CN111240152B - Colored photosensitive resin composition, color filter and display device - Google Patents
Colored photosensitive resin composition, color filter and display device Download PDFInfo
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- CN111240152B CN111240152B CN201911031907.3A CN201911031907A CN111240152B CN 111240152 B CN111240152 B CN 111240152B CN 201911031907 A CN201911031907 A CN 201911031907A CN 111240152 B CN111240152 B CN 111240152B
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- 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
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- 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
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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
- G03F7/0005—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
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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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
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- Optics & Photonics (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Chemical & Material Sciences (AREA)
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- Optical Filters (AREA)
Abstract
The invention provides a coloring photosensitive resin composition, a color filter and a display device. The colored photosensitive resin composition comprises a colored dispersion liquid containing a colorant and a benzophenone compound of chemical formula 1, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the photopolymerization initiator comprises one or more selected from carbazole compounds and fluorene oxime compounds. The colored photosensitive resin composition of the present invention has excellent curing degree even in low-temperature curing, and solvent resistance and adhesiveness of the colored photosensitive resin composition are improved. Chemical formula 1
Description
Technical Field
The present invention relates to a colored photosensitive resin composition, a color filter manufactured using the colored photosensitive resin composition, and a display device including the color filter.
Background
Color filters are widely used in various display devices such as image pickup devices and liquid crystal display devices (LCDs), and the application range thereof is rapidly expanding. The color filters used in the image pickup device, the liquid crystal display device, and the like are formed of coloring patterns of three colors of Red (Red), green (Green), and Blue (Blue), or coloring patterns of three colors of Yellow (Yellow), magenta (Magenta), and Cyan (Cyan).
The color patterns of the color filters are generally formed by using a colored photosensitive resin composition containing a colorant such as a pigment or a dye, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The colored pattern processing using the colored photosensitive resin composition is generally performed by a photolithography process.
The color patterns of the color filters are generally formed by using a colored photosensitive resin composition containing a colorant such as a pigment or a dye, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The colored pattern processing using the colored photosensitive resin composition is generally performed by a photolithography process.
The colored photosensitive resin is an essential material for color filters, liquid crystal display materials, organic light emitting elements, displays, and the like. For example, in a color filter of a color liquid crystal display, a light shielding layer using a black photosensitive composition is formed at a boundary portion between colored layers in order to improve contrast and color development effects of red, green, and blue. In recent years, it has been demanded to perform not only the function of a black matrix formed on an array substrate but also the function of forming a cell gap maintaining spacer at the same time so as to be capable of performing various functions at one time. Thus, not only an optical effect for substantial light shielding but also characteristics excellent in elastic modulus and reliability are required.
Korean laid-open patent No. 10-1648607 discloses a technique for improving characteristics of a color filter manufactured using the above-described ink composition and a display element including the above-described color filter by improving contrast of the ink composition, but it provides an improvement in characteristics limited to red color, and has a problem in that reliability at the time of low-temperature curing is lowered and it is difficult to apply to various processes.
Prior art literature
Patent literature
Patent document 1: korean registered patent No. 10-1648607
Disclosure of Invention
Problems to be solved
In order to solve the above-described problems, an object of the present invention is to provide a colored photosensitive resin composition which contains a carbazole-based and/or fluorene oxime-based photopolymerization initiator, thereby improving the properties such as solvent resistance and adhesion, even when cured at low temperatures, with excellent curing degree.
Further, the present invention aims to provide a color filter which has a blue spectral transmittance of from 435nm to 455nm, has a maximum transmittance of 76% or more, and can realize a half-value width of 93nm or less by adding a benzophenone compound to a colored dispersion.
The present invention also aims to prevent the deterioration of the color characteristics of an element including the produced film by using the colored photosensitive resin composition.
The present invention also provides a color filter produced using the colored photosensitive resin composition and a display device including the color filter.
Means for solving the problems
In order to achieve the above object, the present invention provides a colored photosensitive resin composition comprising a colored dispersion liquid containing a colorant and a benzophenone compound of chemical formula 1, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant contains one or more pigments selected from the group consisting of blue pigments and violet pigments,
the photopolymerization initiator contains at least one selected from carbazole-based compounds and fluorene oxime-based compounds.
[ chemical formula 1]
The present invention also provides a color filter produced from the colored photosensitive resin composition.
Further, the present invention provides a display device including the above color filter.
Effects of the invention
The colored photosensitive resin composition of the present invention contains one or more photopolymerization initiators selected from carbazole-based compounds and fluorene oxime-based compounds, and thus has an effect of improving solvent resistance and adhesion of the colored photosensitive resin composition, even when cured at low temperatures, with excellent curing degree.
