CN106462071B - Photosensitive resin composition for shading and shading layer formed by same - Google Patents
Photosensitive resin composition for shading and shading layer formed by same Download PDFInfo
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- CN106462071B CN106462071B CN201580034918.0A CN201580034918A CN106462071B CN 106462071 B CN106462071 B CN 106462071B CN 201580034918 A CN201580034918 A CN 201580034918A CN 106462071 B CN106462071 B CN 106462071B
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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
- G03F7/075—Silicon-containing compounds
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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
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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
Abstract
The present invention relates to a photosensitive resin composition for light-shielding and a light-shielding layer formed using the photosensitive resin composition. The photosensitive resin composition for light-screening contains: (A) a silicone resin; (B) a pigment; (C) a photopolymerization initiator; and (D) an organic solvent, optionally, may further contain (E) a polyfunctional monomer having an unsaturated bond. A film for a light-shielding layer formed of a photosensitive resin composition for shielding light, characterized in that the coating film has excellent electrical characteristics, excellent adhesion strength to a substrate, and optical density does not deteriorate even after a high-temperature process of 300 ℃ or higher.
Description
Technical Field
The present invention relates to a photosensitive resin composition for light-shielding and a light-shielding layer formed therefrom. More specifically, the present invention relates to a photosensitive resin composition which can be used for preparing a light-shielding layer for use in various types of electronic devices by photolithography; and a light-shielding layer comprising a thin film formed by curing the composition.
This application claims priority to korean patent application No.10-2014-0079876, filed in korea on 27.6.2014, the disclosure of which is incorporated herein by reference.
Background
With the development of technologies for manufacturing electronic products including flat panel display devices such as liquid crystal display devices or touch screen devices, there is a demand for reduction in size and thickness of the products. In order to reduce the size and thickness of the product, the degree of integration of the internal elements of the product is inevitably increased, and accordingly, it is required to improve the electrical properties of the material used in manufacturing the internal elements.
In general, a black matrix photosensitive resin composition is an essential material for manufacturing color filters included in display elements such as liquid crystal display devices, organic electroluminescent elements, and display panels. The black matrix photosensitive resin composition is used to prevent color mixing between R (red), G (green), and B (blue) in a color filter of a liquid crystal display device, or is used to cover a bezel of X and Y metal electrodes in a touch panel device.
As for liquid crystal display devices used for displays, recently, Low Temperature Polysilicon (LTPS) and oxide thin film transistors are being actively studied as devices used with high resolution exceeding Ultra Definition (UD) and high speed driving exceeding 240 Hz.
In general, since the semiconductor characteristics of the oxide thin film transistor vary due to light, a light shielding layer is introduced to minimize the above-mentioned problems. The metal light-shielding layer is mainly used as the light-shielding layer because a subsequent process including PE-CVD is performed at a high temperature after forming the light-shielding layer, however, the light-shielding layer formed of a metal has the following problems: because the metal shading layer has high reflectivity, light is reflected back to enter between the source electrode and the drain electrode and the shading layer; and a parasitic voltage is generated between the source electrode and the drain electrode and acts as a factor given against the operation of the device, resulting in an increase in the load of the data line.
Further, in the touch panel device, in order to reduce the thickness of a product, a single glass solution (OGS) technology, which forms a touch panel on a glass cover plate, is being studied from the conventional technology of bonding the glass cover plate and the touch panel glass together. In the OGS touch panel, a light-shielding layer (bezel) that has been formed on a glass cover plate is first formed, and then a touch panel driving unit is formed. In the process of forming the transparent electrode of the touch panel driving unit, a high temperature vapor deposition or annealing process is required. However, the conventional black matrix photosensitive resin for the light shielding layer has a disadvantage of deterioration of electrical properties in such a high temperature process.
Disclosure of Invention
Problems to be solved by the invention
The present invention provides a photosensitive resin composition for light-screening that produces desired electrical properties (including resistance and dielectric constant) and desired optical properties (including optical density and reflectance) even after a high-temperature process.
Means for solving the problems
In order to achieve the above object, in one embodiment of the present invention, there is provided a photosensitive resin composition comprising: (A) a siloxane resin containing a polymerized unit represented by the following chemical formula 1 and a polymerized unit represented by the following chemical formula 2; (B) a pigment; (C) a photopolymerization initiator; and (D) an organic solvent.
[ chemical formula 1]
In the formula R1Is a straight or branched chain alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylene group having aryl substituents and 7 to 20 carbon atoms in total, an arylene group having alkyl substituents and 7 to 20 carbon atoms in total, or a group having 7 to 20 carbon atoms in total in which an alkylene group is bonded to an arylene group.
X is hydroxyl, carboxylic acid, carboxylic anhydride derivative, imide derivative, amide derivative, amine, or mercapto.
[ chemical formula 2]
R2 nSiO(4-n)/2
In the formula R2Each independently hydrogen, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 10 carbon atoms or an acyloxy group having 2 to 10 carbon atoms in the moleculePlural R of2May be the same or different.
n is an integer of 0 to 3, and a polymerized unit in which n is 3 may be used in combination with another polymerized unit in which n is other than 3.
The siloxane resin may be composed of 5 to 40 mol% of the polymerized unit of chemical formula 1 and 95 to 60 mol% of the polymerized unit of chemical formula 2, based on 100 mol% of the total of the polymerized unit of chemical formula 1 and the polymerized unit of chemical formula 2.
The silicone resin had an acid number in the range of 10-200mg KOH/g resin by KOH titration.
The photosensitive resin composition may further include (E) a polyfunctional monomer having an unsaturated bond.
