CN107272337B - Cyan photosensitive resin composition, cyan color filter comprising same, and display element - Google Patents
Cyan photosensitive resin composition, cyan color filter comprising same, and display element Download PDFInfo
- Publication number
- CN107272337B CN107272337B CN201710197242.8A CN201710197242A CN107272337B CN 107272337 B CN107272337 B CN 107272337B CN 201710197242 A CN201710197242 A CN 201710197242A CN 107272337 B CN107272337 B CN 107272337B
- Authority
- CN
- China
- Prior art keywords
- cyan
- pigment
- resin composition
- photosensitive resin
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to a cyan photosensitive resin composition, a cyan color filter and a display element, wherein the cyan photosensitive resin composition comprises a cyan colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, the cyan colorant comprises a cyan pigment and a black pigment, and when the cyan photosensitive resin composition is formed into a cured film with the thickness of 3 mu m, the spectral transmittance at 425-480 nm is more than 60% and less than 75%, and the spectral transmittance at 530-780 nm is more than 0% and less than 20%.
Description
Technical Field
The present invention relates to a cyan photosensitive resin composition, a cyan color filter and a display device including the same, and more particularly, to a cyan photosensitive resin composition having a spectral transmittance of 60% or more and less than 75% at 425 to 480nm and a spectral transmittance of more than 0% and less than 20% at 530 to 780nm when the cyan photosensitive resin composition is formed into a cured film having a thickness of 3 μm, a cyan color filter and a display device including the same.
Background
Flexible display elements have recently received attention as a next-generation display technology. Among techniques for manufacturing a display using a plastic substrate having bending characteristics, various techniques such as a liquid crystal display device, an organic light emitting element, and an electronic Paper (E-Paper) technique have been effectively utilized in the field of flexible display elements.
However, in order to practically use the flexible display element, it is necessary to realize full color, to reduce power consumption, and to make it easy to read even outdoors, as compared with the present various display products.
In this sense, the organic light emitting element is the most useful resource as a light source of a flexible display element because of its advantages of possibility of realizing full color, low power consumption, and fast response speed.
With the present organic light emitting element, an encapsulation barrier (encapsulation barrier) layer for protecting the organic light emitting element from oxygen and moisture is required, and in order to be easily readable even outdoors, a polarizing plate (polarizer) is required to maintain a high contrast ratio (contrast ratio).
However, if a polarizing plate having hard characteristics is applied, the following disadvantages occur: the flexibility of the flexible display element is reduced, and even the luminance of the element is reduced and the thickness of the element is increased by absorbing light emitted from the light emitting layer of the organic light emitting element.
In contrast, if the polarizing plate is not applied, the following problems occur: the external light is transmitted into the flexible display element, reflected again and emitted, and is mixed with the light originally emitted by the organic light emitting element, so that the light-dark ratio under the external light source is greatly reduced.
Further, korean patent registration No. 10-0398940 discloses that prism structures of various heights included in a display device are formed on a surface, and korean patent publication No. 10-2002-0041819 discloses that prisms having a variable angle structure formed on a surface, but none of them exhibits the desired effect of improving the contrast ratio.
Prior art documents
Patent document
Patent document 1: korean registered patent No. 10-0398940
Patent document 2: korean laid-open patent No. 10-2002-0041819
Disclosure of Invention
Problems to be solved by the invention
In the organic light emitting device, a polarizing plate is used to solve the problem of the reduction of the contrast and visibility due to the reflection of external light.
The polarizing plate absorbs external light incident to the organic light emitting element, thereby minimizing reflection of the incident external light to the outside. However, the polarizing plate also absorbs light emitted from the light-emitting layer of the organic light-emitting element, which reduces the luminance of the element, and the polarizing plate is additionally laminated on the organic light-emitting element, which also causes a problem that the thickness of the entire element increases.
Accordingly, in order to solve the above problems, an object of the present invention is to provide a cyan photosensitive resin composition which can minimize external light reflection without using a polarizing plate in a display device.
Further, an object of the present invention is to provide a cyan photosensitive resin composition which can realize color development by limiting the transmittance in a specific range.
Further, an object of the present invention is to provide a cyan color filter and a display device manufactured using the cyan photosensitive resin composition.
Means for solving the problems
In order to achieve the above object, the present invention provides a cyan photosensitive resin composition comprising a cyan colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the cyan colorant comprises a cyan pigment and a black pigment, and wherein when the cyan photosensitive resin composition is formed into a cured film having a thickness of 3 μm, the spectral transmittance at 425 to 480nm is 60% or more and less than 75%, and the spectral transmittance at 530 to 780nm is more than 0% and less than 20%.
The present invention also provides a cyan color filter produced from the cyan photosensitive resin composition.
Further, the present invention provides a display device including the cyan color filter.
ADVANTAGEOUS EFFECTS OF INVENTION
The cyan photosensitive resin composition of the present invention exhibits the following effects: external light reflection can be minimized without laminating a polarizing plate in the organic light emitting element.
The cyan photosensitive resin composition of the present invention can realize color development by limiting the transmittance to a specific range.
Further, a display element produced from the cyan photosensitive resin composition of the present invention has the following advantages: the polarizing plate is not laminated and is thin.
Drawings
Fig. 1 to 3 are graphs showing the results of experimental example 1. In particular, FIG. 2 is a graph showing the spectral transmittances at 425 to 480nm based on the results of Experimental example 1, and FIG. 3 is a graph showing the spectral transmittances at 530 to 780nm based on the results of Experimental example 1.
Detailed Description
The present invention will be described in more detail below.
The invention relates to a cyan photosensitive resin composition, which comprises a cyan colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the cyan colorant comprises a cyan pigment and a black pigment, and when the cyan photosensitive resin composition is formed into a cured film with the thickness of 3 mu m, the spectral transmittance at 425-480 nm is more than 60% and less than 75%, and the spectral transmittance at 530-780 nm is more than 0% and less than 20%.