Further, a film produced using the colored photosensitive resin composition has a blue spectral transmittance of 76% or more at a maximum transmittance of 435nm to 455nm and a half-value width of 93nm or less, by adding the benzophenone compound represented by chemical formula 1 to the colored dispersion, thereby providing an effect of preventing deterioration in color characteristics of an element including a pattern produced from the colored photosensitive resin composition.
Further, a color filter manufactured using the above colored photosensitive resin composition and a display device including the above color filter provide excellent characteristics in terms of drivability, durability, and the like.
Drawings
Fig. 1 is a view of the adhesion evaluation criteria.
FIG. 2 is a graph showing spectral transmittance in the wavelength range of about 380 to 780.0nm of color filters manufactured from the compositions of examples 1, 4 and 5 and comparative examples 1, 4 and 5.
FIG. 3 is a graph showing spectral transmittance in the wavelength range of about 380 to 580.0nm of color filters manufactured from the compositions of examples 1, 4 and 5 and comparative examples 1, 4 and 5.
FIG. 4 is a graph showing half-value width ranges of examples 1, 4 and 5 and comparative examples 1, 4 and 5 in a wavelength range of about 380 to 580.0 nm.
Detailed Description
The present invention provides a colored photosensitive resin composition, a color filter manufactured by using the colored photosensitive resin composition, and a display device comprising the color filter, wherein the colored photosensitive resin composition comprises: a colored dispersion containing a colorant and a benzophenone compound of chemical formula 1, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant contains one or more selected from blue pigments and violet pigments, and the photopolymerization initiator contains one or more selected from carbazole-based compounds and fluorene oxime-based compounds.
[ chemical formula 1]
Colored photosensitive resin composition
The components constituting the colored photosensitive resin composition of the present application will be described in detail below. However, the present application is not limited to these components.
(A) Coloring dispersion containing coloring agent
The coloring dispersion is characterized by containing one or more pigments selected from blue pigments and violet pigments as a colorant, and containing a benzophenone compound of chemical formula 1.
Coloring agent
Blue and/or violet pigments
In the present application, the blue pigment may be more specifically one or more selected from c.i. pigment blue 15 (15:3, 15:4, 15:6, etc.), 16, 21, 28, 60, 64, and 76, and the violet pigment may be one or more selected from c.i. pigment violet 14, 19, 23, 29, 32, 33, 36, 37, and 38. In the present application, since the film produced using the colored photosensitive resin composition contains pigment blue 15:6 as a blue pigment and pigment violet 23 as a violet pigment and contains a benzophenone compound represented by chemical formula 1, the transmittance at a wavelength of 435nm to 445nm may be 76% or more, more preferably 76% to 100% or less, and the half-value width may satisfy 93nm or less, and still more preferably 50nm to 93 nm.
Benzophenone compounds
The benzophenone compound is characterized by being a compound represented by the following chemical formula 1.
[ chemical formula 1]
When the benzophenone compound is fired at 170 ℃ or lower, the transmittance in the short wavelength region of the blue spectrum is reduced, and therefore, if it is used in combination with a pigment such as pigment blue 15:6 or pigment violet 23, the half-value width of the blue spectrum can be effectively reduced.
The content of the benzophenone compound may be 0.1 to 20.0% by weight, preferably 0.1 to 10.0% by weight, and more preferably 0.1 to 5.0% by weight, based on the total weight of solid components in the colored photosensitive resin composition. When the content of the thermosetting resin is within the above range, it is preferable to effectively reduce the half-value width of the colored photosensitive resin composition and improve the developability with an aqueous alkali solution.
The colorant may further contain one or more pigments (a 1) in addition to the blue pigment and the violet pigment, and may further contain one or more dyes (a 3) as required.
(a1) Pigment
The colorant of the present application may further contain an organic pigment or an inorganic pigment generally used in the art, as required.
The pigment may be subjected to the following treatments as needed: resin treatment; surface treatment with pigment derivatives or the like having an acidic group or a basic group introduced thereto; grafting treatment of the pigment surface with a polymer compound or the like; micronizing treatment by sulfuric acid micronizing method or the like; a washing treatment with an organic solvent, water, or the like for removing impurities; or a removal treatment of ionic impurities by ion exchange method or the like.
The organic pigment may be any of various pigments used in printing inks, inkjet inks, and the like, and specifically includes water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, pyrene pigments, and di-Oxazine pigments, anthraquinone pigments, dianthrone-based pigments, anthrapyrimidine pigments, anthroquinone pigments, indanthrone pigments, flavanthrone pigments, 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, examples thereof include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black, organic black pigment, titanium black, and pigments which are mixed with red, green, and blue colors to exhibit black, and composite metal oxides.
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 present invention is not limited thereto.
