CN114967334A - Photosensitive resin composition, color filter manufactured using the same, and display device including the color filter - Google Patents

Photosensitive resin composition, color filter manufactured using the same, and display device including the color filter Download PDF

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Publication number
CN114967334A
CN114967334A CN202210175670.1A CN202210175670A CN114967334A CN 114967334 A CN114967334 A CN 114967334A CN 202210175670 A CN202210175670 A CN 202210175670A CN 114967334 A CN114967334 A CN 114967334A
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photosensitive resin
resin composition
region
pigment
photopolymerization initiator
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柳廷昊
裵辰哲
梁炳道
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Dongwoo Fine Chem Co Ltd
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Dongwoo Fine Chem Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

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

Abstract

The invention provides a photosensitive resin composition, a color filter manufactured by using the photosensitive resin composition and a display device comprising the color filter, wherein the photosensitive resin composition comprises a photopolymerization initiator, and the area ratio of a region (B) to the region (A) in a region (A) defined by normalized emission spectrum of an exposure machine, a region (P) defined by absorption spectrum of the photopolymerization initiator and a region (B) defined by overlapping region of the region (A) and the region (P) is more than 0.4 in the wavelength of 350-390 nm. According to the photosensitive resin composition of the present invention, the opening (Hole) characteristics can be further improved as compared with conventional photosensitive resin compositions.

Description

Photosensitive resin composition, color filter manufactured using the same, and display device including the color filter
Technical Field
The present invention relates to a photosensitive resin composition, a color filter produced using the photosensitive resin composition, and a display device including the color filter.
Background
Color filters are widely used in various display devices such as image sensors and Liquid Crystal Displays (LCDs), and their application range is rapidly expanding. The color filter is formed of a colored pattern of three colors of Red (Red), Green (Green), and Blue (Blue), or a colored pattern of three colors of Yellow (Yellow), Magenta (Magenta), and Cyan (Cyan).
The colored pattern of each of the color filters is generally formed 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 usually performed by a photolithography step.
Specifically, the photosensitive resin composition is selectively exposed and developed by a photolithography process to form a desired photocured pattern. In this process, a photosensitive resin composition capable of improving pattern characteristics and yield in the process and preventing pattern peeling is required.
On the other hand, the photosensitive resin composition can form a photocured pattern using a wide range of wavelengths. In particular, with the recent improvement and reduction in circuit technology and device structure to achieve a higher density of integrated circuits, the wavelength of an exposure apparatus is becoming shorter as in G-line (436nm), I-line (365nm), and the like.
Korean laid-open patent No. 10-2016-. However, film loss still occurs before and after development, and it is difficult to form an opening (Hole), and pattern peeling occurs, and therefore, a photosensitive resin composition for solving such a problem is required.
Documents of the prior art
Patent document
Patent document 1: korean laid-open patent No. 10-2016-0140652
Disclosure of Invention
Problems to be solved
The invention aims to provide a photosensitive resin composition with improved opening (Hole) characteristics.
Further, an object of the present invention is to provide a photosensitive resin composition in which a film reduction rate before and after development is minimized.
Another object of the present invention is to provide a photosensitive resin composition which can prevent peeling of a formed pattern.
Another object of the present invention is to provide a color filter produced from the photosensitive resin composition, and a display device including the color filter.
Means for solving the problems
The present invention relates to a photosensitive resin composition comprising a photopolymerization initiator, wherein the photopolymerization initiator has an area ratio of a region (B) to a region (A) in a region (A) defined by a normalized emission spectrum of an exposure machine, a region (P) defined by an absorption spectrum of the photopolymerization initiator, and a region (B) defined by an overlapping region of the region (A) and the region (P) of 0.4 or more in a wavelength of 350 to 390 nm.
In a first aspect of the present invention, the normalized emission spectrum may be normalized by a maximum emission wavelength of the exposure machine in a wavelength range of 350 to 390 nm.
In the second aspect of the present invention, the concentration of the photopolymerization initiator used for the measurement of the absorption spectrum may be 10 ppm.
In a third aspect of the present invention, the photopolymerization initiator may have a maximum absorption wavelength at a wavelength of 340 to 380 nm.
In the fourth aspect of the present invention, the ink may further include a colorant, an alkali-soluble resin, a photopolymerizable compound, and a solvent.
In a fifth aspect of the present invention, the colorant may contain a red pigment.
In a sixth aspect of the present invention, the Red Pigment may include c.i. Pigment Red (Pigment Red) 242.
In the seventh aspect of the present invention, the photosensitive resin composition may contain 1 to 50 wt% of a colorant, 5 to 70 wt% of an alkali-soluble resin, 5 to 50 wt% of a photopolymerizable compound, and 1 to 10 wt% of a photopolymerization initiator, based on the total weight of solid components in the photosensitive resin composition, and may contain 60 to 90 wt% of a solvent, based on the total weight of the photosensitive resin composition.
In the eighth aspect of the present invention, the ink-jet recording medium may further comprise one or more selected from the group consisting of a filler, another polymer compound, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-coagulant, a dispersant, and an ink-repellent agent.
In a ninth aspect of the present invention, the exposure device may be an LED exposure device.
The present invention also relates to a color filter produced from the photosensitive resin composition.
Furthermore, the present invention relates to a display device comprising the above color filter.
Effects of the invention
According to the photosensitive resin composition of the present invention, the opening (Hole) characteristics can be further improved as compared with conventional photosensitive resin compositions.
Further, according to the photosensitive resin composition of the present invention, the film reduction rate before and after development can be further minimized as compared with the conventional photosensitive resin composition.
Further, according to the photosensitive resin composition of the present invention, the formed pattern can be more prevented from peeling than the conventional photosensitive resin composition.
Drawings
Fig. 1 to 3 are diagrams showing spectra of an embodiment of the present invention.
Detailed Description
The present invention relates to a photosensitive resin composition containing a photopolymerization initiator satisfying a specific spectral characteristic, a color filter produced using the photosensitive resin composition, and a display device including the color filter.
More specifically, the present invention is characterized by comprising a photopolymerization initiator, wherein the area ratio of a region (B) to a region (A) in a region (A) defined by a normalized emission spectrum of an exposure machine, a region (P) defined by an absorption spectrum of the photopolymerization initiator, and a region (B) defined by an overlapping region of the region (A) and the region (P) is 0.4 or more at a wavelength of 350 to 390 nm.
By using the photosensitive resin composition containing the photopolymerization initiator satisfying the spectral characteristics, the aperture (Hole) characteristics and the film retention rate can be improved, and the formed pattern can be prevented from peeling off, thereby improving the resolution and light efficiency of the color filter and the display device.
The "solid component" described in the present invention means the remaining components except the solvent.
Hereinafter, the contents of the present invention will be described in the following as < photosensitive resin composition >, < color filter >, and < display device >.