In the organic light emitting element, a polarizing plate is used to solve the problem of the reduction of the contrast and visibility due to the reflection of external light.
The polarizing plate absorbs external light incident to the organic light emitting element, thereby minimizing reflection of the incident external light to the outside. However, the polarizing plate also has the following problems: light emitted from the light-emitting layer of the organic light-emitting element is absorbed, and the luminance of the element is reduced.
Therefore, in order to solve the above-mentioned problems, the present invention provides a cyan photosensitive resin composition which can minimize external light reflection without laminating a polarizing plate in an organic light-emitting device.
The cyan photosensitive resin composition of the present invention has the following characteristics: when the cured film is formed to have a thickness of 3 [ mu ] m, the spectral transmittance at 425 to 480nm is 60% or more and less than 75%, and the spectral transmittance at 530 to 780nm is more than 0% and less than 20%, whereby color development can be achieved while minimizing external light reflection.
The components of the cyan photosensitive resin composition of the present invention are described in detail below.
(A) Cyan colorant
The cyan colorant, which is a component of the cyan photosensitive resin composition of the present invention, includes a cyan pigment and a black pigment.
As the cyan pigment and the black pigment, organic pigments or inorganic pigments generally used in this field can be used. The cyan pigment and the black pigment may be subjected to a resin treatment, a surface treatment using a pigment derivative having an acid group or a basic group introduced thereto, a grafting treatment on the surface of the pigment using a polymer compound or the like, a micronization treatment using a sulfuric acid micronization method or the like, a cleaning treatment using an organic solvent, water or the like for removing impurities, a removal treatment of ionic impurities using an ion exchange method or the like, as required.
As the organic pigment, various pigments used in printing inks, inkjet inks, and the like can be used, and specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, peryleneketone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinone pigments, anthrapyrimidine pigments, anthrone pigments, indanthrone pigments, xanthoanthrone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like.
The inorganic pigment may be a metal compound such as a metal oxide or a metal complex salt, and specifically, an oxide or a composite metal oxide of a metal such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black, an organic black pigment, titanium black, and a pigment obtained by mixing cyan, green, and red colors to form black color.
In particular, as The organic pigment and The inorganic pigment, specifically, compounds classified as pigments in The color index (published by The society of Dyers and Colourists), more specifically, pigments in The color index (c.i.) number can be cited, but are not necessarily limited thereto.
The above cyan pigment preferably comprises a pigment selected from c.i. pigment blue 15: 3. 15: 4. 15: 6. 21, 28, 60, 64 and 76, more preferably comprising a pigment selected from c.i. pigment blue 15: 4 and 15: 6 or more than 1.
The black pigment preferably contains 1 or more selected from the group consisting of a pigment obtained by mixing red, cyan, and green, c.i. pigment black 1, c.i. pigment black 7, carbon black, organic black, and titanium black.
More preferably, a coloring dispersion liquid in which carbon black and 2 or more kinds of coloring pigments are mixed is used.
The carbon black is not particularly limited as long as it is a pigment having light-shielding properties, and known carbon blacks can be used. Specific examples of the carbon black as the black pigment include channel black, furnace black, thermal black, and lamp black.
Further, specific examples of the product of the carbon black include
CHBK-17 from Yuguohai Kabushiki Kaisha;
seast 5HIISAFHS, Seast KH, Seast 3HHAF-HS, Seast NH, Seast 3M, Seast 300HAF-LS, Seast 116HMMAF-HS, Seast 116MAF, Seast FMFEF-HS, Seast SOFF, Seast VGPF, Seast SVHSRF-HS, and Seast SSRF of east China sea carbon (strain);
ダイヤグラムブラック II, ダイヤグラムブラック N339, ダイヤグラムブラック SH, ダイヤグラムブラック H, ダイヤグラム LH, ダイヤグラム HA, ダイヤグラム SF, ダイヤグラム N550M, ダイヤグラム M, ダイヤグラム E, ダイヤグラム G, ダイヤグラム R, ダイヤグラム N760M, ダイヤグラム LR, #2700, #2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45L, #25, # CF9, #95, #3030, #3050, MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B from Mitsubishi chemical corporation;
デグサ (strain) PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100 and LAMP BLACK-101;
コロンビアカーボン (strain) RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190, and RAVEN-1170, and the like.
Further, examples of the coloring pigment that can be mixed with the carbon black include magenta 6B (c.i.12490), phthalocyanine green (c.i.74260), phthalocyanine blue (c.i.74160), mitsubishi carbon black MA100, perylene black (BASF k0084.k0086), cyanine black, lithol (リオノール) yellow (c.i.21090), lithol yellow GRO (c.i.21090), benzidine yellow 4T-564D, mitsubishi carbon black MA-40, victoria pure blue (c.i.42595), c.i. pigment red 97, 122, 149, 168, 177, 180, 192, 215, c.i. pigment green 7, 36, c.i. pigment blue 15: 1. 15: 4. 15: 6. 22, 60, 64, c.i. pigment yellow 83, 139, c.i. pigment violet 23, etc., and further, a white pigment, a fluorescent pigment, etc. can be used.
The above cyan pigment and black pigment are preferably mixed in a ratio of 99.9: 0.1-80: 20, more preferably 99: 1-95: 1 by weight ratio.
In the case where the weight ratio of the cyan pigment to the black pigment satisfies the above range, the following may be advantageously employed: when the cyan photosensitive resin composition is formed into a cured film with a thickness of 3 μm, the spectral transmittance at 425-480 nm is more than 60% and less than 75%, and the spectral transmittance at 530-780 nm is more than 0% and less than 20%.
When the spectral transmittance is less than 60% when the cyan photosensitive resin composition is formed into a cured film having a thickness of 3 μm, the cyan photosensitive resin composition has a good external light reflection effect, but poor visibility due to a decrease in brightness, and when the transmittance is 75% or more, the cyan photosensitive resin composition has a good brightness but a small external light reflection effect.
