TWI788367B - Colored photosensitive resin composition and light shielding spacer prepared therefrom - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition that prevents the generation of uneven wrinkles when a cured film is formed, to thereby prevent spots that may be generated on the edges of a display upon the formation thereof, and has a short development time. Accordingly, the colored photosensitive resin composition can be advantageously used as a material for forming a protective film, an interlayer insulating film, a light shielding spacer such as a black column spacer, and the like to be employed in various electronic parts inclusive of a liquid crystal display (LCD) panel and an organic light emitting diode (OLED) display panel.

Description

Colored photosensitive resin composition and light-shielding spacer prepared therefrom

The present invention relates to a colored photosensitive resin composition suitable as a material for forming a protective film, an interlayer insulating film, a spacer, a light-shielding member, and the like for liquid crystal display (LCD) panels, organic light-emitting diodes OLED display panels and the like; and to a light-shielding spacer made from said composition.

Recently, in order to maintain a constant distance between an upper transparent substrate and a lower transparent substrate in a liquid crystal cell of a liquid crystal display (LCD), a spacer made of a photosensitive resin composition is used. In LCDs, which are electro-optical devices driven by a voltage applied to a liquid crystal material injected into a constant gap between two transparent substrates, it is critical to maintain a constant gap between the two substrates. If there is an area where the gap between the transparent substrates is not constant, the voltage applied thereto and the transmittance of light penetrating this area may vary, creating defects of spatially non-uniform brightness. With the recent demand for large LCD panels, maintaining a constant gap between two transparent substrates in LCDs is even more critical.

Such a spacer can be prepared by coating a photosensitive resin composition on a substrate, exposing the coated substrate to ultraviolet light, etc., placing a mask thereon, and then performing development. Recently, efforts to use light-shielding materials for spacers have been made; accordingly, various colored photosensitive resin compositions have been actively developed.

In recent years, a black column spacer (BCS) that uses a colored photosensitive resin composition to integrate the column spacer and the black matrix into a single module aims to simplify the process steps. The colored photosensitive resin composition used to manufacture such black columnar spacers is not only required to be easy to form a step difference, but also to satisfy the elastic recovery rate to withstand the pressure of the upper plate. In addition, when the bezel is formed from the colored photosensitive resin composition in the display panel, if the cured film has uneven wrinkles on its surface, the following serious disadvantages may occur: due to the gap between the upper and lower plates during assembly The gap is defective, so the amount of liquid crystal injected may not be uniform, or spots may appear on the display due to poor electrical signal transmission.

Meanwhile, in order to impart high light-shielding properties to the black column spacer (BCS), it is necessary to increase the content of the pigment added to the resin composition. In this regard, Korean (Korean) Patent No. 0814660 discloses a black photosensitive resin composition, which includes a black organic pigment with good light-shielding properties and low dielectric constant. However, if a large amount of black organic pigment is used, since the amount of the organic pigment insufficient in chemical resistance increases, the pigment dissolves inside the spacer. In addition, as the amount of the pigment in the photosensitive resin composition used to form the spacer increases, the amount of the binder, photopolymerizable compound and the like relatively decreases, which causes a problem that the elastic recovery rate of the spacer decreases.

Technical Problem Therefore, an object of the present invention is to provide a colored photosensitive resin composition capable of forming a cured film that minimizes the occurrence of uneven wrinkles on its surface while satisfying the step difference characteristics, resistance Chemical properties, elastic recovery rate and light-shielding properties without significantly increasing the amount of pigment in the photosensitive resin composition used to form the spacer; and the light-shielding spacer produced thereby. solution to the problem

In order to achieve the above object, the present invention provides a colored photosensitive resin composition, which includes: (A) a copolymer including an epoxy group; (B) a photopolymerizable compound including a double bond; (C) a photopolymerization initiator; and (D) a coloring agent, including a black inorganic coloring agent, wherein the coloring agent includes 50 to 100% by weight of a black inorganic coloring agent based on the total weight of the solid content of the coloring agent, and both of the photopolymerizable compounds (B) The molar ratio of the bond to the epoxy group in the copolymer (A) satisfies the following relationship: 4 ≤ double bond molar number/epoxy group molar number ≤ 35.

In addition, the present invention provides a light-shielding spacer prepared from the colored photosensitive resin composition. Beneficial effects of the present invention

The colored photosensitive resin composition of the present invention prevents uneven wrinkles when forming a cured film, thereby preventing possible spots at the edges of a display when it is formed, and has a short developing time. Therefore, the colored photosensitive resin composition can be advantageously used as a material for forming protective films, interlayer insulating films, light-shielding spacers such as black columnar spacers, and the like for various electronic parts including liquid crystal displays (LCDs). ) panels and organic light emitting diode (OLED) display panels.

In addition, the colored photosensitive resin composition of the present invention is capable of forming a cured film that simultaneously satisfies step difference characteristics, chemical resistance, elastic recovery, and light-shielding properties without significantly increasing the amount of pigment.

The colored photosensitive resin composition of the present invention includes (A) a copolymer including an epoxy group; (B) a photopolymerizable compound including a double bond; (C) a photopolymerization initiator; and (D) a colorant, including a black Inorganic colorant, wherein based on the total weight of the solid content of the colorant, the colorant includes 50 to 100% by weight of a black inorganic colorant, and the double bond in the photopolymerizable compound (B) and the double bond in the copolymer (A) The mole ratio of the epoxy group satisfies the following relationship: 4 ≤ double bond mole number/epoxy group mole number ≤ 35.