< photosensitive resin composition >
The photosensitive resin composition of the present invention may contain a photopolymerization initiator, and the area ratio of the region (B) to the region (a) in the region (a) defined by the normalized emission spectrum of the exposure machine, the region (P) defined by the absorption spectrum of the photopolymerization initiator, and the region (B) defined by the overlapping region of the region (a) and the region (P) is 0.4 or more at a wavelength of 350 to 390 nm. In one embodiment, the photosensitive resin composition may further include a colorant, an alkali-soluble resin, a photopolymerizable compound, and a solvent.
The exposure machine is not particularly limited as long as it can perform photocuring of the photosensitive resin composition, and is preferably a Light Emitting Diode (LED) exposure machine. In this case, there is an advantage in that light having a specific wavelength can be selectively irradiated. In one embodiment, the exposure machine may be an LED exposure machine that emits a wavelength of an I-line (365nm) region, and preferably, may be an LED exposure machine that selects only a wavelength of an I-line (365nm) region.
Coloring agent
The colorant may contain one or more pigments.
The pigment may be an organic pigment or an inorganic pigment commonly used in the art.
The pigment may be any of various pigments used in printing inks, inkjet inks, and the like, and specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, and bisperylene pigments
Figure BDA0003520135830000041
Oxazine pigments, anthraquinone pigments, dianthraquinone-based pigments, anthrapyrimidine pigments, anthanthrone (anthanthrone) pigments, indanthrone (indanthrone) pigments, flavanthrone pigments, pyranthrone (pyranthrone) pigments, diketopyrrolopyrrole pigments, and the like.
Examples of the inorganic pigment include metal compounds such as metal oxides and metal complexes, and specific examples thereof include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black, and composite metal oxides
In particular, as The organic pigment and The inorganic pigment, there may be mentioned, specifically, compounds classified as pigments in The color index (published by The society of Dyers and Colourists), more specifically, pigments numbered in The following color index (c.i.), but The present invention is not limited thereto.
C.i. pigment yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185
C.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71
C.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264
C.i. pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38
C.i. pigment blue 15(15:3, 15:4, 15:6, etc.), 21, 28, 60, 64 and 76
C.i. pigment green 7, 10, 15, 25, 36, 47 and 58
C.i. pigment brown 28
C.I. pigment Black 1 and 7, etc
The above pigments may be used each alone or in combination of two or more.
Among the above-exemplified c.i. pigments (pigments), it is preferable to use a pigment selected from the group consisting of c.i. pigment orange 38, c.i. pigment red 122, c.i. pigment red 166, c.i. pigment red 177, c.i. pigment red 208, c.i. pigment red 242, c.i. pigment red 254, c.i. pigment red 255, c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 150, c.i. pigment yellow 185, c.i. pigment green 7, c.i. pigment green 36, c.i. pigment green 58, c.i. pigment green 59, c.i. pigment violet 23, c.i. pigment blue 15:3 and pigment blue 15: 6.
In one embodiment, the photosensitive resin composition of the present invention may particularly include c.i. pigment red 242. In this case, there is an advantage in that the opening (Hole) characteristics can be improved and peeling of the formed pattern can be prevented.
Specifically, the sensitivity based on the absorbance of the pigment has a trade-off relationship with the opening (Hole) characteristic based on the line width of the pattern. Therefore, when the absorbance of the pigment at a specific wavelength is low, the sensitivity of the photosensitive resin composition at the wavelength increases, and the line width of the pattern formed increases, possibly deteriorating the opening (Hole) characteristics. In addition, when the content of the photopolymerization initiator contained in the photosensitive resin composition is reduced in order to improve the opening (Hole) characteristics, the pattern curing does not proceed sufficiently, and thus a pattern peeling phenomenon occurs after the development.
C.i. pigment red 177 and c.i. pigment red 254 exhibit lower absorbance at the wavelength of the I-line (365nm) region. Therefore, the sensitivity of the photosensitive resin composition in the emission wavelength of the I-line (365nm) region of the exposure apparatus increases, and as a result, the formation of the opening (Hole) becomes difficult.
On the other hand, c.i. pigment red 242 exhibits higher absorbance in the wavelength of the I-line (365nm) region than the pigments such as c.i. pigment red 177 and c.i. pigment red 254. Therefore, by appropriately adjusting the content of the photopolymerization initiator exhibiting high absorbance at the wavelength of the I-line (365nm) region, it is possible to prevent the pattern peeling while improving the opening (Hole) characteristics.
The pigment is preferably a pigment dispersion liquid in which the particle size of the pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of performing a dispersion treatment by adding a pigment dispersant, and a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained by the above method.
The pigment dispersant is added for the purpose of disaggregation and maintenance of stability of the pigment, and any pigment dispersant generally used in the art may be used without limitation.
Specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and other surfactants, and these may be used alone or in combination.
In addition, other resin type pigment dispersants may be used as the pigment dispersant. Examples of the other resin-type pigment dispersants include known resin-type pigment dispersants, and particularly oily dispersants such as polyurethanes, polycarboxylates represented by polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphates, esters of hydroxyl-containing polycarboxylic acids and modified products thereof, or amides or salts thereof formed by reaction of polyesters having free (free) carboxyl groups with poly (lower alkylene imine); water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinyl pyrrolidone; a polyester; a modified polyacrylate; an ethylene oxide/propylene oxide adduct; and phosphate esters and the like. Other resin type pigment dispersants may also be used. Examples of the other resin-type pigment dispersants include known resin-type pigment dispersants, and particularly oily dispersants such as polyurethanes, polycarboxylates represented by polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphates, esters of hydroxyl-containing polycarboxylic acids and modified products thereof, or amides or salts thereof formed by reaction of polyesters having free (free) carboxyl groups with poly (lower alkylene imine); water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinyl pyrrolidone; a polyester; a modified polyacrylate; an ethylene oxide/propylene oxide adduct; and phosphate esters and the like.
As a commercial product of the above resin type dispersant, for example, a cationic resin dispersant is available under a trade name of BYK chemical: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, and DISPER BYK-184; trade name of BASF (BASF) corporation: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; trade name of Lubirzol (lubol) corporation: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; trade name of Chuanjian refining company: HINACT T-6000, HINACT T-7000, HINACT T-8000; trade name of Aomoto corporation: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; trade name of Kyoeisha chemical Co: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc. The resin type pigment dispersants may be used alone or in combination of two or more, or may be used in combination with an acrylic dispersant.
The content of the pigment dispersant may be 5 to 60% by weight, preferably 15 to 50% by weight, based on the total weight of solid components in the pigment dispersion liquid. If the content of the pigment dispersant is more than 60% by weight, the viscosity may be increased, and if the content is less than 5% by weight, the pigment may not be easily micronized, and there may be a problem of gelation after dispersion.
In one embodiment of the present invention, the colorant may further contain a dye generally used in the art.
The dye may be additionally used without limitation as long as it is soluble or dispersible in an organic solvent. It is preferable to use a dye having solubility in an organic solvent and capable of ensuring reliability such as solubility in an alkali developing solution, 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 the acid dyes with nitrogen-containing compounds, sulfonamide compounds of the acid dyes, and derivatives thereof, and azo-based, xanthene-based, phthalocyanine-based acid dyes, and derivatives thereof. Preferably, The dye includes a compound classified as a dye in The color index (The Society of Dyers and Colourists) or a known dye described in a dyeing manual (color dyeing Co., Ltd.).
