KR20150014768A - A colored photosensitive resin composition for formming the frontal light-shielding layer of a display device - Google Patents
A colored photosensitive resin composition for formming the frontal light-shielding layer of a display device Download PDFInfo
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- KR20150014768A KR20150014768A KR1020130090413A KR20130090413A KR20150014768A KR 20150014768 A KR20150014768 A KR 20150014768A KR 1020130090413 A KR1020130090413 A KR 1020130090413A KR 20130090413 A KR20130090413 A KR 20130090413A KR 20150014768 A KR20150014768 A KR 20150014768A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- Nonlinear Science (AREA)
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- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
Description
The present invention relates to a photosensitive resin composition for forming a front light shielding layer of a display device.
Generally, in order to improve the visibility of the display, the reflectance is decreased in the front edge of a display device such as an LCD (Liquid Crystal Display), a PDP (Plasma Display Panel), an OLED (Organic Light Emitting Diode) and an AMOLED (Active Matrix Organic Light Emitting Diode) And a bezel which is a front shading layer of a display device that performs a function of shielding light such that the inside of the display is not visible is formed. As a material of such a bezel part, a black coating composition is widely used in terms of function, but in recent years, a coating composition having various colors has been used in consideration of various taste of consumers and display.
However, when a bright color coating composition such as white or pink having a low light shielding ratio is used as the coating material of the bezel portion, the inside of the display is likely to be exposed through the bezel portion. Therefore, A bezel portion is formed in such a manner that a coating layer of gray or black color is further formed.
However, when the bezel portion is formed of a multilayer coating layer, the light shielding ratio is improved because the optical density (OD) is increased by the coating layer of gray or black color in the lower layer, but the transmittance of the coating layer of the upper- There arises a problem that a coating layer of a gray or black color is seen. Therefore, various methods for improving this point have been studied. In addition, efforts are being made to realize a high reflection luminance in the bezel coating in consideration of the beauty of the display.
Meanwhile, in recent years, the demand and supply of a display device driven by a touch method has been greatly expanded. The touch panel has a resistance method, an electrostatic method, a SAW method, and an infrared method depending on a driving method. In the electrostatic method, electrostatic method, which is a method of sensing static electricity generated in a human body and driving the touch panel, is mainly used. In the past, in addition to the tempered glass corresponding to the front surface of the product, one or two separate inner glass plates or transparent films for vacuum-depositing the ITO pattern inside the tempered glass were inserted into the inner glass plate or the transparent film And then assembled to complete the touch panel. However, since the thickness of the touch panel becomes thick, a method of manufacturing a touch panel including a process of vacuum-depositing the ITO pattern directly on tempered glass has been widely adopted. In this method, a bezel portion is formed on the tempered glass, and a direct ITO pattern is also formed. Accordingly, the bezel portion formed in the tempered glass is exposed to chemical agents in a process such as lithography for forming a pattern of the ITO electrode, and is exposed to a high temperature during the heat treatment of the ITO electrode. Therefore, the chemical resistance and the heat resistance are particularly important for the bezel coating material of the touch panel.
SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems occurring in the prior art,
A photosensitive resin composition for forming a front light-shielding layer of a display device which is excellent in reliability, excellent in pattern forming property and residual film ratio, and excellent in reflection brightness and shielding property since it exhibits excellent chemical resistance and heat resistance even when treated with a chemical or heat treatment at a high temperature And to provide the above objects.
Another object of the present invention is to provide a display device including a front light shielding layer of a display device made of the above composition.
The present invention relates to a photosensitive member for forming a front light-shielding layer of a display device comprising a colorant (A) containing a white pigment, an alkali-soluble binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) As the resin composition,
Wherein the white pigment comprises TiO 2 , the TiO 2 comprises Wherein the photosensitive resin composition comprises at least 10% by weight based on the total weight of the colorant solid content.
In addition,
And a front shading layer formed by coating a photosensitive resin composition for forming a front shading layer of the display device on an upper portion of a transparent substrate.