The pigment may be a black pigment.
Also, the pigment may be any one selected from the group consisting of: carbon black, titanium black, aniline black, perylene black, strontium titanate, chromium oxide, and cerium oxide, or mixtures thereof.
Also, the pigment may be present in an amount of 20 to 130 parts by weight based on 100 parts by weight of the silicone resin or, when a polyfunctional monomer having an unsaturated bond is used, based on 100 parts by weight of the total of the silicone resin and the polyfunctional monomer having an unsaturated bond.
Also, the photopolymerization initiator may be present in an amount of 1 to 30 parts by weight, based on 100 parts by weight of the silicone resin or, when a polyfunctional monomer having an unsaturated bond is used, based on 100 parts by weight of the total of the silicone resin and the polyfunctional monomer having an unsaturated bond.
When a multifunctional monomer having an unsaturated bond is used, the multifunctional monomer may be present in an amount of more than 0 part by weight and less than or equal to 100 parts by weight, based on 100 parts by weight of the silicone resin.
The organic solvent may be present in an amount of 20 to 90 parts by weight, based on 100 parts by weight of the total amount of the photosensitive resin composition.
According to another aspect of the present invention, there is provided a light-shielding layer comprising a thin film formed of the above photosensitive resin composition.
The light shielding layer may have an optical density in a range between 1.0 and 4.0 per unit thickness (μm).
According to still another aspect of the present invention, there is provided a method of preparing a thin film for a light-shielding layer, including: (S1) coating the photosensitive resin composition for light-shielding according to one embodiment of the present invention on a substrate; (S2) removing the solvent from the composition to form a coating film; (S3) exposing and developing the coating film to form a thin film; and (S4) heat-treating the film at a temperature between 200 ℃ or more and less than 300 ℃.
Also, after (S4), the method may further include: (S5) heat-treating the film at a temperature of 300 ℃ or more and 600 ℃ or less.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the photosensitive resin composition for light-shielding of an embodiment of the present invention, a pattern can be formed by aqueous development in an alkaline aqueous solution after exposure, and after the pattern is formed, the formed pattern maintains its shape even after a process at a temperature of 300 ℃ or more.
Moreover, a thin film formed by curing the photosensitive resin composition for light-shielding has an electrical insulating property including a surface resistivity of 1.0E +10 or more and a dielectric constant of 45 or less and maintains light-shielding properties, for example, an optical density per unit thickness (μm) of 1.0 or more, preferably in a range between 1.0 and 4.0, and thus can be used as a light-shielding film.
Detailed Description
Hereinafter, the present invention will be described in detail. It should be understood that the terms used in the specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define the terms appropriately for the best explanation.
A photosensitive resin composition according to an embodiment of the present invention includes: (A) a siloxane resin containing a polymerized unit represented by the following chemical formula 1 and a polymerized unit represented by the following chemical formula 2; (B) a pigment; (C) a photopolymerization initiator; and (D) an organic solvent, if necessary, further comprising (E) a polyfunctional monomer having an unsaturated bond.
[ chemical formula 1]
In the formula R1Is a straight or branched chain alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylene group having aryl substituents and 7 to 20 carbon atoms in total, an arylene group having alkyl substituents and 7 to 20 carbon atoms in total, or a group having 7 to 20 carbon atoms in total in which an alkylene group is bonded to an arylene group.
X is hydroxyl, carboxylic acid, carboxylic anhydride derivative, imide derivative, amide derivative, amine or mercapto.
[ chemical formula 2]
R2 nSiO(4-n)/2
In the formula R2Each independently hydrogen, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 10 carbon atoms or an acyloxy group having 2 to 10 carbon atoms, wherein a plurality of R's in the molecule2May be the same or different.
n is an integer of 0 to 3, and a polymerized unit in which n is 3 may be used in combination with another polymerized unit in which n is other than 3.
R1Non-limiting examples of (a) may include a linear alkylene group having 1 to 20 carbon atoms, which may be a hydrocarbon group such as methylene, ethylene, propylene, butylene, and pentylene; and branched chain alkylenes such as isopropylidene and isobutylidene.
Specific examples of the polymerization unit represented by the following chemical formula 1 are shown, but not limited thereto.
[ chemical formula 1a ]
[ chemical formula 1b ]
[ chemical formula 1c ]
[ chemical formula 1d ]
[ chemical formula 1e ]
[ chemical formula 1f ]
[ chemical formula 1g ]
[ chemical formula 1h ]
[ chemical formula 1i ]
[ chemical formula 1j ]
[ chemical formula 1k ]
[ chemical formula 1l ]
[ chemical formula 1m ]
[ chemical formula 1n ]
(in the respective formulae, m and n are each independently an integer of 1 to 20)
R2Specific examples of (b) may each independently include an aliphatic alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and n-pentyl, and specific examples of the cyclic aliphatic alkyl group may include cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Specific examples of the acyloxy group having 2 to 10 carbon atoms may include acryloyloxymethyl, acryloyloxyethyl, acryloyloxypropyl, acryloyloxybutyl, methacryloyloxymethyl, methacryloyloxyethyl, methacryloyloxypropyl, and methacryloyloxybutyl. Specific examples of the aryl group having 6 to 10 carbon atoms may include phenyl, naphthyl, anthryl, phenanthryl, and pyrenyl groups.