Specific examples of the above dye include c.i. solvent dyes:
red dyes such as c.i. solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179 and the like;
c.i. blue dyes such as solvent blue 5, 35, 36, 37, 44, 59, 67, 70, etc.;
c.i. violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49, etc.;
c.i. yellow dyes such as solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, etc.;
c.i. orange dyes such as solvent orange 2, 7, 11, 15, 26, 56;
c.i. solvent green 1,3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc.
The c.i. solvent dye is preferably c.i. solvent red 8, 49, 89, 111, 122, 132, 146, 179 which is excellent in solubility in an organic solvent; c.i. solvent blue 35, 36, 44, 45, 70; c.i. solvent violet 13, more preferably c.i. solvent red 8, 122, 132.
Further, as the c.i. acid dye, there may be mentioned:
c.i. acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426, etc. red dye;
c.i. yellow dyes such as 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;
orange dyes such as c.i. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173, etc.;
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 and the like blue dye;
violet dyes such as c.i. acid violet 6B, 7, 9, 17, 19, 66;
c.i. acid green 1,3,5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, and the like.
The acid dye is preferably c.i. acid red 92 having excellent solubility in organic solvents; c.i. acid blue 80, 90; c.i. acid violet 66.
Further, as the c.i. direct dye, there can be mentioned:
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 and the like red dye;
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 and the like;
c.i. direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, etc. orange dyes;
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, and the like blue dye;
c.i. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 and the like violet dye;
c.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc.
Further, as the c.i. mediator dye, there may be mentioned:
yellow dyes such as c.i. mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 and the like;
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 and the like red dye;
c.i. intermediate orange 3,4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48 and other orange dyes;
c.i. 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 and the like blue dye;
c.i. intermediate violet 1,2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58 and the like violet dye;
c.i. medium green 1,3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and the like.
These dyes may be used each alone or in combination of two or more.
The content of the colorant may be 1 to 50% by weight, preferably 10 to 45% by weight, based on the total weight of 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 when forming a thin film, the releasability of the non-pixel portion is not reduced during development, and residue is not likely to be generated, which is preferable.
Alkali soluble resin
The alkali-soluble resin has reactivity and alkali solubility due to the action of light or heat, functions as a dispersion medium for solid components contained in the photosensitive resin composition, and any resin known in the art can be selected and used without particular limitation as long as it functions as a binder resin.
Specifically, the alkali-soluble resin is preferably a copolymer of an unsaturated carboxyl group-containing monomer and another monomer copolymerizable therewith.
Examples of the unsaturated carboxyl group-containing monomer include unsaturated carboxylic acids having 1 or more carboxyl groups in the molecule, such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated polycarboxylic acids.
Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α -chloroacrylic acid, and carnosic acid.
Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Further, the above-mentioned unsaturated polycarboxylic acid may be a mono (2-methacryloyloxyalkyl) ester thereof, and for example, may be mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) succinate, mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate or the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxylic polymer at both ends thereof, and examples thereof include ω -carboxy polycaprolactone monoacrylate, ω -carboxy polycaprolactone monomethacrylate and the like.
The unsaturated carboxyl group-containing monomers may be used alone or in combination of two or more.
Examples of the other monomer copolymerizable with the unsaturated carboxyl group-containing monomer include aromatic vinyl compounds such as styrene, α -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and indene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, n-butyl acrylate, isopropyl acrylate, isobutyl acrylate, butyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxypropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures thereof, Unsaturated carboxylic acid esters such as dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; aminoalkyl esters of unsaturated carboxylic acids such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, and dicyanovinylene; unsaturated amides such as acrylamide, methacrylamide, α -chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; unsaturated imides such as maleimide, benzylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1, 3-butadiene, isoprene and chloroprene; and macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, or polysiloxane. These monomers may be used each alone or in combination of two or more.
The alkali-soluble resin may be contained in an amount of 5 to 70 wt%, preferably 5 to 50 wt%, based on the total weight of solid components in the photosensitive resin composition. When the content of the alkali-soluble resin is within the above range, the solubility in a developer is sufficient, a cured film is easily formed, the film is prevented from decreasing in the pixel portion of the exposed portion during development, and the peeling of the non-pixel portion is improved, which is preferable.
The acid value of the alkali-soluble resin is preferably 30 to 150mgKOH/g, so that the stability of the photosensitive resin composition over time can be improved. When the acid value of the alkali-soluble resin is less than 30mgKOH/g, it is difficult to secure a sufficient developing speed in the photosensitive resin composition, and when it is more than 150mgKOH/g, the adhesiveness to the substrate is lowered and a short circuit of a pattern is easily generated, and the stability with time of the photosensitive resin composition is lowered and the viscosity may be increased.
Photopolymerizable compound
The photopolymerizable compound is a compound polymerizable by light and heat, and any polymerizable compound known in the art can be selected and used without particular limitation as long as it can be polymerized by light and heat, and specifically, a monofunctional monomer, a difunctional monomer, another polyfunctional monomer, and the like can be used.
The monofunctional monomer is not particularly limited in kind, and examples thereof include nonylphenylcarbinol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone.
The type of the bifunctional monomer is not particularly limited, and examples thereof 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.
The polyfunctional monomer is not particularly limited in kind, and examples thereof include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and the like.
The content of the photopolymerizable compound may be 5 to 50 wt%, preferably 10 to 40 wt%, based on the total weight of the solid components in the photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, it is preferable from the viewpoint of the intensity and smoothness of the pixel portion.
Photopolymerization initiator
The photopolymerization initiator may have an area ratio of the region (B) to the region (a) in the region (a) defined by the normalized emission spectrum of the exposure machine, the region (P) defined by the absorption spectrum of the photopolymerization initiator, and the region (B) defined by the overlapping region of the region (a) and the region (P) of 0.4 or more, preferably 0.5 to 0.7, in the wavelength of 350 to 390 nm.
When the photopolymerization initiator satisfies the spectral characteristics, the opening (Hole) characteristics can be improved, the reduction of the film before and after development can be minimized, and the peeling of the formed pattern can be prevented.
Specifically, the conventional mercury exposure apparatus emits light in the region of 315nm to 335nm in addition to the I-line (365nm), and can obtain sufficient surface sensitivity by inducing sufficient photoactivity of the conventional photopolymerization initiator, and can easily minimize the film reduction rate before and after development. On the other hand, in the case of an exposure machine that emits only I-line (365nm), such as an LED exposure machine, since short-wavelength light in a conventional mercury exposure machine is not present, there is a problem that sufficient photoactivity cannot be induced and surface sensitivity is deteriorated.
In order to overcome such problems, the present invention can exhibit high photoactivity in the I-line (365nm) region using a specific photopolymerization initiator satisfying the above spectral characteristics, thereby enabling to improve the opening (Hole) characteristics and minimize the film reduction before and after development.
