CN116848465A - Photosensitive resin composition for forming partition wall, partition wall structure manufactured using the same, and display device including the partition wall structure - Google Patents

Photosensitive resin composition for forming partition wall, partition wall structure manufactured using the same, and display device including the partition wall structure Download PDF

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Publication number
CN116848465A
CN116848465A CN202280014788.4A CN202280014788A CN116848465A CN 116848465 A CN116848465 A CN 116848465A CN 202280014788 A CN202280014788 A CN 202280014788A CN 116848465 A CN116848465 A CN 116848465A
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partition wall
photosensitive resin
resin composition
forming
pigment
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权玟廷
金勋植
李在乙
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Dongwoo Fine Chem Co Ltd
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Dongwoo Fine Chem Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Optical Filters (AREA)

Abstract

The present invention relates to a photosensitive resin composition for forming a partition wall, a partition wall structure manufactured by the photosensitive resin composition for forming a partition wall, and a display device including the same, wherein the photosensitive resin composition comprises: the cured film produced from the photosensitive resin composition has a transmittance of 20% or less at a wavelength of 450nm, a reflectance of 10% or more at wavelengths of 550nm and 650nm, and a transmittance of 70% or more at a wavelength of 900nm when the cured film has a thickness of 3 [ mu ] m to 15 [ mu ] m.

Description

Photosensitive resin composition for forming partition wall, partition wall structure manufactured using the same, and display device including the partition wall structure
Technical Field
The present invention relates to a photosensitive resin composition for forming a partition wall, a partition wall structure manufactured using the same, and a display device including the partition wall structure.
Background
In the case of conventional flat panel or liquid crystal display devices, a display using a color conversion panel has recently been studied due to the conventional display structure that loses a large amount of light. As a simple example, in a structure composed of a color conversion panel and a backlight generating blue light, the blue color directly uses the blue color of the backlight and thus the light of the backlight can be completely used. In addition, in a pixel displaying red or green, blue is converted to red or green to display, and thus more light is generated in the pixel than in the conventional manner of using absorption and transmission to express a desired color.
Displays manufactured using low temperature processes have a great feature as compared to previous displays manufactured using high temperature processes. In general, in order to increase the reliability of a material, the reliability of a pattern is generally increased through a high temperature process. However, with recently developed OLEDs, the OLEDs are thermally fragile, and thus it is difficult to perform a high temperature process. Therefore, if the display is manufactured by separately manufacturing and then laminating, it is difficult to manufacture a flexible or rollable display. Therefore, the color conversion pixels must be formed at the upper portion of the OLED panel through a photolithography process, and in order to form the color conversion pixels, the need for a low temperature process is gradually increasing.
Further, in the display device including the color conversion panel, the partition wall is formed between the respective color conversion pixels to prevent color mixing of the respective color conversion pixels, but the partition wall between the respective color conversion pixels is formed with a film thickness of about 3 μm to 15 μm due to the conversion efficiency of the color conversion pixels.
In the conventional photosensitive resin composition for black matrix, when the film thickness produced in the conventional manner is 1 μm to 1.5 μm, although there is no problem in forming the pattern, the film thickness of the partition wall of the color conversion pixel should be formed to be 3 μm to 15 μm, which is not preferable.
In addition, in the case of forming thick film barrier ribs using a conventionally used black matrix, there is a problem in that light cannot be irradiated to the lower end of the pattern due to a decrease in transmittance of Ultraviolet (UV) light in the exposure process. Since the lower portion of the film is not photo-cured, undercut (undercut) is seriously induced after the development process, and there is a disadvantage in that the process margin (process margin) is weak.
Further, if the photosensitive resin composition for a black matrix is used in manufacturing the partition walls of the color conversion pixels, it is difficult to recognize a lower alignment key (alignment key) when aligning the mask pattern in the exposure process after the coating process, and thus there is a problem in that it is difficult to form a pattern at an accurate position. Thus, conventionally used photosensitive resin compositions for black matrices are limited as a substance for forming a partition wall of a color conversion pixel.
In addition, if the reliability such as solvent resistance of the partition wall is low, residues and the like are generated in the inside of the partition wall in the thermal process after the partition wall is manufactured, resulting in a problem of reduced efficiency and lifetime of the color conversion pixel.
The purpose of korean laid-open patent No. 10-2007-0094460 is to provide a photosensitive resin composition for forming a partition wall that is excellent in shape stability against heat, but the above-described problems cannot be overcome in practice.
Disclosure of Invention
Technical problem
The present invention was made to solve the above-described problems, and an object of the present invention is to provide a photosensitive resin composition for forming a partition wall, which is excellent in reliability such as solvent resistance, has no residue except for a pattern formation portion, and is excellent in tapering process characteristics (tapered process characteristics).
Further, the present invention is to provide a photosensitive resin composition for forming a partition wall, which satisfies the transmittance and reflectance in a specific wavelength band, prevents color mixing of a color conversion panel, improves resolution and light efficiency, and allows easy recognition of an alignment key.
The present invention also provides a partition wall structure and a display device manufactured using the photosensitive resin composition for forming a partition wall.
Means for solving the problems
The present invention provides a photosensitive resin composition for forming a partition wall, which is characterized by comprising: the cured film produced from the photosensitive resin composition has a transmittance of 20% or less at a wavelength of 450nm, a reflectance of 10% or more at wavelengths of 550nm and 650nm, and a transmittance of 70% or more at a wavelength of 900nm when the cured film has a thickness of 3 [ mu ] m to 15 [ mu ] m.
The present invention also provides a partition wall structure made of the photosensitive resin composition for forming a partition wall, and a display device including the same.
Effects of the invention
The photosensitive resin composition for forming a partition wall and the partition wall structure of the present invention can provide the following effects: the solvent resistance and other reliability are excellent, no residue is left except for the pattern forming part, and the tapering process characteristic is excellent.