The cyan colorant may additionally contain a violet pigment. By additionally including the violet pigment, the color of the cyan photosensitive resin composition can be adjusted.
The above violet pigment preferably contains 1 or more selected from c.i. pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38.
The violet pigment is contained in an amount of 3 to 30 wt%, preferably 10 to 20 wt%, based on the total weight of the cyan colorant.
The cyan colorant is contained in an amount of 10 to 80 wt%, preferably 10 to 40 wt%, and more preferably 10 to 30 wt%, based on the total weight of solid components in the cyan photosensitive resin composition of the present invention.
When the cyan colorant is contained in an amount of 10 to 80% by weight, the cyan photosensitive resin composition has a low viscosity, excellent storage stability, an increased dispersion efficiency, and an effective increase in contrast.
In the present invention, the total weight of the solid components means the total weight of the remaining components excluding the solvent.
The pigment is preferably a pigment dispersion liquid in which the particle size of the pigment is uniformly dispersed. Examples of the method for uniformly dispersing the particle diameter of the pigment include a method of dispersing the pigment dispersion medium (a1), and a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained by the above method.
(a1) Pigment dispersants
The pigment dispersant is added to maintain the deagglomeration and stability of the pigment, and 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 of 2 or more.
Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.
Specific examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleyl sulfate, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, and alkylaryl sulfonate salts such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate.
Specific examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, ethylene oxide/propylene oxide block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene alkylamines, and the like.
Further, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines are exemplified.
The pigment dispersant preferably contains an acrylate dispersant (hereinafter referred to as an acrylate dispersant) containing Butyl Methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). As the above acrylic ester-based dispersants, there are commercially available products such as DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 and DISPER BYK-2150, and the above acrylic ester-based dispersants may be used singly or in combination of 2 or more kinds.
The pigment dispersant may be other resin type pigment dispersants besides the acrylate type dispersant. Examples of the other resin-type pigment dispersants include known resin-type pigment dispersants, and particularly, oil-based dispersants such as polyurethanes, polycarboxylates typified 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 imines); 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; ethylene oxide/propylene oxide addition products, phosphoric esters, and the like.
As a commercially available product of the above-mentioned other resin type pigment dispersant, examples of the cationic resin dispersant include the 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 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 corporation: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; trade name of Chuanmo Fine chemicals: ヒノアクト (HINACT) T-6000, ヒノアクト T-7000, ヒノアクト T-8000; trade name of Aomoto Co., Ltd: アジスパー (AJISPUR) PB-821, アジスパー PB-822, アジスパー PB-823; trade name of Kyoeisha chemical Co., Ltd: フローレン (FLORENE) DOPA-17HF, フローレン DOPA-15BHF, フローレン DOPA-33, フローレン DOPA-44, etc.
In addition to the acrylate-based dispersant, other resin-based pigment dispersants may be used alone or in combination of 2 or more types, and may be used in combination with the acrylate-based dispersant.
The pigment dispersant is contained in an amount of 5 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content in the pigment. When the content of the pigment dispersant satisfies the above range, the viscosity and the micronization of the pigment are advantageous, and the possibility of occurrence of problems such as gelation after dispersion can be reduced.
(B) Alkali soluble resin
The alkali-soluble resin as 1 component in the cyan photosensitive resin composition of the present invention must be dissolved in a solvent of the cyan photosensitive resin composition and be reactive to the action of light or heat. The type of the acrylic copolymer is not particularly limited as long as it functions as a binder resin for a colorant and is soluble in an alkaline developer.
The alkali-soluble resin may be a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the above monomer.
The carboxyl group-containing monomer may be, for example, an unsaturated carboxylic acid such as an unsaturated polycarboxylic acid having 1 or more carboxyl groups in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid.
The unsaturated monocarboxylic acid may be, for example, acrylic acid, methacrylic acid, crotonic acid, α -chloroacrylic acid, cinnamic acid, or the like.
Specific 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 examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride.
The above-mentioned unsaturated polycarboxylic acid may be a mono (2-methacryloyloxyalkyl) ester, specifically, may be a mono (2-acryloyloxyethyl) succinate, a mono (2-methacryloyloxyethyl) succinate, a mono (2-acryloyloxyethyl) phthalate, a mono (2-methacryloyloxyethyl) phthalate or the like.
The unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxylic polymer at both ends, specifically, may be ω -carboxy polycaprolactone monoacrylate, ω -carboxy polycaprolactone monomethacrylate, or the like.
The carboxyl group-containing monomers may be used in a single amount of 1 kind or in a mixture of 2 or more kinds.
Specific examples of the other monomer copolymerizable with the 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, methoxydiglycol acrylate, methoxydiglycol methacrylate, methoxytriglycol acrylate, methoxytriglycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, allyl acrylate, allyl methacrylate, Unsaturated carboxylic acid esters such as 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 esters 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 vinylidene cyanide;
unsaturated amides such as acrylamide, methacrylamide, α -chloroacrylamide, N-2-hydroxyethyl acrylamide, and N-2-hydroxyethyl methacrylamide;
unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide;
aliphatic conjugated dienes such as 1, 3-butadiene, isoprene and chloroprene; and
giant monomers having a monoacrylyl group or a monomethacrylyl group at the end of a polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane, and the like. The above monomers may be used in a single kind or in a mixture of 2 or more kinds.