In the present invention, "(meth)acrylic acid" means "acrylic acid" and/or "methacrylic acid" and "(meth)acrylate" means "acrylate" and/or "methacrylate".

Hereinafter, each component of the colored photosensitive resin composition will be explained in detail. (A) Copolymers including epoxy groups

The copolymer used in the present invention comprises (a-1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof, (a-2) a structural unit derived from an aromatic-containing Ring ethylenically unsaturated compounds, and (a-3) structural units derived from epoxy group-containing ethylenically unsaturated compounds, and may further include (a-4) structural units derived from different structural units (a-1), (a-2) and (a-3) ethylenically unsaturated compounds.

The copolymer is an alkali-soluble resin for realizing developability, and also functions as a base for forming a film at the time of coating and as a structure for forming a final pattern. (a-1) Structural units derived from ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid anhydrides, or combinations thereof

The structural unit (a-1) is derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof. Ethylenically unsaturated carboxylic acids and ethylenically unsaturated carboxylic acid anhydrides are polymerizable unsaturated monomers containing at least one carboxyl group in their molecules. Specific examples thereof may include: unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids and their anhydrides such as maleic acid, maleic acid, Diic anhydrides, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and methylfumaric acid; trivalent or higher unsaturated polycarboxylic acids and their anhydrides; and di Mono[(meth)acryloxyalkyl]esters of polycarboxylic acids with valence or higher, such as mono[2-(meth)acryloxyethyl]succinate, mono[2-( Meth)acryloxyethyl]phthalate and its analogues. Structural units derived from the above-mentioned exemplary compounds may be included in the copolymer alone, or may be included in the copolymer as a combination of two or more.

The amount of the structural unit (a-1) may be 5 to 65 mol%, or 10 to 50 mol%, based on the total molar number of structural units constituting the copolymer. Within the above amount range, developability may be favorable. (a-2) Structural units derived from ethylenically unsaturated compounds containing aromatic rings

The structural unit (a-2) is derived from an ethylenically unsaturated compound containing an aromatic ring. Specific examples of ethylenically unsaturated compounds containing aromatic rings may include: phenyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, (meth)acrylic acid Phenoxydiethylene glycol, p-nonylphenoxy polyethylene glycol (meth)acrylate, p-nonylphenoxy polypropylene glycol (meth)acrylate, tribromophenyl (meth)acrylate ; Styrene; Styrenes containing alkyl substituents, such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propyl Styrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; styrenes containing halogens, such as fluorostyrene, chlorostyrene, bromostyrene, and iodostyrene; containing alkoxy substituted styrene-based, such as methoxystyrene, ethoxystyrene, and propoxystyrene; 4-hydroxystyrene, p-hydroxy-α-methylstyrene, acetylstyrene; and vinyltoluene , divinylbenzene, vinylphenol, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like. Structural units derived from the above-mentioned exemplary compounds may be included in the copolymer alone, or may be included in the copolymer as a combination of two or more. In view of polymerizability, preferred among the above-mentioned compounds are structural units derived from styrenic compounds.

The amount of the structural unit (a-2) may be 2 to 70 mol%, or 3 to 60 mol%, based on the total number of moles of the structural units constituting the copolymer. Within the above amount range, chemical resistance may be more favorable. (a-3) Structural units derived from ethylenically unsaturated compounds containing epoxy groups

The structural unit (a-3) is derived from an epoxy group-containing ethylenically unsaturated compound. Specific examples of ethylenically unsaturated compounds containing epoxy groups may include: glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 4,5-cyclo(meth)acrylate Oxypentyl ester, 5,6-epoxyhexyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 2,3-epoxycyclopentyl (meth)acrylate , 3,4-epoxycyclohexyl (meth)acrylate, α-glycidyl ethacrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, N -(4 -(2,3-Glycidyloxy)-3,5-Xylylmethyl)acrylamide, N- (4-(2,3-Glycidyloxy)-3,5-Dimethyl Phenylpropyl)acrylamide, 4-hydroxybutyl (meth)acrylate glycidyl ether, allyl glycidyl ether, 2-methallyl glycidyl ether and the like. Structural units derived from the above-mentioned exemplary compounds may be included in the copolymer alone, or may be included in the copolymer as a combination of two or more. Among the above, a structural unit derived from glycidyl (meth)acrylate and/or 4-hydroxybutyl (meth)acrylate glycidyl ether is more preferable in view of improvement in copolymerizability and insulating film strength.

The amount of the structural unit (a-3) may be 1 to 40 mol%, or 5 to 20 mol%, based on the total number of moles of the structural units constituting the copolymer. In the above-mentioned amount range, the residual amount during the process and the balance during pre-baking can be more favorable. (a-4) Structural units derived from ethylenically unsaturated compounds other than structural units (a-1), (a-2) and (a-3)

In addition to structural units (a-1), (a-2) and (a-3), the copolymer used in the present invention may include further derived from different structural units (a-1), (a-2) and Structural unit of ethylenically unsaturated compound of (a-3).

