include known resin-type pigment dispersants, in particular, oil dispersants such as polyurethane, polycarboxylic acid esters represented by polyacrylate, unsaturated polyamide, polycarboxylic acid, (partial) amine salts of polycarboxylic acid, ammonium salts of polycarboxylic acid, alkylamine salts of polycarboxylic acid, polysiloxane, long-chain polyaminoamide phosphate, hydroxyl-containing polycarboxylic acid ester and modified products thereof, or amide formed by the reaction of polyester having free (free) carboxyl group with poly (lower alkylene imine) or salts thereof; a (meth) acrylic acid-styrene copolymer, a (meth) acrylic acid- (meth) acrylate copolymer, a styrene-maleic acid copolymer, a water-soluble resin such as polyvinyl alcohol or polyvinylpyrrolidone, or a water-soluble polymer compound; a polyester; modified polyacrylate; addition products of ethylene oxide/propylene oxide; phosphate esters, and the like.
As the commercial products of the other resin type pigment dispersants, for the cationic resin dispersants, trade names of BYK (pick) chemical company can be exemplified: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DIPER BYK-184; trade name of BASF (BASF) company: 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 Lubirzol (Lu Borun): SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; trade name of Chuanminshen refinement Co., ltd.): HINOACT T-6000, HINOACT T-7000, HINOACT-8000; tradename of Weisu Corp.): AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; trade name of co-Rong chemical Co., ltd.): FLORRENE DOPA-17HF, FLORRENE DOPA-15BHF, FLORRENE DOPA-33, FLORRENE DOPA-44, etc.
The above-mentioned resin type pigment dispersants other than the acrylic acid ester type dispersants may be used alone or in combination of two or more kinds, or may be used in combination with the acrylic acid ester type dispersants.
The content of the pigment dispersant is 1 part by weight or less, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the whole pigment. If the content of the above pigment dispersant is 1 part by weight or less, a pigment having a uniform average particle diameter can be obtained.
The colorant of the present invention may contain additional dyes and/or pigments in addition to the blue dye represented by the above chemical formula 1, the violet dye represented by the above chemical formula 2, and the above blue pigment within a range that does not impair the object of the present invention.
For example, the dye may be a direct dye or a mediator dye, and examples thereof include an oil-soluble dye, an acid dye, a basic dye, an amine salt of an acid dye, and a sulfonamide derivative of an acid dye.
Specifically, examples of the dye include known dyes described in a compound classified as a dye in an index of color (published by the institute of dyeing, the Society of Dyers and Colourists), a dyeing manual (society of dyeing), japanese patent publication No. 2009-235392, japanese patent publication No. 2010-32999, WO10/123071, japanese patent publication No. 2009-51896, japanese patent publication No. 2011-28236, japanese patent publication No. 2010-168831, japanese patent publication No. 2012-219214, japanese patent publication No. 2012-229400, and the like, but are not limited thereto.
Other dyes than the xanthene violet dye represented by chemical formula 2 may be additionally used in an appropriate amount by those skilled in the art within a range that does not impair the object of the present invention. For example, the dye may be contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the entire colorant, but the present invention is not limited thereto.
The pigment may be an organic pigment or an inorganic pigment which is generally used in the art, and various pigments used in printing inks, inkjet inks, and the like may be used.
Specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, pyrenone pigments, and dipyridonesOxazine pigments, anthraquinone pigments, dianthrone-based pigments, anthrapyrimidine pigments, anthra-scarfinquinone (anthanthrone) pigments, indanthrone (indanthrone) pigments, flavanthrone pigments, pyranthrone (pyranthrone) pigments, diketopyrrolopyrrole pigments, and the like.
The inorganic pigment may be a metal compound such as a metal oxide or a metal complex, and specifically, may be a metal oxide or a composite metal oxide such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black, or the like.
In particular, the organic pigment and the inorganic pigment are specifically classified into a pigment in the color index (published by the institute of dyeing (The society of Dyers and Colourists)), and more specifically, a pigment having the following color index (c.i.) number is exemplified, but the pigment is not necessarily limited thereto, and two or more kinds thereof may be used singly or in combination.
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;
c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264;
c.i. pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;
c.i. pigment blue 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.
Among the above-exemplified c.i. pigment pigments, a pigment selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 150, c.i. pigment yellow 185, c.i. pigment orange 38, c.i. pigment red 122, c.i. pigment red 166, c.i. pigment red 177, c.i. pigment red 208, c.i. pigment red 242, c.i. pigment red 254, c.i. pigment red 255, c.i. pigment violet 23, c.i. pigment green 7, c.i. pigment green 36, and c.i. pigment green 58 is preferably used.
The content of the pigment may be 0.1 to 10 parts by weight relative to 100 parts by weight of the entire colorant, but is not limited thereto.
The content of the colorant may be 3 to 10 parts by weight, preferably 4 to 9 parts by weight, more preferably 5 to 9 parts by weight, based on 100 parts by weight of the entire solid content of the blue dye-containing colored curable resin composition, and in this case, there is an advantage that the color density of the pixel is excellent and the occurrence of a residue phenomenon is suppressed.
Alkali-soluble resin
The blue dye-containing colored curable resin composition of the present invention comprises an alkali-soluble resin comprising a first resin and a second resin, wherein the first resin comprises a repeating unit represented by the following chemical formula 3 and has a glass transition temperature of 0 ℃ or higher, and the second resin comprises a repeating unit represented by the following chemical formula 4 and has a glass transition temperature of less than 0 ℃.
The colored curable resin composition containing a blue dye of the present invention contains an alkali-soluble resin containing the first resin, and therefore has advantages of excellent coatability, and excellent reliability, adhesion, and developability.
Further, the colored curable resin composition containing a blue dye of the present invention has the following advantages because it contains an alkali-soluble resin containing the above second resin: the inclined plane (taper) characteristic is improved, and the problem of deterioration of the spectral distribution and the mask matching recognition can be suppressed by having excellent fluidity.
Without wishing to be limited by theory, alkali-soluble resins including the repeating units represented by the following chemical formula 3 and chemical formula 4 are easily decomposed by heat. Specifically, the ether bond between the adjacent oxygen atom and the adjacent carbon atom in the main chain is easily broken, and the compound is decomposed into a stable compound produced on the side of (meth) acrylic acid and further the carbon atom. Therefore, an ester crosslinked structure between the repeating units containing a hydroxyl group is formed, and reliability can be improved.
The first resin contains a repeating unit represented by the following chemical formula 3.
[ chemical formula 3]
In the above-mentioned chemical formula 3,
r21 is hydrogen or methyl, and the catalyst is a catalyst,
r22 is a C1-C7 linear or branched alkyl group.
The straight-chain or branched alkyl group described above may be used in the context of the alkyl group described above.
The glass transition temperature of the first resin is 0 ℃ or higher. Specifically, the glass transition temperature may be 0 to 250 ℃.
Since the glass transition temperature of the first resin satisfies the above range, there is an advantage in that reliability and adhesion can be improved.
In still another embodiment of the present invention, the content of the first resin may be 1 to 5 parts by weight, and preferably 1.5 to 5 parts by weight, based on 100 parts by weight of the entire colored curable resin composition.
The second resin contains a repeating unit represented by the following chemical formula 4.
[ chemical formula 4]
In the above-mentioned chemical formula 4, a catalyst,
r23 is hydrogen or methyl, and the catalyst is a compound,
r24 is a C4-C40 linear or branched alkyl group,
wherein the above chemical formulas 3 and 4 are different from each other.
The above straight-chain or branched alkyl groups may be used as described above.
The glass transition temperature of the second resin is less than 0 ℃. Specifically, the glass transition temperature may be less than 0 ℃ and not less than-100 ℃, more specifically, may be 0 to-40 ℃.
Since the glass transition temperature of the second resin satisfies the above range, there is an advantage in that excellent fluidity can be imparted.
In still another embodiment of the present invention, the content of the second resin may be 1 to 3 parts by weight, and preferably 2 to 3 parts by weight, based on 100 parts by weight of the entire colored curable resin composition.
The first resin and the second resin may be obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group as an essential component in order to be soluble in an alkali developer used in a development treatment step at the time of patterning, in addition to the repeating unit represented by the above chemical formula 3 and the repeating unit represented by the above chemical formula 4.
Specific examples of the ethylenically unsaturated monomer having a carboxyl group 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 their dicarboxylic acids; preferred examples of the mono (meth) acrylate include acrylic acid and methacrylic acid, which are polymers having carboxyl groups and hydroxyl groups at both terminals, such as ω -carboxyl polycaprolactone mono (meth) acrylate.
In order to ensure additional developability of the first resin and the second resin, a hydroxyl group may be added, and in this case, there is an advantage that an ester crosslinked structure with the first resin and the second resin may be formed and reliability becomes more excellent, which is preferable.
The hydroxyl groups are added to the first resin and the second resin, and the resin may be produced by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group, or by additionally reacting a compound having a glycidyl group with a copolymer of an ethylenically unsaturated monomer having a carboxyl group. The compound having a glycidyl group can be produced by further reacting a copolymer of an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group.
Specific examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and N-hydroxyethyl acrylamide, and preferably 2-hydroxyethyl (meth) acrylate, and two or more of them may be used in combination.
Specific examples of the compound having a glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butylbenzoate, glycidyl stearate, allyl glycidyl ether, glycidyl methacrylate, and the like, and preferably butyl glycidyl ether, allyl glycidyl ether, and glycidyl methacrylate may be used in combination of two or more.
The first resin and the second resin may be obtained by copolymerizing the monomers and the unsaturated monomers copolymerizable with the monomers.
Specific examples of the other copolymerizable unsaturated monomer include, but are not limited to, the following: aromatic vinyl compounds such as 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, N-p-methoxyphenylmaleimide and N-p-methoxyphenylmaleimide;
(meth) acrylic acid ringAmyl ester, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ]Alicyclic (meth) acrylates such as decan-8-yl (meth) acrylate, 2-dicyclopentanoxyethyl (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-trifluoromethyloxybutane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, and 2- (methacryloyloxymethyl) -4-trifluoromethyloxybutane. The above exemplified monomers may be used each alone or in combination of two or more.
The alkali-soluble resin preferably has a polystyrene-equivalent weight-average molecular weight (hereinafter, abbreviated as "weight-average molecular weight") of 3,000 to 15,000 as measured by gel permeation chromatography (GPC; tetrahydrofuran is used as an eluting solvent). When the weight average molecular weight of the alkali-soluble resin is within the above range, the film retention rate is high, and the solubility of the non-exposed portion in the developer is excellent, so that the resolution can be improved.
In order to ensure compatibility with the dye and stability with time of the colored curable resin composition containing the blue dye, the acid value of the alkali-soluble resin is preferably in the range of 10 to 110KOH mg/g. When the acid value of the alkali-soluble resin is less than 10KOH mg/g, it is difficult for the colored curable resin composition containing a blue dye to secure sufficient developability, and when it exceeds 110KOH mg/g, the linearity of the pattern tends to decrease, the compatibility with the dye tends to decrease, and the dye in the colored curable resin composition containing a blue dye precipitates or the stability with time of the colored curable resin composition containing a blue dye tends to decrease, and the viscosity tends to increase.
Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the alkali-soluble resin, and is usually obtained by titration using an aqueous potassium hydroxide solution.
In still another embodiment of the present invention, the alkali-soluble resin may be contained in an amount of 2 to 8 parts by weight, preferably 1.5 to 6 4 parts by weight, and more preferably 2 to 4 parts by weight, based on 100 parts by weight of the entire colored curable resin composition.
When the content of the alkali-soluble resin is within the above range, there is an advantage that compatibility with blue and violet dyes is improved and reliability is improved, so that it is preferable.
In still another embodiment of the present invention, one or more selected from the group consisting of a photopolymerizable compound, a photopolymerization initiator, a solvent, and an additive may be further included.
Photopolymerizable compound
The photopolymerizable compound is a compound polymerizable by the action of light and a photopolymerization initiator, and examples thereof include monofunctional monomers, difunctional monomers, and other polyfunctional monomers.
Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. 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, butanediol dimethacrylate, hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, and the like.
Specific examples of the trifunctional 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, and 3-methylpentanediol di (meth) acrylate.
Specific examples of the tetrafunctional monomer include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol tetraacrylate, tetramethylolmethane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, glycerol tetramethacrylate, and the like.
Specific examples of the pentafunctional monomer include dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol monohydroxypentamethacrylate, and the like.
Specific examples of the hexafunctional monomer include dipentaerythritol hexaacrylate and dipentaerythritol hexamethacrylate.
Among them, the photopolymerizable compound is preferably a polyfunctional monomer having a difunctional or higher functionality, and particularly preferably a polyfunctional monomer having a five-functional or higher functionality.
The content of the photopolymerizable compound may be 5 to 50 parts by weight, and preferably 7 to 45 parts by weight, based on 100 parts by weight of the entire solid content of the blue dye-containing colored curable resin composition. When the content of the photopolymerizable compound is within the above range, the strength and smoothness of the pixel portion are improved, which is preferable.
Photopolymerization initiator
The photopolymerization initiator preferably contains an acetophenone compound. Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1 (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzil dimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, and oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propan-1-one, and preferable examples include 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one.
The acetophenone compound may be used alone or in combination of two or more. The photopolymerization initiator may be used in combination with other types of photopolymerization initiators other than acetophenone-based compounds. Examples of the photopolymerization initiator of the other type include a living radical generator, a sensitizer, and an acid generator, which generate living radicals by irradiation with light. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, and triazine compounds.
Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Specific examples of the benzophenone-based compound include methyl o-benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4 ' -methyl diphenyl sulfide, 3', 4' -tetra (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone. Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone. Specific examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, and 2, 4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethylene]-1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethylene]-1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethylene ]-1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) ethylene]-1,3, 5-triazine, and the like. Specific examples of the sensitizer include 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide and 2,2-bis (o-chlorophenyl) -4,4', 5' -tetraphenyl-1, 2' -biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzil, 9, 10-phenanthrenequinone, camphorquinone, phenylglyoxylic acid methyl ester, titanocene compound, and the like. Specific examples of the acid generator include 4-hydroxyphenyl dimethyl sulfideP-toluenesulfonate, 4-hydroxyphenyl dimethyl sulfide->Hexafluoroantimonate, 4-acetoxyphenyl dimethyl sulfide->P-toluenesulfonate, 4-acetoxyphenyl methyl benzylthio->Hexafluoroantimonate, triphenylthio +.>P-toluenesulfonate, triphenylthio ∈ ->Hexafluoroantimonate, diphenyliodo +.>P-toluenesulfonate, diphenyliodo->Hexafluoroantimonate and the like->Salts, or nitrobenzyl tosylate, benzoin tosylate, and the like.
Among the above compounds, there are also compounds that simultaneously generate active radicals and acids, and for example, triazine compounds are also used as acid generators.
The content of the photopolymerization initiator may be 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the entire alkali-soluble resin and the photopolymerizable monomer.
When the content of the photopolymerization initiator is within the above range based on the above standard, the colored curable resin composition containing the blue dye is preferably provided with an advantage that the exposure time is shortened by increasing the sensitivity, and thus the productivity can be improved while maintaining high resolution.
The photopolymerization initiator may be used in combination with a photopolymerization initiator auxiliary. The photopolymerization initiator aid may be used for promoting polymerization of a photopolymerizable monomer that is polymerized by a photopolymerization initiator.
Examples of the photopolymerization initiator include amine compounds and alkoxyanthracene compounds.
Specific examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4' -bis (dimethylamino) benzophenone (generally known as Michler's ketone), 4' -bis (diethylamino) benzophenone, and 4,4' -bis (ethylmethylamino) benzophenone, and among these, 4' -bis (diethylamino) benzophenone is preferable.