That is, the alkali-soluble resin may be, for example, a (meth) acrylic acid/methyl (meth) acrylate copolymer, a (meth) acrylic acid/benzyl (meth) acrylate copolymer, a (meth) acrylic acid/2-hydroxyethyl (meth) acrylate/benzyl (meth) acrylate copolymer, a (meth) acrylic acid/methyl (meth) acrylate/polystyrene macromonomer copolymer, a (meth) acrylic acid/methyl (meth) acrylate/polymethyl (meth) acrylate macromonomer copolymer, a (meth) acrylic acid/benzyl (meth) acrylate/polystyrene macromonomer copolymer, a (meth) acrylic acid/benzyl (meth) acrylate/polymethyl (meth) acrylate macromonomer copolymer, a (meth) acrylic acid/2-hydroxyethyl (meth) acrylate/benzyl (meth) acrylate Polystyrene macromonomer copolymer, (meth) acrylic acid/2-hydroxyethyl (meth) acrylate/benzyl (meth) acrylate/polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid/styrene/(meth) benzyl (meth) acrylate/N-phenylmaleimide copolymer, (meth) acrylic acid/mono (2-acryloyloxy) succinate/styrene/(meth) benzyl (meth) acrylate/N-phenylmaleimide copolymer, (meth) acrylic acid/mono (2-acryloyloxyethyl) succinate/styrene/(meth) allyl (acrylate/N-phenylmaleimide copolymer, and (meth) acrylic acid/benzyl (meth) acrylate/N-phenylmaleimide/styrene/glycerol mono (meth) acrylate copolymers, and the like. The above (meth) acrylate means acrylate or methacrylate.
The alkali-soluble resin is preferably a (meth) acrylic acid/benzyl (meth) acrylate copolymer, a (meth) acrylic acid/benzyl (meth) acrylate/styrene copolymer, a (meth) acrylic acid/methyl (meth) acrylate copolymer, or a (meth) acrylic acid/methyl (meth) acrylate/styrene copolymer.
The alkali-soluble resin has a weight average molecular weight of 5,000 to 50,000, preferably 8,000 to 40,000, and more preferably 10,000 to 30,000 in terms of polystyrene as measured by Gel Permeation Chromatography (GPC) using tetrahydrofuran as an elution solvent.
When the weight average molecular weight of the alkali-soluble resin is 5,000 to 50,000, the hardness of the coating film is increased, an excellent film residue rate is exhibited, and good solubility in a developer and improved resolution of unexposed portions can be exhibited.
The acid value of the alkali-soluble resin is 50 to 150(mgKOH/g), preferably 60 to 140, and more preferably 80 to 130.
In the acid value range of 50 to 150, the solubility of the alkali-soluble resin in a developer is improved, unexposed portions are easily dissolved and have high sensitivity, and a pattern of exposed portions remains during development, whereby the residual film ratio can be improved.
The alkali-soluble resin is contained in an amount of 5 to 80 wt%, preferably 10 to 60 wt%, based on the total weight of solid components in the cyan photosensitive resin composition of the present invention. When the above range is satisfied, the possibility of occurrence of the problems of the decrease in the residual film ratio and the decrease in reliability is reduced, and the pattern formation is easy.
(C) Photopolymerizable compound
The photopolymerizable compound that is 1 component in the cyan photosensitive resin composition of the present invention is necessarily a compound polymerizable by the action of the photopolymerization initiator (D) described later.
The photopolymerizable compound may be a monofunctional monomer, a 2-functional monomer or a polyfunctional monomer, and preferably a 2-functional monomer, but is not limited thereto.
Specific examples of the monofunctional monomer include, but are not limited to, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone.
Specific examples of the 2-functional monomer include, but are not limited to, 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol a, and 3-methylpentanediol di (meth) acrylate.
Specific examples of the polyfunctional monomer include, but are not limited to, 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 dipentaerythritol hexa (meth) acrylate.
The photopolymerizable compound is preferably contained in an amount of 5 to 50 wt%, more preferably 7 to 45 wt%, based on the total weight of the cyan photosensitive resin composition of the present invention. When the photopolymerizable compound is in the range of 5 to 50 wt%, the strength and reliability of the pixel portion can be improved.
(D) Photopolymerization initiator
The photopolymerization initiator as 1 component in the cyan photosensitive resin composition of the present invention can be used without particular limitation as long as it is a photopolymerization initiator that polymerizes the photopolymerizable compound (C).
In particular, the photopolymerization initiator preferably uses 1 or more compounds selected from acetophenone compounds, benzophenone compounds, triazine compounds, bisimidazole compounds, oxime compounds and thioxanthone compounds from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, and the like.
Specific examples of the above 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-methylthiophenyl) -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 2- (4- Methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.
Specific examples of the benzophenone-based compound include benzophenone, methyl 0-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) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (furan-2- Yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, and 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine, and the like.
Specific examples of the biimidazole 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, and imidazole compounds in which the phenyl group at the 4,4 ', 5, 5' position is substituted with an alkoxycarbonyl group, and the like. Of these, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyl biimidazole, 2 ' -bis (2, 3-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyl biimidazole and 2, 2-bis (2, 6-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole are preferably used.
Specific examples of the oxime ester compound include 1,2-Octanedione (1,2-Octanedione) and 1- [4- (phenylthio) phenyl group]-, 2- (O-benzoyl oxime) (1- [4- (phenylthio) phenyl ] oxime]-, 2- (O-benzoxyimine)) and 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]Ethanone1- (O-acetyl oxime) (1- [9-Ethyl-6- (2-methylbenzol) -9H-carbozol-3-yl]ethanone1- (O-acetoxyimine)), and the like. Examples of oxime ester compounds commercially available include those available from BASF corporation
OXE01、
OXE02 and
OXE03, and the like.
Specific examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone and 1-chloro-4-propoxythioxanthone.
In addition, in order to improve the sensitivity of the cyan photosensitive resin composition of the present invention, the photopolymerization initiator may further include a photopolymerization initiation auxiliary (d 1). The cyan photosensitive resin composition of the present invention contains the photopolymerization initiation auxiliary (d1), so that the sensitivity is further improved and the productivity can be improved.
As the photopolymerization initiation auxiliary, for example, 1 or more compounds selected from amine compounds, carboxylic acid compounds, and organic sulfur compounds having a thiol group can be preferably used.
As the amine compound, an aromatic amine compound is preferably used, and specifically, for example, 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), and 4,4 ' -bis (diethylamino) benzophenone.