Specific examples of structural units derived from ethylenically unsaturated compounds other than structural units (a-1), (a-2) and (a-3) may include unsaturated carboxylic acid esters such as methacrylate (meth)acrylate Ester, ethyl (meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, Cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, methyl tetrahydrofuryl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylate Base) 2-hydroxy-3-chloropropyl acrylate, 4-hydroxybutyl (meth)acrylate, glyceryl (meth)acrylate, α-hydroxymethyl methacrylate, α-hydroxyethyl methacrylate, α-Hydroxypropyl methacrylate, α-Hydroxybutyl methacrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl (meth)acrylate Oxydiethylene glycol ester, methoxytriethylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, Tetrafluoropropyl (meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecane (meth)acrylate Fluorodecanyl, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate and ( Dicyclopentenyloxyethyl meth)acrylate; tertiary amines containing N -vinyl groups, such as N -vinylpyrrolidone, N -vinylcarbazole and N -vinylmorpholine; unsaturated ethers , such as vinyl methyl ether and vinyl ethyl ether; unsaturated imides, such as N -phenylmaleimide, N- (4-chlorophenyl)maleimide, N- (4-hydroxyphenyl)maleimide, N -cyclohexylmaleimide and the like. Structural units derived from the above-mentioned exemplary compounds may be included in the copolymer alone, or may be included in the copolymer as a combination of two or more. Among the above, structural units derived from unsaturated imides, especially N -substituted maleimides are more preferable in view of copolymerizability and improvement of insulating film strength.

The amount of the structural unit (a-4) may be 0 to 80 mol%, or 30 to 70 mol%, based on the total number of moles of the structural units constituting the copolymer. Within the above amount range, the storage stability of the colored photosensitive resin composition can be maintained, and the film retention rate can be more advantageously improved.

Examples of copolymers having structural units (a-1) to (a-4) may include: copolymers of (meth)acrylic acid/styrene/methyl (meth)acrylate/glycidyl methacrylate, ( Copolymer of meth)acrylic acid/styrene/methyl (meth)acrylate/glycidyl methacrylate/ N -phenylmaleimide, (meth)acrylic acid/styrene/(methyl) ) methyl acrylate/ N -cyclohexylmaleimide copolymer, (meth)acrylic acid/styrene/n-butyl (meth)acrylate/glycidyl (meth)acrylate/ N -benzene Copolymer of phenylmaleimide, copolymer of (meth)acrylic acid/styrene/glycidyl (meth)acrylate/ N -phenylmaleimide, (meth)acrylic acid /Styrene/4-Hydroxybutyl (meth)acrylate glycidyl ether/ N -phenylmaleimide copolymer and the like. One, two or more copolymers may be included in the colored photosensitive resin composition.

When measured by gel permeation chromatography (eluent: tetrahydrofuran) with reference to polystyrene, the weight average molecular weight (Mw) of the copolymer can be in the range of 5,000 to 30,000 g/mol, or 10,000 to 20,000 g/mol within range. If the weight average molecular weight of the copolymer is within the above range, the difference in step size formed from a lower pattern can be advantageously improved, and the pattern profile at the time of development can be favorable.

The amount of the copolymer in the colored photosensitive resin composition may be 5 to 60% by weight, or 8 to 45% by weight, based on the total weight of the solid content of the colored photosensitive resin composition (that is, excluding the weight of the solvent). %. Within the above range, the pattern profile at the time of development may be favorable, and the development time, surface characteristics, and the like of a cured film formed from the resin composition may be improved.

The copolymer can be prepared by feeding a radical polymerization initiator, a solvent, and structural units (a-1) to (a-4) into a reactor, then feeding nitrogen gas thereinto and slowly stirring the mixture for polymerization .

Free radical polymerization initiators can be azo compounds, such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile) and 2,2'-azobis Nitrobis(4-methoxy-2,4-dimethylvaleronitrile); or benzoyl peroxide, lauryl peroxide, tert-butyl peroxypivalate and 1,1 - Bis(tert-butylperoxy)cyclohexane or the like, but not limited thereto. The radical polymerization initiators may be used alone or in combination of two or more.

The solvent may be any conventional solvent commonly used in the preparation of copolymers, and may include, for example, propylene glycol monomethyl ether acetate (PGMEA). (B) Photopolymerizable compounds including double bonds

The photopolymerizable compound used in the present invention is a compound that has a double bond and is polymerizable by the action of a polymerization initiator. Specifically, the photopolymerizable compound may include monofunctional or polyfunctional ester compounds having at least one ethylenically unsaturated double bond, and may preferably include polyfunctional ester compounds having at least two functional groups from the viewpoint of chemical resistance. functional compound.

The photopolymerizable compound may be selected from the group consisting of ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, Meth)acrylate, 1,6-Hexanediol Di(meth)acrylate, Polyethylene Glycol Di(meth)acrylate, Polypropylene Glycol Di(meth)acrylate, Glyceryl Tri(meth)acrylate ester, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, monoester of pentaerythritol tri(meth)acrylate and succinic acid, pentaerythritol tetra(meth)acrylate, dipentaerythritol Penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate and monoester of succinic acid, pentaerythritol triacrylate hexamethylene diisocyanate (pentaerythritol triacrylate and Hexamethylene diisocyanate), tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, bisphenol A epoxy acrylate and ethylene glycol monomethyl ether acrylate and others Mixtures, but not limited to.