The normalization of the emission spectrum of the above exposure machine is not particularly limited as long as it is used to obtain a constant structure by repeated experiments. In one embodiment, the maximum emission wavelength of the exposure machine can be normalized by the maximum emission wavelength of the exposure machine in the I-line region (350-390 nm), for example, by dividing the emission spectrum of the I-line region (350-390 nm) of the exposure machine by the spectral value of the maximum emission wavelength of the I-line region, thereby normalizing the spectral value of the maximum emission wavelength to 1.
In order to make it possible for a person having ordinary skill in the art to clearly understand the contents of the present invention and easily reproduce the same, the meanings of the regions (a), (P), and (B) will be described with reference to fig. 1 to 3 as an example, and the area calculation methods of the regions (a), (P), and (B) will be described with reference to tables 1 and 2 of reference examples described later, specifically as follows.
FIGS. 1 to 3 are diagrams showing spectra of an embodiment of the present invention. Specifically, fig. 1 is a view showing a region (a) defined by a normalized emission spectrum of an LED exposure machine at wavelengths of 350 to 390nm, fig. 2 is a view showing a region (P) defined by an absorption spectrum of 10ppm of DFI-020 (manufactured by datolong chemical corporation) which is an example of a photopolymerization initiator satisfying the above spectral characteristics at wavelengths of 350 to 390nm, and fig. 3 is a view showing a region (B) defined by an overlapping region of the region (a) and the region (P).
Referring to FIG. 1, the area (A) defined by the normalized emission spectrum of the exposure machine in the wavelength of 350-390 nm may mean: when the Wavelength (Wavelength; λ) is set as the x-axis (nm) and the value of the normalized emission spectrum is set as the y-axis, the region surrounded by the normalized emission spectrum curve of the exposure machine, the straight lines (λ 350nm and 390nm) having the wavelengths (Wavelength; λ) of 350nm and 390nm, and the Wavelength (Wavelength; λ) axis (i.e., the x-axis).
Referring to fig. 2, the region (P) defined by the absorption spectrum of the photopolymerization initiator in a wavelength of 350 to 390nm may mean: when the Wavelength (Wavelength; λ) is set to the x-axis (nm) and the absorbance is set to the y-axis, the region surrounded by the absorption spectrum curve of the photopolymerization initiator, the straight lines (λ: 350nm and 390nm) having the wavelengths (Wavelength; λ) of 350nm and 390nm, and the Wavelength (Wavelength; λ) axis (i.e., the x-axis).
Referring to fig. 3, the region (B) defined by the overlapping region of the region (a) and the region (P) in the wavelength of 350 to 390nm may mean: the region (A) overlaps with the region (P) when the Wavelength (Wavelength; lambda) is set to the x-axis (nm) and the normalized emission spectrum value and absorbance are set to the y-axis (i.e., when the spectra of FIGS. 1 and 2 are overlapped).
Referring to tables 1 and 2 of the reference example, first, the emission spectrum of light in the I-line (365nm) region of the exposure machine was measured, and the emission spectrum measured above was divided at intervals of 1nm to calculate the spectral integral ratio for each wavelength. For example, as disclosed in table 1, the integration ratio of the exposer emission spectrum in the 350nm wavelength may be 0.0358, and the integration ratio of the exposer emission spectrum of each wavelength may be calculated to 390nm at 1nm intervals.
Then, the exposer emission spectral integral ratio for each wavelength is divided by the maximum value 0.7763(367nm) in the exposer emission spectral integral ratio, thereby obtaining a normalized emission spectrum of the exposer. For example, as disclosed in table 1, the normalized emission spectra values in the 350nm and 367nm wavelengths may be 0.0461 and 1.0000, respectively.
Then, the area of the region (A) can be calculated by summing the values of the normalized emission spectra in the wavelengths of 350 to 390 nm. For example, as disclosed in table 2, the area of the region (a) may be 8.7225.
On the other hand, in addition to calculating the area of the region (A), the absorption spectrum was measured for DFI-020 of 10ppm to define a region (P). The absorption spectrum measured above was divided at intervals of 1nm, and the average absorbance at each wavelength was calculated. For example, as disclosed in Table 1, the average absorbance of the DFI-020 absorption spectrum at a wavelength of 350nm may be 0.5700, and the average absorbance of the DFI-020 absorption spectrum at each wavelength may be calculated to 390nm at 1nm intervals.
Then, the value of the normalized emission spectrum of the exposure machine or the average absorbance of the photopolymerization initiator corresponding to the overlapping region of the region (a) and the region (P), i.e., the region (B), is extracted. For example, as disclosed in table 2, the extraction value at 350nm wavelength may be 0.0461, and the extraction value at each wavelength may be extracted to 390nm at 1nm intervals.
Then, the area of the region (B) can be calculated by adding the extracted values at the wavelengths of 350 to 390 nm. For example, as disclosed in Table 2, the area of region (B) of DFI-020 can be 5.8959.
Then, the ratio of the area of the region (B) to the area of the region (A) is 0.68, whereby DFI-020 can be defined as a photopolymerization initiator in which the area ratio of the region (B) to the region (A) is 0.4 or more.
On the other hand, the area calculation methods of the regions (a), (P), and (B) are exemplary, and as described above, the present invention is not limited thereto.
The concentration of the photopolymerization initiator sample for measuring the absorption spectrum of the photopolymerization initiator is not particularly limited, and may be appropriately selected according to the method for normalizing the emission spectrum of the exposure machine. In one embodiment, the concentration of the photopolymerization initiator used for measuring the absorption spectrum of the photopolymerization initiator may be 1 to 50ppm, and preferably 10 ppm.
In one embodiment, the photopolymerization initiator preferably has a maximum absorption wavelength in a wavelength range of 340 to 380 nm. Commercially available products include "DFI-020" from Dadong chemical company, "PBG-345" from Changzhou Kangqiao corporation, "OXE-03" from Pasteur corporation, and "NCI-831" from ADEKA corporation, and the photopolymerization initiators may be used alone or in combination of two or more.
The content of the photopolymerization initiator may be 1 to 10% by weight, preferably 1 to 7% by weight, based on the total weight of solid components in the photosensitive resin composition. In this case, the photosensitive resin composition is preferably high in sensitivity and short in exposure time, because productivity can be improved and high resolution can be maintained. Further, the strength of a pixel portion formed using the photosensitive resin composition and the smoothness of the surface of the pixel portion can be improved.
In some examples, a photopolymerization initiator other than the above photopolymerization initiators may be used in combination.
Typically, one or more compounds selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, bisimidazole compounds, thioxanthone compounds, and carbazole compounds are preferably used.
Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethylketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylphenylsulfanyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propan-1-one, and mixtures thereof, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.
Examples of the benzophenone-based compound include benzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3',4,4' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone.
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, and 2, 4-bis (trichloromethyl) -6- [2- (furan-2- Yl) ethylene ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethylene ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) ethylene ] -1,3, 5-triazine, and the like.