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.
Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), and tetraethyleneglycol bis (3-mercaptopropionate).
The photopolymerization initiator may be contained in an amount of 0.1 to 40 wt%, preferably 1 to 30 wt%, based on the total weight of solid components in the cyan photosensitive resin composition of the present invention.
When the photopolymerization initiator is contained in an amount of 0.1 to 40% by weight, the cyan photosensitive resin composition can be made highly sensitive, and the exposure time can be shortened, so that the productivity can be improved and the high resolution can be maintained. Further, the strength of the pixel portion and the smoothness of the surface of the pixel portion can be improved.
The photopolymerization initiator further contains 10 to 100 wt%, preferably 20 to 100 wt%, of the photopolymerization initiation auxiliary, based on the total weight of the photopolymerization initiator.
When the content of the photopolymerization initiation auxiliary agent satisfies the above range, the sensitivity to the dye can be reduced, and the possibility of short-circuiting of the pattern in the developing process can be reduced.
(E) Solvent(s)
The solvent is not particularly limited as long as it is effective for dissolving other components contained in the cyan photosensitive resin composition, and a solvent used in a usual cyan photosensitive resin composition can be used, and ethers, acetates, aromatic hydrocarbons, ketones, alcohols, esters, amides, and the like are particularly preferable.
Examples of the ethers 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.
Examples of the above-mentioned acetates include 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, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy-1-butyl acetate, 1, 2-propylene glycol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1, 3-butylene glycol diacetate, diethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, amyl acetate, ethylene glycol monoacetate, ethyl lactate, methyl propionate, amyl acetate, methyl acetate, ethyl acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, and the like.
Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene, and the like.
Examples of the ketones include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.
Examples of the alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, and 4-hydroxy-4-methyl-2-pentanone.
Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and γ -butyrolactone.
Examples of the amides include Dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP).
The solvents can be used individually or in combination of 2 or more.
The solvent is preferably an organic solvent having a boiling point of 100 to 200 ℃ in terms of coatability and drying property, and examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate.
The solvent is contained in an amount of 25 to 80 wt%, preferably 30 to 70 wt%, based on the total weight of the cyan photosensitive resin composition. When the solvent is contained in the range of 25 to 80% by weight, the coating properties are improved when the coating is performed by a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater), or an ink jet.
(F) Additive agent
The additive may be optionally added, and may contain, for example, 1 or more selected from fillers, other polymer compounds, curing agents, surfactants, adhesion promoters, ultraviolet absorbers, and anti-coagulation agents.
As the filler, glass, alumina, or the like can be used, but the type is not limited thereto.
Specific examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.
The curing agent is used for improving the deep-section curing and the mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds, and the like.
Specific examples of the epoxy compound include 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 the above epoxy resins, aliphatic, alicyclic, or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co) polymer epoxides, isoprene (co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.
Of the above curing agents, specific examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexane dicarboxylic acid bisoxetane, and the like.
The curing agent may be used together with a curing auxiliary compound capable of ring-opening polymerizing an epoxy group of the epoxy compound or an oxetane skeleton of the oxetane compound.
Examples of the curing auxiliary compound include polycarboxylic acids, polycarboxylic acid anhydrides, and acid generators. The polycarboxylic acid anhydride may be a commercially available product as an epoxy resin curing agent. Examples of the commercially available products include Adeka Harden EH-700 (manufactured by Adeka industries, Ltd.), Rikacid HH (manufactured by Nissian chemistry, Ltd.), and MH-700 (manufactured by Nissian chemistry, Ltd.). The curing agents exemplified above can be used alone or in combination of 2 or more.
In order to further improve the film formation of the cyan photosensitive resin composition, the above-mentioned surfactant can be used, and a silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric surfactant, or the like can be preferably used.
Examples of the silicone surfactants include commercially available silicone surfactants such as DC3PA, DC7PA, SH11PA, SH21PA and SH8400 available from Dow Corning Toray Silicone Co., Ltd, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 available from GE Toshiba Silicone Co., Ltd.
As the above-mentioned fluorine-based surfactant, there are commercially available, for example, メガピース F-470, F-471, F-475, F-482 and F-489 from Dainippon ink chemical industries, Inc.
Further, other commercially available products that can be used include KP (shin-Etsu chemical Co., Ltd.), ポリフロー (POLYFLOW) (Kyoeisha chemical Co., Ltd.), エフトップ (EFTOP) (トーケムプロダクツ K., Ltd.), メガファック (MEGAFAC) (Dainippon ink chemical Co., Ltd.), フロラード (Flourad) (Sumitomo 3M (Ltd.), アサヒガード (Asahi guard), サーフロン (Surflon) (manufactured by Asahi glass Co., Ltd.), ソルスパース (SOLSPERSE) (Lubrisol), EFKA (EFKA ケミカルズ Co., Ltd.), PB821 (gourmet powder Co., Ltd.), and Disperbyk series (BYK-chemi).
The above-exemplified surfactants may be used each alone or in combination of 2 or more.
The kind of the adhesion promoter is not particularly limited, and specific examples of usable adhesion promoters include 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-chloropropyltrimethoxysilane, and, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like.
The adhesion promoters exemplified above may be used individually or in combination of 2 or more. The adhesion promoter may be contained in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of the solid components in the cyan photosensitive resin composition.
The kind of the ultraviolet absorber is not particularly limited, and specific examples of the ultraviolet absorber that can be used include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like.
The kind of the above-mentioned anti-agglomerating agent is not particularly limited, and specific examples of the agent that can be used include sodium polyacrylate and the like.
The method for producing the cyan photosensitive resin composition of the present invention is as follows.
First, the cyan colorant (A) is mixed with a solvent (E), and dispersed by a bead mill or the like until the average particle size of the pigment becomes about 0.2 μm or less. In this case, if necessary, a part or all of the pigment dispersant (a1) and the alkali-soluble resin (B) may be mixed together with the solvent (E) to be dissolved or dispersed.