Examples of commercially available photopolymerizable compounds may include: (i) monofunctional (meth)acrylates such as Aronix M-101, M-111 and M-111 manufactured by Toagosei Co., Ltd. 114, KAYARAD T4-110S and T4-120S manufactured by Nippon Kayaku Co., Ltd., and V-158 and V-2311 manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.; (ii) Difunctional (meth)acrylates, such as Aronix M-210, M-240, and M-6200 manufactured by Toagosei Co., Ltd., KAYARAD HDDA, HX-220, and R-604 manufactured by Nippon Kayaku Co., Ltd., and Osaka Yuki V-260, V-312 and V-335HP manufactured by Kagaku Kogyo Co., Ltd.; and (iii) trifunctional and more functional (meth)acrylates such as Aronix M-309 manufactured by Toagosei Co., Ltd. , M-400, M-403, M-405, M-450, M-7100, M-8030, M-8060 and TO-1382, KAYARAD TMPTA, DPHA and DPHA-40H manufactured by Nippon Kayaku Co., Ltd., and V-295, V-300, V-360, V-GPT, V-3PA, V-400 and V-802 manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.

Based on the total weight of the solid content of the colored photosensitive resin composition (ie, excluding the weight of the solvent), the amount of the photopolymerizable compound may be 5 to 50% by weight, or 10 to 40% by weight. If the amount of the photopolymerizable compound is within the above-mentioned range, the pattern can be easily developed because it is possible to prevent the development time from prolonging and thereby affecting the process and residue problems, and it is possible to prevent the deterioration of the pattern resolution and The problem of wrinkles.

The molar ratio of the double bond in the photopolymerizable compound (B) to the epoxy group in the copolymer (A) may satisfy the following relationship: 4 ≤ double bond molar number/epoxy group molar number ≤ 35.

If the cured film used for the display frame has uneven wrinkles on its surface, the following disadvantages may arise: the amount of injected liquid crystal may not be uniform due to defects in the gap between the upper and lower plates during assembly, Or due to poor electrical signal transmission, it may cause spots on the display. However, if the colored photosensitive resin composition of the present invention satisfies the molar ratio defined by the above relationship, the occurrence of uneven wrinkles on the surface of the cured film is minimized, and it is possible to form step differences and high-resolution patterns.

If the molar ratio exceeds 35 as the molar number of double bonds increases, curing of the surface of the coating film strongly occurs during exposure to light, while materials having unreacted double bonds remain inside it, which improves the The fluidity (ie, mobility) of such unreacted materials during the subsequent thermal curing process. As a result, the polymer near the surface and the polymer deep inside the pattern will have different mobility during thermal curing, creating uneven wrinkles on the cured film surface. In addition, if the molar ratio is less than 4, since the molar number of the epoxy group is relatively larger than that of the double bond, it is difficult to control the degree of crosslinking according to the change of temperature, which makes the development process according to the change of temperature Headroom is poor, and thus resolution is reduced.

Specifically, the molar ratio of the double bond in the photopolymerizable compound (B) to the epoxy group in the copolymer (A) can satisfy the following relationship: 11 ≤ double bond molar number/epoxy group molar number ≤ 35. (C) Photopolymerization initiator

The photopolymerization initiator used in the present invention may be any known polymerization initiator.

The photopolymerization initiator can be selected from the group consisting of: acetophenone compounds, non-imidazole compounds, triazine compounds, onium salt compounds, benzoin compounds, benzophenone compounds, polynuclear quinone compounds, thiophene compounds, Xanthone compounds, diazo compounds, imide sulfonate compounds, oxime compounds, carbazole compounds, boric acid cobalt compounds, ketone compounds, and mixtures thereof. Specifically, the photopolymerization initiator may be at least one selected from the group consisting of oxime compounds, triazine compounds, and ketone compounds. More specifically, combinations of oxime compounds, triazine compounds, and ketone compounds may be used.

Specific examples of photopolymerization initiators may include: 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-bis Methylvaleronitrile), benzoyl peroxide, dodecyl peroxide, tert-butyl peroxypivalate, 1,1-bis(tert-butylperoxy)cyclohexane, p-dimethyl Aminoacetophenone, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-hydroxy-2-methyl -1-Phenyl-propan-1-one, benzyl dimethyl ketal, benzophenone, benzoin propyl ether, diethylthioxanthone, 2,4-bis(trichloromethyl)-6 -p-methoxyphenyl-s-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 9-phenylacridine, 3-methyl-5-amine Base-((s-triazin-2-yl)amino)-3-phenylcoumarin, 2-(o-chlorophenyl)-4,5-phenylimidazolyl dimer, 1-phenyl-1 ,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(o-benzoyl oxime), o-benzoyl-4'-(mercaptophenyl)benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluoro Trialkylphenyl percited phosphate, 2-mercaptobenzimidazole, 2,2'-benzothiazyl disulfide, ( E )-2-(4-styrylphenyl)-4,6-bis (Trichloromethyl)-1,3,5-triazine, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butane -1-one and mixtures thereof, but not limited thereto.

For reference only, examples of commercially available oxime photopolymerization initiators include OXE-01 (BASF), OXE-02 (BASF), OXE-03 (BASF), N-1919 (ADEKA), NCI-930 (ADEKA) and NCI-831 (ADEKA).