The photosensitive resin composition for forming the front light-shielding layer of the display device of the present invention exhibits excellent chemical resistance and heat resistance even when chemically treated or heat-treated at a high temperature, and thus is excellent in reliability.
In addition, it provides excellent pattern formation and retention ratio, and provides high reflectance and shielding.
The present invention relates to a photosensitive member for forming a front light-shielding layer of a display device comprising a colorant (A) containing a white pigment, an alkali-soluble binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) As the resin composition,
Wherein the white pigment comprises TiO 2 , the TiO 2 comprises And a photosensitive resin composition for forming a front light-shielding layer of a display device, wherein the photosensitive resin composition comprises 10 wt% or more based on the total weight of the colorant.
Hereinafter, the colored photosensitive resin composition will be described in detail for each component.
Coloring material (A)
Wherein said colorant (A) comprises a white pigment, said white pigment comprises TiO 2 , said TiO 2 By weight, more preferably 30 to 100% by weight, still more preferably 60 to 100% by weight, based on the total weight of the colorant solid content . If TiO 2 is included outside the above range, it does not have the capability of shielding the light-shielding layer. Above the above range, there is no function to improve the light-shielding layer performance, and causes various disadvantages such as deterioration of the developing speed and residue in the manufacturing process of the display device.
Examples of the white pigment include white inorganic pigments commonly used in this field. Specifically, CI Pigment White 4, 5, 6, 6: 1, 7, 18, 18: 1, 19, 20, 22, 25, 26, 27, 28, 32, and the like. Among the white inorganic pigments, CI Pigment White 6 or White 22 may preferably be used in terms of reflection efficiency and whiteness. These may be used alone or in combination of two or more.
The TiO 2 contained in the CI Pigment White 6 is cheap and has a high refractive index and thus has excellent reflectance, so that it can be used as an effective white colorant.
The TiO 2 preferably has a rutile structure. TiO 2 having a rutile structure can be preferably used because it has an excellent whiteness.
The white pigment TiO 2 may be subjected to a surface treatment using a pigment derivative or the like into which a resin treatment, an acidic group or a basic group has been introduced as required, a graft treatment on the surface of the pigment with a polymer compound, an atomization treatment using a sulfuric acid atomization method, A cleaning treatment with an organic solvent or water for removing the ionic impurities, a treatment for removing ionic impurities by an ion exchange method, or the like.
The surface of the TiO 2 is made of SiO 2 , Al 2 O 3 And ZrO 2 can be preferably used.
More preferably, SiO 2 , Al 2 O 3 And ZrO 2 may be used.
Even more preferably, the outermost surface of the surface-treated TiO 2 Surface treated with organic matter can be used. Examples of the organic material include trimethyl propane (TMP), pentaerythritol, and the like. Coating and surface treatment of TiO 2 with a single molecular layer of low polarity using the above components lowers the energy required for TiO 2 dispersion and prevents TiO 2 from being compressed and aggregated.
The surface treatment of TiO 2 as described above while lowering the photocatalytic activity of the TiO 2 improves the reflected luminance characteristic. In particular, when the surface treatment of each of SiO 2 , Al 2 O 3 and ZrO 2 is applied to the TiO 2 , reliability such as heat resistance and chemical resistance is improved. The surface treatment may be treatment by encapsulation.
The surface-treated TiO 2 preferably has a TiO 2 core content of 85 to 95% by weight. When the surface of the TiO 2 core is treated within the above range, excellent whiteness and excellent reflection brightness are exhibited.
Wherein the TiO 2 is R-101's DuPont (dupont) is commercially available and specific examples, R-102, R-103 , R-104, R-105, R-350, R-706, R-794, R-796, R-900, R-900, R-900, R-902, R-902, R-931 and R- ) CR-57 manufactured by Mitsubishi Chemical Corporation.
In addition to the white pigment, the colorant (A) may further include other pigments known in the art.