The cyan photosensitive resin composition of the present invention can be produced by further adding the remaining part of the alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D), and, if necessary, the additive (F) and the solvent (E) to the above-mentioned mixed colored material so as to have a predetermined concentration.
In addition, the invention provides a color filter manufactured by the cyan photosensitive resin composition and a display element with the color filter.
In one embodiment, the display element may be an organic light emitting element.
In another embodiment, the display element may be a flexible display element.
First, a cyan photosensitive resin composition is applied to a substrate (usually glass) or a layer composed of a solid component of a previously formed cyan photosensitive resin composition, and then dried by heating to remove volatile components such as a solvent, thereby obtaining a smooth coating film.
The coating method is carried out by, for example, spin coating, cast coating, roll coating, slit and spin coating, slit coating, or the like. After the coating, the coating is dried by heating (prebaking), or dried under reduced pressure and then heated to volatilize volatile components such as a solvent. Wherein the heating temperature is usually 70-200 ℃, preferably 80-130 ℃. The thickness of the coating film after the heating and drying is usually about 1 to 8 μm. The coating 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 in order to uniformly irradiate the entire exposure portion with parallel light beams and to accurately align the mask and the substrate. When ultraviolet rays are irradiated, the ultraviolet-irradiated portion is cured.
As the ultraviolet ray, g-line (wavelength: 436nm), h-line, i-line (wavelength: 365nm) and the like can be used. The dose of the ultraviolet ray irradiation may be appropriately selected as necessary, and is not limited in the present invention. If the cured coating film is brought into contact with a developer to dissolve and develop the unexposed portion, a spacer having a desired pattern shape can be obtained.
The developing method is not particularly limited, and is a liquid addition method, a dipping method, a spraying method, or the like. In addition, the substrate may be tilted at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkali compound and a surfactant.
The basic compound may be an inorganic or organic basic compound, and is not particularly limited. Examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, diammonium hydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia.
Examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine.
The inorganic or organic basic compounds can be used alone or in combination of 2 or more. The concentration of the alkali compound in the developer is 0.01 to 10 wt%, preferably 0.03 to 5 wt%, based on the total weight of the developer.
The surfactant in the developer may be at least one selected from the group consisting of the nonionic surfactants, the anionic surfactants, and the cationic surfactants. The concentration of the surfactant in the developer is 0.01 to 10 wt%, preferably 0.05 to 8 wt%, and more preferably 0.1 to 5 wt% based on the total weight of the developer. After the development, the resultant is washed with water and, if necessary, post-baked at 150 to 230 ℃ for 10 to 60 minutes.
By using the cyan photosensitive resin composition of the present invention, a specific pattern can be formed on a substrate through the above-described steps.
The present invention will be described in detail below with reference to examples. However, the embodiments of the present invention may be modified into various forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.
Synthesis example 1 Synthesis of alkali-soluble resin
In a 1000mL flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube, 120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 13 parts by weight of acrylic acid, 10 parts by weight of benzyl methacrylate, 57 parts by weight of styrene, 20 parts by weight of methyl methacrylate and 3 parts by weight of n-dodecylmercaptan were charged and nitrogen substitution was performed. Then, the temperature of the reaction mixture was raised to 110 ℃ by stirring, and the reaction was carried out for 6 hours after the temperature was raised.
The alkali-soluble resin thus produced had an acid value of the solid content of 100.2mgKOH/g and a weight-average molecular weight Mw of about 15110 as measured by GPC.
< production of cyan photosensitive resin composition >
Examples 1 to 6 and comparative examples 1 to 2.
Cyan photosensitive resin compositions of examples 1 to 6 and comparative examples 1 to 2 were produced with the compositions shown in Table 1 below.
[ TABLE 1 ] weight parts
(A-1) cyan pigment: c.i. pigment blue 15: 6
(A-2) cyan pigment: c.i. pigment blue 15: 4
(A-3) purple pigment: c.i. pigment violet 23
(A-4) Black pigment: PBk 7: carbon-black (MA-8 Mitsubishi corporation)
(B) Alkali-soluble resin: synthesis of alkali-soluble resin produced in Synthesis example 1
(C) Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARD DPHA; manufactured by Nippon Kagaku Co., Ltd.)
(D) Photopolymerization initiator: 2-O-benzoyloxime-1- [4- (phenylthio) phenyl ] -1, 2-octanedione (OXE-01; manufactured by BASF)
(E) Solvent: propylene glycol monomethyl ether acetate
Experimental example 1 production of color Filter and measurement of spectral transmittance
The cyan photosensitive resin compositions of examples 1 to 6 and comparative examples 1 to 2 were applied to a 2-inch glass substrate (manufactured by corning, "EAGLE XG") by a spin coating method, and then placed on a hot plate and maintained at a temperature of 100 ℃ for 3 minutes to form a thin film.
Then, a test photomask having a pattern in which the transmittance was changed stepwise within a range of 1 to 100% and an exposed portion pattern of 3 × 3cm was placed on the film, and irradiated with ultraviolet light with a distance of 100 μm from the test photomask. At this time, the ultraviolet ray was irradiated at 100mJ/cm using a 1kW high pressure mercury lamp containing all g, h and i lines2The illumination of (2) is performed without using a special optical filter.
The film irradiated with the ultraviolet ray was immersed in a KOH aqueous solution developing solution having a ph of 10.5 for 2 minutes, and developed. Then, the glass plate coated with the thin film was washed with distilled water, and then dried by spraying nitrogen gas, and heated in a heating oven at 200 ℃ for 25 minutes, thereby producing each color filter.
The thickness of the obtained film was 3 μm, and the thickness of the film was measured by using a film thickness measuring apparatus (DEKTAK 6M; manufactured by Veeco).