The photopolymerization initiator may be used in an amount of 0.1 to 15% by weight, or 0.1 to 10% by weight, based on the total weight of the solid content of the colored photosensitive resin composition (ie, excluding the weight of the solvent). Specifically, 0.1 to 2% by weight of oxime compounds, 0.1 to 2% by weight of triazine compounds and 0.1 to 2% by weight of a ketone compound can be used as a photopolymerization initiator. More specifically, 0.5 to 1.5% by weight of an oxime compound, 0.5 to 1.5% by weight of a triazine compound based on the total weight of the solid content of the colored photosensitive resin composition (that is, excluding the weight of the solvent) And 0.5 to 1.5% by weight of ketone compounds can be used as a photopolymerization initiator. When the oxime compound is used within the above-mentioned amount range, development and coating characteristics can be improved with high sensitivity. Moreover, if a triazine compound is used in the said amount range, the coating film which has the outstanding chemical resistance and taper angle at the time of pattern formation can be obtained. In addition, if the ketone compound is used within the above-mentioned amount range, the colored photosensitive resin composition thus prepared can form a coating film having excellent chemical resistance through curing deep inside the coating film. (D) Colorant

The colored photosensitive resin composition of this invention contains the coloring agent which provides light-shielding property to it. A colorant may be a mixture of two or more inorganic or organic colorants. It preferably has high color rendering properties and high heat resistance.

Colorants include black inorganic colorants. In addition, the colorant may contain a black organic colorant. In addition, the colorant may include colored colorants such as blue, purple, and the like other than black.

Any black inorganic colorant and black organic colorant known in the art may be used. For example, any compound classified as a pigment in the Color Index (published by The Society of Dyers and Colourists) and any dye known in the art may be used.

The black inorganic colorant may include at least one selected from the group consisting of carbon black, titanium black, copper-iron-manganese oxides, and metal oxides. Specifically, carbon black is preferably used as the black inorganic colorant in consideration of pattern characteristics and chemical resistance.

Copper-iron-manganese-based oxides include, for example, Cu _1.5 Mn _1.5 O ₄ , CuFeMnO ₄ , MnO ₂ , FeMn ₂ O ₄ and the like.

The metal oxide may be a metal oxide such as synthetic iron black, and examples thereof include FeO, Fe ₂ O ₃ , Fe ₃ O ₄ and the like.

Specific examples of black organic colorants may include nigrosine, lactam black, perylene black, and the like. In view of optical density, dielectric properties and the like, lactamide black (eg Black 582 from BASF) is preferred among these.

The colorant includes 50 to 100% by weight of a black inorganic colorant based on the total weight of the solid content of the colorant. Specifically, the colorant may include 50 to 100% by weight of a black inorganic colorant and 0 to 50% by weight of a black organic colorant, based on the total weight of the solid content of the colorant. More specifically, the colorant may include 80 to 100% by weight of a black inorganic colorant and 0 to 20% by weight of a black organic colorant, based on the total weight of the solid content of the colorant. If the amount of the black inorganic colorant and/or the black organic colorant in the colorant is within the above range, it is more advantageous to obtain a high optical density capable of preventing light leakage in the visible light and infrared light regions.

Based on the total weight of the solid content of the colored photosensitive resin composition (that is, excluding the weight of the solvent), the amount of the black colorant may be 10 to 60% by weight, 20 to 50% by weight, 20 to 45% by weight, 25 to 50% by weight or 30 to 50% by weight. Within the above range, it is more favorable to obtain a high optical density capable of preventing light leakage.

Meanwhile, the colorant used in the present invention may be added to the colored photosensitive resin composition in the form of a millbase mixed with a dispersion resin, a solvent or the like.

The dispersion resin is used to uniformly disperse the pigment in the solvent, and specifically may be at least one selected from the group consisting of a dispersant and a dispersion binder.

Examples of the dispersant may include any known dispersants used for colorants. Specific examples thereof include: cationic surfactants, anionic surfactants, nonionic surfactants, zwitterionic surfactants, silicon-based surfactants, fluorine-based surfactants, polyester-based compounds, polycarboxylate-based compounds , unsaturated polyamide compounds, polycarboxylic acid compounds, polycarboxylate alkyl salt compounds, polyacrylic acid compounds, polyethyleneimine compounds, polyurethane compounds, polyurethanes, polycarboxylates represented by polyacrylates, not Saturated polyamide, polycarboxylic acid, amine salt of polycarboxylic acid, ammonium salt of polycarboxylic acid, alkylamine salt of polycarboxylic acid, polysiloxane, long-chain polyaminoamide phosphate, hydroxyl substituted Esters of polycarboxylic acids and their modified products, amides formed by the reaction of polyesters with free carboxyl groups and poly(lower alkylene imines) or their salts, (meth)acrylic acid-styrene copolymers, (Meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble resin or water-soluble polymer compound such as polyvinylpyrrolidone, modified polyacrylic acid Esters, ethylene oxide/propylene oxide adducts, phosphate esters and the like. Commercially available dispersants may include Disperbyk-182, -183, -184, -185, -2000, -2150, -2155, -2163, and -2164 from BYK Co. These compounds may be used alone or in combination of two or more. The dispersant may have an amine group and/or an acid group as a pigment affinity group, and may have an ammonium salt type as the case may be.

When preparing the colored photosensitive resin composition, the dispersant may be added to the colorant in advance by surface-treating the colorant with the dispersant, or may be added together with the colorant.

The amine value of the dispersant may be 10 to 200 mg KOH/g, 40 to 200 mg KOH/g or 50 to 150 mg KOH/g. When the amine value of the dispersant is within the above range, the dispersibility and storage stability of the colorant are excellent, and the surface roughness of the cured film formed from the resin composition is improved.

The dispersant can be used in an amount of 1 to 20% by weight or 2 to 15% by weight based on the total weight of the colored dispersion. If the amount of the dispersant is within the above range, the colorant is effectively dispersed to improve dispersion stability, and optical, physical and chemical properties are improved by maintaining an appropriate viscosity upon application. Therefore, it is desirable in terms of an excellent balance between dispersion stability and viscosity.

In addition, the colorant includes a dispersion resin, and the dispersion resin has an amine value of 3 mg KOH/g or less, and may include 50 mole % or less of maleic acid in terms of the total number of moles of constituent units imine monomer. In such cases, the dispersion resin may be a dispersion binder.

If the dispersion binder has an acid value, it may include a monomer having a carboxyl group and an unsaturated bond. Specific examples of monomers having a carboxyl group and an unsaturated bond include: monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and dicarboxylic acids acid anhydrides; mono(meth)acrylates of polymers having carboxyl and hydroxyl groups at both ends, such as ω-carboxy polycaprolactone mono(meth)acrylate and the like. Acrylic acid and methacrylic acid are preferred.

In addition, the dispersion binder may include a monomer having a carboxyl group and an unsaturated bond and a monomer having a copolymerizable unsaturated bond. Examples of monomers having copolymerizable unsaturated bonds may include, for example: aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene Oxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl methyl ether benzyl glycidyl ether and p-vinylbenzyl glycidyl ether; alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate , isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate and third butyl (meth)acrylate; alicyclic family of (meth)acrylates, such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ] Dec-8-yl (meth)acrylate, 2-dicyclopentyloxyethyl (meth)acrylate, and isobornyl (meth)acrylate; aryl (meth)acrylates such as (meth)acrylic acid Phenyl esters and benzyl (meth)acrylates; hydroxyalkyl (meth)acrylates, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; N -substituted maleic butene Diamide imide compounds, such as N -cyclohexylmaleimide, N -benzylmaleimide, N -phenylmaleimide, N -o-hydroxyphenylmaleimide Butenediimide, N -m-hydroxyphenylmaleimide, N -p-hydroxyphenylmaleimide, N -o-methylphenylmaleimide, N -m-methylphenylmaleimide, N -p-methylphenylmaleimide, N -o-methoxyphenylmaleimide, N -m-formaldehyde Oxyphenylmaleimide and N -p-methoxyphenylmaleimide; unsaturated amides such as (meth)acrylamide and N , N -dimethyl (Meth)acrylamide; unsaturated oxetane compounds such as 3-(methacryloxymethyl)oxetane, 3-(methacryloxymethyl)-3 -Ethyloxetane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2-benzene oxetane, 2-(methacryloxymethyl)oxetane, and 2-(methacryloxymethyl)-4-trifluoromethyloxetane , which can be used alone or in combination of two or more.

Based on the total number of moles of constituent units, the dispersion binder may include 50 mole % or less of maleimide monomer.

The dispersion binder may have an acid value of 30 to 200 mg KOH/g. Specifically, the dispersion binder may have an acid value of 50 to 150 mg KOH/g. If the acid value of the dispersing binder is within the above range, the influence of the dispersant surrounding the pigment on the amine value is reduced, resulting in the effect of excellent stability and uniform particle size of the colored dispersion.

Furthermore, if the amine value of the dispersion binder exceeds 3 mg KOH/g, the stability of the dispersant surrounding the pigment may be adversely affected, which may in turn adversely affect the storage stability of the entire resin composition. Therefore, the amine value of the dispersion binder is preferably 3 mg KOH/g or less. If the amine value of the dispersed binder is within the above range, the unexposed portion can be easily developed during the developing process, and problems such as residue generation can be improved.

The dispersion binder can be used in an amount of 1 to 20% by weight or 2 to 15% by weight based on the total weight of the colored dispersion. If the dispersion binder is used within the above-mentioned amount range, the resin composition can maintain an appropriate viscosity level, and it is preferable in terms of dispersion stability and developability.

The colored dispersion liquid may be used in an amount of 10 to 80% by weight or 20 to 60% by weight based on the total weight of the solid content of the colored photosensitive resin composition. (E) Compounds derived from epoxy resins and having double bonds

The colored photosensitive resin composition of the present invention may further include a compound derived from an epoxy resin and having a double bond. The compound derived from epoxy resin has at least one double bond, may have a cardo main chain structure, may be a novolac type resin, or may be an acrylic resin containing a double bond in its side chain.

Compounds derived from epoxy resins may have a weight average molecular weight (Mw) in the range of 3,000 to 18,000 g/mol or 5,000 to 10,000 g/mol when determined by gel permeation chromatography with reference to polystyrene . If the weight average molecular weight of the compound derived from the epoxy resin is within the above range, the pattern profile at the time of development may be favorable, and the difference in step size resulting from a lower pattern may be advantageously improved.