The colorant (A) is contained in the solid content in the photosensitive resin composition for forming the front light-shielding layer of the display device in an amount of 10 to 90 wt%, more preferably 30 to 70 wt%. When the colorant is included in the above-described range, it is preferable that the whiteness when forming the front light-shielding layer of the display device is excellent and the reflection brightness is excellent. In the present invention, a solid content means a component excluding a solvent.
The alkali-soluble binder resin (B)
The alkali-soluble binder resin is not particularly limited as long as it is soluble in the solvent of the present invention, functions as a binder resin for the colorant, and is soluble in an alkaline developer.
The alkali-soluble binder resin includes, for example, a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the monomer.
Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated polycarboxylic acids having at least one carboxyl group in the molecule such as unsaturated tricarboxylic acid and the like .
Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like.
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. The unsaturated polycarboxylic acid may also be a mono (2-methacryloyloxyalkyl) ester thereof, for example, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxy Ethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be mono (meth) acrylate of the dicarboxylic polymer at both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. have.
The carboxyl group-containing monomers may be used alone or in combination of two or more.
Examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o- P-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p Aromatic vinyl compounds such as vinylbenzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Acrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Acrylate, methoxypropylene glycol methacrylate, methoxypropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentane Dienyl acrylate, dicyclopentadiethyl methacrylate, 2-hydroxy-3-phenoxy Unsaturated carboxylic acid esters such as cyproxy acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; Aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as methyl acrylate, ethyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Acid amino alkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters 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,? -Chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, And the like. These monomers may be used alone or in combination of two or more.
In the case where the alkali-soluble binder resin is a copolymer of a carboxyl group-containing monomer and another monomer capable of copolymerizing with the monomer, the content ratio of the constituent unit derived from the carboxyl group- 10 to 50% by weight, preferably 15 to 40% by weight, and more preferably 25 to 40% by weight. The content of the constituent unit derived from the carboxyl group-containing monomer is preferably from 10 to 50% by weight because the solubility in the developer is good and the pattern at the time of development is accurately formed.
The alkali-soluble binder resin is not particularly limited, but its weight average molecular weight in terms of polystyrene is preferably in the range of 3,000 to 100,000, more preferably in the range of 3,000 to 50,000, particularly 5,000 to 50,000. When the weight average molecular weight of the alkali-soluble binder resin is in the range of 3,000 to 100,000, it is preferable because the colorant is easily dispersed, the viscosity is low, and the storage stability is excellent.
The alkali-soluble binder resin (B) may be contained in an amount of 1 to 60% by weight, preferably 5 to 50% by weight based on the total weight of the solid content of the photosensitive resin composition for forming the front light-shielding layer of the display device. When the alkali-soluble binder resin (B) is contained in the above range, the solubility is good and the pattern forming property is excellent.
Photopolymerization The compound (C)
The photopolymerizable compound (C) is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers, bifunctional monomers, and other polyfunctional monomers.
The photopolymerizable compound (C) used in the present invention is a compound having two or more different structures or functional groups of the functional group in order to improve developability, sensitivity, adhesion, surface problems, etc. of the photosensitive resin composition for forming the front light- And a photopolymerizable compound may be mixed and used. As long as it is generally used in this field, the kind thereof is not particularly limited.
Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Money and so on.
Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.
Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (metha) acrylate, propoxylated dipenta (Meth) acrylate, erythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.
Of these, multifunctional monomers having two or more functional groups are preferably used.
The photopolymerizable compound (C) may be contained in an amount of 1 to 60% by weight, preferably 5 to 50% by weight based on the total weight of the solid content of the photosensitive resin composition for forming the front light shielding layer of the display device. When the photopolymerizable compound (C) is contained in the above range, the strength and smoothness of the pixel portion are improved.
Light curing Initiator (D)
As the photopolymerization initiator (D), at least one selected from the group consisting of triazine-based compounds, acetophenone-based compounds, nonimidazole-based compounds and oxime compounds can be used.
Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- - (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, (Trichloromethyl) -6- [2- (5-methylfuran-2- (4-methoxystyryl) -1,3,5-triazine, Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.
Specific examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-methylcyclohexyl phenyl ketone, 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.
Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis (2,3- Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) , 2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) Imidazole compounds in which 4'5,5'-tetraphenyl-1,2'-biimidazole or phenyl groups at 4,4 ', 5,5' positions are substituted by carboalkoxy groups. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole is preferably used do.
Specific examples of the oxime compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and OXE01 and OXE02 of BASF Corporation.
As long as the effect of the present invention is not impaired, other photopolymerization initiators commonly used in this field may be further used in combination. The photopolymerization initiator may be used in combination with a photopolymerization initiator generally used in this field.
Specifically, an amine compound and a carboxylic acid compound can be exemplified. Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4- Aromatic amine compounds such as bis (dimethylamino) benzophenone (commonly known as Michler's ketone) and 4,4'-bis (diethylamino) benzophenone. Preferably, the amine compound may be an aromatic amine compound.
Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, And aromatic heteroacetic acids such as dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.
The photopolymerization initiator (D) is preferably contained in an amount of 1 to 40% by weight, and more preferably 3 to 20% by weight based on the total weight of the solid content of the photosensitive resin composition for forming the front light shielding layer of the display device. If the photopolymerization initiator (D) is included in the above content range, the exposure time can be shortened and the productivity can be improved by increasing the sensitivity.
Solvent (E)
The solvent (E) is not particularly limited, and various organic solvents used in this field can be used. Specific examples thereof 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 dimethyl ether, diethylene glycol diethyl ether, di Diethylene glycol dialkyl ethers such as ethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as? -butyrolactone.
Of these solvents, organic solvents having a boiling point of 100 ° C to 200 ° C can be preferably used in terms of coatability and dryness, more preferably alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, -Methoxypropionate, and the like. Of these, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate And the like. These solvents (E) may be used alone or in combination of two or more.
The solvent (E) is used in an amount of 20 to 90% by weight, preferably 20 to 60% by weight, based on the total weight of the photosensitive resin composition for forming the front light- % ≪ / RTI > by weight. When the solvent (E) is contained in the above-described range, the coating property is improved when the coating composition is applied by a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) desirable.
Additive (F)
In the photosensitive resin composition for forming the front light-shielding layer of the display device of the present invention, a filler, another polymer compound, a curing agent, a pigment dispersant may be added as needed. (F) such as an adhesion promoter, an antioxidant, an ultraviolet absorber and an anti-aggregation agent.
Specific examples of the filler include glass, silica and alumina.
Specific examples of 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 increasing the curing depth and mechanical strength, and an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound can be used.
Examples of the epoxy compound include a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, a Novolak epoxy resin, other aromatic epoxy resins, an alicyclic epoxy Aliphatic, alicyclic or aromatic epoxy compounds other than the brominated derivatives, epoxy resins and brominated derivatives of such epoxy resins, butadiene (co) polymeric epoxides, isoprene (co) polymeric epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.
Examples of the oxetane compound include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like.
The curing agent may include a curing assistant compound capable of ring-opening polymerization of an epoxy group of an epoxy compound and an oxetane skeleton of an oxetane compound together with a curing agent. Examples of the curing aid compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, acid generators, and the like.
As the carboxylic acid anhydrides, those commercially available as an epoxy resin curing agent can be used. Examples of the epoxy resin curing agent include trade names (ADEKA HARDONA EH-700) (ADEKA INDUSTRIAL CO., LTD.), Trade names (RICACIDO HH) (manufactured by New Japan Chemical Co., Ltd.) (Manufactured by Shin-Etsu Chemical Co., Ltd.). These curing agents may be used alone or in combination of two or more.
As the pigment dispersant, commercially available surfactants can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. These may be used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, (Trade name) manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), Mega (Manufactured by Asahi Glass Co., Ltd.), Surfon (manufactured by Asahi Glass Co., Ltd.), Mitsubishi Kagaku Kogyo Co., Ltd., MEGAFAC (manufactured by Dainippon Ink and Chemicals Inc.), Flourad (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon SOLSPERSE (manufactured by Genene), EFKA (manufactured by EFKA Chemical), PB 821 (manufactured by Ajinomoto), and the like.
Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane , N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Propyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like.
These adhesion promoters may be used alone or in combination of two or more. The amount of the adhesion promoter may be 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of the photosensitive resin composition for forming the front light- .
Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone.
Examples of the anti-aggregation agent include sodium polyacrylate and the like.
The present invention also relates to
And a front light shielding layer formed by applying a photosensitive resin composition for forming a front light shielding layer of the display device on an upper portion of a transparent substrate.
The front light-shielding layer may be formed by a method known in the art such as a photolithography or an inkjet method.
For example, the photolithography method is a method in which a photosensitive resin composition for forming a front light shielding layer of the display device is applied on a tempered glass substrate or a transparent film, volatile components such as a solvent are removed to form a light shielding layer, And exposing the light-shielding layer to light and developing the light-shielding layer.
Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
Manufacturing example 1: Preparation of colorant dispersion composition
SiO 2, Al 2 O 3, ZrO 2 , and an organic material and surface treatment of TiO TIOXIDE® TR81 the content of the second core 93% by weight (HUNTMAN Co.) 54.78g, BYK-180 (BYK社, Ltd.) as a dispersing agent and 1.00g 44.22 g of propylene glycol monomethyl ether acetate as a solvent was mixed / dispersed by a bead mill for 2 hours to prepare a colorant dispersion composition
Manufacturing example 2: Preparation of colorant dispersion composition
Except that TIOXIDE 占 TR92 (manufactured by HUNTMAN) having a TiO 2 core content of 92.5 wt% was surface-treated with SiO 2 , Al 2 O 3 , ZrO 2 and an organic material to prepare a colorant To prepare a dispersion composition.
Manufacturing example 3: Preparation of colorant dispersion composition
SiO 2, Al 2 O 3, and to an organic substance surface-treated by the same manner as in the Preparation Example 1, except for using R350 (DUPONT Company) in the amount of the TiO 2 core 95% by weight to prepare a colorant dispersion composition .
Manufacturing example 4: Preparation of colorant-dispersed composition
SiO 2 , Al 2 O 3 and an organic material, and R706 (manufactured by DUPONT Co., Ltd.) having a content of TiO 2 core of 93% by weight was used as a colorant dispersion composition. .
Manufacturing example 5: Preparation of colorant dispersion composition
And is carried out in the same manner as Preparation Example 1 except that the SiO 2, surface-treated with Al 2 O 3 and TiO 2 surface-treated with an organic substance with a content of TiO2 of 97.5% by weight of the core TIOXIDE® RFC5 (HUNTMAN Company) To prepare a colorant dispersion composition
Manufacturing example 6: Preparation of colorant dispersion composition
Except that R931 (manufactured by DUPONT Co., Ltd.) having a TiO 2 core content of 80 wt% was surface-treated with SiO 2 , Al 2 O 3 and an organic material, and the colorant dispersion composition was prepared Respectively.
Manufacturing example 7: Preparation of colorant dispersion composition
SiO 2 , Al 2 O 3 and an organic material, and R101 (manufactured by DUPONT Co., Ltd.) having a content of TiO 2 core of 97 wt% was used as a colorant dispersion composition. .
Manufacturing example 8: Preparation of colorant dispersion composition
SiO 2 , Al 2 O 3 and an organic material, and R104 (manufactured by DUPONT Co., Ltd.) having a content of TiO 2 core of 97% by weight was used as a colorant dispersion composition. .
Example 1: Front of the display device Shading layer Preparation of photosensitive resin composition for forming
50.2 g of the colorant dispersion composition prepared in Preparation Example 1, a copolymer of methacrylic acid and benzyl methacrylate (the ratio of methacrylic acid unit to benzyl methacrylate unit was 31:69 in terms of molar ratio, and the weight average molecular weight in terms of polystyrene (20,000), 11.1 g of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), 2 g of methyl 2- (4-methylthiophenyl) 1.1 g of 2,4-diethylthioxanthone (Speedcure DETX, manufactured by LAMBSON), 3 g of 3-methacryloxypropyl trimethoxysilane (KBM-503, manufactured by Shin-Etsu) ) And 5.5 g of propylene glycol monomethyl ether acetate were mixed to prepare a photosensitive resin composition for forming a front shading layer of a display device.
Example 2: Front of the display device Shading layer Preparation of photosensitive resin composition for forming
A photosensitive resin composition for forming a front light shielding layer of a display device was prepared in the same manner as in Example 1 except that the colorant dispersion composition prepared in Preparation Example 2 was used.
Example 3: Front of the display device Shading layer Preparation of photosensitive resin composition for forming
A photosensitive resin composition for forming a front light shielding layer of a display device was prepared in the same manner as in Example 1 except that the colorant dispersion composition prepared in Preparation Example 3 was used.
Example 4: Front of display device Shading layer Preparation of photosensitive resin composition for forming
A photosensitive resin composition for forming a front shading layer of a display device was prepared in the same manner as in Example 1 except that the colorant dispersion composition prepared in Preparation Example 4 was used.
Example 5: Front of the display device Shading layer Preparation of photosensitive resin composition for forming
A photosensitive resin composition for forming a front shading layer of a display device was prepared in the same manner as in Example 1 except that the colorant dispersion composition prepared in Preparation Example 5 was used.
Example 6: Front of display device Shading layer Preparation of photosensitive resin composition for forming
A photosensitive resin composition for forming a front shading layer of a display device was prepared in the same manner as in Example 1 except that the colorant dispersion composition prepared in Preparation Example 6 was used.
Example 7: Front of the display device Shading layer Preparation of photosensitive resin composition for forming
A photosensitive resin composition for forming a front shading layer of a display device was prepared in the same manner as in Example 1 except that the colorant dispersion composition prepared in Preparation Example 7 was used.
Example 8: Front of the display device Shading layer Preparation of photosensitive resin composition for forming
A photosensitive resin composition for forming a front light shielding layer of a display device was prepared in the same manner as in Example 1 except that the colorant dispersion composition prepared in Preparation Example 8 was used.
Example 9: Display Front of device Shading layer formation
The front light shielding layer of the display device was formed using the photosensitive resin composition for forming the front light shielding layer of the display device manufactured in Examples 1 to 8. That is, the photosensitive resin composition for forming the front light-shielding layer of the display devices of Examples 1 to 8 was coated on a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100 캜 for 3 minutes to form a thin film. Subsequently, a photomask having a line pattern of 3 mu m to 100 mu m was placed on the thin film and irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated at a light intensity of 100 mJ / cm 2 using a 1 kW high-pressure mercury lamp containing g, h, and i lines. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 20 seconds to develop. The glass plate coated with the thin film was washed with distilled water, dried using nitrogen gas, and heated in a heating oven at 150 ° C for 20 minutes to prepare a front light-shielding layer of the display device. The thickness of the front light shielding layer of the display device manufactured above was 25.0 탆.
Experimental Example 1: Front of the display device The light- Reflection luminance evaluation
The reflection brightness of the front light-shielding layer of the display device formed in Example 9 was measured five times in Y (D65) using MINOLTA SPECTROPHOTOMETER CM-3700d, and the average value thereof is shown in Table 1 below.
Luminance
(weight%)
As shown in Table 1, it can be seen that the reflection brightness is excellent in all of Examples 1 to 8 including TiO 2 according to the present invention. In particular, in Examples 1 to 4, in which TiO 2 was surface-treated and the content of the core thereof was included within the preferred range of the present invention, the content of the core thereof was inferior to that of Examples 5 to 8, And that it exhibits more excellent reflection luminance characteristics. Also, it was confirmed that the reflection brightness of the front light-shielding layer of the display device formed by applying the TiO 2 pigment dispersion composition surface-treated with SiO 2 , Al 2 O 3 and ZrO 2 was the best as in Examples 1 and 2.
Experimental Example 2: Front of the display device The light- Residual film ratio evaluation
The change in film thickness was confirmed by measuring the front light shielding layer of the display device formed in Example 9 at room temperature (23 ° C) and high temperature (230 ° C). The results are shown in Table 2 below.
<Change rate calculation formula>
Rate of change =
All of the front shading layers of the display device formed by the photosensitive resin composition for forming the front shading layer of the display devices of Examples 1 to 8 exhibited excellent residual film ratios.
In particular, the front light-shielding layer of the display device formed by the photosensitive resin composition for forming the front light-shielding layer of the display devices of Examples 1 to 4 showed a slight decrease in thickness at high temperature, The front shading layer of the display device formed with the photosensitive resin composition for layer formation showed a higher reduction rate.
Experimental Example 3: Front of the display device The light- Reliability evaluation
The front light-shielding layer of the display device, which was additionally formed at the front light-shielding layer of the display device formed in Example 9 and the exposure amounts of 150 mJ / cm2 and 60 mJ / cm2, was applied to SPS-250EL solvent of BASF Co., And the color change before and after the evaluation was compared and evaluated. The equation used here is shown below as a color change in a three-dimensional colorimetric system defined by L *, a *, b *. Table 3 shows the results calculated by the following formula. As the color change value is smaller, it is possible to manufacture a front light shielding layer of a highly reliable display device.
△ E * ab = [(△ L *) 2 + (△ a *) 2 + (△ b *) 2] (1/2)
All of the front light-shielding layers of the display device formed by the photosensitive resin composition for forming the front light-shielding layer of the display devices of Examples 1 to 8 exhibited excellent reliability.
Particularly, good color change values were shown in Examples 1 to 4, and higher color change values were shown in Examples 5 to 8. Thus, it can be seen that the reliability of the photosensitive resin compositions of Examples 1 to 4, in which TiO 2 is surface-treated and the content of its core is within the preferred range of the present invention, shows higher reliability. In particular, it was confirmed that the color change value of the front shading layer of the display device formed by applying the TiO 2 pigment dispersion composition surface-treated with SiO 2 , Al 2 O 3 and ZrO 2 as in Examples 1 and 2 was the smallest, This indicates that the heat resistance property was improved by the surface treatment of TiO 2 .
Claims (8)
Wherein the white pigment comprises TiO 2 , the TiO 2 comprises Wherein the photosensitive resin composition comprises 10 wt% or more based on the total weight of the colorant solid content.
(A), 1 to 60% by weight of an alkali-soluble binder resin (B), 1 to 60% by weight of a photopolymerizable compound (B) in an amount of 1 to 60% by weight based on the total weight of the photosensitive resin composition solid content for forming a front light- (C), and 1 to 40% by weight of a photopolymerization initiator (D); (E) based on the total weight of the photosensitive resin composition for forming the front light-shielding layer of the display device.
Wherein the light-shielding layer is a white light-shielding layer.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130090413A KR20150014768A (en) | 2013-07-30 | 2013-07-30 | A colored photosensitive resin composition for formming the frontal light-shielding layer of a display device |
| JP2014128097A JP2015028619A (en) | 2013-07-30 | 2014-06-23 | Photosensitive resin composition for forming front light-shielding layer of display device |
| CN201410324103.3A CN104345553B (en) | 2013-07-30 | 2014-07-08 | Front light shield layer, which is formed, uses photosensitive polymer combination and display device |
| TW103124922A TW201504761A (en) | 2013-07-30 | 2014-07-21 | A colored photosensitive resin composition for forming a frontal light-shielding layer of a display device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130090413A KR20150014768A (en) | 2013-07-30 | 2013-07-30 | A colored photosensitive resin composition for formming the frontal light-shielding layer of a display device |
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| KR20150014768A true KR20150014768A (en) | 2015-02-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1020130090413A KR20150014768A (en) | 2013-07-30 | 2013-07-30 | A colored photosensitive resin composition for formming the frontal light-shielding layer of a display device |
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