The spectral transmittances in the visible light region in the range of 380nm to 780nm of the color filters of examples 1 to 6 and comparative examples 1 to 2 produced as described above were measured using a colorimeter (OSP-200, manufactured by olympus corporation), and the results are shown in the following tables 2 and 3, and fig. 1 to 3.
[ TABLE 2 ]
[ TABLE 3 ]
| Wavelength (nm) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Comparative example 1 | Comparative example 2 |
| 530 | 6.8％ | 6.7％ | 6.7％ | 7.5％ | 7.5％ | 7.0％ | 8.2％ | 7.5％ |
| 550 | 2.6％ | 2.6％ | 2.6％ | 3.1％ | 3.0％ | 2.7％ | 2.7％ | 2.8％ |
| 570 | 0.8％ | 0.7％ | 0.7％ | 0.8％ | 0.8％ | 0.8％ | 0.8％ | 0.8％ |
| 590 | 0.5％ | 0.5％ | 0.5％ | 0.5％ | 0.5％ | 0.5％ | 0.6％ | 0.6％ |
| 610 | 0.5％ | 0.4％ | 0.4％ | 0.5％ | 0.5％ | 0.5％ | 0.5％ | 0.5％ |
| 630 | 0.6％ | 0.6％ | 0.6％ | 0.6％ | 0.6％ | 0.7％ | 0.7％ | 0.7％ |
| 650 | 1.6％ | 1.6％ | 1.6％ | 1.5％ | 1.5％ | 1.7％ | 1.7％ | 1.7％ |
| 670 | 3.2％ | 3.2％ | 3.2％ | 2.8％ | 2.8％ | 3.3％ | 3.2％ | 3.4％ |
| 690 | 3.6％ | 3.6％ | 3.6％ | 2.9％ | 2.9％ | 3.7％ | 3.5％ | 3.8％ |
| 710 | 3.3％ | 3.2％ | 3.2％ | 2.6％ | 2.5％ | 3.3％ | 3.1％ | 3.4％ |
| 730 | 1.7％ | 1.7％ | 1.7％ | 2.2％ | 2.2％ | 1.7％ | 1.8％ | 1.8％ |
| 750 | 1.4％ | 1.4％ | 1.4％ | 3.5％ | 3.5％ | 1.4％ | 1.5％ | 1.5％ |
| 770 | 2.6％ | 2.6％ | 2.6％ | 6.9％ | 6.9％ | 2.6％ | 2.9％ | 2.7％ |
| 780 | 7.6％ | 7.5％ | 7.5％ | 15.6％ | 15.6％ | 7.6％ | 8.1％ | 8.0％ |
Examples 1 to 6, which are cyan photosensitive resin compositions of the present invention comprising a cyan pigment and a black pigment, show the following results: when the cyan photosensitive resin composition is formed into a cured film with a thickness of 3 μm, the spectral transmittance at 425-480 nm is more than 60% and less than 75%, and the spectral transmittance at 530-780 nm is more than 0% and less than 20%.
In contrast, comparative examples 1 and 2, which did not contain a black pigment, had a transmittance of 82% at maximum at 425nm to 480nm when the cyan photosensitive resin composition was formed into a cured film having a thickness of 3 μm.
Therefore, it is found that the cyan photosensitive resin composition of the present invention has a spectral transmittance of 60% or more and less than 75% at 425 to 480nm and a spectral transmittance of more than 0% and less than 20% at 530 to 780nm when formed into a cured film having a thickness of 3 μm, and thus the following effects can be produced: external light reflection is minimized and color development is enabled.
In addition, the cyan photosensitive resin composition of the invention can be used for manufacturing a color filter, and a display element comprising the color filter is provided.
Claims (11)
1. A cyan photosensitive resin composition comprising a cyan colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the cyan colorant comprises a cyan pigment, a violet pigment and a black pigment, the photopolymerization initiator comprises an oxime ester compound, and when the cyan photosensitive resin composition is formed into a cured film having a thickness of 3 [ mu ] m, the spectral transmittance at 425 to 480nm is 60% or more and less than 75%, and the spectral transmittance at 530 to 780nm is more than 0% and less than 20%.
2. The cyan photosensitive resin composition according to claim 1, wherein the ratio of 99.9: 0.1-80: 20 parts by weight of a cyan pigment and a black pigment were mixed.
3. The cyan photosensitive resin composition according to claim 1, wherein the violet pigment is contained in an amount of 3 to 30 wt% based on the total weight of the cyan colorant.
4. The cyan photosensitive resin composition according to claim 1, wherein the cyan pigment comprises a pigment selected from c.i. pigment blue 15: 3. 15: 4. 15: 6. 21, 28, 60, 64 and 76.
5. The cyan photosensitive resin composition according to claim 1, wherein the black pigment comprises 1 or more selected from the group consisting of a pigment in which red, cyan and green are mixed, c.i. pigment black 1, c.i. pigment black 7, carbon black, organic black and titanium black.
6. The cyan photosensitive resin composition according to claim 1, wherein the violet pigment contains 1 or more selected from the group consisting of c.i. pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38.
7. The cyan photosensitive resin composition according to claim 1, comprising 10 to 80% by weight of a cyan colorant, 5 to 80% by weight of an alkali-soluble resin, 5 to 50% by weight of a photopolymerizable compound and 0.1 to 40% by weight of a photopolymerization initiator, based on the total weight of solid components in the cyan photosensitive resin composition, and comprising 25 to 80% by weight of a solvent, based on the total weight of the cyan photosensitive resin composition.