The monomer constituting the polymerized unit represented by chemical formula 2 may include, but is not limited to, for example: tetraalkoxysilane, trialkoxysilane, methyltrialkoxysilane, ethyltrialkoxysilane, n-propyltrialkoxysilane, isopropyltrialkoxysilane, n-butyltrialkoxysilane, t-butyltrialkoxysilane, phenyltrialkoxysilane, naphtha trialkoxysilane, vinyltrialkoxysilane, methacryloxymethyltrialkoxysilane, 2-methacryloxyethyltrialkoxysilane, 3-methacryloxypropyltrialkoxysilane, 3-methacryloxypropylmethyldialkoxysilane, 3-methacryloxypropylethyldialkoxysilane, acryloxymethyltrialkoxysilane, 2-acryloxyethyltrialkoxysilane, 3-acryloxypropyltrialkoxysilane, 3-acryloxypropylmethyldialkoxysilane, methacryloxypropylmethyltrialkoxysilane, organoxytrialkoxysilane, organoxyalkyltrialkoxysilane, trialkoxysilane, 3-acryloxypropylethyldialkoxysilane, 3-glycidoxypropyltrialkoxysilane, 2-epoxycyclohexylethyltrialkoxysilane, 3-epoxycyclohexylpropyltrialkoxysilane, dimethylalkoxysilane, diethyldialkoxysilane, dipropyldialkoxysilane, diphenyldialkoxysilane, diphenylsilanediol, and phenylmethyldialkoxysilane. Here, the alkoxy group is a linear, branched or cyclic aliphatic or aromatic alkoxy group having 1 to 7 carbon atoms, and may be a hydrolyzable halogen-containing compound.
Preferably, the present invention is characterized in that at least one of the polymerization units represented by the above chemical formula 2 is methacryloxymethyltrialkoxysilane, 2-methacryloxyethyltrialkoxysilane, 3-methacryloxypropyltrialkoxysilane, 3-methacryloxypropylmethyldialkoxysilane, 3-methacryloxypropylethyldialkoxysilane, acryloxymethyltrialkoxysilane, 2-acryloxyethyltrialkoxysilane, 3-acryloxypropyltrialkoxysilane, 3-acryloxypropylmethyldialkoxysilane, and 3-acryloxypropyl.
By KOH titration, (A) the silicone resin may have an acid number in the range of from 10 to 200mg KOH/g resin.
When the silicone resin is used, the distance between the carbon particles used as the pigment can be suitably maintained even after a high-temperature process of greater than or equal to 300 ℃, due to the thermal stability of the silicone resin, exhibiting high electrical insulation.
The acid value of the silicone resin is preferably 10 to 200mg of [ KOH ] per 1g of the binder resin by titration with a 0.1N KOH solution.
When the acid value of the silicone resin is less than or equal to 10mg of [ KOH ]/g of the resin, a residual film is produced due to lack of feasibility of developing photosensitivity, and when the acid value exceeds or is equal to 200mg of [ KOH ]/g of the resin, problems such as pattern loss occur.
(B) The pigment is a pigment having light-shielding properties, and preferably a black pigment having light-shielding properties. As non-limiting examples of the pigment, carbon black, titanium black, aniline black, perylene black, strontium titanate, chromium oxide, and cerium oxide may be used based on their properties, but the pigment is not limited thereto. Carbon black is preferred.
Carbon blacks may include the Cisto series available from Tokai Carbon, the Diagram series and MA series available from Mitsubishi Chemical, the PRINTEX series available from DK Dong Shin, and the Raven series available from Columbian Chemicals.
The particle size of the pigment is preferably adjusted to a range between 50 and 150nm, more preferably to a range between 50 and 80 nm. When a pigment having a particle size of less than 50nm is dispersed in the photosensitive resin composition, the optical density may be reduced even if the same pigment content is used. In addition, when a pigment having a particle size of more than 150nm is dispersed in the photosensitive resin composition, electrical insulation and roughness characteristics of the thin film are deteriorated.
The pigment is present in an amount of 20 to 130 parts by weight, based on 100 parts by weight of the silicone resin, or when a polyfunctional monomer having an unsaturated bond is used, based on 100 parts by weight of the total of the silicone resin and the polyfunctional monomer having an unsaturated bond, and the content may vary within a numerical range depending on the purpose of use. When the pigment is present in an amount of less than 20 parts by weight, the sensitivity of the photosensitive resin composition and the electrical insulation and roughness of the film are improved, but it is difficult to expect an optical density of 1.0 or more per unit thickness (μm). Also, when the pigment content exceeds 130 parts by weight, an optical density of 4.0 or more per unit thickness (μm) is satisfied, but electrical insulation becomes low and sensitivity of the photosensitive resin composition decreases.
(C) The photopolymerization initiator is a material that generates radicals and induces crosslinking by light, and non-limiting examples thereof are preferably at least one selected from the group consisting of: triazine-based compounds, acetophenone-based compounds, imidazole-based compounds, and oxime-based compounds.
Non-limiting examples of triazine compounds include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl ] -1,3, 5-triazine, and 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl ] -1,3, 5-triazine. Non-limiting examples of the acetophenone-based compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin butyl ether, 2-dimethoxy-2-phenylacetophenone, 2-methyl- (4-methylthio) phenyl-2-morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -one Butane-1-one, 2- (4-bromo-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one.
Further, non-limiting examples of the biimidazole-based compound include 2, 2-bis (2-chlorophenyl) -4,4',5,5' -tetraphenylbiimidazole, 2' -bis (o-chlorophenyl) -4,4',5,5' -tetrakis (3,4, 5-trimethoxyphenyl) -1,2' -biimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4',5,5' -tetraphenylbiimidazole, and 2,2' -bis (o-chlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole.