Further, the photosensitive resin composition for forming a partition wall and the partition wall structure of the present invention can provide the following effects: by preventing color mixing of the color conversion panel by satisfying the transmittance and reflectance conditions in a specific wavelength band, resolution and light efficiency can be improved, and an alignment key (alignment key) can be easily recognized.
Drawings
Fig. 1 is a graph showing transmittance and reflectance spectra of a cured film of a partition pattern produced from the photosensitive resin composition for forming a partition of example 1 and example 3 of the present invention.
Fig. 2 is a graph showing transmittance and reflectance spectra of a cured film of a partition pattern produced from the photosensitive resin composition for forming a partition of comparative example 2 of the present invention.
Fig. 3 is a view showing a method of measuring the taper shoulder angle of a cured film of a partition wall pattern produced from a photosensitive resin composition for forming a partition wall of examples and comparative examples of the present invention.
Fig. 4 is a graph showing the evaluation criteria of the residue characteristics of the cured films of the partition wall patterns produced from the photosensitive resin compositions for forming partition walls of the examples and comparative examples of the present invention.
Detailed Description
The present invention relates to a photosensitive resin composition for forming a partition wall, a partition wall structure manufactured by the photosensitive resin composition for forming a partition wall, and a display device including the same, wherein the photosensitive resin composition comprises: the cured film produced from the photosensitive resin composition has a transmittance of 20% or less at a wavelength of 450nm, a reflectance of 10% or more at wavelengths of 550nm and 650nm, and a transmittance of 70% or more at a wavelength of 900nm when the cured film has a thickness of 3 [ mu ] m to 15 [ mu ] m.
Further, when the thickness of the cured film is 3 μm to 15 μm, the maximum value of the transmittance at a wavelength of 450nm may be 20% or less, preferably 15% or less, more preferably 10% or less.
Further, when the thickness of the cured film is 3 μm to 15 μm, the minimum value of the reflectance at wavelengths of 550nm and 650nm may be 10% or more, preferably 15% or more, more preferably 20% or more.
Further, when the thickness of the cured film is 3 μm to 15 μm, the maximum value of the transmittance at a wavelength of 900nm may be 70% or more, preferably 80% or more.
When the above cured film satisfies the specific transmittance and specific reflectance conditions at the above specific wavelength, the following effects can be provided: the color mixture of the color conversion panel can be prevented, resolution and light efficiency are improved, and an alignment key (alignment key) is easily recognized.
The present invention will be described in detail below.
< photosensitive resin composition for Forming partition wall >
The photosensitive resin composition for forming the partition wall of the present invention comprises: (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent.
(A) Coloring agent
The colorant contained in the photosensitive resin composition for forming a partition wall of the present invention may contain one or more of (a 1) a white pigment, (a 2) a black pigment and (a 3) a yellow pigment, and preferably may contain (a 1) a white pigment, (a 2) a black pigment and (a 3) a yellow pigment.
In the case of a conventional photosensitive resin composition for forming a partition wall, which contains scattering particles such as metal oxides to improve the light efficiency of pixels, the transmittance is adjusted by adjusting only the content of black pigment. However, when the transmittance is reduced by using only a black pigment, the content of the white pigment required for improving the reflectance is greatly increased, the total content of the whole pigment in the photosensitive resin composition is increased, and the content of the alkali-soluble resin, the photopolymerizable compound and other components affecting the process stability is reduced, resulting in a problem of deterioration of the process characteristics of the photosensitive resin composition.
In the case where the photosensitive resin composition of the present invention contains (a 1) a white pigment, (a 2) a black pigment and (a 3) a yellow pigment, not only the light leakage phenomenon but also the light efficiency of the pixel can be effectively improved, the total amount of the pigment in the composition decreases with the decrease in the amount of the white pigment required for securing the reflectance, and the effect of improving the process characteristics can be provided, which is preferable.
(a1) White pigment
The white pigment is used for the reflection characteristics of the partition wall structure, and specifically, by increasing the reflectivity of the partition wall structure for light of red and/or green series wavelengths, light in a specific wavelength range in the partition wall direction is reflected from the light generated from the color conversion element, and the luminance can be improved.
The average particle size of the above white pigment is preferably 150nm to 400nm, and in the case where the average particle size is less than 150nm, UV light blocking characteristics are exhibited and UV light is not sufficiently transmitted to the lower portion during the exposure process, resulting in a problem that patterning is not easy, and the particle size is too small, resulting in an increase in transmittance in the visible light region, possibly resulting in a problem that shielding characteristics are lowered. When the average particle size is larger than 400nm, problems may occur such as poor dispersibility and storage stability, reduced surface smoothness of the exposed portion, and uneven interface between the exposed portion and the unexposed portion.
The White pigment (pigment White) may be selected from titanium oxide (TiO) 2 ) Silicon dioxide (SiO) 2 ) Alumina (Al) 2 O 3 ) Tin oxide (SnO) 2 ) Iron oxide (Fe) 2 O 3 ) Zinc oxide (ZnO), magnesium oxide (MgO), zirconium oxide (ZrO) 2 ) Cerium oxide (CeO) 2 ) Lithium oxide (Li) 2 O), silver oxide (AgO), antimony oxide (Sb) 2 O 3 ,Sb 2 O 5 ) More than one kind selected from the group consisting of calcium oxide (CaO), preferably titanium oxide (TiO) 2 )。
As the upper White pigment, a White pigment (c.i. pigment White) known in the art can be used in the case where the above condition is satisfied, and as the above White pigment, c.i. pigment White 4, 5, 6, 6:1, 7, 18, 18:1, 19, 20, 22, 25, 26, 27, 28, and 32 can be cited. From the viewpoints of reflection efficiency and whiteness (white), c.i. pigment white 6 or 22 is preferably contained, and c.i. pigment white 6 is more preferably contained. They may be used singly or in combination of two or more.
Titanium oxide (TiO) contained in pigment white 6 2 ) Since it is inexpensive, has a high refractive index and is excellent in reflectance, it is useful as an effective white pigment, and it is preferable to have a rutile (rutile) structure in terms of colorability and whiteness.