8. A cyan color filter produced from the cyan photosensitive resin composition according to claim 1.
9. A display element comprising the cyan color filter of claim 8.
10. A display element according to claim 9, characterised in that the display element is a flexible display element.
11. The display element according to claim 9, wherein the display element is an organic light-emitting element.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20160039186 | 2016-03-31 | ||
| KR10-2016-0039186 | 2016-03-31 | ||
| KR1020160153641A KR102558671B1 (en) | 2016-03-31 | 2016-11-17 | A blue photosensitive resin composition, blue color filter and display device comprising the same |
| KR10-2016-0153641 | 2016-11-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107272337A CN107272337A (en) | 2017-10-20 |
| CN107272337B true CN107272337B (en) | 2021-03-30 |
Family
ID=60045648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710197242.8A Active CN107272337B (en) | 2016-03-31 | 2017-03-29 | Cyan photosensitive resin composition, cyan color filter comprising same, and display element |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP6867843B2 (en) |
| CN (1) | CN107272337B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI741223B (en) * | 2017-10-20 | 2021-10-01 | 南韓商東友精細化工有限公司 | A pigment dispersion, a photo sensitive resin composition comprising the pigment dispersion, a pattern layer prepared by using the composition, a color filter comprising the pattern layer, and a display device comprising the color filter |
| JP7203573B2 (en) * | 2017-11-16 | 2023-01-13 | 住友化学株式会社 | Blue curable resin composition, blue color filter and display device containing the same |
| KR102221151B1 (en) * | 2019-03-20 | 2021-02-26 | 동우 화인켐 주식회사 | A photo sensitive resin composition, a display partition wall structure prepared using the composition, and a display devide comprising the same |
| TW202112842A (en) * | 2019-07-30 | 2021-04-01 | 日商富士軟片股份有限公司 | Colored resin composition, film, color filter, solid-state image pickup element, and image display device |
| JP7344379B2 (en) * | 2020-05-22 | 2023-09-13 | 富士フイルム株式会社 | Resin compositions, films, optical filters, solid-state imaging devices, and image display devices |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4370112B2 (en) * | 2003-03-14 | 2009-11-25 | 東洋インキ製造株式会社 | Blue coloring composition for color filter and color filter |
| JP2005331796A (en) * | 2004-05-21 | 2005-12-02 | Toppan Printing Co Ltd | Color filter and color display device |
| TWI444674B (en) * | 2008-05-28 | 2014-07-11 | Toppan Printing Co Ltd | Process for producing color filter, process for producing substrate having pattern and miniature photomask |
| JP5262691B2 (en) * | 2008-12-25 | 2013-08-14 | 東レ株式会社 | Color filter substrate for liquid crystal display device and liquid crystal display device using the same |
| JP5051858B2 (en) * | 2010-07-16 | 2012-10-17 | 住友ベークライト株式会社 | Manufacturing method of color filter for display device |
| JP2013011845A (en) * | 2011-05-31 | 2013-01-17 | Mitsubishi Chemicals Corp | Photosensitive colored resin composition for color filter, color filter, liquid crystal display device, and organic electroluminescent display |
| JP2013222028A (en) * | 2012-04-16 | 2013-10-28 | Toppan Printing Co Ltd | Photosensitive black resin composition, color filter and liquid crystal display device |
| JP2013238812A (en) * | 2012-05-17 | 2013-11-28 | Toppan Printing Co Ltd | Photosensitive blue colored composition |
| JP6163054B2 (en) * | 2013-09-03 | 2017-07-12 | 富士フイルム株式会社 | Photosensitive resin composition, cured resin and color filter |
-
2017
- 2017-03-28 JP JP2017063411A patent/JP6867843B2/en active Active
- 2017-03-29 CN CN201710197242.8A patent/CN107272337B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP6867843B2 (en) | 2021-05-12 |
| JP2017187765A (en) | 2017-10-12 |
| CN107272337A (en) | 2017-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106019837B (en) | Colored photosensitive resin composition, color filter, and image display device provided with same | |
| CN104423148B (en) | Colored photosensitive resin composition, color filter and display device comprising same | |
| CN107229183B (en) | Red photosensitive resin composition, color filter manufactured using the same, and display device including the color filter | |
| CN107272337B (en) | Cyan photosensitive resin composition, cyan color filter comprising same, and display element | |
| JP2015148800A (en) | Colored photosensitive resin composition, and color filter and display device including the same | |
| TWI612382B (en) | Colored photosensitive resin composition for red pixel, color filter using thereof and display device having the same | |
| CN107229186B (en) | Colored photosensitive resin composition, color filter and display device comprising same | |
| KR102572680B1 (en) | Red colored photosensitive resin composition, color filter and display device comprising the same | |
| JP2021051327A (en) | Blue photosensitive resin composition, blue color filter containing the same and display element | |
| KR102335628B1 (en) | Colored photosensitive resin composition, color filter and image display device produced using the same | |
| KR20140106282A (en) | Colored photosensitive resin composition | |
| CN108062002B (en) | Colored photosensitive resin composition, color filter and image display device | |
| KR102348810B1 (en) | A color photosensitive resin composition, color filter and display device comprising the same | |
| KR102172686B1 (en) | A color photosensitive resin composition, color filter and display device comprising the same | |
| CN108459466B (en) | Colored photosensitive resin composition for red pixel, color filter and application thereof | |
| JP4161677B2 (en) | Colored photosensitive resin composition | |
| KR20040065163A (en) | Photosensitive resin composition | |
| KR102543947B1 (en) | Colored Photosensitive Resin Composition for Solid State Imaging Device, Color Filter and Solid State Imaging Device | |
| KR102397093B1 (en) | A photosensitive resin composition, color filter and display device comprising the same | |
| CN105988290B (en) | Colored photosensitive resin composition, color filter and display device comprising the same | |
| KR20220122364A (en) | A photosensitive resin composition, a color filter prepared using the composition, and a display device comprising thereof | |
| KR20200064769A (en) | Colored Photosensitive Resin Composition for Solid State Imaging Device, Color Filter and Solid State Imaging Device | |
| KR20180107475A (en) | A photosensitive resin composition, color filter and display device comprising the same | |
| KR20180108095A (en) | A photosensitive resin composition, color filter and display device comprising the same | |
| KR20170107154A (en) | A red photosensitive resin composition, red color filter and display device comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |