KR20170043307A - Photosensitive resin composition and photosensitive material comprising the same - Google Patents
Photosensitive resin composition and photosensitive material comprising the same Download PDFInfo
- Publication number
- KR20170043307A KR20170043307A KR1020150142901A KR20150142901A KR20170043307A KR 20170043307 A KR20170043307 A KR 20170043307A KR 1020150142901 A KR1020150142901 A KR 1020150142901A KR 20150142901 A KR20150142901 A KR 20150142901A KR 20170043307 A KR20170043307 A KR 20170043307A
- Authority
- KR
- South Korea
- Prior art keywords
- ether
- solvent
- resin composition
- ethyl
- glycol
- Prior art date
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
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
Abstract
The present invention relates to a photosensitive resin composition and a photosensitive material containing the photosensitive resin composition. The photosensitive resin composition according to one embodiment of the present application comprises a binder resin, a polymerizable compound containing an ethylenically unsaturated bond, a colorant, a photoinitiator, and a solvent, wherein the solvent has a boiling point of from 110 ° C to less than 160 ° C A second solvent having a boiling point of from 160 캜 or more to less than 200 캜 and a third solvent having a boiling point of 200 캜 or more and 280 캜 or less based on the total weight of the solvent, % By weight, the content of the second solvent is more than 35% by weight and less than 60% by weight, and the content of the third solvent is more than 1% by weight and less than 10% by weight.
Description
The present invention relates to a photosensitive resin composition and a photosensitive material containing the photosensitive resin composition.
Between the color pixels of the color filter, it is common to arrange a lattice-like black pattern called a black matrix for the purpose of improving the contrast. In the conventional black matrix, chromium (Cr) is deposited and etched on the entire glass substrate as a pigment to form a pattern. However, high cost is required in the process, and problems such as high reflectivity of chromium, environmental pollution A problem has occurred.
For this reason, studies of black matrix by pigment dispersion method capable of micromachining have been actively carried out, and studies for producing a black composition using color pigments other than carbon black have been carried out, but color pigments other than carbon black The blending amount thereof must be increased to an extremely large amount. As a result, the viscosity of the composition is increased, which makes handling difficult, or the strength of the formed film or adhesiveness to the substrate remarkably deteriorated.
There are many studies on the photosensitive resin composition in accordance with the demand for continuous improvement of the industry. For example, a color filter composition using a newly developed binder and a high sensitivity photopolymerization initiator are used to improve the sensitivity , A photopolymerization initiator, and a black matrix resin composition having improved sensitivity by introducing an organic phosphoric acid compound into the composition.
In recent years, the proportion of LCDs in flat panel displays is rapidly increasing. The LCD field, where conventional small and mid-sized mobile displays and monitors were dominant, is now shifting to large monitors and TVs. As the screen becomes larger, there is a demand for high sensitivity for shortening the process time. In addition, since the size of the screen increases and the brightness becomes a problem, a brighter backlight is adopted. As the backlight brighter, the black matrix also requires a higher light shielding characteristic than the conventional one.
Accordingly, as the content of carbon black, which is a pigment used in the composition, is continuously increased to improve the light-shielding property, the process characteristic of the black mattress continuously deteriorates, thereby lowering the process margin and causing many defects in each process step. There has been a problem of deterioration.
Defects occurring in each process due to increased content of carbon black for higher order light include defects, stains, and the like which are fatal in vacuum drying (VCD process). Pin stains occurring in the pre-bake stage; Chuck smudges generated in the exposure step; Unevenness of patterns, dropouts of patterns, residues, protrusions, and the like, which are generated in the developing step.
In addition, in the industry, efforts are being made to reduce processing time to increase production, and the process equipment is controlled to an extreme limit, so the standard required for a photosensitive composition is further increased.
In Korean Patent Laid-Open Publication No. 2006-86999, a photosensitive resin composition comprising a binder polymer, a polymerizable compound having an ethylenically unsaturated bond, a photoinitiator, and a solvent, the solvent is (i) a first solvent having a boiling point in the range of 140 to 159 ° C At least one solvent selected from the group consisting of: (ii) at least one solvent selected from the second solvent group having a boiling point in the range of 160 to 179 DEG C; And (iii) a third solvent group having a boiling point in the range of 180 to 200 ° C, wherein the ratio of the first solvent: the second solvent: the third solvent is 50 to 90% by weight: 10 to 40 % By weight: 2 to 40% by weight.
However, since the content of the first solvent having a relatively low boiling point is 50 to 90% by weight in the total solvent, it can not be used for a black matrix having a uniform thin film without surface defects. Do. Actually, all the embodiments of the above-mentioned patent only show the composition for the color filter, but the examples applied to the black matrix are not described.
It is an object of the present invention to develop a specific combination of solvents for the production of a high-order black matrix which is excellent in processability and has no defects in the photosensitive resin composition necessary for producing a black matrix.
In one embodiment of the present application,
A binder resin, a polymerizable compound containing an ethylenic unsaturated bond, a colorant, a photoinitiator, and a solvent,
Wherein the solvent comprises a first solvent having a boiling point of more than 110 ° C and less than 160 ° C, a second solvent having a boiling point of 160 ° C or more and less than 200 ° C, and a third solvent having a boiling point of 200 ° C or more and 280 ° C or less,
Wherein the content of the first solvent is greater than 30 wt% to less than 55 wt%, the content of the second solvent is greater than 35 wt% and less than 60 wt%, and the content of the third solvent is greater than 30 wt% And more than 1 wt% to less than 10 wt% of the photosensitive resin composition.
Further, another embodiment of the present application provides a photosensitive material characterized by using the photosensitive resin composition.
Further, another embodiment of the present application,
Applying the photosensitive resin composition on a substrate,
Drying and prebaking the applied photosensitive resin composition, and
A step of exposing and developing the applied photosensitive resin composition
The present invention also provides a method for producing a photosensitive material.
The photosensitive resin composition according to one embodiment of the present application can include a solvent having a specific composition ratio to obtain a uniform thin film having no surface defects even under the enhanced process conditions and can have excellent process characteristics while securing high order lightness . In addition, the photosensitive resin composition according to one embodiment of the present application can be applied to a liquid crystal display device because a black matrix pattern with few defects can be obtained.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a film according to Example 1 of the present application. Fig.
2 is a view showing a film according to Embodiment 2 of the present application.
3 is a view showing a film according to Example 3 of the present application.
4 is a view showing a film according to Example 4 of the present application.
5 is a view showing a film according to Comparative Example 1 of the present application.
6 is a view showing a film according to Comparative Example 2 of the present application.
7 is a view showing a film according to Comparative Example 3 of the present application.
Hereinafter, the present invention will be described in more detail.
In the case of the black matrix composition, it is generally composed of a light-shielding material (mainly carbon black), a binder resin, a polymerizable compound containing an ethylenic unsaturated bond, a photoinitiator, a solvent and the like.
In the case of carbon black used as a light-shielding material, since it is produced through a combustion process at a high temperature, there is a high possibility that foreign matter may be generated from the manufacturing process. The carbon black dispersion is prepared by subjecting the above-mentioned carbon black to various steps and adding a dispersant, a binder, and the like to stabilize the dispersion. Although the foreign matter is removed through filtering several times during the production of the carbon black dispersion liquid, it is almost impossible to completely remove fine inorganic particles having a small size.
The fine particles remaining in the dispersion become seeds and foreign matter is likely to be generated. Therefore, in the case of the black matrix, there is a characteristic of being vulnerable to the occurrence of projections by foreign matter. Therefore, it is preferable to provide a sufficient filter at the time of preparing the black matrix composition.
In order to reduce the generation of foreign matter in the black matrix composition, several conditions are required. First, the black matrix composition must be highly soluble. The re-solubility refers to the property that the hardened photoresist dissolves again by the solvent. The black matrix composition is subjected to a photolithography process for producing a color filter. In the photolithography process, a hardened photoresist is formed in a pipe, a coater nozzle, or the like, and if the solubility is poor, the black matrix composition is likely to be formed as a protrusion.
Second, the black matrix composition should have moderate volatility. If the volatility is too good, the volatilization of the solvent at the end of the coating nozzle is likely to occur, resulting in a hardened photoresist. In this case, the foreign matter formed at the tip of the nozzle tends to be scratched when the next coating is applied. However, if the volatility is too low, adequate volatility control is required because the vacuum drying process time is prolonged in the next process.
Thirdly, the solubility of the solvent to the constituents of the black matrix composition should be excellent. The above two conditions must be satisfied in the selection of the solvent, but more importantly, it is the solubility in the component. Depending on the material, may not be sufficiently dissolved in a commonly used solvent, and in such a case, the stability with time may deteriorate or protrusion may easily occur. Thus, the solvent must have a proper solvation effect to maintain proper dispersion in the black matrix composition and to inhibit protrusion formation.
In the conventional black matrix composition, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate or the like is used as a main solvent, and diethylene glycol methyl butyl ether, butyl carbitol acetate or the like, which is a high boiling solvent, is partially used Respectively. In particular, 3-methoxybutyl acetate has suitable boiling point and volatility and is mainly used as the main solvent. However, in the case of some cardo binders used in the black matrix, the solubility in 3-methoxybutyl acetate was lowered, which deteriorated the stability with time and caused the projection to be easily generated.
In addition, in order to evaporate a large amount of solvent in a solvent evaporation process (VCD process) in the past, the use of a relatively low boiling point solvent was required to be the greatest. Accordingly, the VCD process has a problem that a lot of defects are generated on the surface of the thin film. Especially, in the case of the black matrix, there is a problem that the black matrix can not be used if there are surface defects.
In addition, the stain is not a problem in the decompression process due to changes in the process conditions, but problems may occur in the subsequent baking process. Particularly, in a model forming a large line width of a TV or the like, dirt is not a serious problem, but in a process of forming a smaller line width of a monitor or a notebook, existing solvent conditions are problematic due to enhanced stain characteristics. Thus, the present inventors have been able to optimize the solvent composition to improve the stain in the baking process and to form a coating film free from surface defects.
Therefore, in this application, the composition ratio of the three kinds of solvents having different boiling points was optimized so that the surface of the black matrix thin film was free of crystals. That is, optimizing the composition of the solvent so that there are no defects on the surface of the thin film is a very important factor in the composition of the black matrix, and the present application has developed a specific composition ratio of the solvent.
The photosensitive resin composition according to one embodiment of the present application comprises a binder resin, a polymerizable compound containing an ethylenically unsaturated bond, a colorant, a photoinitiator, and a solvent, wherein the solvent has a boiling point of from 110 ° C to less than 160 ° C A second solvent having a boiling point of from 160 캜 or more to less than 200 캜 and a third solvent having a boiling point of 200 캜 or more and 280 캜 or less based on the total weight of the solvent, % By weight, the content of the second solvent is more than 35% by weight and less than 60% by weight, and the content of the third solvent is more than 1% by weight and less than 10% by weight.
In the present application, the first solvent is characterized by a boiling point of greater than 110 ° C and less than 160 ° C.
The first solvent is selected from the group consisting of methyl-3-methoxypropionate (144 ° C), ethylene glycol methyl ether (125 ° C), ethylene glycol ethyl ether (135 ° C), ethylene glycol diethyl ether Propyleneglycol methyl ether acetate (146 占 폚), n-butyl acetate (125 占 폚), isobutyl acetate (116 占 폚), amyl acetate (140 占 폚), ethyl pyruvate (143 deg. C), isoamyl acetate (143 deg. C), butyl propionate (146 deg. C), isoamyl propionate (156 deg. C), ethyl butyrate Methoxyisobutyrate (148 占 폚), methyl glycolate (150 占 폚), methyl lactate (145 占 폚), ethyl lactate (154 占 폚), methyl-2-hydroxyisobutyrate Acetate (156 占 폚), 2-methoxyethyl acetate (145 占 폚), ethylene glycol methyl ether acetate (145 占 폚) Cyclohexanone (155 占 폚), 2-hexanone (127 占 폚), 3-hexanone (123 占 폚), Heptanone (145 DEG C), 2-methyl-3-heptanone (159 DEG C) (158 占 폚), and the like are contained in an amount of at least one kind selected from the group consisting of 1-methoxy-2-propanol (118 占 폚), ethyl-2-hydroxypropionate But is not limited thereto.
Based on the total weight of the solvent, the content of the first solvent is more than 30 wt% to less than 55 wt%. When the content of the first solvent is 30 wt% or less, the amount of the solvent having a high boiling point is relatively large. In this case, not only the time for vacuum drying (VCD) is prolonged, but also the film is soft and vulnerable to stains in the prebaking process. When the content of the first solvent is 55 wt% or more, the solvent having a low boiling point evaporates excessively during the depressurization step, resulting in surface defects and drying of the nozzle head during coating with the slit coater, easy.
In the present application, the second solvent has a boiling point of 160 ° C or higher and lower than 200 ° C.
The second solvent is selected from the group consisting of 2-methoxyethyl ether (162 占 폚), 3-methoxybutyl acetate (170 占 폚), 2-ethoxyethyl ether (185 占 폚), 2-butoxyethanol Propanol (161 캜), diethylene glycol dodecyl ether (169 캜), dipropylene glycol methyl ether (188 캜), 2,6-dimethyl-4-heptanone (169 캜) 173 ° C), 3-octanone (168 ° C), 3-nonanone (188 ° C), 5-nonanone (187 ° C), 4-hydroxy- -Methylcyclohexanone (170 DEG C), 2,6-dimethylcyclohexanone (175 DEG C), 2,2,6 Hexyl acetate (169 占 폚), amyl butyrate (185 占 폚), isopropyl lactate (167 占 폚), butyl lactate (186 占 폚), ethyl Hydroxybutyrate (180 占 폚), propyl-2-hydroxypropionate (170 占 폚), ethyl-3-ethoxypropionate Propylene glycol diethyl ether (162 占 폚), diethylene glycol dimethyl ether (169 占 폚), propylene glycol diacetate (186 占 폚), propylene glycol butyl ether (170 占 폚), propylene glycol methyl ether propionate (171 占 폚), diethylene glycol methyl ethyl ether (176 占 폚), diethylene glycol (178 占 폚), diethylene glycol monomethyl ether (179 ° C), diethylene glycol diethyl ether (189 ° C), butyl butyrate (165 ° C), ethyl 3-ethoxypropionate (170 ° C), diethylene glycol monomethyl ether ), 4-ethylcyclohexanone (193 DEG C), 2-butoxyethylacetate (192 DEG C), and the like, but the present invention is not limited thereto.
And the content of the second solvent is more than 35% by weight and less than 60% by weight based on the total weight of the solvent. When the content of the second solvent is 35% by weight or less, the content of the first solvent having a relatively low boiling point is increased, so that surface defects tend to occur during the reduced pressure drying. If the content of the second solvent is 60 wt% or more, a reduced pressure drying time may be applied, which may lead to a decrease in productivity. In the pre-baking step, the film quality is relatively smooth and stains are likely to occur.
In the present application, the third solvent has a boiling point of 200 ° C or higher and 280 ° C or lower.
The third solvent is selected from the group consisting of diethylene glycol monoethyl ether (202 ° C), butyrolactone (204 ° C), hexyl butyrate (205 ° C), diethylene glycol methyl ether acetate (209 ° C), diethylene glycol butyl methyl ether 212 ° C), tripropyl glycol dimethyl ether (215 ° C), triethylene glycol dimethyl ether (216 ° C), diethylene glycol ethyl ether acetate (217 ° C), diethylene glycol butyl ether acetate (245 ° C) Diethyleneglycol monobutyl ether (231 占 폚), tripropylglycol methyl ether (242 占 폚), diethylene glycol (245 占 폚), 1,2-propanediol (222 占 폚) Butylene glycol diacetate (230 캜), 2- (2-butoxyethoxy) ethyl acetate 245 캜, catechol 245 캜, triethylene glycol methyl ether 249 캜, diethylene glycol dibutyl Ether (256 占 폚), triethylene glycol ethyl ether (256 占 폚), diethylene glycol monohexyl ether (260 ° C), triethylene glycol butyl methyl ether (261 ° C), triethylene glycol butyl ether (271 ° C), tripropyl glycol (273 ° C), tetraethylene glycol dimethyl ether But is not limited thereto.
The content of the third solvent is more than 1% by weight and less than 10% by weight based on the total weight of the solvent. If the content of the third solvent is less than 1% by weight, defects tend to occur during drying under reduced pressure. If the content of the third solvent is more than 10% by weight, not only the reduced pressure drying time becomes long, So that it is possible to cause the fine pattern to fall off during the developing process.
In the photosensitive resin composition according to the present application, the binder resin may be an alkali-soluble resin known in the art. Examples of the alkali-soluble resin include, but are not limited to, an acrylic resin containing a carboxyl group. The weight average molecular weight of the alkali-soluble resin may be 3,000 to 150,000. When the weight average molecular weight is 3,000 or more, heat resistance and chemical resistance can be maintained. When the weight average molecular weight is 150,000 or less, the solubility of the developer can be more than a certain level, and the viscosity of the solution can be maintained.
The alkali-soluble resin may have an acid value of 30 to 300 KOH mg / g. The acid value should be 30 KOH mg / g or more to obtain a clean pattern. If the acid value is 300 KOH mg / g or less, the washing property is excessively improved and the pattern can be prevented from falling off.
Further, the binder resin may use a cadmium resin known in the art. The cadogy resin refers to an acrylate resin containing a fluorene group in its main chain and is not particularly limited in structure.
The binder resin used in the present invention is an alkali soluble resin, and is a copolymer resin of a monomer giving mechanical strength and a monomer giving alkali solubility.
Monomers that can contribute to the mechanical strength of the film include benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) (Meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, ethylhexyl- Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, 3-methoxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol Ethoxydiethylene glycol (Me Acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, glycidyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, (Meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, Dicyclopentenyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl acrylate, isobornyl methacrylate, adamantyl methacrylate, methyl? -Hydroxymethyl Methacrylate, ethyl α- hydroxymethyl acrylate, propyl α- hydroxy methyl acrylate, and butyl α- hydroxymethyl-unsaturated carboxylic acid ester at least one selected from the group consisting of acrylates;
At least one aromatic compound selected from the group consisting of styrene,? -Methylstyrene, (o, m, p) -vinyltoluene, (o, m, p) -methoxystyrene, and (o, m, p) Vinyl;
One or more unsaturated ethers selected from the group consisting of vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether;
At least one unsaturated imide selected from the group consisting of N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide and N-cyclohexylmaleimide; And
Maleic anhydride, and maleic anhydride such as maleic anhydride and methylmaleic anhydride may be used alone, but not limited thereto.
Examples of the monomer capable of imparting alkali solubility include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, 5-norbornene- It is preferable to use at least one member selected from the group consisting of ethyl phthalate, mono-2 - ((meth) acryloyloxy) ethyl succinate, and omega -carboxylic polycaprolactone mono (meth) But is not limited thereto.
In addition to the above monomers, a binder resin represented by the following general formula (1) may also be used.
[Chemical Formula 1]
Wherein Rx is a structure in which a carboxylic acid anhydride or diisocyanate of a 5-membered ring is subjected to addition reaction to form an ester bond, Ry is selected from hydrogen, acryloyl, and methacryloyl, and n is 3 to 8 to be.
Examples of the specific compound of carboxylic acid anhydride constituting Rx include succinic anhydride, methyl succinic anhydride, 2,2-dimethyl succinic anhydride, isobutenyl succinic anhydride, 1,2-cyclohexanedicarboxylic anhydride, hexahydro- 4-methylphthalic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, mell-5-norbornene-2,3-dicarboxylic anhydride, 1,2,3 , 4-cyclobutane tetracarboxylic dianhydride, maleic anhydride, citraconic anhydride, 2,3, -dimethyl maleic anhydride, 1-cyclopentene-1,2-dicarboxylic dianhydride, 3,4,5,6 -Tetrahydrophthalic anhydride, phthalic anhydride, bisphthalic anhydride, 4-methylphthalic anhydride, 3,6-dichlorophthalic anhydride, 3-hydrophthalic anhydride, 1,2,4-benzenetricarboxylic anhydride, 4-nitrophthalic anhydride , And diethylene glycol-1,2-bistrimelic acid anhydride. Group, but is not limited thereto.
Specific examples of the diisocyanate constituting Rx include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1 , 3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, w, w'-diisocyanate-1,3-dimethylbenzene, w, w'-diisocyanate- Dimethylbenzene, w, w'-diisocyanate-1,3-diethylbenzene, 1,4-tetramethylxylene diisocyanate, 1,3-tetramethylxylene diisocyanate,
1,3-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclo Hexane diisocyanate, 4,4'-methylene bisisocyanate methylcyclohexane, 2,5-isocyanate methylbicyclo [2,2,2] heptane, and 2,6-isocyanate methylbicyclo [2,2,1] heptane , But is not limited thereto.
The content of the binder resin is preferably 1 to 30% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.
The functional monomer according to the present invention has an ethylenically unsaturated double bond and specifically includes a compound having at least one addition polymerizable unsaturated group in the molecule and having a boiling point of 100 ° C or higher or a functional monomer having caprolactone introduced therein .
(Meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate as the compound having at least one addition polymerizable unsaturated group in the molecule and having a boiling point of 100 ° C or higher At least one monofunctional monomer selected from the group consisting of (Meth) acrylates such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, trimethylol ethane triacrylate, trimethylolpropane triacrylate, neopentyl glycol (meth) acrylate, pentaerythritol tetraacrylate, At least one polyfunctional monomer selected from the group consisting of triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate can be used.
As the polyfunctional monomer into which the caprolactone was introduced, KAYARAD DPCA-20, 30, 60, 120, which was introduced into dipentaerythritol; KAYARAD TC-110S introduced into tetrahydrofuryl acrylate; And KAYARAD HX-220 and KAYARAD HK-620 which are introduced into neopentyl glycol hydroxy pivalate.
U-324A, U15HA, U-4HA and the like, which are epoxy acrylates, novolac-epoxy acrylates and urethane-based polyfunctional acrylates, of bisphenol A derivatives can be used in addition to the above monomers. These monomers may be used singly or in combination of two or more.
The functional monomer having an ethylenically unsaturated double bond is preferably contained in the black matrix photosensitive resin composition in an amount of 1 to 20% by weight. When the content is less than 1% by weight, the photosensitivity or the strength of the coating film is lowered. If the amount is more than 10% by weight, the adhesive property of the photosensitive resin layer is excessively excessive, the strength of the film is not sufficient and the pattern is lost during development, which is not preferable.
The photoinitiator used in the present invention is a material which generates radicals by light to induce crosslinking, and is a compound which is selected from the group consisting of an acetophenone compound, a nonimidazole compound, and a triazine compound or a oxime compound Are preferably used in combination.
Examples of the acetophenone compound that can be used as the photoinitiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin iso Butyl ether, benzoin butyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- (4-methylthio) phenyl- 2-dimethylamino-1- (4-morpholinophenyl) -butane, 2- (4-bromo- -1-one and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one,
Examples of the nonimidazole-based compounds include 2,2-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- 4 ', 5,5'-tetrakis (3,4,5-zimethoxyphenyl) -1,2'-biimidazole, 2,2'-bis (2,3-dichlorophenyl) 4 ', 5,5'-tetraphenylbiimidazole, and 2,2'-bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'- Group,
Examples of the triazine compound include 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propionic acid, 1,1,1,3,3,3- (Trichloromethyl) -s-triazine-6-yl] phenylthio} propionate, ethyl 2- {4- [2,4 Bis (trichloromethyl) -s-triazin-6-yl] phenylthio} acetate, 2- epoxyethyl-2- {4- [ Yl] phenylthio} acetate, benzyl-2- {4- [2- (4-fluorophenyl) (Trichloromethyl) -s-triazine-6-yl] phenylthio} acetate, 3- {chloro-4- [ (Phenylthio) propionic acid, 2,4- bis (trichloromethyl) -s-triazine-6-yl] Methyl) -6- p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p- Aminophenyl) -1,3-butadienyl -s- triazine, and 2-trichloromethyl-4-amino -6-p- methoxy styryl -s- will selected from the group consisting of a triazine,
Examples of the oxime compounds include 1,2-octadione-1- (4-phenylthio) phenyl-2- (o-benzoyloxime) (Ciba Geigy, CGI 124), and ethanone- (CGI 242), oxime OX-03 (Shiba Kagaku), NCI-831 (Adeca), PI-102 (LG Biotechnology Co., Chemical), PBG 304, PBG 305, and PBG 3057 (Tronnis).
The content of the photoinitiator is preferably 0.1 to 10% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.
As the colorant, one or more pigments, dyes, or mixtures thereof may be used. Specifically, for example, a colored dispersion containing a black pigment can be used. Examples of usable carbon black include Sysho 5HIISAF-HS, Sisato KH, Sisato 3HHAF-HS, Sisato NH, Sisato 3M, Sisso 300HAF-LS, Sisso 116HMMAF-HS, 116MAF, Cysto FMFEF-HS, Cysto SOFEF, Cysto VGPF, Cysto SVHSRF-HS, and Cysto SSRF; Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR, # 2700, # 2600, # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 900, MCF88, # 52, # 50, # 47, # 45, # 45L, CF9, # 95, # 3030, # 3050, MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B; PRINTEX-55, PRINTEX-55, PRINTEX-45, PRINTEX-35, PRINTEX-55, PRINTEX-85, PRINTEX-75, PRINTEX- SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101; PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A; SPECIAL BLACK-550; RAVEN-1080 ULTRA, RAVEN-1060ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN- 420, RAVEN-410, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN- RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170 can be used.
Examples of color pigments usable in combination with the carbon black include carmine 6B (CI12490), phthalocyanine green (CI 74260), phthalocyanine blue (CI 74160), Mitsubishi carbon black MA100, perylene black (BASF K0084. K0086) , Linol Yellow (CI 21090), Linol Yellow GRO (CI 21090), Benzidine Yellow 4T-564D, Mitsubishi Carbon Black MA-40, Victoria Pure Blue (CI42595) PIGMENT RED97, 122, 149, 168, 177, 180, 192, 215, C.I. PIGMENT GREEN 7, 36, C.I. PIGMENT 15: 1, 15: 4, 15: 6, 22, 60, 64, C.I. PIGMENT 83, 139 C.I. PIGMENT VIOLET 23, etc. In addition, white pigments, fluorescent pigments, etc. may be used.
The content of the coloring agent may be 5 to 20% by weight based on the total weight of the photosensitive resin composition.
The photosensitive resin composition according to the present application may further contain at least one selected from the group consisting of a dispersant, a curing accelerator, a thermal polymerization inhibitor, a surfactant, a photosensitizer, a plasticizer, a contact promoter, a filler, As shown in FIG.
The dispersant may be used either in a manner of internally adding to the pigment in the form of surface-treating the pigment in advance, or in a method of externally adding the pigment. As the dispersing agent, a polymeric, nonionic, anionic or cationic dispersing agent may be used. Examples thereof include polyalkylene glycols and esters thereof, polyoxyalkylene polyhydric alcohols, ester alkylene oxide adducts, alcohol alkylene oxides But are not limited to, at least one selected from the group consisting of adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, carboxylic acid salts, alkylamide alkylene oxide adducts and alkylamines.
Examples of the curing accelerator include 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercaptan-1,3,4-thiadiazole, 2- (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis Trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris And trimethylol ethane tris (3-mercaptopropionate). However, the present invention is not limited thereto and may include those generally known in the art.
Examples of the thermal polymerization inhibitor include p-anisole, hydroquinone, pyrocatechol, t-butyl catechol, N-nitrosophenylhydroxyamine ammonium salt, N-nitrosophenylhydroxy Amine aluminum salt, and phenothiazine. However, the present invention is not limited thereto, and may include those generally known in the art.
The silicone surfactant may be selected from the group consisting of BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK- -307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, , BYK-354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK- F-443, F-444, F-445, F-444, F-450, F-493, F- F-484, F-472, F-474, F-474, F-474, F-477, F-478, F- , F-486, F-487, F-552, F-553, F-554, F-555, F-556, F-557, F- F-562, F-563, F-565, F-567, F-568, F569, F-570, F-571, F-172D, R-40, R41, R-43, , Rs-75, and the like may be used, but the present invention is not limited thereto.
The adhesion promoter may be selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) -silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- 2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- glycidoxypropylmethyldimethoxysilane, 2- 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane, And trimethoxysilane can be used.
Any of the above photosensitizer, plasticizer, adhesion promoter, filler and the like may be used in the conventional photosensitive resin composition.
The content of the additive is preferably 0.01 to 5% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.
Meanwhile, the photosensitive resin composition according to the present invention is used for a roll coater, a curtain coater, a spin coater, a slot die coater, various printing, Or the like. It is also possible to apply it onto a support such as a film and then transfer it to another support or coat it on a first support, transfer it to a blanket or the like, and transfer it to a second support again.
Examples of the light source for curing the photosensitive resin composition according to the present application include, but are not limited to, a mercury vapor arc, a carbon arc, and an Xe arc, which emit light having a wavelength of 250 to 450 nm.
In addition, the photosensitive resin composition may further include at least one secondary additive selected from the group consisting of a carbon black dispersion, a functional resin binder, a polyfunctional monomer, a radiation-sensitive compound, and other additives have.
Further, the present application provides a photosensitive material characterized by being formed using the above photosensitive resin composition.
The photosensitive resin composition according to the present invention is preferably used for a pigment dispersing type photosensitive material for manufacturing a TFT LCD color filter, a photosensitive material for forming a black matrix of a TFT LCD or an organic light emitting diode, a photosensitive material for forming an overcoat layer, and a photosensitive material for a column spacer , Photo-curable paints, photo-curable inks, photocurable adhesives, printing plates, photosensitive materials for printed wiring boards, other transparent photosensitive materials, and PDP manufacture. In particular, the photosensitive resin composition according to the present invention is preferably used for a photosensitive material for a color filter or a photosensitive material for a black matrix.
(2) a step of subjecting the applied photosensitive resin composition to vacuum drying and prebaking (soft baking); and (3) a step of drying the applied photosensitive resin composition under reduced pressure. And exposing and developing the applied photosensitive resin composition.
In the method for producing a photosensitive material according to the present invention, the step 1) may be a step of applying the photosensitive resin composition, for example, the method may be applied on a substrate using a method known in the art. More specifically, the method of applying the photosensitive resin composition may be a spraying method, a roll coating method, a spin coating method, a bar coating method, a slit coating method, or the like. However, the present invention is not limited thereto.
At this time, the substrate may be made of metal, paper, glass, plastic, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide and the like. Treatment, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum deposition, or the like. In addition, the substrate may have an optional thin film transistor for driving, and a nitrided silicon film may be sputtered.
In the method for producing a photosensitive material according to the present application, the step 2) is a step of drying under reduced pressure at a reduced pressure drying and prebaking step under reduced pressure until the pressure reaches 30 pascal to 90 pascal, preferably 60 to 70 pascal It is good to dry until reaching.
As a pre-baking condition, it is dried at a temperature of 90 ° C to 120 ° C on a hot plate for 90 seconds to 180 seconds, preferably at a temperature of 100 ° C to 110 ° C for 90 seconds to 120 seconds.
In the method for producing a photosensitive material according to the present application, the step 3) is a step of exposing and developing the applied photosensitive resin composition.
More specifically, the prebaked coating film can be patterned by irradiating ultraviolet rays through a predetermined pattern mask and developing it with an aqueous alkaline solution to remove unnecessary portions. At this time, as a developing method, a dipping method, a shower method, and the like can be applied without limitation. The developing time is usually about 30 to 180 seconds. Examples of the developer include aqueous alkaline solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, sodium metasilicate and ammonia; Primary amines such as ethylamine and N-propylamine; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine and dimethylethylamine; Tertiary alcohol amines such as dimethylethanolamine, methyldiethanolamine and triethanolamine; Diazabicyclo [4.3.0] hept-2-ene, 1,1-diazabicyclo [5.4.0] Cyclic tertiary amines such as cyclohexane-5-nonene; Aromatic tertiary amines such as pyridine, coridine, lutidine and quinoline; An aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used.
After development, water-repellent cleaning is performed for about 30 to 90 seconds, and the pattern can be formed by drying with air or nitrogen. This pattern can be obtained through a post-bake using a heating device such as a hot plate or an oven. At this time, it is preferable to heat post-baking at 150 to 250 DEG C for 10 to 90 minutes.
Examples of the light source for curing the photosensitive resin composition of the present application include, but are not necessarily limited to, mercury vapor arc, carbon arc, and Xe arc, which emits light having a wavelength of 250 to 450 nm.
The photosensitive material according to the present invention is excellent in surface-defect free properties, developability, light-shielding property, and insulation, and is excellent in adhesion with a substrate and excellent in impact resistance after a substrate adhesion process, a liquid crystal injection process, and a panel.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
< Example >
< Example 1>
950 parts by weight of a carbon dispersion (carbon content 20%), 10 parts by weight of an alkali-soluble resin binder (bisphenol fluorene epoxy acrylate / 1,3-cyclohexyldiisocyanate-moly ratio (65/35, Mw = 5,000, 30 parts by weight of dipentaerythritol hexaacrylate (DPHA) as a polyfunctional monomer, 25 parts by weight of a photoinitiator (BASF OX03), 5 parts by weight of an adhesion promoter (Shinetsusa KBM 503) , And 1 part by weight of a leveling agent (DIC F475), 658 parts by weight of PGMEA as a solvent, 905 parts by weight of 3-MBA and 82 parts by weight of BGDA were mixed and stirred for 5 hours to prepare a black matrix photosensitive resin composition .
< Example 2 to 4 and Comparative Example 1 to 3>
A black matrix photosensitive resin composition was prepared in the same manner as in Example 1 except that the kind and content of the solvent were adjusted as shown in Table 1 below.
[Table 1]
PGMEA: Propylene glycol methyl ether acetate
3-MBA: 3-methoxybutylacetate
MEDG: Diethylene glycol methyl ethyl ether
MBDG: diethylene glycol methyl butyl ether
BGDA: Butylene glycol diacetate
The solvent ratio means a ratio including the solvent contained in the carbon dispersion, and the total solvent amount in the composition.
< Experimental Example >
The photosensitive resin composition solution prepared as in Examples 1 to 4 and Comparative Examples 1 to 3 was spin-coated on glass, vacuum dried to about 65 Pa (VCD), and heat treated at about 100 캜 for about 2 minutes to about 1.22 Thereby forming a coating film having a thickness of [mu] m. Then, after cooling at room temperature, the substrate was post-baked in a convection oven at 230 ° C for 100 minutes after the front exposure to measure adhesion. Further, in order to observe developability and pattern shape, a photomask was used to expose under a high-pressure mercury lamp at an energy of 40 mJ / cm 2. The exposed substrate was developed in a 0.04% aqueous solution of KOH at 25 ° C by spraying method, washed with pure water, and dried, post-baked in a convection oven at 230 ° C for 20 minutes.
The film thus obtained was observed for surface defects using an optical microscope, and the results are shown in Figs. 1 to 6. Surface defects (stains) and pattern characteristics (dropout) were observed and are shown in Table 2 below.
As shown in Figs. 1 to 6, surface irregularities occurred in Comparative Examples 1 and 2, in which the surface irregularities did not occur in the present application but were out of the solvent composition ratios of the present application.
[Table 2]
The photosensitive resin composition according to one embodiment of the present application can include a solvent having a specific composition ratio to obtain a uniform thin film having no surface defects even under the enhanced process conditions and can have excellent process characteristics while securing high order lightness . In addition, the photosensitive resin composition according to one embodiment of the present application can be applied to a liquid crystal display device because a black matrix pattern with few defects can be obtained.
Claims (9)
Wherein the solvent comprises a first solvent having a boiling point of more than 110 ° C and less than 160 ° C, a second solvent having a boiling point of 160 ° C or more and less than 200 ° C, and a third solvent having a boiling point of 200 ° C or more and 280 ° C or less,
Wherein the content of the first solvent is greater than 30 wt% to less than 55 wt%, the content of the second solvent is greater than 35 wt% and less than 60 wt%, and the content of the third solvent is greater than 30 wt% And more than 1 wt% to less than 10 wt%.
2) drying and prebaking the applied photosensitive resin composition under reduced pressure, and
3) exposing and developing the applied photosensitive resin composition
Wherein the photosensitive material is a photosensitive material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150142901A KR20170043307A (en) | 2015-10-13 | 2015-10-13 | Photosensitive resin composition and photosensitive material comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150142901A KR20170043307A (en) | 2015-10-13 | 2015-10-13 | Photosensitive resin composition and photosensitive material comprising the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20170043307A true KR20170043307A (en) | 2017-04-21 |
Family
ID=58705423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150142901A KR20170043307A (en) | 2015-10-13 | 2015-10-13 | Photosensitive resin composition and photosensitive material comprising the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20170043307A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109814335A (en) * | 2017-11-21 | 2019-05-28 | 东友精细化工有限公司 | Photosensitive composition, colour filter and image display device |
| CN110515268A (en) * | 2018-05-22 | 2019-11-29 | 日铁化学材料株式会社 | Photosensitve resin composition, the hardening thing of the Photosensitve resin composition and the display device containing the hardening thing |
| CN113508337A (en) * | 2019-04-24 | 2021-10-15 | Jsr株式会社 | Photosensitive resin composition, method for producing resist pattern film, and method for producing plated article |
-
2015
- 2015-10-13 KR KR1020150142901A patent/KR20170043307A/en active Search and Examination
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109814335A (en) * | 2017-11-21 | 2019-05-28 | 东友精细化工有限公司 | Photosensitive composition, colour filter and image display device |
| CN109814335B (en) * | 2017-11-21 | 2022-03-04 | 东友精细化工有限公司 | Colored photosensitive resin composition, color filter and image display device |
| CN110515268A (en) * | 2018-05-22 | 2019-11-29 | 日铁化学材料株式会社 | Photosensitve resin composition, the hardening thing of the Photosensitve resin composition and the display device containing the hardening thing |
| CN113508337A (en) * | 2019-04-24 | 2021-10-15 | Jsr株式会社 | Photosensitive resin composition, method for producing resist pattern film, and method for producing plated article |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5177914B2 (en) | Black matrix photosensitive resin composition, method for producing black matrix photosensitive resin composition, black matrix and liquid crystal display device | |
| KR101472174B1 (en) | Photosensitive resin composition and photosensitive material comprising the same | |
| KR101682825B1 (en) | Photosensitive resin composition, pattern formed by using the same and display panel comprising the same | |
| JP5329430B2 (en) | Black matrix high-sensitivity photosensitive resin composition for liquid crystal display and black matrix produced using the same | |
| KR101068622B1 (en) | The high lightshielding blackmatrix composition having improved adhesion properties | |
| JP5326175B2 (en) | Color dispersion, photoresist composition and black matrix | |
| JP6018704B2 (en) | Touch panel including a photosensitive resin composition and a bezel pattern manufactured from the photosensitive resin composition | |
| JP5371950B2 (en) | Color filter manufacturing method and color filter manufactured thereby | |
| KR101390709B1 (en) | Photoresist resin composition and the Liquid crystal display comprising micropattern thereof | |
| KR20170043307A (en) | Photosensitive resin composition and photosensitive material comprising the same | |
| KR101367525B1 (en) | Photo-sensitive resin composition for black matrix | |
| KR20150063016A (en) | Photo-sensitive resin composition for black matrix | |
| KR101623618B1 (en) | Photosensitive resin composition, pattern formed by using the same and display panel comprising the same | |
| KR101735155B1 (en) | Photosensitive resin composition, organic film manufactured by using the same and liquid crystal display device comprising the same | |
| KR101604151B1 (en) | Photosensitive resin composition and photosensitive material using the same | |
| KR101560870B1 (en) | New compound and photosensitive resin composition comprising the same | |
| KR20150062995A (en) | Photo-sensitive resin composition | |
| KR20130039101A (en) | Photosensitive resin composition, photosensitive material comprising the same and method for preparation of phtosensitive material | |
| KR20150063015A (en) | Photo-sensitive resin composition for black column spacer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E601 | Decision to refuse application | ||
| AMND | Amendment |