The titanium oxide (TiO) 2 ) The resin treatment may be carried out as needed, and the introduction of an acidic group may be used Surface treatment of pigment derivatives of groups or basic groups, grafting treatment of pigment surfaces with polymer compounds or the like, micronization treatment using sulfuric acid micronization method or the like, cleaning treatment using organic solvent or water to remove impurities, ion impurity removal treatment using ion exchange method, or the like.
The titanium oxide (TiO) 2 ) The silicon oxide (SiO) 2 ) Alumina (Al) 2 O 3 ) Zirconium oxide (ZrO) 2 ) And at least one surface-treated titanium oxide (TiO 2 ) Preferably, a method of sequentially using silicon oxide (SiO 2 ) Alumina (Al) 2 O 3 ) And zirconia (ZrO 2 ) The surface-treated titanium oxide is more preferably one obtained by subjecting the surface-treated titanium oxide (TiO 2 ) Titanium oxide obtained by treating the outermost surface of the steel sheet. The organic material may be prepared by coating titanium oxide (TiO 2 ) Surface treatment is performed to reduce the content of dispersed titanium oxide (TiO 2 ) Energy required for the time and prevents titanium oxide (TiO 2 ) Compression to agglomerate is not particularly limited, and in one or more embodiments, stearic acid (stearic acid), trimethylpropane (TMP), pentaerythritol, and the like may be used.
By applying the above-mentioned method to titanium oxide (TiO 2 ) Surface treatment is performed to reduce the content of titanium oxide (TiO) 2 ) In particular, according to the preferred embodiment of the surface treatment described above, which may be a treatment by cladding (encapsulation), there is a benefit in improving reliability such as heat resistance and chemical resistance.
Relative to surface-treated titanium oxide (TiO) 2 ) The above-mentioned surface-treated titanium oxide (TiO) 2 ) Titanium oxide (TiO) 2 ) The core content is preferably 85 to 95% by weight. When the titanium oxide (TiO) is treated within the above range 2 ) The surface of the core exhibits excellent whiteness and excellent reflection brightness.
As the aboveTitanium oxide (TiO) 2 ) Examples of the commercial products of DuPont (DuPont) include R-101, R-102, R-103, R-104, R-105, R-350, R-706, R-794, R-796, TS-6200, R-900, R-902, R-902+, R-931, and R-960, and examples of the commercial products include R-FC5, TR81, and TR88 of Hunstman, and CR-57 of ISK.
The content of the white pigment may be 1 to 30% by weight, preferably 1 to 28% by weight, relative to the total weight of the photosensitive resin composition for forming a partition wall of the present invention. When the content of the white pigment is less than 1% by weight, the reflectance for the red and/or green-series light may decrease; when the content is more than the above, the transmittance at 900nm is excessively lowered, so that it may be difficult to recognize the alignment key, and in the exposure step, light is scattered at the surface portion of the coating film due to the white pigment, curing of the unexposed portion may occur, and reverse taper (reverse taper) and shoulder taper at the upper portion of the pattern occur, and thus the shape of the pattern may be deteriorated.
(a2) Black pigment
The black pigment (a 2) contained in the colorant (a) of the present invention can be used for absorbing light in the ultraviolet and visible wavelength bands.
The above black pigment may be appropriately selected from black organic pigments and black inorganic pigments.
As the black organic pigment, one or more selected from the group consisting of lactam black, perylene black, cyanine black, and aniline black can be used. From the viewpoint of improving blue light shielding property and transmittance in the infrared region, it is preferable to use lactam black.
As the black inorganic pigment, one or more selected from the group consisting of carbon black, chromium oxide, iron oxide, and titanium black can be used, and carbon black is preferably used.
Further, according to the purpose, the black organic pigment and the black inorganic pigment may be used singly or in combination of two or more.
The content of the above-mentioned black pigment may be 0.03 to 5% by weight, preferably 0.05 to 5% by weight, relative to the total weight of the photosensitive resin composition for forming a partition wall of the present invention. When the content of the black pigment is less than the above content, as the transmittance of light in the blue backlight wavelength region increases, the light shielding property becomes weak, and color mixing between pixels may occur. When the content of the black pigment is more than 5 wt%, the transmittance for light of a wavelength band of 900nm or more is lowered, and thus it may be difficult to recognize an alignment key at a lower part and to form a pattern at an accurate position when aligning the mask in an exposure process. Further, problems such as undercut may occur due to insufficient deep curing, and a decrease in light emitting efficiency of the display may occur due to a decrease in reflectivity of the barrier ribs.
(a3) Yellow pigment
The (a 3) yellow pigment contained in the (a) colorant of the present invention can be used in order not to block transmission and reflection of light to other regions while absorbing light in a low wavelength region (shielding blue light) in the visible region.
As the above yellow pigment, when the above conditions are satisfied, a pigment known in the art can be used. Preferably, the yellow pigment may use one or more selected from anthraquinone compounds, isoindolinone compounds, and azo compounds, and specifically c.i. pigment yellow classified as a pigment in color index (published by the institute of dyestuffs (The Society of Dyers and Colourists)) may be used.
The yellow pigment may be, for example, one or more selected from the group consisting of c.i. pigment yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, and 185, and preferably one or more selected from the group consisting of c.i. pigment yellow 129, c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 150, and c.i. pigment yellow 185 may be used.
The content of the yellow pigment may be 0.03 to 5% by weight, preferably 0.05 to 5% by weight, relative to the total weight of the photosensitive resin composition for forming a partition wall of the present invention. When the content of the yellow pigment is lower than the above content, the transmittance of light for a wavelength band of around 450nm increases, so that color mixing between pixels may occur. When the content of the yellow pigment is more than 5 wt%, the reflectance of light in a wavelength region (550 nm to 650 nm) generated for the red pixel and the green pixel is lowered, so that a problem of lowering of the light emitting efficiency of the display may occur.
(a4) Additional pigments or dyes
The colorant (a) of the present invention may further contain an organic pigment, an inorganic pigment, a dye, etc. which are commonly used in the art, within a range not prejudice to the object of the present invention.
As the organic pigment, various pigments used for printing inks, inkjet inks, and the like can be used, and specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, pyrenone pigments, dioxazine pigments, anthraquinone pigments, dianthrone (dianhydroquinone) pigments, anthrapyrimidine pigments, anthanthrone (anthantone) pigments, indanthrene (indanthorone) pigments, xanthone (flavanthrone) pigments, pyranthrone (pyrenthrone) pigments, or diketopyrrolopyrrole (diketopyrrolopyrrole) pigments can be cited.
The inorganic pigment may be a metal compound such as a metal oxide or a metal complex salt, and specifically may be an oxide or a composite metal oxide of a metal such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, or antimony.
Examples of the organic pigment and the inorganic pigment include compounds classified into pigments in color index (published by the institute of dyeing), and more specifically, the following color index (c.i.) numbered pigments are given, but the present invention is not limited thereto:
C.i. pigment red 9, 81, 97, 105, 122, 123, 144, 149, 150, 155, 166, 168, 171, 175, 176, 177, 179, 180, 185, 192, 202, 208, 209, 214, 215, 216, 220, 222, 224, 242, 254, 255, 264, 269, 270, 272, etc.;
yellow pigments such as c.i. pigment yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, and 185;
orange pigments such as c.i. pigment orange 13, 15, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71;
green pigments such as c.i. pigment green 7, 10, 15, 25, 36, 47, 58, and 59;
c.i. pigment blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64, 76, etc. blue pigments;
violet pigments such as c.i. pigment violet 1, 14, 19, 23, 29, 32, 33, 36, 37, and 38;
brown pigment such as pigment brown 28.
The dye is not limited as long as it has solubility or dispersibility in an organic solvent. It is preferable to use a dye which has solubility in an organic solvent and can ensure solubility in an alkaline 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, sulfonamides of acid dyes, and derivatives thereof. In addition, azo-based, xanthene-based, phthalocyanine-based acid dyes and derivatives thereof may be selected.
Preferably, the dye is a compound classified into a dye in a color index (published by the institute of dyeing), or a known dye described in a dyeing manual (society of dyeing).
Specific examples of the dye include:
c.i. solvents green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35;
c.i. solvent yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, and 163;
c.i. solvent blues 18, 35, 36, 45, 58, 59, 59:1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136 and 139;
c.i. solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, and 179;
c.i. acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, and 426.
The above pigments and dyes may each be used alone or in combination of two or more.
(a5) Pigment dispersants
The pigment dispersant is added for the purpose of resolving and maintaining stability of the pigment, and pigment dispersants commonly 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 alone or in combination of two or more.
The pigment dispersant preferably includes an acrylic dispersant (hereinafter referred to as an acrylic dispersant) containing Butyl Methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). The acrylic acid ester-based dispersant is preferably one produced by the activity control method (living control method), and examples of commercial products include DIPER BYK-2000, DIPER BYK-2001, DIPER BYK-2070, and DIPER BYK-2150, and the acrylic acid ester-based dispersants may be used singly 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, 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, modified products thereof, and oil dispersants such as amides or salts thereof formed by the reaction of polyester having free (free) carboxyl groups with poly (lower alkylene imine), copolymers of (meth) acrylic acid and styrene, (meth) acrylic acid- (meth) acrylic acid ester, copolymers of styrene and maleic acid, water-soluble resins such as polyvinyl alcohol and polyvinylpyrrolidone, and water-soluble polymer compounds; a polyester; modified polyacrylate; an addition product of ethylene oxide/propylene oxide; phosphate esters, and the like.
Examples of the commercial products of the other resin type pigment dispersants include those sold under the trade names DIPER BYK-160, DIPER BYK-161, DIPER BYK-162, DIPER BYK-163, DIPER BYK-164, DIPER BYK-166, DIPER BYK-171, DIPER BYK-182 and DIPER BYK-184 of the cationic resin dispersants; trade names of Basf (BASF) corporation, EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, and EFKA-4800; lu Borun (Lubrizol) under the trade names SOLSPERS-24000, SOLSPERS-32550 and NBZ-4204/10; trade names HINOACT T-6000, HINOACT T-7000 and HINOACT T-8000 of Chuanyan refining Co; tradenames of Weisu corporation, AJISPUR PB-821, AJISPUR PB-822, and AJISPUR PB-823; trade names of FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, and the like, which are available from co-Rong chemical company.
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 1 to 5 parts by weight, preferably 5 to 30 parts by weight, relative to 100 parts by weight of the solid content in the colorant. When the content of the pigment dispersant is within the above range, a dispersed pigment having a uniform particle diameter can be obtained, which is preferable. If the content of the pigment dispersant is more than 50 parts by weight, the viscosity may be increased, and if the content of the pigment dispersant is less than 1 part by weight, problems such as difficulty in pigment atomization or gelation after dispersion may be caused.
(B) Alkali-soluble resin
The alkali-soluble resin of the present invention is a component that imparts solubility to an alkali developer used in a developing process, and functions as a dispersion medium for pigments.
The alkali-soluble resin may be used without limitation as long as it is soluble in an alkali developer, and it may preferably contain Cardo-based alkali-soluble resin, acrylic-based alkali-soluble resin, or a mixture thereof.
The Cardo-based alkali-soluble resin has reactivity and alkali solubility by the action of light or heat, and the Cardo-based alkali-soluble resin contained in the photosensitive resin composition for forming a partition wall of the present invention is not limited as long as it functions as a binder resin for a colorant containing a white pigment and is soluble in an alkali developer.
The Cardo alkali-soluble resin of the present invention may contain one or more of the compounds represented by chemical formulas 1-1 and 1-2.
[ chemical formula 1-1]
[ chemical formulas 1-2]
In the above chemical formula 1-1 or chemical formula 1-2, R1, R2, R3 and R4 are each independently an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms or
X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group,
R 5 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
In the present invention, the compound represented by the above chemical formula 1-1 may be synthesized from the compound represented by the following chemical formula 2-1, and the compound represented by the chemical formula 1-2 may be synthesized using the compound represented by the chemical formula 2-2.
[ chemical formula 2-1]
[ chemical formula 2-2]
The acrylic alkali-soluble resin is preferably produced by copolymerizing an ethylenically unsaturated monomer having a 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; anhydrides of the above dicarboxylic acids; preferred examples of the mono (meth) acrylate of the polymer having a carboxyl group and a hydroxyl group at both ends thereof include ω -carboxyl polycaprolactone mono (meth) acrylate and the like, acrylic acid and methacrylic acid.
Further, the above alkali-soluble resin can be produced by polymerizing an ethylenically unsaturated monomer having a carboxyl group with a copolymerizable unsaturated monomer.
Specific examples of the copolymerizable unsaturated monomer include: glycidyl methacrylate as an unsaturated monomer having a glycidyl group; hydroxy-containing ethylenically unsaturated monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and hydroxyethyl (meth) acrylate such as N-hydroxyethyl acrylamide; 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, and the like, but are not limited thereto.
The copolymerizable unsaturated monomers mentioned above may each be used alone or in combination of two or more.
The acid value of the above alkali-soluble resin is preferably 30mg KOH/g to 200mg KOH/g. When the acid value of the alkali-soluble resin is less than 30mg KOH/g, it is difficult to ensure a sufficient development speed of the photosensitive resin composition for forming a partition wall. When the acid value of the alkali-soluble resin is more than 200mg KOH/g, the adhesion to the substrate is lowered, pattern short-circuiting is likely to occur, and compatibility with the color material is likely to occur, resulting in precipitation of the color material in the photosensitive resin composition or lowering of the storage stability of the photosensitive resin composition, and increase of the viscosity.
The "acid value" is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1g of the acrylic polymer, and is usually obtained by titration using an aqueous potassium hydroxide solution.
Further, it is preferably a Cardo-based resin or an acrylic alkali-soluble resin having a polystyrene-equivalent weight average molecular weight (hereinafter, simply referred to as "weight average molecular weight") of 2,000 to 20,000, preferably 3,000 to 10,000, measured by gel permeation chromatography (GPC; using tetrahydrofuran as an eluting solvent). In the molecular weight range, the film loss in the developing step can be suppressed and the pattern stability can be improved.
The content of the alkali-soluble resin may be 5 to 85 wt%, preferably 5 to 60 wt%, relative to the total weight of the photosensitive resin composition for forming a partition wall of the present invention. When the content of the alkali-soluble resin is within the above range, the solubility in the developer is sufficient and a cured film is easily formed, and the film of the pixel portion of the exposed portion is prevented from decreasing and the omission of the unexposed portion becomes preferable at the time of display.
(C) Photopolymerizable compound
As the photopolymerizable compound, a monofunctional monomer, a difunctional monomer, a polyfunctional monomer, or the like, preferably a polyfunctional monomer having two or more functions can be used as a compound polymerizable by the action of the following photopolymerization initiator (D).
Specific examples of the above monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like, but are not limited thereto.
Specific examples of the above-mentioned difunctional monomer include 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol a, 3-methylpentanediol di (meth) acrylate, and the like, but are not limited thereto.
Specific examples of the above-mentioned polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and the like, but are not limited thereto.
The content of the photopolymerizable compound may be 5 to 50 wt% with respect to the total weight of the photosensitive resin composition for forming a partition wall. The content of the photopolymerizable compound is preferably within the above range from the viewpoint of strength and smoothness.
(D) Photopolymerization initiator
The photopolymerization initiator of the present invention is a compound that generates radicals capable of initiating polymerization of the photopolymerizable compound by exposure to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, or X rays.
Examples of the photopolymerization initiator include acetophenone compounds, benzophenone compounds, biimidazole compounds, triazine compounds, oxime ester compounds, and thioxanthone compounds.
Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzildimethylketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylsulfanyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.
Specific examples of the benzophenone-based compound include benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3', 4' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone.
Specific examples of the above-mentioned bisimidazole compound include 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4', 5' -tetraphenylbisimidazole, 2' -bis (2-chlorophenyl) -4,4', and 5,5' -tetrakis (alkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4,4', 5' -tetrakis (trialkoxyphenyl) biimidazole, 2-bis (2, 6-dichlorophenyl) -4,4', 5' -tetraphenyl-1, 2' -biimidazole, or biimidazole compounds wherein the phenyl group at the 4,4', 5' position is substituted with an alkoxycarbonyl group. Among them, 2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4' are preferably used, 5,5' -tetraphenyl-biimidazole, 2-bis (2, 6-dichlorophenyl) -4,4', 5' -tetraphenyl-1, 2' -biimidazole.
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-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, 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, and 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyethylene ] -1,3, 5-triazine.
Specific examples of the oxime ester compound include o-ethoxycarbonyl-. Alpha. -oxyimino-1-phenylpropane-1-one and 1- [4- (phenylthio) phenyl group]-1, 2-octanedione 2- (O-benzoyloxime) (1, 2-octanedione, -1- (4-phenylthio) phenyl, -2- (O-benzoyloxy)), 1- (9-ethyl) -6- (2-methylbenzoyl-3-yl) ethanone 1- (O-acetooxime) (ethane, -1- (9-ethyl) -6- (2-methylbenzoyl-3-y)l) -,1- (o-acetyloxide)), etc., examples of commercial products include CGI-124 and CGI-224 from Ciba Geigy, and BASF from Barba Geigy OXE-01、/>OXE-02 and->OXE-03, ai Dike (Adeka) N-1919 and NCI-831, etc.
Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.
The photopolymerization initiator may be used alone or in combination of two or more.
The content of the photopolymerization initiator may be 0.01 to 10 wt%, and preferably 0.01 to 5 wt%, with respect to the total weight of the photosensitive resin composition for forming a partition wall. When the content of the photopolymerization initiator is within the above range, the photopolymerization reaction rate is appropriate, and the overall process time can be prevented from increasing, and the physical properties of the final cured film due to excessive reaction can be prevented from being lowered, which is preferable.
The photosensitive resin composition for forming a partition wall of the present invention may further contain a photopolymerization initiator auxiliary agent in the photopolymerization initiator. When a photopolymerization initiator is used together with a photopolymerization initiator, the photosensitive resin composition has higher sensitivity and improves productivity, and is therefore preferable.
The photopolymerization initiator is a compound used for promoting polymerization of the photopolymerizable compound polymerized by the photopolymerization initiator, and preferably one or more compounds selected from the group consisting of amine and carboxylic acid compounds can be used.
When the photopolymerization initiator is contained, the content of the photopolymerization initiator may be generally more than 0 mol and 10 mol or less, preferably 0.01 to 5 mol, relative to 1 mol of the photopolymerization initiator. When the content of the photopolymerization initiator is within the above range, the effect of improving the productivity can be expected by improving the photopolymerization efficiency, and thus it is preferable.
(E) Solvent(s)
As the above-mentioned solvent, an organic solvent known in the art can be used without particular limitation.
Specific examples of the solvent include: ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, and dipropylene glycol dibutyl ether; 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; ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentanyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, and esters such as gamma-butyrolactone. The above-mentioned solvents may be used in combination of one or two or more selected from the group consisting of exemplified solvents.
Among the above solvents, an organic solvent having a boiling point of 100 to 200 ℃ is preferably used, more preferably an alkylene glycol alkyl ether acetate, ketone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate or other esters are used, and still more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate or the like are used, from the viewpoint of coatability and drying properties. These solvents may be used each alone or in combination of two or more.
The content of the solvent may be such that the content of the photosensitive resin composition for forming the partition wall is 100% by weight. Specifically, in the present invention, the term "balance" means a balance in which the total weight of the composition including the essential components of the present invention and other additional components is 100% by weight, and the photosensitive resin composition for forming a partition wall of the present invention does not include any additional component because of the meaning of the term "balance".
For example, the content of the solvent may be 60 to 90 wt%, preferably 70 to 85 wt%, with respect to the total weight of the photosensitive resin composition for forming a partition wall, but is not limited thereto. However, when the content of the solvent is within the above-described content range, the effect of improving the coating property is preferably provided when coating is performed by a coating device such as a roll coater, a spin coater, a slit coater (sometimes referred to as a die coater), or an inkjet printer.
Additive agent
The photosensitive resin composition for forming a partition wall of the present invention may further contain additives such as a filler, other polymer compound, curing agent, surfactant, adhesion promoter, antioxidant, ultraviolet absorber, and anti-coagulant, if necessary. The above additives may be used singly or in combination of two or more.
As the filler, glass, silica, alumina, or the like can be used specifically, but is not limited thereto.
As the other polymer compound, a curable resin such as an epoxy resin or a maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane, or the like can be specifically used, but the present invention is not limited thereto.
Examples of the surfactant include silicon-based, fluorine-based, ester-based, cationic-based, anionic-based, amphoteric-based, and the like, and each of them may be used alone or in combination of two or more.
The antioxidant may include, for example, one or more selected from the group consisting of a phosphorus-based antioxidant, a sulfur-based antioxidant, and a phenol-based antioxidant, and in this case, discoloration that may occur at a high temperature in a process or yellowing that may be caused by a light source after manufacturing a display can be suppressed. The antioxidant may contain one or more selected from the group consisting of a phenol compound, a phosphorus compound and a sulfur compound, and they may be used in combination of a phenol-phosphorus compound, a phenol-sulfur compound, a phosphorus-sulfur compound or a phenol-phosphorus-sulfur compound.
As the adhesion promoter, specifically, one selected from the group consisting of 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 (3-isocynatepropyrimethoxysilane) and 3-isocyanatopropyl triethoxysilane (3-isocynateproxypropate) or a mixture thereof may be used.
The anti-coagulant may be sodium polyacrylate, for example, but is not limited thereto.
The above-described additives may be appropriately added by those skilled in the art within a range that does not hinder the effects of the present invention. For example, the content of the above-mentioned additive may be 0.05 to 10% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, relative to the total weight of the photosensitive resin composition for forming a partition wall, but is not limited thereto.
Spacer structure and display device
The invention provides a partition wall structure made of a photosensitive resin composition for forming a partition wall, and a display device comprising the same.
In a display device including a color conversion panel, since each pixel is driven to form a color, a partition wall structure capable of distinguishing each pixel must be formed. The display device including the partition wall structure formed using the photosensitive resin composition for forming a partition wall of the present invention can be formed as follows: the color mixing between pixels is prevented, the formation of fine patterns is facilitated, and the line width variation caused by the development time variation of the development process is small. When the line width variation of the partition wall is small, there is an advantage in that the color conversion pixel can secure a sufficient space and can realize a high-quality image.
Further, it is preferable that the partition wall structure is formed to have a height or thickness of 3 μm to 20 μm, preferably 3 μm to 15 μm.
As the display device described above, a liquid crystal display device, an organic light emitting diode, a flexible display, or the like may be included, but not limited thereto, and all display devices known in the art that are applicable may be exemplified.
In order to manufacture the color conversion barrier rib, the barrier rib-forming composition of the present invention can be used, and a method commonly used in the art is not particularly limited.
For example, the above composition may be coated on one side of a substrate and a cured film is formed by a photo-curing and developing process to form a partition wall. A photolithography process may be used to form the color conversion pixels and the color conversion panel spacer structures to distinguish the pixels.
Specifically, in order to form the barrier ribs, each photosensitive resin composition is applied to one surface of a substrate, and then heated and dried to remove volatile components such as solvents, thereby obtaining a smooth cured film.