Further, non-limiting examples of the oxime-based compounds include OXE-02 (trademark, available from BASF), N1919, NCI-831 (trademark, available from Adeka), 1, 2-octanedione (octadion) -1- (4-phenylthio) phenyl-2- (O-benzoyloxime), and ethanone-1- (9-ethyl) -6- (2-methylbenzoyl-3-yl) -1- (O-acetyloxime).
The photopolymerization initiator may be present in an amount of 1 to 30 parts by weight, based on 100 parts by weight of the silicone resin, or based on 100 parts by weight of the total of the silicone resin and the polyfunctional monomer having an unsaturated bond when the polyfunctional monomer having an unsaturated bond is used.
In the photosensitive resin composition of the present invention, (D) the organic solvent includes, without limitation, any solvent as long as it can dissolve the silicone resin-containing ingredient and does not inhibit dispersion of the pigment. Specific examples of the organic solvent include, but are not limited to, ketone-based solvents such as methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2, 4-pentanedione, acetonyl acetone, γ -butyrolactone, and γ -valerolactone; ether-based solvents such as methyl ethyl ether, methyl di-n-propyl ether, diisopropyl ether, tetrahydrofuran, methyl tetrahydrofuran, ethylene glycol dimethyl ether, glycol ether, ethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, propylene glycol-n-propyl ether, propylene glycol dibutyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol monomethyl ether, diethylene glycol ethyl ether, propylene glycol monomethyl ether; ether acetate-based solvents such as ethylene glycol methyl ether propionate, ethylene glycol ethyl ether propionate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol propyl ether acetate; acetonitrile, N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, N-dimethylsulfoxide, toluene, and xylene; and alcohol-based solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, cyclohexanol, methylcyclohexanol, benzyl alcohol, ethylene glycol, 1, 2-propanediol, and diethylene glycol, which may be used singly or in combination.
The content of the organic solvent may be appropriately adjusted based on the content of the silicone resin, the pigment, the photopolymerization initiator, and the polyfunctional monomer having an unsaturated bond, and may vary according to the method of applying the photosensitive resin composition to form the light-shielding layer on the substrate. For example, the content of the organic solvent may range from 20 to 90 parts by weight based on 100 parts by weight of the total amount of the photosensitive resin composition, but is not limited thereto.
(E) The polyfunctional monomer having an unsaturated bond is a reactive unsaturated compound having at least one addition-polymerizable unsaturated group in the molecule, and the compounds may be used either singly or in combination.
Non-limiting examples of the multifunctional monomer having an unsaturated bond may include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, 1, 6-hexanediol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, bisphenol a epoxy acrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol dimethacrylate, or 1, 6-hexanediol dimethacrylate.
The content of the polyfunctional monomer having an unsaturated bond is 0 to 200 parts by weight based on 100 parts by weight of the silicone resin. When the content exceeds 200 parts by weight, compatibility of the silicone resin and the carbon particles may be reduced, which may make it difficult to control the pattern shape.
The polyfunctional monomer having an unsaturated bond (wherein the unsaturated bond is included in the binder resin) may not be included in the photosensitive resin composition, but may be used for pattern shape control and sensitivity.
In addition, if necessary, the photosensitive resin composition for light-shielding may further include additives commonly used in the art, such as a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a solvent, a leveling agent, and an antifoaming agent. The thermal polymerization inhibitor may be hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, or phenothiazine. The plasticizer may be dibutyl phthalate, dioctyl phthalate, or trimethylphenyl. The filler may be glass filler, silica, mica, or alumina. The defoaming agent or leveling agent may be, for example, a silicone compound, a fluorine compound, or an acrylic compound.
One embodiment of forming a light-shielding layer (black matrix) using the photosensitive resin composition may include (S1) a step of coating the photosensitive resin composition for light-shielding according to the present invention on a substrate; (S2) a step of removing the solvent in the composition to form a coating film; (S3) a step of exposing and developing the coating film to form a thin film; and (S4) a step of heat-treating the film at a temperature of 200 ℃ or more and less than 300 ℃. In addition, after (S4), the method may further include (S5) a step of heat-treating the film at a temperature from 300 ℃ or more to 600 ℃ or less.
In one embodiment of the process of (S1) coating the photosensitive resin composition for light-shielding on the substrate, the coating may be performed on a glass substrate having a clean surface with a thickness of 0.5 to 1.1mm using a contact transfer coater such as a roll coater, a reverse roll coater, and a bar coater, or a non-contact coater such as a spin coater and a curtain flow coater.
In the preparation and coating, in order to improve the adhesion of the glass substrate to the photosensitive resin composition, a silane coupling agent may be added or may be applied on the substrate.
Subsequently, (S2) removing the solvent from the composition to form a coating film.
To perform this step, the coating film thickness may be adjusted to a range of 0.5 to 5 μm after drying the composition at a temperature of 80 to 120 ℃, preferably 90 to 100 ℃ for 60 to 120 seconds using a hot plate, or maintaining the composition at room temperature for several hours to several days, or removing the solvent by placing the composition in a hot air heater or an infrared heater for several minutes to several hours.
Subsequently, (S3) the coating film is exposed and developed to form a thin film.
Non-limiting embodiments thereof can include exposure to active energy radiation through a negative mask, for example, at a radiation energy dose of from 30 to 2000mJ/cm2Violet in the range betweenOuter line and excimer laser. The amount of the radiant energy may vary depending on the type of photosensitive composition used for light-shielding. The thin film obtained by the exposure is developed by a dipping method or a spraying method using a developing solution to form a black matrix pattern. The developing solution for development may include an organic solution of monoethanolamine, diethanolamine, and triethanolamine, or an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.