Specific examples of the alkoxyanthracene compound include 9, 10-dimethoxy anthracene, 2-ethyl-9, 10-dimethoxy anthracene, 9, 10-diethoxy anthracene, and 2-ethyl-9, 10-diethoxy anthracene. The photopolymerization initiator may be used alone or in combination of two or more. As the photopolymerization initiator, those having trade names of EAB-F (manufactured by Baogu chemical Co., ltd.) and the like can be used.
Specific examples of the preferable combination of the photopolymerization initiator and the photopolymerization initiator auxiliary agent include: diethoxyacetophenone with 4,4' -bis (diethylamino) benzophenone; 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one with 4,4' -bis (diethylamino) benzophenone; 2-hydroxy-2-methyl-1-phenylpropane-1-one with 4,4' -bis (diethylamino) benzophenone; 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one with 4,4' -bis (diethylamino) benzophenone; 1-hydroxycyclohexylphenyl ketone with 4,4' -bis (diethylamino) benzophenone; oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propan-1-one with 4,4' -bis (diethylamino) benzophenone; the combination of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 4,4 '-bis (diethylamino) benzophenone is preferred, and the combination of 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and 4,4' -bis (diethylamino) benzophenone is preferred.
When the photopolymerization initiator and the photopolymerization initiator auxiliary are used together, the content of the photopolymerization initiator auxiliary is preferably 0.01 to 5 mol based on 1 mol of the photopolymerization initiator.
When the content of the photopolymerization initiator is within the above content range, the sensitivity of the colored curable resin composition containing a blue dye is further improved, and the productivity of a color filter formed using the composition is improved, which is preferable.
Solvent(s)
The solvent used in the general color curable resin composition may be used without any particular limitation as long as it is effective in dissolving other components contained in the color curable resin composition, and ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, and the like are particularly preferable.
Specific examples of the solvent 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, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxyamyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ -butyrolactone.
The solvent is preferably an organic solvent having a boiling point of 100 to 200℃in terms of coatability and drying properties, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like can be used.
The above exemplified solvents may be used singly or in combination of two or more, and may be 60 to 90 parts by weight, preferably 70 to 85 parts by weight, based on 100 parts by weight of the entire blue dye-containing colored curable resin composition of the present invention.
When the content of the solvent is within the above range, the effect of improving the coating property can be provided when the coating is performed by a coating device such as a roll coater, a spin coater, a slot coater (sometimes referred to as a die coater), or an inkjet printer.
Additive agent
The colored curable resin composition containing a blue dye of the present invention may further contain a usual additive within a range not impairing the object of the present invention. Specifically, the additive may be optionally added, and examples thereof include other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-coagulants.
Specific examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester and polyurethane.
The curing agent is used for deep curing and for 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 epoxy resin, hydrogenated bisphenol a epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, glycidyl ester resin, glycidyl amine resin, brominated derivatives of such epoxy resin, aliphatic, alicyclic or aromatic epoxy compounds other than 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 include carbonate dioxetane, xylene dioxetane, adipate dioxetane, terephthalate dioxetane, and cyclohexanedicarboxylic acid dioxetane.
The curing agent may be used in combination with a co-curing compound, and the co-curing compound may be used together with the curing agent to ring-open polymerize the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound. Examples of the auxiliary curing 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 trade name ADEKA HARDENER EH-700 (manufactured by ADEKA corporation), trade name RIKACID HH (manufactured by new japan physical and chemical Co., ltd.), trade name MH-700 (manufactured by new japan physical and chemical Co., ltd.), and the like. The above-exemplified curing agents may be used singly or in combination.
The surfactant may be used to further improve the film forming property of the colored curable resin composition containing a blue dye, and a fluorine-based surfactant, a silicone-based surfactant, or the like is preferably used.
Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc. of Dow Kang Ningdong silicone company, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452, etc. of GE Toshiba silicone company. Examples of the fluorine-based surfactant include Megafac F-470, F-471, F-475, F-482, F-489, commercially available from Dain ink chemical industry Co., 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-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 trimethoxysilane, and 3-isocyanatopropyl triethoxysilane. The above-exemplified adhesion promoters may be used singly or in combination of two or more. The adhesion promoter may be contained in an amount of usually 0.01 to 10 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the entire solid content of the colored curable resin composition containing the blue dye.
Specific examples of the antioxidant include 2,2' -thiobis (4-methyl-6-t-butylphenol) and 2, 6-di-t-butyl-4-methylphenol.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like.
Specific examples of the anticoagulant include sodium polyacrylate.
The above-mentioned additives may be used in addition in an appropriate amount within a range not impairing the object of the present application. For example, the content of the additive may be 0.01 to 10 parts by weight, preferably 0.02 to 5 parts by weight, more preferably 0.02 to 3 parts by weight, based on 100 parts by weight of the entire curable resin composition containing the blue dye.
< color Filter >
Another embodiment of the present application relates to a color filter comprising a cured product of the above-described colored curable resin composition containing a blue dye.
The color filter of the present application has advantages of excellent pattern angle, excellent chemical resistance and mechanical properties, especially excellent heat resistance, light resistance and reliability when applied to an image display device.
The color filter includes a substrate and a pattern layer formed on an upper portion of the substrate.
The substrate may be a substrate of the color filter itself or may be a portion of a display device or the like where the color filter is located, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyether sulfone (PES), polycarbonate (PC), or the like.
The pattern layer may be a layer containing the blue dye-containing curable resin composition of the present invention, which is formed by applying the blue dye-containing curable resin composition, exposing the resultant layer to light in a predetermined pattern, developing the resultant layer, and thermally curing the resultant layer.
The color filter including the substrate and the pattern layer as described above may further include a partition wall formed between the patterns, and may further include a black matrix. In addition, the color filter may further include a protective film formed on an upper portion of the pattern layer of the color filter.
< image display device >
Still another embodiment of the present invention relates to an image display device including the above-described color filter.
The color filter of the present invention can be applied not only to a general liquid crystal display device but also to various image display devices such as an electroluminescent display device, a plasma display device, and a field emission display device.
The color filter and the image display device comprising the cured product of the colored curable resin composition containing a blue dye of the present invention have the advantages of excellent pattern angle, excellent residue characteristics, film retention, chemical resistance, and mechanical properties, in particular, excellent heat resistance, light resistance, and reliability.
Hereinafter, for the purpose of specifically describing the present specification, examples will be described in detail. However, the embodiments of the present specification may be modified into various other forms, and the scope of the present specification should not be construed as being limited to the embodiments described in detail below. The embodiments of the present description are provided to more fully explain the present description to one skilled in the art. The content "%" and "parts" are expressed by weight unless otherwise specified.
< synthesis example: colorant-
Synthesis example 1: coloring agent (A-1)
The following reaction was carried out under a nitrogen atmosphere. 15.3 parts by weight of N-methylaniline (manufactured by Tokyo chemical industry Co., ltd.) and 60 parts by weight of N, N-dimethylformamide were placed in a flask equipped with a condenser and a stirring device, and the mixed solution was cooled with ice. 5.7 parts by weight of 60% sodium hydride (manufactured by Tokyo chemical industries Co., ltd.) was slowly added thereto over 30 minutes under ice-cooling, and then stirred for 1 hour while being warmed to room temperature. 10.4 parts by weight of 4, 4' -difluorobenzophenone (manufactured by Tokyo chemical industry Co., ltd.) was slowly added to the reaction solution, and the mixture was stirred at room temperature for 24 hours. After 200 parts by weight of ice water was slowly added to the reaction solution, the reaction solution was allowed to stand at room temperature for 15 hours, and water was removed by decantation to obtain a viscous solid as a residue. After 60 parts by weight of methanol was added to the viscous solid, the mixture was stirred at room temperature for 15 hours. The precipitated solid was separated by filtration and purified by column chromatography. The refined pale yellow solid was dried at 60℃under reduced pressure, thereby obtaining 9.8 parts by weight of the compound of chemical formula 5.
[ chemical formula 5]
/>
[ chemical formula 6]
Into a flask equipped with a condenser and a stirring device, 8.2 parts by weight of the compound represented by the above chemical formula 6, 10 parts by weight of the compound represented by the above chemical formula 5, and 20 parts by weight of toluene were charged, followed by adding 12.2 parts by weight of phosphorus oxychloride, and stirring at 98℃for 3 hours. Then, the reaction mixture was cooled to room temperature, and then diluted with 170 parts by weight of isopropanol. Then, the diluted reaction solution was poured into 300 parts by weight of saturated brine, and 100 parts by weight of toluene was added thereto and stirred for 30 minutes. Then, stirring was stopped, and the mixture was allowed to stand for 30 minutes to separate an organic layer and an aqueous layer. After the aqueous layer was removed by a liquid separation operation, the organic layer was washed with 300 parts by weight of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The resulting organic layer was distilled off the solvent with an evaporator, thereby obtaining a blue-violet solid. The bluish violet solid was further dried at 60 ℃ under reduced pressure, thereby obtaining 18.4 parts by weight of the compound of the following chemical formula 7.
[ chemical formula 7]
Into a flask equipped with a condenser and a stirring apparatus, 8 parts by weight of the compound of chemical formula 7 and 396 parts by weight of methanol were charged, and then stirred at room temperature for 30 minutes to prepare a blue solution. Then, 396 parts by weight of water was added to the blue solution, followed by stirring at room temperature for 30 minutes, to obtain a reaction solution. Into a beaker, 53 parts by weight of water was charged, and 11.8 parts by weight of Keggin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts by weight of methanol were further charged into the water, and mixed at room temperature under an air atmosphere to prepare a phosphotungstic acid solution. The resulting phosphotungstic acid solution was added dropwise to the previously produced reaction solution over 1 hour. After stirring for 30 minutes at room temperature, the mixture was filtered to give a blue solid. The blue solid obtained was poured into 200 parts by weight of methanol, dispersed for 1 hour, and then, the filtration was repeated 2 times. The blue solid obtained by the corresponding operation was poured into 200 parts by weight of water, dispersed for 1 hour, and then the filtration operation was repeated 2 times. The blue solid obtained by the corresponding operation was dried at 60 ℃ under reduced pressure, thereby obtaining 17.1 parts by weight of the compound of chemical formula 8.
[ chemical formula 8]
Synthesis example 2: coloring agent (A-2)
According to the method described in synthesis example 1, a phosphomolybdic acid solution was added instead of Keggin-type phosphotungstic acid to obtain a compound represented by chemical formula 9.
[ chemical formula 9]
< synthesis example: alkali-soluble resin ]
Synthesis example 3: compounds of formula 3 (formulas 3-1, B-1)
800g of propylene glycol monomethyl ether acetate was introduced into a reaction vessel equipped with a thermometer, a stirrer, a gas introduction pipe, a condenser, and a drip introduction port, and after nitrogen substitution, the reaction vessel was heated to 90 ℃. On the other hand, as the dropping tank (A), 60g of N-benzylmaleimide, 80g of glycidyl methacrylate, 120g of methacrylic acid and 100g of t-butyl methacrylate were stirred and mixed in a beaker, and as the dropping tank (B), 21g of N-dodecylmercaptan and 84g of propylene glycol monomethyl ether acetate were stirred and mixed. After the temperature of the reaction tank reached 90 ℃, the same temperature was maintained, and the polymerization was carried out by starting the dropwise addition from the dropwise addition tank over 3 hours. After the completion of the dropwise addition, the temperature was raised to 115℃for 30 minutes at 90℃and maintained for 90 minutes.
The obtained alkali-soluble resin solution was analyzed, and as a result, the weight-average molecular weight was 19000, the acid value was 100 mg KOH/g, and the resin solid content was 34.2% by mass.
Synthesis example 4: compounds of formula 3 (formulas 3-2, B-2)
800g of propylene glycol monomethyl ether acetate was introduced into a reaction vessel equipped with a thermometer, a stirrer, a gas introduction pipe, a condenser, and a drip introduction port, and after nitrogen substitution, the reaction vessel was heated to 90 ℃. On the other hand, as the dropping tank (A), 60g of N-benzylmaleimide, 60g of glycidyl methacrylate, 100g of methacrylic acid and 140g of t-butylphenyl methacrylate were stirred and mixed in a beaker, and as the dropping tank (B), 21g of N-dodecylmercaptan and 84g of propylene glycol monomethyl ether acetate were stirred and mixed. After the temperature of the reaction tank reached 90 ℃, the same temperature was maintained, and the polymerization was carried out by starting the dropwise addition from the dropwise addition tank over 3 hours. After the completion of the dropwise addition, the temperature was raised to 115℃for 30 minutes at 90℃and maintained for 90 minutes.
The obtained alkali-soluble resin solution was analyzed, and as a result, the weight-average molecular weight was 19000, the acid value was 100 mg KOH/g, and the resin solid content was 34.5% by mass.
Synthesis example 5: compounds of formula 4 (formulas 4-1, B-3)
800g of propylene glycol monomethyl ether acetate was introduced into a reaction vessel equipped with a thermometer, a stirrer, a gas introduction pipe, a condenser, and a drip introduction port, and after nitrogen substitution, the reaction vessel was heated to 90 ℃. On the other hand, 50g of N-benzylmaleimide, 100g of glycidyl methacrylate, 120g of methacrylic acid and 100g of isopropyl methacrylate were stirred and mixed in a beaker as a dropping tank (A), and 21g of N-dodecylmercaptan and 84g of propylene glycol monomethyl ether acetate were stirred and mixed as a dropping tank (B). After the temperature of the reaction tank reached 90 ℃, the same temperature was maintained, and the polymerization was carried out by starting the dropwise addition from the dropwise addition tank over 3 hours. After the completion of the dropwise addition, the temperature was raised to 115℃for 30 minutes at 90℃and maintained for 90 minutes.
The obtained alkali-soluble resin solution was analyzed, and as a result, the weight-average molecular weight was 12000, the acid value was 50 mg KOH/g, and the resin solid content was 35.8% by mass.
Synthesis example 6: compounds of formula 4 (formulas 4-2, B-4)
800g of propylene glycol monomethyl ether acetate was introduced into a reaction vessel equipped with a thermometer, a stirrer, a gas introduction pipe, a condenser, and a drip introduction port, and after nitrogen substitution, the reaction vessel was heated to 90 ℃. On the other hand, 50g of N-benzylmaleimide, 100g of glycidyl methacrylate, 120g of methacrylic acid and 100g of isodecyl methacrylate were stirred and mixed in a beaker as a dropping tank (A), and 21g of N-dodecylmercaptan and 84g of propylene glycol monomethyl ether acetate were stirred and mixed as a dropping tank (B). After the temperature of the reaction tank reached 90 ℃, the same temperature was maintained, and the polymerization was carried out by starting the dropwise addition from the dropwise addition tank over 3 hours. After the completion of the dropwise addition, the temperature was raised to 115℃for 30 minutes at 90℃and maintained for 90 minutes.
The obtained alkali-soluble resin solution was analyzed, and as a result, the weight-average molecular weight was 12000, the acid value was 50 mg KOH/g, and the resin solid content was 35.8% by mass.
Synthesis example 7: alkali-soluble resin (B-5)
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02L/min to prepare a nitrogen atmosphere, and 200 parts by weight of 3-methoxy-1-butanol and 105 parts by weight of 3-methoxybutyl acetate were added thereto and heated to 70℃while stirring. Then, 60 parts by weight of methacrylic acid and 240 parts by weight of 3, 4-epoxytricyclo [5.2.1.02,6] decyl acrylate were dissolved in 140 parts by weight of 3-methoxybutyl acetate to prepare a solution, and the solution was added dropwise to a flask kept at 70℃over 4 hours using a dropping funnel. On the other hand, a solution of 30 parts by weight of the polymerization initiator 2, 2' -azobis (2, 4-dimethylvaleronitrile) dissolved in 225 parts by weight of 3-methoxybutyl acetate was added dropwise to the flask via another dropping funnel over 4 hours. After completion of the dropwise addition of the solution of the polymerization initiator, the temperature was maintained at 70℃for 4 hours, and then the mixture was cooled to room temperature, whereby a resin (B-1) solution having a solid content of 32.6% and an acid value of 110mg-KOH/g (in terms of solid content) was obtained. The weight average molecular weight Mw of the resulting resin (B-1) was 13,400 and the molecular weight distribution was 2.50.
Production example 1: production of coloring Dispersion (1)
10 parts by weight of a compound of chemical formula 8, 2 parts by weight of a dispersant (BYK (registered trademark) -LPN6919 (manufactured by Pick chemical Japan)), 4 parts by weight of a resin B-1 (converted into a solid content), 84 parts by weight of propylene glycol monomethyl ether acetate, and 300 parts by weight of zirconia beads of 0.2mm were mixed, and the mixture was shaken for 6 hours using a paint conditioner (manufactured by Red Devil) and then the zirconia beads were removed by filtration, thereby producing a colored dispersion (1).
Production example 2: production of coloring Dispersion (2)
A colored dispersion (2) was produced in the same manner as in the production of the colored dispersion (1), except that the compound of the above chemical formula 9 was used instead of the compound of the above chemical formula 8.
Examples and comparative examples: production of colored curable resin composition containing blue dye
Colored curable alkali-soluble resin compositions (unit: parts by weight) prepared in accordance with the components and ratios described in the following table 1 were produced.
TABLE 1
Experimental example
Color filters were produced using the curable resin compositions containing blue dye produced according to examples and comparative examples, and the tinting strength, brightness, contrast, sensitivity, development speed, adhesion, heat resistance, light resistance, and NMP solvent resistance at this time were measured according to the following methods, and the results are shown in table 2 below.
Color filter fabrication
The colored curable resin compositions containing blue dye produced according to examples and comparative examples were applied to a glass substrate (# 1737, manufactured by dakanin corporation) by spin coating, and then placed on a hot plate, and maintained at a temperature of 100 ℃ for 3 minutes to form a thin film. Next, a test photomask having a pattern in which the transmittance was stepwise changed in the range of 1 to 100% was placed on the film, the distance between the test photomask and the test photomask was set to 1000 μm, and the test photomask was irradiated with an extra-high pressure mercury lamp (USH-250D, manufactured by Niuwei motor Co., ltd.) at 40mJ/cm under an atmospheric atmosphere 2 Light irradiation was performed at an exposure dose (365 nm). The film irradiated with ultraviolet rays was developed in a KOH aqueous solution developing solution having a pH of 12.5 for 70 seconds by a spray development instrument. The glass substrate coated with the thin film was washed with distilled water, then dried by blowing nitrogen gas, and heated in a heating oven at 230 ℃ for 20 minutes to produce a color filter. The pattern shape (film) thickness of the manufactured color filter was 2.7 μm.
(1) Tinting strength
The content ratio of the pigment added to the color curable resin composition was measured for the purpose of producing a target coating film thickness for the produced color filter, and the coloring power was evaluated according to the following criteria, and the results are shown in table 2 below.
< benchmark >
O: tinting strength <0.45
Delta: the tinting strength is more than or equal to 0.45 and less than or equal to 0.5
X: the tinting strength is more than or equal to 0.5
(2) Brightness of light
For the pixel, a chromaticity coordinate value (x, Y) and a luminance (Y) of CIE color coordinates were measured with a C light source and a 2-degree viewing angle by using a spectrocolorimeter (manufactured by tokyo electric color (ltd.) to obtain a luminance (Y) at the time of (x, Y) = (0.141,0.089).
The larger the Y value, the higher the luminance. The evaluation results are shown in table 2 below.
< benchmark >
O: the brightness is more than or equal to 4.7
Delta: the brightness is more than or equal to 4.5 and less than or equal to 4.7
X: brightness <4.5
(3) Contrast ratio
The contrast of the colored layer (film) produced as described above was measured by a contrast meter BM-5A type of the rubbing company, and evaluated according to the following evaluation criteria, and the results are shown in Table 2 below. The measurement standard was defined as a standard of 1/30,000 of the contrast of the glass substrate (before the colored layer was formed).
< benchmark >
◎：CR≥12,000
○：10,000≤CR<12,000
△：8,000≤CR<10,000
×：CR<8,000
(4) Sensitivity and development speed
The development speed was measured by measuring the time for the non-exposed thin film portion to start peeling off during development in the process of manufacturing the color filter. In addition, in order to form an unpatterned peeled film after development in the course of the above-mentioned color filter production, the minimum exposure (mJ/cm) required was measured 2 ) I.e., sensitivity, and the results are shown in table 2 below.
(5) Adhesion of
The colored substrate manufactured according to the above (1) was cut into 100 lattice structures in a region of 10×10mm, and then an adhesive tape was attached thereto, and the number of lattices (remaining number/100) left without dropping when pulled up by a vertical force was marked, and the results thereof are described in the following table 2.
(6) Heat resistance
After the final patterning, the color difference (heat resistance) before and after 230 ℃/2hr was evaluated by comparison. At this time, the color difference is represented by L * 、a * 、b * The color difference in the defined three-dimensional colorimeter is calculated by the following equation 1, and the smaller the color difference is, the more reliable the color filter can be manufactured. The results are shown in Table 2 below.
[ mathematics 1]
△Eab * ＝[(△L * ) 2 +(△a * ) 2 +(△b * ) 2 ] 1/2
(7) Light resistance
After the final pattern was formed, the color difference (light resistance) of the Xe lamp before and after 300W/200hr was evaluated by comparison. In this case, the expression L is * 、a * 、b * The above equation (1) defining the color difference in the three-dimensional colorimeter, the smaller the color difference is, the more reliable the color filter can be manufactured. The results are shown in Table 2 below.
(8) NMP solvent resistance
After cutting the colored substrate produced according to the production of the colored substrate (1) above into 3×3cm, the substrate was immersed in 14.6ml of NMP solution at 80 ℃ for 40 minutes. Thereafter, absorbance was evaluated for the liquid by an ultraviolet-visible light spectrometer (UV-Vis spectrometer), and the results thereof are shown in table 2 below.
TABLE 2
As shown in table 2, it was confirmed that the colored curable resin compositions containing blue dye of examples 1 to 6 exhibited excellent spectroscopic characteristics, sensitivity and development speed, and excellent adhesion, heat resistance, light resistance and reliability such as NMP solvent resistance, as compared with the colored curable resin compositions of comparative examples 1 to 4.

Claims (7)

1. A colored curable resin composition containing a blue dye, which comprises a colorant, an alkali-soluble resin, a photopolymerizable compound containing a photopolymerizable monomer having a functionality of more than two, a photopolymerization initiator and a solvent,
The colorant comprises a blue dye represented by the following chemical formula 1, a violet dye represented by the following chemical formula 2, and a copper phthalocyanine blue pigment,
the alkali-soluble resin comprises a first resin having a repeating unit represented by the following chemical formula 3 and a glass transition temperature of 0 ℃ or higher, a second resin having a repeating unit represented by the following chemical formula 4 and a glass transition temperature of less than 0 ℃,
the content of the blue dye represented by chemical formula 1 is 20 to 40 parts by weight relative to 100 parts by weight of the entire colorant,
the content of the violet dye represented by chemical formula 2 is 5 to 25 parts by weight relative to 100 parts by weight of the whole colorant,
the content of the copper phthalocyanine blue pigment is 40 to 60 parts by weight based on 100 parts by weight of the entire colorant,
the content of the photopolymerizable compound is 5 to 50 parts by weight based on 100 parts by weight of the solid content of the colored curable resin composition as a whole,
the content of the photopolymerization initiator is 0.1 to 40 parts by weight relative to 100 parts by weight of the total of the alkali-soluble resin and the photopolymerizable compound,
the content of the solvent is 60 to 90 parts by weight relative to 100 parts by weight of the whole colored curable resin composition,
Chemical formula 1
In the above-mentioned chemical formula 1,
r1 to R4 each independently represent an amino group which may be substituted, a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, an alkyl group having 2 to 20 carbon atoms which may be substituted with an oxygen atom by a methylene group contained in the alkyl group, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, or a hydrogen atom,
r1 and R2 may be bonded to form a ring together with the nitrogen atom to which they are bonded, R3 and R4 may be bonded to form a ring together with the nitrogen atom to which they are bonded,
r5 to R12 each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom may be inserted between methylene groups constituting the alkyl group,
r6 and R10 may be bonded to each other, and can be formed with-NH- -O-, -S-or-SO 2 -，
In R1 to R4 and R5 to R12, adjacent methylene groups are not simultaneously substituted with oxygen atoms, and a terminal methylene group of an alkyl group is not substituted with an oxygen atom,
t1 represents an aromatic heterocycle which may have a substituent,
[Y] m- represents an m-valent anion containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus,
m represents an integer of 2 to 14,
chemical formula 2
In the chemical formula 2 described above, a compound having a structure of,
r13 to R18 are each independently hydrogen or C1-C5 alkyl,
r19 and R20 are each independently hydrogen, COOH, COO - 、SO 3 - 、SO 3 H、SO 3 Na、COOCH 3 Or COOCH 2 CH 3 ，
Chemical formula 3
In the chemical formula 3 described above, the chemical formula,
r21 is hydrogen or methyl, and the catalyst is a catalyst,
r22 is a C1-C7 linear or branched alkyl group,
chemical formula 4
In the chemical formula 4 described above, the chemical formula,
r23 is hydrogen or methyl, and the catalyst is a compound,
r24 is a C4-C40 linear or branched alkyl group,
wherein the chemical formulas 3 and 4 are different from each other.
2. The blue dye-containing colored curable resin composition according to claim 1, wherein the content of the first resin is 1 to 5 parts by weight based on 100 parts by weight of the entire colored curable resin composition.
3. The blue dye-containing colored curable resin composition according to claim 1, wherein the content of the second resin is 1 to 3 parts by weight based on 100 parts by weight of the entire colored curable resin composition.
4. The blue dye-containing colored curable resin composition according to claim 1, wherein the alkali-soluble resin is contained in an amount of 2 to 8 parts by weight based on 100 parts by weight of the entire colored curable resin composition.
5. The colored curable resin composition containing a blue dye according to claim 1, further comprising an additive.
6. A color filter comprising a cured product of the colored curable resin composition containing a blue dye according to any one of claims 1 to 5.
7. An image display device comprising the color filter of claim 6.
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