The coating method of the composition is not particularly limited, and examples thereof include spin coating, flexible coating (flexible coating method), roll coating, slit spin coating, slit coating, and the like.
After the composition is applied, the composition is dried by heating (pre-baking and pre-baking) or dried under reduced pressure and then heated to volatilize volatile components such as solvents. The heating temperature may be generally 70 to 150 ℃, preferably 80 to 130 ℃, but is not limited thereto.
In order to form a target pattern on the coating film thus formed, ultraviolet rays are irradiated through a mask to cure the portion irradiated with the ultraviolet rays. In this case, the exposure portion is uniformly irradiated with parallel light, and a mask aligner, a stepper, or the like is preferably used to precisely align the mask with the substrate. As the ultraviolet rays, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm) and the like can be used, and the irradiation amount of the ultraviolet rays can be appropriately selected as required,
The cured coating film is brought into contact with a developer to dissolve the unexposed portions and developed, thereby forming a cured film of the target pattern.
The cured film thus formed can be cured to be harder than the cured product by adding a heat curing step (pre-baking and post-baking), and in this case, the heating temperature may be 90 ℃ to 230 ℃ and the heating time may be 5 minutes to 180 minutes, preferably 15 minutes to 90 minutes, but is not limited thereto.
Description of the embodiments
Hereinafter, the present invention will be described in more detail by way of examples.
However, the following examples are provided to illustrate the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following embodiments may be modified and changed appropriately by those skilled in the art within the scope of the present invention.
In addition, below, "%" and "parts" indicating contents are weight basis unless otherwise indicated.
Examples and comparative examples: production of photosensitive resin composition
Photosensitive resin compositions of examples and comparative examples were produced with reference to the compositions and parts by weight described in tables 1 and 2 below.
TABLE 1
TABLE 2
-white pigment (a 1-1): tiO (titanium dioxide) 2 (Ti-Pure R-101, duPont Co.)
-black pigment (a 2)
-a2-1: lactam black (100 cf, basiff Co.)
-a2-2: perylene Black (C.I. pigment Black 32, basf company)
Yellow pigment (a 3)
-a3-1: C.I. pigment Y138 (Basiff Co.)
-a3-2: C.I. pigment Y139 (Basiff Co.)
-a3-3: C.I. pigment Y185 (Basiff Co.)
-a dispersant: DISPERBYK-2000
Alkali-soluble resin: acrylic alkali-soluble resin (CX-65-C, showa electric (SHOWA DENKO K.K.))
Photopolymerisable compounds: ethoxylated dipentaerythritol pentaacrylate (A-DPH-12E, new Zhongcun chemical)
Photopolymerization initiator: PBG-327 (Tronly Co., ltd.)
-additives: f554 (DIC Co.)
Experimental example
(1) Manufacture of a cured film of a spacer pattern
A5 cm by 5cm glass substrate (Corning Co.) was washed with a neutral detergent and water, and then dried. The feel of examples and comparative examples was measured on the glass substrate using Propylene Glycol Methyl Ether Acetate (PGMEA) solventThe solids of the light-emitting resin composition were each diluted to a concentration of 30%. Spin coating was performed in such a manner that the thickness of the final film was 10 μm, pre-baking was performed at 80 deg.c, and drying was performed for 2 minutes, thereby removing the solvent. Then, for a mask containing a line/space pattern of 1 μm to 100 μm or a pattern of 40mm×40mm, a mask is used at a rate of 100mJ/cm 2 Exposure is performed, and an alkali aqueous solution is used to remove the unexposed portion. The cured film thus produced was then baked at 180℃for 30 minutes to produce a 10 μm thick cured film having a spacer pattern.
(2) Measuring the angle of a conical shoulder (tapered shoulders)
The cured films of the spacer patterns produced from the photosensitive resin compositions of the above examples and comparative examples were examined using an electron microscope (model: SU-8010, hitachi), and the angles of the tapered shoulders were measured in the manner shown in FIG. 3, and the results are shown in Table 3 below.
Evaluation criterion of Cone shoulder Angle
O: greater than 140 DEG
Delta: more than 110 DEG and less than 140 DEG
X: less than or equal to 110 DEG
(3) Evaluation of solvent resistance
The cured films of the spacer patterns produced from the photosensitive resin compositions of examples and comparative examples were immersed in a PGMEA solvent at 90 ℃ for 10 minutes, and the film thickness variation before and after immersion was measured and compared and evaluated, and the results are shown in table 3 below.
< criterion for evaluation of solvent resistance >
And (3) the following materials: less than or equal to 0.1 mu m
O: greater than 0.1 μm and less than or equal to 0.3 μm
Delta: more than 0.3 μm and less than or equal to 0.7 μm
X: greater than 0.7 μm
(4) Evaluation of residue
The surfaces of the cured films of the spacer patterns produced from the photosensitive resin compositions of examples and comparative examples were observed with an optical microscope, evaluated based on the residue measurement standard shown in fig. 4, and the results are shown in table 3 below.
< residue evaluation criterion >
O: no residue is produced
Delta: generating a small amount of residue
X: generating a great amount of residues
TABLE 3
Process characteristics Taper angle Solvent resistance Residues from the treatment of plant diseases
Example 1 ○ ○ ○
Example 2 ○ ◎ ○
Example 3 ○ ◎ ○
Example 4 ○ ○ ○
Example 5 △ △ △
Example 6 ○ ○ ○
Example 7 ○ ○ ○
Example 8 ○ ◎ ○
Example 9 ○ ◎ ○
Comparative example 1 × ○ ×
Comparative example 2 △ ○ ○
Comparative example 3 ○ △ ○
Comparative example 4 △ × ○
(5)Determination of transmittance and reflectance
The transmittance and reflectance of the above 10 μm thick cured film of the spacer pattern were measured at each wavelength using a Spectrophotometer (CM-3700 d).
The transmittance or reflectance evaluation criteria at each wavelength are shown below, and the results are shown in table 4 below.
< transmittance at wavelength of 450nm >
O: less than or equal to 5%
Delta: more than 5% and less than or equal to 20%
X: more than 20%
< reflectance at wavelength 550nm >
And (3) the following materials: more than or equal to 20 percent
O: 15% or more and 20% or less
Delta: more than or equal to 10 percent and less than 15 percent
X: less than 10%
< reflectance at wavelength 650nm >
And (3) the following materials: more than or equal to 20 percent
O: 15% or more and 20% or less
Delta: more than or equal to 10 percent and less than 15 percent
X: less than 10%
< transmittance at 900nm wavelength >
O: more than or equal to 70 percent
Delta: 55% or more and less than 70%
X: less than 55%
TABLE 4
Light characteristics Transmittance at 450nm Reflectance at 550nm 650nm reflectivity Transmittance at 900nm
Example 1 ○ ◎ ◎ ○
Example 2 ○ ◎ ◎ ○
Example 3 ○ ○ ○ ○
Example 4 ○ ◎ ◎ ○
Example 5 △ ○ ○ ○
Example 6 △ ○ ○ ○
Example 7 ○ ◎ ◎ ○
Example 8 ○ ○ ○ ○
Example 9 ○ ○ ○ ○
Comparative example 1 ○ ○ ○ ×
Comparative example 2 △ △ × ○
Comparative example 3 ○ × × ○
Comparative example 4 × ○ △ ○
Referring to tables 3 and 4, it was confirmed that the cured films of the spacer patterns produced using the photosensitive resin compositions of examples had a transmittance of 20% or less at a wavelength of 450nm, a reflectance of 10% or more at wavelengths of 550nm and 650nm, and a transmittance of 70% or more at a wavelength of 900 nm. Therefore, when the photosensitive resin composition of the present invention is used to form a cured film of a spacer pattern of a display device, it is possible to provide effects of effectively preventing color mixing of a color conversion panel, improving resolution and light efficiency, and easily recognizing an alignment key.
In addition, it was confirmed that in the case of the cured film of the spacer pattern produced using the photosensitive resin composition of examples, particularly in the case of the cured film of the spacer pattern produced using the photosensitive resin compositions of examples 1 to 4 and examples 7 to 9, the reliability such as solvent resistance was excellent, no residue was found except for the pattern formation portion, and the taper process characteristics were excellent.
On the other hand, it was confirmed that cured films of spacer patterns produced using the photosensitive resin compositions of comparative examples 1 to 4, which did not contain one or more of white pigment, black pigment and yellow pigment, did not satisfy the transmittance and reflectance ranges at the wavelength of the present invention, and that the process characteristics such as taper shoulder angle, solvent resistance and residues were also inferior to those of examples.
Industrial applicability
The photosensitive resin composition for forming a partition wall and the partition wall structure of the present invention can provide the following effects: the solvent resistance and other reliability are excellent, no residue is left except for the pattern forming part, and the tapering process characteristic is excellent.

Claims (14)

1. A photosensitive resin composition for forming a partition wall, characterized by comprising: (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent,
a cured film produced from the photosensitive resin composition has a transmittance of 20% or less at a wavelength of 450nm, a reflectance of 10% or more at wavelengths of 550nm and 650nm, and a transmittance of 70% or more at a wavelength of 900nm when the thickness of the cured film is 3 [ mu ] m to 15 [ mu ] m.
2. The photosensitive resin composition for forming a partition wall according to claim 1, wherein the colorant comprises a white pigment, a black pigment, and a yellow pigment.
3. The photosensitive resin composition for forming a partition wall according to claim 2, wherein the white pigment has an average particle size of 150nm to 400nm.
4. The photosensitive resin composition for forming a partition wall according to claim 2, wherein the white pigment comprises titanium oxide (TiO 2 )。
5. The photosensitive resin composition for forming a partition wall according to claim 4, wherein the titanium oxide (TiO 2 ) Is selected toFree silicon oxide (SiO) 2 ) Alumina (Al) 2 O 3 ) Zirconium oxide (ZrO) 2 ) And one or more of the group consisting of organic substances.
6. The photosensitive resin composition for forming a partition wall according to claim 2, wherein the black pigment contains one or more selected from the group consisting of lactam black, perylene black, cyanine black and aniline black.
7. The photosensitive resin composition for forming a partition wall according to claim 2, wherein the c.i. yellow pigment contains one or more selected from the group consisting of c.i. yellow pigments 138, 139, 150, and 185.
8. The photosensitive resin composition for forming a partition wall according to claim 2, wherein the content of the white pigment is 1 to 28% by weight with respect to the total weight of the photosensitive resin composition.
9. The photosensitive resin composition for forming a partition wall according to claim 2, wherein the content of the black pigment is 0.05 to 5% by weight with respect to the total weight of the photosensitive resin composition.
10. The photosensitive resin composition for forming a partition wall according to claim 2, wherein the content of the yellow pigment is 0.05 to 5% by weight with respect to the total weight of the photosensitive resin composition.
11. The photosensitive resin composition for forming a partition wall according to claim 1, wherein the alkali-soluble resin contains any one or more of Cardo alkali-soluble resin and acrylic alkali-soluble resin.
12. The photosensitive resin composition for forming a partition wall according to claim 1, further comprising at least one selected from the group consisting of a filler, a polymer compound, a curing agent, a surfactant, an adhesion promoter, an antioxidant, and an anti-coagulant.
13. A partition wall structure produced from the photosensitive resin composition for forming a partition wall according to any one of claims 1 to 12.
14. A display device comprising the spacer structure of claim 13.
CN202280014788.4A 2021-02-26 2022-02-24 Photosensitive resin composition for forming partition wall, partition wall structure manufactured using the same, and display device including the partition wall structure Pending CN116848465A (en)

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PCT/KR2022/002700 WO2022182157A1 (en) 2021-02-26 2022-02-24 Photosensitive resin composition for forming partition walls, partition wall structure manufactured using same, and display device comprising partition walls

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