In addition, in one embodiment of the preparation method of the present invention, the method may further include (S4) heat-treating the thin film at a temperature between 200 ℃ or more and less than 300 ℃, and after (S4), may further include (S5) heat-treating the thin film at a temperature between 300 ℃ or more and 600 ℃ or less.
The heat treatment in (S4) may be performed at a temperature between 200 ℃ or more and less than 300 ℃ for 5 to 60 minutes, and the heat treatment method may use a general oven, but is not limited thereto.
In addition, the heat treatment in (S5) may be performed at a temperature between 300 ℃ and 600 ℃ for 5-60 minutes, and the heat treatment method may use a conventional method in the art, such as an oven, but is not particularly limited.
In general, it is known that additional heat treatment at 200 ℃ or higher than 200 ℃ reduces the electrical insulation of the thin film and the light-shielding layer including the thin film, and that additional heat treatment at 300 ℃ or higher than 300 ℃ further reduces the electrical insulation. This is because of the conductive properties of pigments such as carbon black. That is, if the heat treatment temperature is increased in the process of preparing the thin film, the resin surrounding the pigments may be deteriorated to reduce the distance between the pigments, resulting in increasing the conductivity. As a result, the electrical insulation of the thin film is deteriorated.
However, in the thin film manufactured from the photosensitive resin composition according to one embodiment of the present invention, the thin film may have good electrical insulation after heat treatment at 200 ℃ or more than 200 ℃ (even after heat treatment at 300 ℃ or more than 300 ℃), and also improve electrical insulation of the light shielding layer including the thin film.
The light-shielding layer (black matrix) obtained by the above-described preparation method can be used for various display devices such as liquid crystal panels and plasma display panels.
Hereinafter, the present invention will be described in detail by examples to help understanding thereof. However, embodiments of the invention may take many other forms and the scope of the invention should not be construed as being limited to the following examples. The embodiments of the present invention are provided to more fully explain the present invention to those having ordinary skill in the art to which the present invention pertains.
< Synthesis of Silicone resin >
Synthesis example 1
In a flask equipped with a cooling tube and a stirrer, 250g (1.0mol) of methyl 3- (triethoxysilyl) propionate (hereinafter also referred to as 'propionic acid'), 198g (1.0mol) of phenyltrimethoxysilane (hereinafter also referred to as 'phenyl'), 136g (1.0mol) of methyltrimethoxysilane (hereinafter also referred to as 'methyl'), 497g (2.0mol) of methacryloxypropyltrimethoxysilane (hereinafter also referred to as 'methacryloyl'), and 2000g of propylene glycol monomethyl ether acetate were weighed. While the solution was stirred, a mixed solution of 13.0g (0.125mol) of a 35% aqueous hydrochloric acid solution and 270g of water was added dropwise. After completion of the dropwise addition, the reaction temperature was increased to 85 ℃, and the reaction was carried out at the increased temperature for 6 hours. After completion of the reaction, extraction was carried out by adding ether and water, the organic phase was recovered, and residual alcohol and solvent were removed by evaporation, yielding 657g of siloxane resin. The resulting silicone resin was dissolved in 657g of propylene glycol monomethyl ether acetate. The weight average molecular weight of the silicone resin was 4,800.
Synthesis example 2
In a flask equipped with a cooling tube and a stirrer, 250g (1.0mol) of methyl 3- (triethoxysilyl) propionate, 297g (1.5mol) of phenyltrimethoxysilane, 204g (1.5mol) of methyltrimethoxysilane, 248g (1.0mol) of methacryloxypropyltrimethoxysilane and 2000g of propylene glycol monomethyl ether acetate were weighed. While the solution was stirred, a mixed solution of 13.0g (0.125mol) of a 35% aqueous hydrochloric acid solution and 270g of water was added dropwise. After completion of the dropwise addition, the reaction temperature was increased to 85 ℃, and the reaction was carried out at the increased temperature for 6 hours. After completion of the reaction, extraction was carried out by adding ether and water, the organic phase was recovered, and residual alcohol and solvent were removed by evaporation, yielding 608g of siloxane resin. The obtained silicone resin was dissolved in 608g of propylene glycol monomethyl ether acetate. The weight average molecular weight of the silicone resin was 4,200.
Synthesis example 3
In a flask equipped with a cooling tube and a stirrer, 264g (1.0mol) of methyl 3- (triethoxysilyl) propionate, 396g (2.0mol) of phenyltrimethoxysilane, 272g (2.0mol) of methyltrimethoxysilane, and 2000g of propylene glycol monomethyl ether acetate were weighed. While the solution was stirred, a mixed solution of 13.0g (0.125mol) of a 35% aqueous hydrochloric acid solution and 270g of water was added dropwise. After completion of the dropwise addition, the reaction temperature was increased to 85 ℃, and the reaction was carried out at the increased temperature for 6 hours. After completion of the reaction, extraction was carried out by adding ether and water, the organic phase was recovered, and the residual alcohol and solvent were removed by evaporation, yielding 560g of a siloxane resin. The obtained silicone resin was dissolved in 560g of propylene glycol monomethyl ether acetate. The weight average molecular weight of the silicone resin was 3,800.
< preparation of photosensitive resin for Black matrix >
Example 1
12 parts by weight of an alkali-soluble silicone resin (the silicone resin synthesized in synthesis example 1, phenyl/methyl/methacryloyl/propionic acid 20/20/40/20, Mw 4800, acid value 36mg [ KOH ]/g [ resin ]), 3.6 parts by weight of carbon black (100nm particle size) (used in the form of a dispersion containing 20% carbon black, 18 parts by weight in terms of carbon black dispersion) were mixed based on 100 parts by weight of the total resin composition, 1 part by weight of ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl ] -1- (o-acetyloxime) (OXE-02, BASF), and 69 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent to prepare a photosensitive resin composition.