Specific examples of the biimidazole-based compound include 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenylbiimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4',5,5' -tetraphenylbiimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (alkoxyphenyl) biimidazole, 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetrakis (trialkoxyphenyl) biimidazole, 2-bis (2, 6-dichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole, or biimidazole compounds in which the phenyl group at the 4,4',5,5' position is substituted with an alkoxycarbonyl group, and the like. Among them, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenyl biimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4',5,5' -tetraphenyl biimidazole, 2-bis (2, 6-dichlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole are preferably used.
Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.
Examples of the carbazole-based compound include 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3- (2-methyl-2-morpholinopropionyl) -9-methylcarbazole, 3- (2-methyl-hydroxypropionyl) -9-methylcarbazole, and 3- (1-hydroxycyclohexanoyl) -9-butylcarbazole.
In addition, in order to improve the sensitivity of the colored photosensitive resin composition of the present invention, the photopolymerization initiator may further contain a photopolymerization initiation aid. The colored photosensitive resin composition of the present invention contains a photopolymerization initiation aid, and therefore, the sensitivity is further increased and the productivity can be improved.
The photopolymerization initiator may preferably be one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and polyfunctional thiol compounds.
As the amine compound, an aromatic amine compound is preferably used, and specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, and the like, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N-dimethyl-p-toluidine, 4' -bis (dimethylamino) benzophenone (known as Michler's ketone), 4' -bis (diethylamino) benzophenone, and the like can be used.
The carboxylic acid compound is preferably an aromatic heteroacetic acid, and specific examples thereof include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid and the like.
Examples of the polyfunctional thiol compound include tris- [ (3-mercaptopropionyloxy) -ethyl ] -isocyanurate, trimethylolpropane tri-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, dipentaerythritol hexa-3-mercaptopropionate, and the like.
When the photopolymerization initiator is further contained, the content of the photopolymerization initiator may be 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total weight of the solid components of the alkali-soluble resin and the photopolymerizable compound. When the content of the photopolymerization initiator is within the above range, the sensitivity of the colored photosensitive resin composition can be further improved, and the productivity of a color filter formed using the colored photosensitive resin composition can be improved.
Solvent(s)
The solvent may be any organic solvent known in the art without particular limitation.
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, butyl methoxyacetate 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, ketones such as ethanol, propanol, butanol, hexanol, cyclohexanol, and ethylene glycol dibutyl ether, ketones such as ethanol, butanol, cyclohexanol, and methyl ethyl ketone, Alcohols such as ethylene glycol and glycerol, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ -butyrolactone.
From the viewpoint of coating properties and drying properties, the solvent is preferably an organic solvent having a boiling point of 100 to 200 ℃, more preferably an ester such as alkylene glycol alkyl ether acetate, a ketone, ethyl 3-ethoxypropionate, or methyl 3-methoxypropionate, and further preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, or methyl 3-methoxypropionate.
The above solvents may be used each alone or in combination of two or more.
The content of the solvent may be 60 to 90% by weight, preferably 75 to 90% by weight, based on the total weight of the photosensitive resin composition. When the content of the solvent is within the above content range, the coating apparatus such as a roll coater, a spin coater, a slit coater (also referred to as a die coater), or a spray printer provides an effect of improving coating properties.
Additive agent
The photosensitive resin composition of the present invention may further contain an additive as needed, and the kind of the additive may be determined according to the needs of the user, and the present invention is not particularly limited, and examples thereof include fillers, other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-coagulant agents, dispersants, and ink repellents. The above-exemplified additives may be used singly or in combination of two or more.
As the filler, glass, silica, alumina, and the like can be used, but the filler is not limited thereto.
As the other polymer compound, specifically, a curable resin such as an epoxy resin or a maleimide resin; thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane; and the like, but not limited thereto.
The curing agent is used for enhancing deep-section curing and mechanical strength, and specifically, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, and the like can be used, but the curing agent is not limited thereto. Specific examples of the epoxy compound include, but are not limited to, bisphenol a epoxy resins, hydrogenated bisphenol a epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, novolac epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, brominated derivatives of these epoxy resins, aliphatic, alicyclic, or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, epoxy compounds of butadiene (co) polymers, epoxy compounds of isoprene (co) polymers, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate. Specific examples of the oxetane compound include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexane dicarboxylic acid bisoxetane, but the oxetane compound is not limited thereto.
The curing agent may be used in combination with a co-curing compound capable of ring-opening polymerizing an epoxy group of the epoxy compound or an oxetane skeleton of the oxetane compound. Specifically, polycarboxylic acids, polycarboxylic anhydrides, acid generators, and the like can be used as the curing assistant compound. The polycarboxylic acid anhydride may be a commercially available epoxy resin curing agent. Examples of the commercially available epoxy resin curing agent include ADEKA HARDENER EH-700 (trade name, manufactured by ADEKA industries, Ltd.), RIKACID HH (trade name, manufactured by Nissian Chemicals Co., Ltd.), MH-700 (trade name, manufactured by Nissian Chemicals Co., Ltd.), and the like.
The curing agent and the co-curing compound exemplified above may be used each alone or in combination of two or more.
As the surfactant, commercially available surfactants can be used, and examples thereof include silicone surfactants, fluorine surfactants, and mixtures thereof. Examples of the silicone surfactant include surfactants having a siloxane bond. Examples of commercially available products include Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toray silicone 29SHPA, Toray silicone SH30PA, polyether-modified silicone SH8400 (manufactured by Toray silicone Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by shin-Etsu silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by TSGE TSToshiba silicone Co., Ltd.).
The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain. Specifically, the strains include FLUORAD (trade name) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M), MEGAFAC (trade name) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F251, MEGAFAC F410, MEGAFAC F430, MEGAFAC F444, MEGAFAC F477, MEGAFAC F551, MEGAFAC F553, MEGAFAC F554, MEGAFAC F556, MEGAFAC F557, MEGAFAC F558, MEGAFAC F559, MEGAFAC F562, MEGAFAC F5631, MEGAFAC F1100, MEGAFAC F570, MEGAFAC R30, MEGAFAC R26, MEGAFAC 6754, MEGAFAC F43, MEGAFAC F565, MEGAFAC F382, MEGAFAC F185, MEGAFAC F351, MEGAFAC F382, MEGAFAC F53, TOPEF 3644, TOP FAF 382, TOPEFEF 3644, TOPEFE 3644, TOPEFEFE FAF 3644, and TOPEFE FAF 3658, and so on.
As the adhesion promoter, a silane compound selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane, or a mixture thereof.
The antioxidant may include one or more selected from the group consisting of a phosphorus antioxidant, a sulfur antioxidant, and a phenol antioxidant, and in this case, it is possible to suppress a color change phenomenon that may occur at a high temperature in a process or yellowing that may occur due to a light source after display manufacturing. The antioxidant may include one or more selected from the group consisting of a phenol-based compound, a phosphorus-based compound, and a sulfur-based compound, and they may be used in combination with a phenol-based-phosphorus-based compound, a phenol-sulfur-based compound, a phosphorus-sulfur-based compound, or a phenol-phosphorus-sulfur-based compound.