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, 185;
c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71;
c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264;
c.i. pigment green 7, 10, 15, 25, 36, 47, 58, 59;
c.i. pigment brown 28;
c.i. pigment black 1, 7;
the pigment which may be additionally contained is preferably selected from 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 179, c.i. pigment red 208, c.i. pigment red 242, c.i. pigment red 254, c.i. pigment red 255, c.i. pigment green 7, c.i. pigment green 36, c.i. pigment green 58 and c.i. pigment green 59.
In the present application, the total content of the pigments included in the present application including the blue pigment and the violet pigment which are necessary to be included may be 5 to 100% by weight, and preferably 25 to 60% by weight, based on the total weight of the solid components of the colored dispersion. When the pigment content is within the above range, the color density of the thin film pixel is sufficient, and the non-pixel portion is preferably not reduced in the removability during development, and no residue is generated.
The pigment is preferably a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of the method for uniformly dispersing the particle size of the pigment include a method in which the pigment dispersion is dispersed by adding the pigment dispersant (a 2), and a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained by the above method.
(a2) Pigment dispersants
The pigment dispersant is added for the purpose of resolving and maintaining stability of the pigment, and pigment dispersants generally used in the art can be used without limitation, and specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine and other surfactants, which may be used singly 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.
Specific examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkylaryl ethers, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.
In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, and polyethylene imines may be mentioned.
The pigment dispersant preferably includes 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.
As the pigment dispersant, other resin-type pigment dispersants other than the acrylic acid ester-based dispersant can be used. 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.
Examples of the commercial products of the other resin type pigment dispersants include cationic resin dispersants, which are commercially available from BYK (pick) chemical company under the trade name: 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 resin-type pigment dispersants other than the acrylic acid ester-based dispersants may be used alone or in combination of two or more kinds, or may be used in combination with the acrylic acid ester-based dispersants.
The content of the pigment dispersant may be 5 to 60% by weight, and preferably 15 to 50% by weight, based on 100% by weight of the solid content of the pigment. When the content of the pigment-dispersing agent is within the above range, a suitable viscosity level for easily producing a colored photosensitive resin composition can be maintained, and the steps of atomizing the pigment and gelling after dispersion are easy, so that it is preferable.
(a3) Dye
In the present application, the dye as a colorant may contain one or more kinds as required, and the dye may be used without limitation as long as it has solubility in an organic solvent. It is preferable to use a dye which has solubility in an organic solvent and can ensure solubility in an alkali developer and reliability such as heat resistance and solvent resistance.
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-based, xanthene-based, and phthalocyanine-based acid dyes, and derivatives thereof. The dye may be a compound classified into a dye according to an index of color (published by the institute of dyeing (The Society of Dyers and Colourists)), or a known dye described in a dyeing manual (society for dyeing).
As specific examples of the above-mentioned dye, for c.i. solvent dyes, there may be:
yellow dyes such as c.i. solvent yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163;
c.i. solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179, etc. red dyes;
orange dyes such as c.i. solvent orange 2, 7, 11, 15, 26, 41, 45, 56, 62;
c.i. blue dyes such as solvent blue 5, 35, 36, 37, 44, 59, 67, 70;
c.i. violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49, etc.;
c.i. solvents green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc.,
among the c.i. solvent dyes, c.i. solvent yellow 14, 16, 21, 56, 151, 79, 93 having excellent solubility in an organic solvent is preferable, and c.i. solvent yellow 21, 79 is more preferable.
Furthermore, for c.i. acid dyes, it is possible to:
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;
C.i. red dyes of 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 oranges 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
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, etc.;
c.i. acid violet 6B, 7, 9, 17, 19, 66, etc. violet dyes;
c.i. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc.,
Among the c.i. acid dyes, c.i. acid yellow 42 and c.i. acid green 27 which are excellent in solubility in an organic solvent are more preferable.
Furthermore, for c.i. direct dyes, it is possible to:
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;
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 oranges 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;
C.i. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104, etc. violet dye;
green dyes such as c.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82.
Furthermore, for c.i. mediator dyes, it is possible to:
yellow dyes such as medium yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
c.i. medium 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, etc.;
orange dyes such as c.i. medium orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
c.i. blue dyes such as medium 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. vehicle violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Green dyes such as c.i. media green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;
the above dyes may be used each alone or in combination of two or more.
When the dye is further contained in the colorant, the content of the dye may be 0.5 to 50% by weight, preferably 1 to 40% by weight, and more preferably 1 to 20% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. When the content of the dye is within the above-described content range, the problem of deterioration in reliability of elution of the dye due to an organic solvent after patterning can be prevented, and the sensitivity is improved, which is preferable.
The content of the colorant may be 5 to 60% by weight, and preferably 10 to 45% by weight, based on the total weight of the solid components in the colored photosensitive resin composition. When the content of the colorant is within the above range, the color density of the pixel is sufficient at the time of forming a thin film, and the non-pixel portion is preferably not reduced in the releasability at the time of development, so that residue is less likely to occur.
In the present invention, the total weight of the solid components in the colored photosensitive resin composition refers to the total weight of the remaining components excluding the solvent of the colored photosensitive resin composition.
(B) Alkali-soluble resin
The alkali-soluble resin is produced by copolymerizing an ethylenically unsaturated monomer (b 1) having a carboxyl group as an essential component so as to be soluble in an alkali developer used in a development treatment step for patterning.
(b1) Ethylenically unsaturated monomer having carboxyl group
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 these 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.
The alkali-soluble resin may be produced by copolymerizing the above-mentioned ethylenically unsaturated monomer having a carboxyl group with the ethylenically unsaturated monomer (b 2) having a hydroxyl group. The alkali-soluble resin can be produced by copolymerizing a copolymer of the above-mentioned ethylenically unsaturated monomer having a carboxyl group with a compound (b 3) having a glycidyl group. The alkali-soluble resin may be produced by copolymerizing the carboxyl group-containing ethylenically unsaturated monomer, the hydroxyl group-containing ethylenically unsaturated monomer, and the glycidyl group-containing compound.
(b2) Ethylenically unsaturated monomer having 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.
(b3) Compounds having glycidyl groups
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, aryl glycidyl ether, glycidyl methacrylate, and the like, and preferably butyl glycidyl ether, aryl glycidyl ether, and glycidyl methacrylate, and two or more kinds of these compounds may be used in combination.
The alkali-soluble resin can be produced by copolymerizing an unsaturated monomer (b 4).
(b4) Unsaturated monomer
The above-mentioned unsaturated monomers may be used singly or in combination of two or more kinds, and are not limited to the following examples.
Aromatic vinyl compounds such as styrene, vinyltoluene, α -methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether;
n-substituted maleimide compounds such as N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide and N-p-methoxyphenylmaleimide;
alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate; alicyclic (meth) acrylates such as cyclopentylacrylate, cyclohexylacrylate, 2-methylcyclohexylacrylate, tricyclo [5.2.1.0, 2,6] decan-8-yl (meth) acrylate, 2-dicyclopentyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate;
Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;
unsaturated oxetane compounds such as 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, and 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane.
The content of the alkali-soluble resin may be 10 to 80% by weight, and preferably 10 to 70% by weight, based on the total weight of solid components in the colored photosensitive resin composition. When the content of the alkali-soluble resin is within the above range, the solubility in the developer is sufficient to facilitate patterning, and the film of the pixel portion of the exposed portion is prevented from decreasing during development, so that the non-pixel portion is preferably peeled off.
The acid value of the alkali-soluble resin is preferably 30mgKOH/g to 150mgKOH/g, whereby the compatibility with the dye and the stability with time of the colored photosensitive resin composition can be improved. When the acid value of the alkali-soluble resin is less than 30mgKOH/g, it is difficult to ensure a sufficient development speed of the colored photosensitive resin composition, and when the acid value is more than 150mgKOH/g, adhesion to a substrate is reduced to easily cause short-circuiting of a pattern, and compatibility with the dye is problematic to cause precipitation of the dye in the colored photosensitive resin composition or stability of the colored photosensitive resin composition with time is lowered to possibly increase viscosity.
In order to ensure additional developability of the alkali-soluble resin, a hydroxyl group may be added. When hydroxyl groups are added to the alkali-soluble resin, the development speed is improved.
The sum of the hydroxyl values of the alkali-soluble resin and the photopolymerizable compound described later is preferably 50mgKOH/g to 250mgKOH/g. When the sum of the hydroxyl values of the alkali-soluble resin and the photopolymerizable compound is less than 50mgKOH/g, a sufficient development speed cannot be ensured, and when it is more than 250mgKOH/g, the dimensional stability of the formed pattern is lowered and the straightness of the pattern is easily deteriorated, and the compatibility with the dye is lowered, and the problem of stability with time may occur.
(C) Photopolymerizable compound
The photopolymerizable compound is a compound polymerized by the action of a photopolymerization initiator described later, and examples thereof include mono-tubular monomers, difunctional monomers, other polyfunctional monomers, and the like.
Specific examples of the mono-tube 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, and 3-methylpentanediol di (meth) acrylate. Specific examples of the other polyfunctional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Among them, a polyfunctional monomer having two or more functions is preferably used.
The content of the photopolymerizable compound may be 5 to 50% by weight, and preferably 7 to 45% by weight, based on the total weight of the solid components in the colored photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, the strength and smoothness of the pixel portion tend to be improved, and thus it is preferable.
(D) Photopolymerization initiator
The photopolymerization initiator of the present application may contain one or more photopolymerization initiators selected from carbazole-based compounds and fluorene oxime-based compounds.
The photopolymerization initiator is characterized by comprising a compound represented by the following chemical formula 2.
[ chemical formula 2]
In the above chemical formula 2, A may be-CH-or nitrogen (N).
R is as described above 1 ～R 8 Each independently may be hydrogen, alkyl group having 1 to 20 carbon atoms, or a compound represented by the following chemical formula 3, -COR 16 or-NO 2 。
R is as described above 16 The aryl group may be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and preferably may be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms with one or more substituents selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms.
R is as described above 13 The alkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkyl group, phenyl group or naphthyl group is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 12 carbon atoms, cycloalkenyl group having 4 to 8 carbon atoms, alkynyl group having 2 to 12 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, phenyl group or naphthyl group.
[ chemical formula 3]
In the chemical formula 3, R is 14 Can be hydrogen, cycloalkyl, alkenyl, alkoxy, alkyl, phenyl or naphthyl, preferably can be hydrogen, cycloalkyl of 3 to 8 carbon atoms, alkenyl of 2 to 5 carbon atoms, alkoxy of 1 to 20 carbon atoms, alkyl of 1 to 20 carbon atoms, phenyl or naphthyl,
r is as described above 15 The compound may be an aryl group, a heteroaryl group or an alkyl group, and preferably may be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and X may be-CO-or a direct bond.
In the chemical formula 2, A is-CH-or N, and R is 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 5 And R is 6 、R 6 And R is 7 Or R 7 And R is 8 At least one group of (a) may be the following chemical formula 4.
[ chemical formula 4]
/>
R is as described above 9 ～R 12 Each independently may be hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted phenyl group.
The photopolymerization initiator may include a photopolymerization initiator generally used in the art in an amount of 5 to 40% by weight based on the total weight of the photopolymerization initiator, in addition to the compound represented by the chemical formula 2. Examples of the photopolymerization initiator generally used include triazine compounds, acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, and oxime compounds.
Examples of the triazine compound 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) -6-triazine, 2, 4-trichloromethyl (4' -methoxystyryl) -6-triazine.
Specific examples of the acetophenone-based compound include 2,2' -diethoxyacetophenone, 2' -dibutoxyacetophenone, 2-hydroxy-2-methylpropenone, 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-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acryloylbenzophenone, 4' -bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 4' -dimethylaminobenzophenone, 4' -dichlorobenzophenone, and 3,3' -dimethyl-2-methoxybenzophenone.
Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, and 2-chlorothioxanthone.
Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin dimethyl ketal.
Examples of the oxime compound include 2- (o-benzoyl oxime) -1- [4- (phenylthio) phenyl ] -1, 2-octanedione and 1- (o-acetyl oxime) -1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone.
In addition to the photopolymerization initiator exemplified above, a diketone compound, a sulfonium borate compound, a diazo, a bisimidazole compound, or the like may be used as the photopolymerization initiator.
The content of the photopolymerization initiator may be 0.1 to 10% by weight, and more preferably 3 to 8% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. When the content of the photopolymerization initiator is within the above range, sufficient photopolymerization can be initiated at the time of exposure in the patterning step, and the transmittance is not lowered by the unreacted initiator remaining after photopolymerization.
(E) Solvent(s)
The solvent used in a general colored photosensitive resin composition may be used without particular limitation as long as it is effective in dissolving other components contained in the colored photosensitive resin composition, and particularly, ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, and the like are 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 methoxypentyl 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; cyclic esters such as gamma-butyrolactone, etc.
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 the content thereof may be 30 to 90% by weight, preferably 60 to 90% by weight, more preferably 70 to 85% by weight, based on the total weight of the colored photosensitive resin composition of the present invention. In the case where the content of the solvent is within the above range, it is preferable to provide an effect of improving the coating property when coating is performed by a coating apparatus such as a roll coater, a spin coater, a slot die coater (also referred to as a die coater), a spray coater, or the like.
(F) Additive agent
The colored photosensitive resin composition of the present invention may further contain an additive as needed, and as a specific example, at least one or more selected from a dispersant, a wetting agent, a silane coupling agent, an anti-coagulant, and the like may be used.
As the dispersant, a commercially available surfactant can be used, and examples of the surfactant include a silicone surfactant, a fluorine surfactant, a silicone surfactant having a fluorine atom, and a mixture thereof. Examples of the silicone surfactant include surfactants having a siloxane bond. Examples of the commercial products include Toray Silicone DC3PA, toray Silicone SH7PA, toray Silicone DC PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone 29SHPA, toray Silicone SH PA, polyether modified Silicone oil SH8400 (manufactured by Torili Silicone Co., ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Xinyue Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicone Co., ltd.), and the like.
Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, fluorine (trade name) FC430, fluorine FC431 (manufactured by Sumitomo 3M Co., ltd.), megafac F142D, megafac F171, megafac F172, megafac F173, megafac F177, megafac F183, megafac R30 (manufactured by Dain ink chemical industry Co., ltd.), F-Top EF301, F-Top EF303, F-Top EF351, F-Top EF352 (manufactured by New Qkuda chemical Co., ltd.), surflon S381, surflon S382, surflon SC101, surflon SC105 (manufactured by Asahi glass Co., ltd.), E5844 (manufactured by Dain gold refining research Co., ltd.), BM-1000, BM-1100 (manufactured by BMChemie Co., ltd.), and the like can be cited.
Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, there may be mentioned Megafac (trade name) R08, megafac BL20, megafac F475, megafac F477, megafac F443 (manufactured by Dain ink chemical industry Co., ltd.), and the like.
Examples of the wetting agent include glycerin, diethylene glycol, ethylene glycol, and the like, and may contain one or more kinds selected from the group consisting of these.
Examples of the silane coupling agent include aminopropyl triethoxysilane, γ -mercaptopropyl trimethoxysilane, and γ -methacryloxypropyl trimethoxysilane, and commercially available products include SH6062, SZ6030 (manufactured by Torile Corning Silicone company (Toray-Dow Corning Silicon co., ltd.), KBE903, KBM803 (manufactured by Xin-Etsu Silicone company (Shin-Etsu silicone co., ltd.), and the like.
Examples of the anticoagulants include sodium polyacrylate.
Color filter and liquid crystal display device
The present invention also provides a color filter produced from the colored photosensitive resin composition of the present invention and a display device including the color filter.
Examples of display devices that can be provided with such color filters include liquid crystal display devices, OLEDs, and flexible displays, but are not limited thereto, and all display devices known in the art that can be applied thereto may be exemplified.
The color filter can be produced by applying the colored photosensitive resin composition of the present invention described above to a substrate, and then performing photo-curing and development to form a pattern.
First, the colored photosensitive resin composition is applied to a substrate, and then heated and dried to remove volatile components such as solvents, thereby obtaining a smooth coating film.
The coating method may be performed by, for example, spin coating, flexible coating, roll coating, slit spin coating, slit coating, or the like. After the application, the solvent and other volatile components are volatilized by heating after drying by heating (pre-baking) or drying under reduced pressure. The heating temperature is usually 70 to 200 ℃, preferably 70 to 170 ℃, more preferably 80 to 130 ℃. The thickness of the coating film after heat drying is usually about 1 to 8. Mu.m. For the coating film thus obtained, ultraviolet rays are irradiated through a mask for forming a target pattern. In this case, it is preferable that the exposure portion is uniformly irradiated with parallel light as a whole, and a mask aligner, a stepper, or the like is used to perform precise alignment of the mask and the substrate. When ultraviolet rays are irradiated, the portion irradiated with the ultraviolet rays is cured.
As the ultraviolet rays, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm) and the like can be used. The amount of ultraviolet irradiation may be appropriately selected according to need, and is not limited in the present invention. If the cured coating film is brought into contact with a developer to dissolve and develop the non-exposed portion, a target pattern shape can be formed.
The developing method may be any of a liquid adding method, a dipping method, a spraying method, and the like. In addition, the substrate may be inclined at an arbitrary angle during development. The developer is an aqueous solution containing a general alkaline compound and a surfactant. The above basic compound may be any of inorganic and organic basic compounds. Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, monoammonium phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia, and the like. Specific examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine.
These inorganic and organic basic compounds may be used each alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.
The surfactant in the alkaline developer may be at least one selected from the group consisting of nonionic surfactants, anionic surfactants, and cationic surfactants.
Specific examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene derivatives other than polyoxyethylene alkyl aryl ethers, oxyethylene/oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, fatty acid glycerides, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, and the like.
Specific examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleyl sulfate, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, and alkylaryl sulfonate salts such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate.
Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. These surfactants may be used each alone or in combination of two or more.
The concentration of the surfactant in the developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass. After development, washing with water is carried out, and if necessary, post-baking may be carried out at 90 to 170℃and preferably 90 to 150℃for 10 to 60 minutes. The reference for low temperature curing may refer to the temperature in the post-baking process being a low temperature.
The present invention will be described in more detail below based on 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 present invention is defined by the appended claims, and 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 the content are based on mass unless otherwise specified.
Production of colored photosensitive resin compositions of examples 1 to 5 and comparative examples 1 to 5
Example 1:
the colored resin composition of example 1 was produced by mixing 10 parts of c.i. pigment blue 15:6 (pigment) as a colorant (a), 5 parts of c.i. pigment violet 23 (pigment), 5 parts of benzophenone compound represented by the following chemical formula 1 (C), 5 parts of BYK-20014.0 as a pigment dispersant, and 76 parts of propylene glycol monomethyl ether acetate, sufficiently dispersing the pigment by a bead mill, and then mixing 10 parts of SPCY-6L (a polymer company of sho) as an alkali-soluble resin (B), 9555 parts of a 9555 as a photopolymerizable compound (D), 4 parts of OXE-02 (basf) as a photopolymerization initiator (E), and 50 parts of propylene glycol monomethyl ether acetate as a solvent (F) with 31 parts of the pigment dispersion.
[ chemical formula 1]
The compositions of examples 2 to 5 and comparative examples 1 to 5 were prepared as shown in Table 1 below by changing the components in order to confirm the effects of the benzophenone compound (C) and the photopolymerization initiator (E).
TABLE 1
(Unit: portion)
* Pouring
[ chemical formulas 1-2]
[ chemical formulas 1-3]
OXE-03 (Basf Co.)
SPI-03 (Sanyang Co., ltd.)
I-369 (Irgacure-369; ciba Co., ltd.)
I-907 (Irgacure-907; ciba company)
Manufacturing example: color filter production using colored photosensitive resin composition
The colored photosensitive resin compositions of examples 1 to 5 and comparative examples 1 to 5 were applied to a base glass (bare glass) substrate by spin coating, and then placed on a hot plate, and maintained at a temperature of 100℃for 2 minutes to form a film. Next, a test photomask having a pattern in which the transmittance was stepwise changed in the range of 1 to 100% and a line/space pattern of 1 μm to 100 μm was placed on the film, and ultraviolet light was irradiated while setting the interval between the test photomask and the test photomask to 200 μm. In this case, a high-pressure mercury lamp of 1KW containing all of g, h and i lines was used as the ultraviolet light source, and the ultraviolet light source was used at a speed of 50mJ/cm 2 The irradiation was performed without using a special optical filter. The film irradiated with ultraviolet rays was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 2 minutes, and developed. Post process Bake (Bake) was performed on a hot plate (hotplate) at 130 ℃ for 60 minutes. The film thickness of each color filter produced by using the colored photosensitive resin compositions of examples 1 to 5 and comparative examples 1 to 5 was 2.6. Mu.m.
Test example: evaluation of physical Properties of color Filter Using colored photosensitive resin composition
1-1 evaluation of solvent resistance
The color filters of examples 1 to 5 and comparative examples 1 to 5 were immersed in a PGMEA solvent at 60 ℃ for 10 minutes, and the color difference between the front and rear sides was evaluated. At this time, the color difference is calculated using the following [ formula 1], and the value calculated using the following [ formula 1] is shown in the following [ table 2 ].
[ mathematics 1]
△Eab*＝[(△L*) 2 +(△a*) 2 +(△b*) 2 ] 1/2
The above [ formula 1] represents a color difference in the three-dimensional colorimeter defined by L, a, and b, and the smaller the color difference calculated by the above [ formula 1], the more highly reliable the color filter can be manufactured.
< evaluation criterion >
Excellent (no pattern change and delta (Eab) less than 3.0)
Good delta (slight pattern change or delta (Eab x)) of 3.0 or more and less than 5.0
Defective (change in pattern or delta (Eab x) of 5.0 or more)
The evaluation results are shown in [ Table 2 ].
1-2 evaluation of adhesion
After immersing the color filters of examples 1 to 5 and comparative examples 1 to 5 in PGMEA at normal temperature for 10 minutes, OK and NG were determined by the detachment of the formed pattern. Fig. 1 is a diagram showing a reference for evaluating such adhesion. The pattern after dipping was judged to be OK if it remained, and NG if it was detached, and it was shown in the following [ table 2 ].
1-3 determination of spectral transmittance
The spectral transmittance of the color filters of examples 1, 4, and 5 and comparative examples 1, 4, and 5 was measured by a micro spectrophotometer (Microscopic spectrophotometer) OSP-SP2000 (Olympus), and shown in FIGS. 2 to 4, and half-value widths and maximum transmittance of the spectral transmittance of each color filter are shown in [ Table 2 ].
Since the color filters of examples 2 to 3 and comparative examples 2 and 3 contain the same colorant and actually exhibit the same spectral transmittance, fig. 1 only illustrates the spectral transmittance of examples 1, 4, 5 and comparative examples 1, 4, and 5.
Referring to FIG. 2 and Table 2, it is clear that the color filters of examples 1, 4 and 5 manufactured by using the colored photosensitive resin composition of the present invention have a maximum spectral transmittance of 76% or more and a half-value width of 93nm or less.
Definition of half value width:
a% = highest transmittance x 1/2
B nm=short wavelength side x-axis wavelength corresponding to a% transmittance
Cnm=long wavelength side x-axis wavelength corresponding to a% transmittance
Half value width (nm) =c-B
TABLE 2
| Differentiation of | Solvent resistance | Adhesion of | Maximum spectral transmittance | Half value width |
| Example 1 | O | OK | 77％ | 91nm |
| Example 2 | O | OK | 77％ | 91nm |
| Example 3 | O | OK | 77％ | 91nm |
| Example 4 | O | OK | 77％ | 90nm |
| Example 5 | O | OK | 77％ | 93nm |
| Comparative example 1 | O | OK | 77％ | 100nm |
| Comparative example 2 | X | NG | 77％ | 91nm |
| Comparative example 3 | X | NG | 77％ | 91nm |
| Comparative example 4 | O | OK | 78％ | 101nm |
| Comparative example 5 | O | OK | 78％ | 101nm |
Therefore, when a color filter is produced using the colored photosensitive resin composition of the present invention, the degree of curing, solvent resistance and adhesion, which are important characteristics of a low-temperature cured product, are improved, the reliability of the color filter is improved, and a characteristic blue spectrum having a maximum transmittance of 76% or more and a half-value width of 93nm or less at a wavelength of 435nm to 445nm can be realized.
Claims (9)
1. A colored photosensitive resin composition comprising, relative to the total weight of solid components in the colored photosensitive resin composition:
5 to 60 weight percent of colorant,
0.1 to 20.0% by weight of a benzophenone compound represented by the following chemical formula 1,
10 to 80 weight percent of alkali soluble resin,
5 to 50% by weight of a photopolymerizable compound,
0.1 to 10 wt% of a photopolymerization initiator,
the solvent content is 60 to 90 wt% relative to the total weight of the colored photosensitive resin composition,
the colorant comprises one or more pigments selected from the group consisting of blue pigments and violet pigments,
the photopolymerization initiator contains at least one selected from carbazole-based compounds and fluorene oxime-based compounds,
chemical formula 1
2. The colored photosensitive resin composition according to claim 1,
the blue pigment is one or more selected from the group consisting of c.i. pigment blue 15:3, 15:4, 15:6, 21, 28, 60, 64 and 76,
the violet pigment is one or more selected from the group consisting of c.i. pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38.
3. The colored photosensitive resin composition according to claim 1, wherein the photopolymerization initiator comprises a structure represented by the following chemical formula 2,
Chemical formula 2
In the chemical formula 2 described above, a compound having a structure of,
a is-CH-or nitrogen,
the R is 1 ～R 8 Each independently is hydrogen, alkyl group having 1 to 20 carbon atoms, or a compound represented by the following chemical formula 3, -COR 16 、-NO 2 Or said R 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 5 And R is 6 、R 6 And R is 7 Or R 7 And R is 8 At least one group of the following chemical formula 4,
the R is 16 Is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,
the R is 13 Is alkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkyl, phenyl or naphthyl,
chemical formula 3
In the chemical formula 3 described above, the chemical formula,
the R is 14 Is hydrogen, cycloalkyl, alkenyl, alkoxy, alkyl, phenyl orA naphthalene group,
the R is 15 Is aryl, heteroaryl or alkyl,
x is-CO-or direct connection,
chemical formula 4
In the chemical formula 4 described above, the chemical formula,
the R is 9 ～R 12 Each independently represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted phenyl group.
4. The colored photosensitive resin composition according to claim 3, wherein,
in the chemical formula 2 described above, a compound having a structure of,
the R is 13 Is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 12 carbon atoms, cycloalkenyl group having 4 to 8 carbon atoms, alkynyl group having 2 to 12 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, phenyl group or naphthyl group,
The R is 16 Is an aryl group having 6 to 20 carbon atoms which is substituted or unsubstituted with one or more substituents selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms.
5. The colored photosensitive resin composition according to claim 3, wherein,
in the chemical formula 2 described above, a compound having a structure of,
the R is 14 Is hydrogen, cycloalkyl having 3 to 8 carbon atoms, alkenyl having 2 to 5 carbon atoms, alkoxy having 1 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms, phenyl or naphthyl,
the R is 15 Is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.
6. The colored photosensitive resin composition according to claim 1, wherein a film produced from the colored photosensitive resin composition has a transmittance of 76% or more at a wavelength of 435nm to 445 nm.
7. The colored photosensitive resin composition according to claim 1, wherein a half width of a film produced from the colored photosensitive resin composition is 93nm or less.
8. A color filter comprising a colored pattern produced from the colored photosensitive resin composition according to any one of claims 1 to 7.
9. A display device comprising the color filter of claim 8.
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