Example 2
10 parts by weight of the alkali-soluble silicone resin used in example 1 (the silicone resin synthesized in synthesis example 1, phenyl/methyl/methacryloyl/propionic acid: 20/20/40/20, Mw 4800, acid value 36mg [ KOH ]/g [ resin ]), 6 parts by weight of carbon black (100nm particle size) (used in the form of a dispersion containing 20% carbon black, 30 parts by weight in terms of carbon black dispersion), 1 part by weight of ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl ] -1- (o-acetyl oxime) (OXE-02, BASF), and 59 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent to prepare a photosensitive resin composition.
Example 3
Based on 100 parts by weight of the total resin composition, 9 parts by weight of the alkali-soluble silicone resin used in example 1 (the silicone resin synthesized in synthesis example 1, phenyl/methyl/methacryloyl/propionic acid: 20/20/40/20, Mw 4800, acid value 36mg [ KOH ]/g [ resin ]), 8 parts by weight of carbon black (100nm particle size) (used in the form of a dispersion containing 20% of carbon black, 40 parts by weight in terms of the dispersion of carbon black), 1 part by weight of ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl ] -1- (o-acetyl oxime) (OXE-02, BASF), and 50 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent to prepare a photosensitive resin composition.
Example 4
8 parts by weight of the alkali-soluble silicone resin used in example 1 (the silicone resin synthesized in synthesis example 1, phenyl/methyl/methacryloyl/propionic acid: 20/20/40/20, Mw 4800, acid value 36mg [ KOH ]/g [ resin ]), 9.4 parts by weight of carbon black (100nm particle size) (used in the form of a dispersion containing 20% carbon black, 47 parts by weight in terms of the dispersion of carbon black), 1 part by weight of ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl ] -1- (o-acetyl oxime) (OXE-02, BASF), 44 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent to prepare a photosensitive resin composition.
Example 5
Based on 100 parts by weight of the total resin composition, 10 parts by weight of an alkali-soluble silicone resin (silicone resin synthesized in synthesis example 2, phenyl/methyl/methacryloyl/propionic acid of 30/30/20/20, Mw 3600, acid value 42mg [ KOH ]/g [ resin ]), 2 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer having an unsaturated bond, 3.6 parts by weight of carbon black (100nm particle size) (used in the form of a dispersion containing 20% carbon black, 18 parts by weight in terms of the dispersion of carbon black), 1 part by weight of ethanone-1- [ 9-ethyl-6- (2-methyl-tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl ] -1- (o-acetyloxime) (OXE-02, BASF), 69 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent to prepare a photosensitive resin composition.
Example 6
Based on 100 parts by weight of the total resin composition, 8 parts by weight of the alkali-soluble silicone resin used in example 5 (the silicone resin synthesized in synthesis example 2, phenyl/methyl/methacryloyl/propionic acid: 30/30/20/20, Mw 3600, acid value 42mg [ KOH ]/g [ resin ]), 4 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer having an unsaturated bond, 3.6 parts by weight of carbon black (particle size of 100 nm) (used in the form of a dispersion containing 20% carbon black, 18 parts by weight in terms of the dispersion of carbon black), 1 part by weight of ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl ] -1- (o-acetyloxime) (OXE-02, BASF), and 69 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent to prepare a photosensitive resin composition.
Example 7
6 parts by weight of the alkali-soluble silicone resin used in example 5 (the silicone resin synthesized in synthesis example 2, phenyl/methyl/methacryloyl/propionic acid: 30/30/20/20, Mw 3600, acid value 42mg [ KOH ]/g [ resin ]), 6 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer having an unsaturated bond, 3.6 parts by weight of carbon black (100nm particle size) (used in the form of a dispersion containing 20% of carbon black; 18 parts by weight in terms of the dispersion of carbon black), 1 part by weight of ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl ] -1- (o-acetyloxime) (OXE-02, BASF), and 69 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent to prepare a photosensitive resin composition.
Example 8
Based on 100 parts by weight of the total resin composition, 4 parts by weight of the alkali-soluble silicone resin used in example 5 (the silicone resin synthesized in synthesis example 2, phenyl/methyl/methacryloyl/propionic acid: 30/30/20/20, Mw 3600, acid value 42mg [ KOH ]/g [ resin ]), 4 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer having an unsaturated bond, 9.4 parts by weight of carbon black (100nm particle size) (used in the form of a dispersion containing 20% carbon black, 47 parts by weight in terms of the dispersion of carbon black), 1 part by weight of ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl ] -1- (o-acetyloxime) (OXE-02, BASF), 44 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent to prepare a photosensitive resin composition.
Comparative example 1
4 parts by weight of an alkali-soluble cardo-based resin (Mw 5000, acid value 80mg [ KOH ]/g [ resin ], Adeka), 4 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer having an unsaturated bond, 9.4 parts by weight of carbon black (100nm particle size) (used in the form of a dispersion containing 20% carbon black, 47 parts by weight in terms of a dispersion of carbon black) were mixed based on 100 parts by weight of the total resin composition, 1 part by weight of ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl ] -1- (o-acetyloxime) (OXE-02, BASF), and 44 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent to prepare a photosensitive resin composition.
Comparative example 2
Based on 100 parts by weight of the total resin composition, 4 parts by weight of an alkali-soluble silicone resin (the silicone resin synthesized in synthesis example 3, phenyl/methyl/propionic acid: 40/40/20, Mw 3800, acid value 40mg [ KOH ]/g [ resin ]), 4 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer having an unsaturated bond, 9.4 parts by weight of carbon black (100nm particle size) (47 parts by weight in terms of carbon black dispersion used in the form of a dispersion containing 20% carbon black), 1 part by weight of ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl ] -1- (o-acetyloxime) (OXE-02, BASF), and 44 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent to prepare a photosensitive resin composition.
<Test example>
The photosensitive resin compositions for light-shielding (for black matrix) prepared in examples and comparative examples were coated on a glass substrate for LCD-panel by spin coating at a thickness of 1.2 μm and soft-baked at 100 ℃ to remove the solvent, forming a coating film. The formed coating film is exposed to light and developed in an aqueous alkali solution to form a thin film. After the glass substrate having the thin film thereon was heat-treated in an oven at 230 ℃ for 30 minutes to obtain a final thin film, surface resistivity, dielectric constant, optical density, pinholes (pinholes), and adhesion were measured. Thereafter, a further heat treatment was carried out in an oven at 380 ℃ for 30 minutes and the above evaluations were measured in the same manner. The results according to the evaluation criteria are shown in table 1 and table 2.
Determination of surface resistivity
To measure the surface resistivity of the formed film, the surface resistivity was measured using a high resistance meter (high resistance meter) from Keithley.
Determination of dielectric constant
In order to measure the dielectric constant of the formed thin film, the thin film was formed on a glass substrate having an ITO-coated lower electrode, and an upper electrode was formed by aluminum deposition. The dielectric constant was measured using an Agilent 4284LCR meter.
Optical Density measurement
To measure the optical density of the formed film, the optical density o.d was measured using X-rite 361T.
Pinhole determination
Pinhole determination of the formed film included measuring the number of pinholes in a 10cm X10 cm glass substrate using an optical microscope. 0 to 10 needle holes are represented by O, 10 to 30 needle holes are represented by Delta, and 30 or more needle holes are represented by X.
Adhesion test
To measure adhesion, after forming a film on a glass substrate, the finally cured sample was scratched using a cross cutter (crosscut) to expose the substrate, and peeled off after applying a 3M adhesive tape. In this case, the area of the peeled area exceeds 65% of the entire test surface and is represented by 0B, 35-65% by 1B, 15-35% by 2B, 5-15% by 3B, less than 5% by 4B, and the non-peeled area is represented by 5B.
[ Table 1]
[ Table 2]
Referring to examples 1 to 4, it can be seen that as the content of the silane epoxy resin in the resin composition increases, the dielectric constant of the film manufactured from the resin composition decreases, that is, the electrical insulation is improved.
Further, examples 5 to 8 are directed to resin compositions comprising dipentaerythritol hexaacrylate as a polyfunctional monomer having an unsaturated bond, and it can be seen that for the films prepared in examples 5 to 8, they show lower dielectric constants and have better electrical insulation properties as the content of the silicone resin increases.
Further, when example 5 and example 8 are compared with example 1 and example 4, respectively, example 5 and example 8 are examples in which a part of the content of the silicone resin in the resin compositions of example 1 and example 4 is replaced with a polyfunctional monomer having an unsaturated bond, and the films formed from example 5 and example 8 (such as the above replacement) have an effect of inferior electrical insulation with respect to the films formed from example 1 and example 4.
Meanwhile, the film manufactured from the resin composition of comparative example 1 using the carden multi-resin showed a significantly high dielectric constant and had very poor electrical insulation, compared to the films manufactured from the resin compositions of examples 1 to 8.
As shown in tables 1 and 2, the film prepared by the present invention has much better electrical insulation, optical properties, adhesion, pattern resolution and sensitivity even after the high temperature process at 380 ℃, compared to the comparative example, and is suitable for the preparation process requiring high temperature treatment. Further, the light-shielding layer comprising the thin film can also exhibit good electrical insulation, optical properties, pattern resolution, and sensitivity.
Claims (15)
1. A photosensitive resin composition for light-screening, comprising: a siloxane resin containing a polymerized unit represented by the following chemical formula 1 and a polymerized unit represented by the following chemical formula 2; a pigment; a photopolymerization initiator; and an organic solvent:
[ chemical formula 1]
In the chemical formula 1, the metal oxide is represented by,
R1is a straight or branched chain alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylene group having 7 to 20 carbon atoms in total with aryl substituents, an arylene group having 7 to 20 carbon atoms in total with alkyl substituents, a cyclic alkyl group,Or groups of 7 to 20 carbon atoms in total in which alkylene is attached to arylene;
x is hydroxyl, carboxylic acid, carboxylic anhydride derivative, imide derivative, amide derivative, amine or mercapto;
[ chemical formula 2]
R2 nSiO(4-n)/2
In the chemical formula 2, the first and second organic solvents,
R2each independently hydrogen, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 10 carbon atoms or an acyloxy group having 2 to 10 carbon atoms, a plurality of R's in the molecule2May be the same or different; and is
n is an integer of 0 to 3, and a polymerized unit in which n is 3 may be used in combination with another polymerized unit in which n is other than 3,
wherein the siloxane resin is composed of 5 to 40 mol% of the polymerized unit of chemical formula 1 and 95 to 60 mol% of the polymerized unit of chemical formula 2, based on 100 mol% of the total of the polymerized unit of chemical formula 1 and the polymerized unit of chemical formula 2.
2. The photosensitive resin composition for lightscreening of claim 1, wherein the polymerized unit represented by chemical formula 1 is selected from the group consisting of the following chemical formula 1a to chemical formula 1 n:
[ chemical formula 1a ]
[ chemical formula 1b ]
[ chemical formula 1c ]
[ chemical formula 1d ]
[ chemical formula 1e ]
[ chemical formula 1f ]
[ chemical formula 1g ]
[ chemical formula 1h ]
[ chemical formula 1i ]
[ chemical formula 1j ]
[ chemical formula 1k ]
[ chemical formula 1l ]
[ chemical formula 1m ]
[ chemical formula 1n ]
In each formula, m and n are each independently an integer of 1 to 20.
3. The photosensitive resin composition for light-screening according to claim 1, wherein the polymerized unit represented by chemical formula 2 is formed of any one selected from the group consisting of: tetraalkoxysilane, trialkoxysilane, methyltrialkoxysilane, ethyltrialkoxysilane, n-propyltrialkoxysilane, isopropyltrialkoxysilane, n-butyltrialkoxysilane, t-butyltrialkoxysilane, pentyltrialkoxysilane, naphtha trialkoxysilane, vinyltrialkoxysilane, methacryloxymethyltrialkoxysilane, 2-methacryloxyethyltrialkoxysilane, 3-methacryloxypropyltrialkoxysilane, 3-methacryloxypropylmethyldialkoxysilane, 3-methacryloxypropylethyldialkoxysilane, acryloxymethyltrialkoxysilane, 2-acryloxyethyltrialkoxysilane, 3-acryloxypropyltrialkoxysilane, 3-acryloxypropylmethyldialkoxysilane, methacryloxypropylmethyltrialkoxysilane, organoxytrialkoxysilane, organoxyalkyltrialkoxysilane, trialkoxysilane, 3-acryloxypropylethyldialkoxysilane, 3-glycidoxypropyltrialkoxysilane, 2-epoxycyclohexylethyltrialkoxysilane, 3-epoxycyclohexylpropyltrialkoxysilane, dimethylalkoxysilane, diethyldialkoxysilane, dipropyldialkoxysilane, diphenyldialkoxysilane, diphenylsilanediol and phenylmethyldialkoxysilane, or mixtures thereof.
4. The photosensitive resin composition for light-screening according to claim 3, wherein the polymerized unit represented by chemical formula 2 is formed of any one selected from the group consisting of: methacryloxymethyltrialkoxysilane, 2-methacryloxyethyltrialkoxysilane, 3-methacryloxypropyltrialkoxysilane, 3-methacryloxypropylmethyldialkoxysilane, 3-methacryloxypropylethyldialkoxysilane, acryloxymethyltrialkoxysilane, 2-acryloxyethyltrialkoxysilane, 3-acryloxypropyltrialkoxysilane, 3-acryloxypropylmethyldialkoxysilane and 3-acryloxypropylethyldialkoxysilane or mixtures thereof.
5. The photosensitive resin composition for light-screening according to claim 1, wherein the silicone resin has an acid value in the range of 10-200mg KOH/g resin by KOH titration.
6. The photosensitive resin composition for lightscreening according to claim 1, further comprising: a polyfunctional monomer having an unsaturated bond.
7. The photosensitive resin composition for lightscreening of claim 1, wherein the pigment is a black pigment.
8. The photosensitive resin composition for lightscreening of claim 1, wherein the pigment is any one selected from the group consisting of: carbon black, titanium black, aniline black, perylene black, strontium titanate, chromium oxide and cerium oxide or mixtures thereof.
9. The photosensitive resin composition for light-shielding according to claim 1 or 6, wherein the pigment is present in an amount of 20 to 130 parts by weight based on 100 parts by weight of the silicone resin or, when the polyfunctional monomer having an unsaturated bond is used, based on 100 parts by weight of the total of the silicone resin and the polyfunctional monomer having an unsaturated bond.
10. The photosensitive resin composition for light-shielding according to claim 1 or 6, wherein the photopolymerization initiator is present in an amount of 1 to 30 parts by weight based on 100 parts by weight of the silicone resin or, when the polyfunctional monomer having an unsaturated bond is used, based on 100 parts by weight of the total of the silicone resin and the polyfunctional monomer having an unsaturated bond.
11. The photosensitive resin composition for light-screening according to claim 6, wherein the polyfunctional monomer having an unsaturated bond is present in an amount of more than 0 part by weight and less than or equal to 100 parts by weight based on 100 parts by weight of the silicone resin.
12. The photosensitive resin composition for light-screening according to claim 1, wherein the organic solvent is present in an amount of 20 to 90 parts by weight based on 100 parts by weight of the total amount of the photosensitive resin composition for light-screening.
13. A light-shielding layer comprising a thin film formed from the photosensitive resin composition for light-shielding according to any one of claims 1 to 12.
14. A light-shield layer according to claim 13, wherein the light-shield layer has an optical density per unit thickness (μ ι η) in the range between 1.0-4.0.
15. A method of preparing a thin film for a light-shielding layer, comprising:
(S1) coating the photosensitive resin composition for light-shielding according to claim 1 or 6 on a substrate;
(S2) removing the solvent from the composition to form a coating film;
(S3) exposing and developing the coating film to form a thin film;
(S4) heat-treating the thin film at a temperature between 200 ℃ or more and less than 300 ℃; and
(S5) heat-treating the film at a temperature of 300 ℃ or more and 600 ℃ or less.
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| PCT/KR2015/006454 WO2015199449A1 (en) | 2014-06-27 | 2015-06-24 | Photosensitive resin composition for light shielding and light-shielding layer formed therefrom |
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