Specific examples of the ultraviolet absorber include, but are not limited to, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.
Specific examples of the anti-gelling agent include, but are not limited to, sodium polyacrylate and the like.
The dispersant is added to maintain the dispersion stability of the pigment, and any dispersant generally used in the art may be used without limitation.
The ink repellent has a fluorine atom in the molecule. Thus, the ink repellent has a property of moving to the upper surface (upper surface mobility) and an ink repellency in the process of forming a cured film using the photosensitive resin composition containing the same. By using the ink-repellent agent, an upper layer portion including the upper surface of the obtained cured film becomes a layer in which the ink-repellent agent is densely present (hereinafter, preferably also referred to as "ink-repellent layer"), and ink repellency is imparted to the upper surface of the cured film. Further, from the viewpoint of improving the fixing property of the ink repellent in the ink repellent layer, the ink repellent is preferably a compound having an ethylenic double bond. Since the ink repellent has an ethylenic double bond, a radical acts on the ethylenic double bond of the ink repellent moving to the upper surface, and crosslinking by (co) polymerization can be performed between the ink repellers or between the ink repellers and other components having an ethylenic double bond contained in the photosensitive resin composition for partition wall formation.
The type of the ink repellent is not particularly limited, and examples thereof include a partial hydrolysis condensate of a hydrolyzable silane compound. The hydrolyzable silane compound may be used alone or in combination of two or more. An ink repellent having a fluorine atom and comprising a partially hydrolyzed condensate of a hydrolyzable silane compound can be used, and an ink repellent comprising a compound having a hydrocarbon chain as its main chain and a fluorine atom in its side chain can be used.
The additives may be added as appropriate by those skilled in the art within a range not impairing the effects of the present invention. For example, the additive may be used in an amount of 0.05 to 10 wt%, preferably 0.1 to 10 wt%, more preferably 0.1 to 5 wt% based on the total weight of the photosensitive resin composition, but is not limited thereto.
The photosensitive resin composition of the present invention can be produced by a general method known in the art, and the present invention is not particularly limited, and can be produced by, for example, the following method.
First, the pigment in the colorant is mixed with a solvent and dispersed by a bead mill or the like until the average particle diameter of the pigment becomes 30 to 300 nm. At this time, a pigment dispersant, a part or the whole of the alkali-soluble resin, or a dye may be mixed together with a solvent and dissolved or dispersed as necessary. The colored photosensitive resin composition of the present invention can be produced by further adding the remaining alkali-soluble resin, photopolymerizable compound, photopolymerization initiator, photoacid generator, epoxy compound, scatterer, and additive, and optionally a solvent, to the mixed dispersion liquid so as to have a predetermined concentration.
< color Filter >
The present invention provides a color filter manufactured by using the photosensitive resin composition.
In one embodiment, the color filter includes a pattern formed by applying the photosensitive resin composition on a substrate, and then exposing and developing the photosensitive resin composition in a predetermined pattern.
Hereinafter, a method for forming a pattern using the photosensitive resin composition of the present invention will be described in detail.
The method for forming a pattern using the photosensitive resin composition of the present invention may use a method known in the art, but generally includes a coating step, an exposure step, and a removal step. The photosensitive resin composition of the present invention can be applied to a substrate, photocured, and developed to form a pattern, thereby being used as a pixel (colored image).
First, the photosensitive resin composition is applied onto a substrate, and then heated and dried to remove volatile components such as a solvent, thereby forming a smooth coating film.
The coating method may be performed by spin coating, a flex coating method, a roll coating method, slit spin coating, slit coating, or the like. After the coating, the coating is dried by heating (prebaking) or drying under reduced pressure, and then volatile components such as a solvent are volatilized by heating. Wherein the heating temperature is usually 70-150 ℃, preferably 80-130 ℃. The thickness of the coating film after the heating and drying is usually about 2.0 to 3.5 μm.
The cured film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. In this case, it is preferable to use a mask aligner, a stepper, or the like so as to irradiate the entire exposure portion with uniform parallel light and to perform precise position alignment of the mask and the substrate.
Preferably, the ultraviolet ray is i-line (365nm), and the ultraviolet-irradiated site forms a radical by the photopolymerization initiator and reacts with the polymerizable compound to effect photocuring.
The coating film having been cured by light is brought into contact with a developer to dissolve the unexposed portion, thereby forming a desired pattern in the color filter. Such a process is repeatedly performed according to the required number of red (R), green (G), and blue (B), so that a color filter having a desired pattern can be obtained.
The pattern shape thus obtained can be hardened by a post-curing step, and the heating temperature is usually 150 to 250 ℃, preferably 180 to 230 ℃. The heating time is usually 5 to 30 minutes, preferably 15 to 20 minutes.
< display device >
The present invention provides a display device including the color filter.
The Display device of the present invention may include a Display device developed in the past or in the future, and in one or more embodiments, there may be a Liquid Crystal Display device (LCD), an Electro Luminescence (EL) Display device, a Plasma Display device (PDP), a Field Emission Display device (FED), an Organic Light Emitting element (OLED) Display device, and the like.
The display device may include a configuration generally known in the art, in addition to the color filter.
The image display device according to an embodiment of the present invention may further include a color filter including a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles, in addition to the color filter. In this case, the light emitted from the light source applied to the display device is not particularly limited, and a light source emitting blue light is preferably used in view of more excellent color reproducibility.
The image display device according to an embodiment of the present invention may further include a color filter including only two color pattern layers of a red pattern layer, a green pattern layer, and a blue pattern layer, in addition to the color filter. In this case, the color filter further includes a transparent pattern layer containing no quantum dot particles. In the case of a pattern layer having only two colors, a light source that emits light exhibiting wavelengths of the remaining colors that are not included may be used. For example, in the case of including only a red pattern layer and a green pattern layer, a light source emitting blue light may be used. In this case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer directly transmits blue light to show blue color.
The present invention will be described in more detail below with reference to examples, 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 intended to be embraced therein. In the following examples and comparative examples, "%" and "part(s)" representing the content are based on weight unless otherwise mentioned.
<Reference example: spectral analysis of different wavelengths of an exposure machine and a photopolymerization initiator>
Measuring the emission spectrum and the normalized emission spectrum of the LED exposure machine emitting light in an I-line (365nm) region in the wavelength of 350-390 nm according to different wavelengths; and an absorption spectrum of the photopolymerization initiator of 10ppm relative to the total weight of Propylene Glycol Monomethyl Ether Acetate (PGMEA), which is shown in table 1 below.
In addition, the values of the normalized emission spectrum of the exposure machine or the values of the absorption spectrum of the photopolymerization initiator corresponding to the region (B) defined by the overlapping region of the region (A) defined by the normalized emission spectrum of the exposure machine and the region (P) defined by the absorption spectrum of the photopolymerization initiator in the wavelength of 350 to 390nm are shown in the following Table 2.
In addition, the area ratio of the region (B) to the region (a) is shown in table 2 below for each photopolymerization initiator.
For the emission spectrum of the above exposure machine, the spectral value at the maximum emission wavelength of 367nm was normalized as 1.
[ Table 1]
Figure BDA0003520135830000241
Figure BDA0003520135830000251
[ Table 2]
Figure BDA0003520135830000252
Figure BDA0003520135830000261
Figure BDA0003520135830000271
Referring to tables 1 and 2 above, the photopolymerization initiators having an area ratio of the region (B) to the region (A) of 0.4 or more were DFI-020, PBG-345, OXE-03 and NCI-831, and the remaining photopolymerization initiators showed an area ratio of less than 0.4.
In order to evaluate the performance of the photopolymerization initiator satisfying the spectral characteristics described above and the performance of the photopolymerization initiator not satisfying the spectral characteristics described above, the following experiment was performed.
<Preparation example: production of pigment dispersion>
Production example 1: pigment Dispersion M1
14.0 parts by weight of c.i pigment red 254 as a pigment, 8.0 parts by weight of LPN-6919 (manufactured by BYK corporation) as a pigment dispersant, 13 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 65.0 parts by weight of propylene glycol monomethyl ether acetate were mixed and dispersed for 12 hours by a bead mill, thereby producing a pigment dispersion M1.
Production example 2: pigment Dispersion M2
14.0 parts by weight of c.i pigment red 242 as a pigment, 8.0 parts by weight of LPN-6919 (manufactured by BYK corporation) as a pigment dispersant, 13 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 65.0 parts by weight of propylene glycol monomethyl ether acetate were mixed and dispersed for 12 hours by a bead mill, thereby producing a pigment dispersion M2.
Production example 3: pigment Dispersion M3
C.i pigment red 177 as a pigment in an amount of 14.0 parts by weight, LPN-6919 (manufactured by BYK corporation) as a pigment dispersant in an amount of 8.0 parts by weight, 4-hydroxy-4-methyl-2-pentanone as a solvent in an amount of 13 parts by weight, and propylene glycol monomethyl ether acetate in an amount of 65.0 parts by weight were mixed and dispersed for 12 hours by a bead mill, thereby producing pigment dispersion M3.
Production example 4: pigment Dispersion M4
14.0 parts by weight of c.i pigment green 58 as a pigment, 8.0 parts by weight of LPN-6919 (manufactured by BYK corporation) as a pigment dispersant, 13 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 65.0 parts by weight of propylene glycol monomethyl ether acetate were mixed and dispersed for 12 hours by a bead mill, thereby producing a pigment dispersion M4.
Production example 5: pigment Dispersion M5
14.0 parts by weight of c.i pigment green 63 as a pigment, 8.0 parts by weight of LPN-6919 (manufactured by BYK corporation) as a pigment dispersant, 13 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 65.0 parts by weight of propylene glycol monomethyl ether acetate were mixed and dispersed for 12 hours by a bead mill, thereby producing a pigment dispersion M5.
Production example 6: pigment Dispersion M6
14.0 parts by weight of c.i pigment yellow 138 as a pigment, 8.0 parts by weight of LPN-6919 (manufactured by BYK corporation) as a pigment dispersant, 13 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 65.0 parts by weight of propylene glycol monomethyl ether acetate were mixed and dispersed for 12 hours by a bead mill, thereby producing a pigment dispersion M6.
Production example 7: pigment Dispersion M7
14.0 parts by weight of c.i pigment blue 15:6 as a pigment, 8.0 parts by weight of LPN-6919 (manufactured by BYK corporation) as a pigment dispersant, 13 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 65.0 parts by weight of propylene glycol monomethyl ether acetate were mixed and dispersed for 12 hours by a bead mill, thereby producing a pigment dispersion M7.
Production example 8: pigment Dispersion M8
11.0 parts by weight of c.i pigment blue 15:6 as a pigment, 3.0 parts by weight of c.i pigment violet 23, 8.0 parts by weight of LPN-6919 (manufactured by BYK corporation) as a pigment dispersant, 13 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 65.0 parts by weight of propylene glycol monomethyl ether acetate were mixed and dispersed for 12 hours by a bead mill, thereby producing a pigment dispersion M8.
<Synthesis example: synthesis of alkali soluble resins>
100 parts by weight of propylene glycol monomethyl ether acetate, 100 parts by weight of propylene glycol monomethyl ether, 5 parts by weight of AIBN, 15 parts by weight of vinyltoluene, 20.0 parts by weight of 2-phenylthioethyl acrylate, 3 parts by weight of methacrylate and 30 parts by weight of methacrylic acid were charged into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube, and then replaced with nitrogen gas. Then, the temperature of the reaction solution was raised to 80 ℃ with stirring, and the reaction was carried out for 6 hours.
Then, 15 parts by weight of glycidyl methacrylate was added to the resultant reaction mixture, and the temperature was raised to 110 ℃ to carry out a reaction for 4 hours.
The alkali-soluble resin thus synthesized had a solid acid value of 71.9mgKOH/g and a weight-average molecular weight (Mw) of about 12,160 as measured by GPC.
<Examples and comparative examples: production of photosensitive resin composition>
Photosensitive resin compositions of examples 1 to 15, comparative examples 1 to 13 and reference examples 1 to 3 were prepared according to the compositions of the following tables 3 to 5, respectively.
[ Table 3]
Figure BDA0003520135830000301
[ Table 4]
Figure BDA0003520135830000311
[ Table 5]
Figure BDA0003520135830000321
M1: pigment Dispersion M1 of production example 1
M2: pigment Dispersion M2 of production example 2
M3: pigment Dispersion M3 of production example 3
M4: pigment Dispersion M4 of production example 4
M5: pigment Dispersion M5 of production example 5
M6: pigment Dispersion M6 of production example 6
M7: pigment Dispersion M7 of production example 7
M8: pigment Dispersion M8 of production example 8
Resin: synthesis example alkali-soluble resin
Photopolymerizable compound: KAYARAD DPHA (manufactured by Nippon chemical Co., Ltd.)
PI 1: PBG-345 (manufactured by Changzhou Qiangli Co., Ltd.)
PI 2: NCI-831 (manufactured by ADEKA Co., Ltd.)
PI 3: OXE-03 (manufactured by BASF corporation)
PI 4: OXE-02 (manufactured by BASF corporation)
PI 5: PBG-327 (manufactured by Changzhou Qiangli Co., Ltd.)
Solvent: propylene Glycol Monomethyl Ether Acetate (PGMEA)
<Examples of the experiments>
(1) Manufacture of color filters
Color filters were produced using the photosensitive resin compositions of examples 1 to 15, comparative examples 1 to 13, and reference examples 1 to 3.
Specifically, a photosensitive resin composition is applied to a glass substrate by a spin coating methodThereafter, the sheet was placed on a hot plate and maintained at a temperature of 100 ℃ for 3 minutes to form a color layer film. Next, a test photomask having an opening (Hole) pattern of 30x 30 μm and a line/space pattern of 1 to 100 μm was placed, and ultraviolet rays were irradiated with the test photomask at a distance of 250 μm. In this case, the ultraviolet light source was irradiated with 50mJ/cm light using a 60mW LED exposure machine containing only I-line (365nm) 2 The amount of light of (2) is not limited to a specific optical filter. The color layer film irradiated with ultraviolet rays was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 2 minutes to be developed. The glass substrate on which the developed color layer film was formed was washed with distilled water, then dried in a nitrogen atmosphere, and heated in a heating oven at 230 ℃ for 30 minutes to be thermally cured, thereby manufacturing a color filter.
(2) Opening (Hole) characteristic evaluation
Coating films having openings (holes) formed in the respective color filters manufactured by using the photosensitive resin compositions of examples 1 to 15, comparative examples 1 to 13, and reference examples 1 to 3 were obtained. Then, the size of the opening (Hole) was measured by an optical microscope, and the evaluation results are shown in tables 6 to 8 below.
< evaluation criteria for opening (Hole) characteristics >
O: forming an opening of 10 μm or more (Hole)
X: with or without openings smaller than 10 μm (Hole)
(3) Evaluation of film Retention
The photosensitive resin compositions of examples 1 to 15, comparative examples 1 to 13 and reference examples 1 to 3 were evaluated for film retention before and after development, and the evaluation results are shown in tables 6 to 8 below.
Film remaining rate { film thickness after development after exposure and thermal curing at 230 ℃/film thickness after exposure } × 100
< evaluation criteria for film deposition >
Very good: the film retention rate is more than 85 percent
O: the film retention rate is more than 80 percent and less than 85 percent
And (delta): the film retention rate is more than 75 percent and less than 80 percent
X: the film retention rate is less than 75 percent
(4) Evaluation of adhesion
The patterns formed by the photosensitive resin compositions of examples 1 to 15, comparative examples 1 to 13, and reference examples 1 to 3 were observed by an optical microscope, and adhesion was evaluated according to the degree of pattern peeling, and the evaluation results are shown in tables 6 to 8 below.
< evaluation criteria for adhesion >
Very good: no peeling of the pattern
O: 1 peeling off of the pattern
And (delta): 2-4 peeling of the pattern
X: pattern peeling 5 or more
[ Table 6]
Open (Hole) feature Film retention rate Adhesion Property
Example 1 O O O
Example 2 ◎ O O
Example 3 O O O
Example 4 O ◎ ◎
Example 5 O ◎ ◎
Example 6 O ◎ ◎
Example 7 O ◎ ◎
Example 8 O ◎ ◎
Example 9 ◎ O O
Example 10 ◎ O O
Example 11 ◎ O O
Example 12 ◎ O O
Example 13 ◎ O O
Example 14 ◎ O O
Example 15 ◎ ◎ ◎
[ Table 7]
Open (Hole) feature Film retention rate Adhesion Property
Comparative example 1 O × ×
Comparative example 2 O × ×
Comparative example 3 O × ×
Comparative example 4 O × ×
Comparative example 5 O × ×
Comparative example 6 O × ×
Comparative example 7 O × ×
Comparative example 8 O × ×
Comparative example 9 O × ×
Comparative example 10 O × ×
Comparative example 11 O × ×
Comparative example 12 × × O
Comparative example 13 × × O
[ Table 8]
Open (Hole) feature Film retention rate Adhesion
Reference example 1 O △ O
Reference example 2 O △ O
Reference example 3 O △ O
Referring to tables 6 to 8 above, it is seen that the photosensitive resin compositions of examples 1 to 15, which include the photopolymerization initiator in which the area ratio of the region (B) to the region (a) in the region (a) defined by the normalized emission spectrum of the exposure machine at a wavelength of 350 to 390nm, the region (P) defined by the absorption spectrum of the photopolymerization initiator, and the region (B) defined by the overlapping region of the region (a) and the region (P) is 0.4 or more, are excellent in the opening (Hole) characteristics, and all of the film retention rate and adhesion are improved, as compared with the photosensitive resin compositions of comparative examples 1 to 13 which do not include the photopolymerization initiator.
Further, referring to examples 1 and 3 containing c.i pigment red 254, example 15 containing c.i pigment red 242, and the like, the inclusion of c.i pigment red 242 as a red pigment is more advantageous in that not only the open (Hole) characteristic film retention rate and the adhesion are improved. Specifically, it is found that the photosensitive resin composition of example 15 or the like containing c.i pigment red 242 can contain a larger amount of photopolymerization initiator than the photosensitive resin compositions of examples 1 and 3 containing c.i pigment red 254, and thus can further improve the film retention rate and adhesion while maintaining the opening (Hole) characteristics.
Further, it is found that when the content of the photopolymerization initiator of the present invention is 1% by weight or more based on the total weight of the solid content in the photosensitive resin composition, the opening (Hole) characteristics, the film retention rate, and the adhesion can be further improved.

Claims (12)

1. A photosensitive resin composition comprising a photopolymerization initiator, wherein the photopolymerization initiator has an area ratio of a region (B) to a region (A) in a region (A) defined by a normalized emission spectrum of an exposure machine, a region (P) defined by an absorption spectrum of the photopolymerization initiator, and a region (B) defined by an overlapping region of the region (A) and the region (P) of 0.4 or more in a wavelength of 350 to 390 nm.
2. The photosensitive resin composition according to claim 1, wherein the normalized emission spectrum is normalized by the exposer maximum emission wavelength in the wavelength range of 350 to 390 nm.
3. The photosensitive resin composition according to claim 1, wherein a concentration of the photopolymerization initiator used for the measurement of the absorption spectrum is 10 ppm.
4. The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator has a maximum absorption wavelength in a wavelength of 340 to 380 nm.
5. The photosensitive resin composition according to claim 1, further comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, and a solvent.
6. The photosensitive resin composition according to claim 5, wherein the colorant comprises a red pigment.
7. The photosensitive resin composition according to claim 6, wherein the red pigment comprises C.I. pigment Red 242.
8. The photosensitive resin composition according to claim 5, comprising 1 to 50 wt% of a colorant, 5 to 70 wt% of an alkali-soluble resin, 5 to 50 wt% of a photopolymerizable compound, and 1 to 10 wt% of a photopolymerization initiator, based on the total weight of solid components in the photosensitive resin composition, and
the photosensitive resin composition comprises 60 to 90 wt% of a solvent based on the total weight of the photosensitive resin composition.
9. The photosensitive resin composition according to claim 5, further comprising one or more selected from the group consisting of a filler, another high molecular compound, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-coagulant, a dispersant, and an ink repellent.
10. The photosensitive resin composition according to claim 1, wherein the exposure machine is an LED exposure machine.
11. A color filter produced from the photosensitive resin composition according to any one of claims 1 to 10.
12. A display device comprising the color filter of claim 11.
CN202210175670.1A 2021-02-26 2022-02-25 Photosensitive resin composition, color filter manufactured using the same, and display device including the color filter Pending CN114967334A (en)

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