在上述式1中，X各自獨立地為

、

、

或

；L¹ 各自獨立地為C_1-10 伸烷基、C_3-20 伸環烷基或C_1-10 伸烷氧基；R₁ 至R₇ 各自獨立地為H、C_1-10 烷基、C_1-10 烷氧基、C_2-10 烯基或C_6-14 芳基；R₈ 為H、甲基、乙基、CH₃ CHCl-、CH₃ CHOH-、CH₂ =CHCH₂ -或苯基；且n為0至10之整數。Specifically, the epoxy resin may be a compound having a cardo main chain structure represented by Formula 1 below. [Formula 1]

In the above formula 1, each X is independently

,

,

or

; L ¹ is each independently C _1-10 alkylene, C _3-20 cycloalkylene or C _1-10 alkoxyl; R ₁ to R ₇ are each independently H, C _1-10 alkyl , C _1-10 alkoxy, C _2-10 alkenyl or C _6-14 aryl; R ₈ is H, methyl, ethyl, CH ₃ CHCl-, CH ₃ CHOH-, CH ₂ =CHCH ₂ - or phenyl; and n is an integer from 0 to 10.

Specific examples of C _1-10 alkylene groups may include: methylene, ethylidene, propylidene, isopropylidene, butylene, isobutylene, second butylene, tertiary butylene , Pentyl, isopentyl, the third pentyl, hexyl, heptyl, octyl, isooctyl, the third octyl, 2-ethylhexyl, nonyl, iso Nonyl, Decyl, Idecyl and the like. Specific examples of _C3-20 cycloalkylene groups may include: cyclopropylidene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptyl, decahydronaphthylene, adamantylene, and analog. Specific examples of C _1-10 alkyleneoxy may include: methoxy, ethoxy, propoxy, butoxy, second butoxy, third butoxy, Pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethyl-hexyloxy and the like. Specific examples of C _1-10 alkyl groups may include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, isopentyl, third Tripentyl, hexyl, heptyl, octyl, isooctyl, tertoctyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl and the like. Specific examples of _C1-10 alkoxy may include: methoxy, ethoxy, propoxy, butoxy, second butoxy, third butoxy, pentyloxy, hexyloxy, heptoxy Oxy, octyloxy, 2-ethyl-hexyloxy and the like. Specific examples of _C2-10 alkenyl may include vinyl, allyl, butenyl, propenyl, and the like. Specific examples of C _6-14 aryl may include phenyl, tolyl, xylyl, naphthyl and the like.

在上述反應方案1中，Hal為鹵素；且X、R₁ 、R₂ 及L₁ 與式1中定義的相同。As an example, an epoxy resin with a cardo backbone structure can be prepared via the following synthetic route: [Reaction Scheme 1]

In the above reaction scheme 1, Hal is halogen; and X, R ₁ , R ₂ and L ₁ are the same as defined in formula 1.

A compound derived from an epoxy resin having a cardo main chain structure can be produced by reacting an epoxy resin having a cardo main chain structure with an unsaturated basic acid to produce an epoxy adduct, and then making the thus obtained epoxy The adducts are obtained by reacting polybasic anhydrides or by further reacting the products thus obtained with monofunctional or polyfunctional epoxy compounds. Any unsaturated basic acid known in the art may be used, such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, and the like. Any polybasic anhydride known in the art can be used, such as succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hexahydrophthalic anhydride Anhydrides and their analogs. Any monofunctional or polyfunctional epoxy compound known in the art can be used, such as glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, Butyl glycidyl ether, isobutyl glycidyl ether, bisphenol Z glycidyl ether and the like.

As an example, a compound derived from an epoxy resin having a cardo backbone structure can be prepared via the following synthetic route: [Reaction Scheme 2]

In the above reaction scheme 2, R ₉ is each independently H, C _1-10 alkyl, C _1-10 alkoxy, C _2-10 alkenyl or C _6-14 aryl; R ₁₀ and R ₁₁ are each are independently saturated or unsaturated C ₆ aliphatic or aromatic rings; n is an integer from 1 to 10; and X, R ₁ , R ₂ and L ₁ are the same as defined in Formula 1.

When a compound derived from an epoxy resin having a cardo main chain structure is used, the cardo main chain structure can improve the adhesion of the cured material to a substrate, alkali resistance, workability and strength, and the like. In addition, once the uncured portion is removed during development, images with high resolution can be patterned.

Based on the total weight of the solid content of the colored photosensitive resin composition (ie, excluding the weight of the solvent), the amount of the compound derived from the epoxy resin may be 0 to 40% by weight, or 0 to 30% by weight. If the compound derived from the epoxy resin is used within the above-mentioned amount range, the pattern profile at the time of development may be favorable, and the development time and surface characteristics of the cured film formed from the resin composition may be improved.

In the colored photosensitive resin composition of the present invention, the molar ratio of the double bond in the photopolymerizable compound (B) and the compound (E) derived from epoxy resin to the epoxy group in the copolymer (A) satisfies The following relationship: 4 ≤ number of moles of double bonds/number of moles of epoxy groups ≤ 35.

Specifically, in the colored photosensitive resin composition of the present invention, the double bond in the photopolymerizable compound (B) and the compound (E) derived from epoxy resin and the epoxy group in the copolymer (A) The molar ratio satisfies the following relationship: 11 ≤ molar number of double bonds/molar number of epoxy groups ≤ 35. (F) epoxy compound

The colored photosensitive resin composition of the present invention may further include an epoxy compound to increase the internal density of the resin, thereby improving the chemical resistance of a cured film prepared therefrom.

The epoxy compound may be an unsaturated monomer containing at least one epoxy group, or a homo-oligomer or hetero-oligomer thereof. Examples of unsaturated monomers containing at least one epoxy group may include: glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 5,6-epoxyhexyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 2,3 (meth)acrylate - Epoxycyclopentyl, 3,4-epoxycyclohexyl (meth)acrylate, α-glycidyl ethacrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate , N -(4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl)acrylamide, N- (4-(2,3-epoxypropoxy)-3 ,5-dimethylphenylpropyl) acrylamide, allyl glycidyl ether, 2-methylallyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether , p-vinylbenzyl glycidyl ether or mixtures thereof. Specifically, glycidyl (meth)acrylate can be used.

Examples of commercially available homo-oligomers of unsaturated monomers containing at least one epoxy group may include GHP03 (glycidyl methacrylate, Miwon Commercial Co., Ltd., Korea).

The epoxy compound (F) may further include the following structural units.

Specific examples may comprise any structural unit derived from styrene; styrenes with alkyl substituents such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene , triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene and octylstyrene; styrene with halogen, such as fluorostyrene, chlorostyrene, bromostyrene and Iodostyrene; styrenes with alkoxy substituents, such as methoxystyrene, ethoxystyrene and propoxystyrene; p-hydroxy-α-methylstyrene, acetylstyrene; with aromatic Cyclic ethylenically unsaturated compounds, such as divinylbenzene, vinylphenol, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether and p-vinylbenzyl methyl ether; unsaturated carboxylic acid esters , such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylate ) Tertiary butyl acrylate, (meth) cyclohexyl acrylate, (meth) ethylhexyl acrylate, (meth) tetrahydrofurfuryl acrylate, (meth) hydroxyethyl acrylate, (meth) acrylic acid 2-Hydroxypropyl, 2-Hydroxy-3-chloropropyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate, Glyceryl (meth)acrylate, α-Hydroxymethyl methacrylate, α -Hydroxyethyl methacrylate, α-hydroxypropyl methacrylate, α-hydroxybutyl methacrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate ester, ethoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, poly(ethylene glycol) methyl Ether (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate , p-nonylphenoxy polyethylene glycol (meth)acrylate, p-nonylphenoxy polypropylene glycol (meth)acrylate, tetrafluoropropyl (meth)acrylate, (meth)acrylic acid 1, 1,1,3,3,3-Hexafluoroisopropyl ester, octafluoropentyl (meth)acrylate, heptadecanylfluorodecyl (meth)acrylate, tribromophenyl (meth)acrylate, (meth) ) isobornyl acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate and dicyclopentenyloxy (meth)acrylate ethyl esters; tertiary amines with N -vinyl groups, such as N - N -vinylpyrrolidone, N -vinylcarbazole and N -vinylmorpholine; unsaturated ethers, such as vinyl methyl ether and Vinyl ethyl ether; unsaturated imides such as N -phenylmaleimide, N- (4-chlorophenyl)maleimide, N- (4-hydroxyphenyl ) maleimide and N -cyclohexylmaleimide. Structural units derived from the above exemplary compounds may be contained in the epoxy compound (F) alone or in combination of two or more thereof.

The epoxy compound (F) may have a weight average molecular weight of 100 to 30,000 g/mol. Specifically, the epoxy compound (F) may have a weight average molecular weight of 100 to 15,000 g/mol. If the weight average molecular weight of the epoxy compound is 100 g/mol or higher, the hardness of the film will be more excellent. If the weight average molecular weight of the epoxy compound is 30,000 g/mol or less, the thickness of the film becomes uniform and the difference in step size is small, which is more suitable for planarization. The weight average molecular weight was measured by gel permeation chromatography (eluent: tetrahydrofuran) with reference to polystyrene.

Based on the total weight of the solid content of the colored photosensitive resin composition (ie, excluding the weight of the solvent), the amount of the epoxy compound may be 0 to 10% by weight, or 0 to 8% by weight. If the amount of the epoxy compound is within the above-mentioned amount range, the pattern profile at the time of development can be favorable, properties such as chemical resistance and elastic recovery force can be improved, and it is possible to prevent the following problems: peeling or The storage stability of the composition deteriorates.

In the colored photosensitive resin composition of the present invention, the molar ratio of the double bond in the photopolymerizable compound (B) to the epoxy group in the copolymer (A) and the epoxy compound (F) can satisfy the following relationship: 4 ≤ Mole number of double bond/Mole number of epoxy group ≤ 35.

In addition, in the colored photosensitive resin composition of the present invention, the double bond in the photopolymerizable compound (B) and the compound (E) derived from epoxy resin is the same as that in the copolymer (A) and the epoxy compound (F). The molar ratio of epoxy groups can satisfy the above relationship.

Specifically, in the colored photosensitive resin composition, the molar ratio of the double bond in the photopolymerizable compound (B) to the epoxy group in the copolymer (A) and the epoxy compound (F) can satisfy the following relationship . In addition, in the colored photosensitive resin composition of the present invention, the double bond in the photopolymerizable compound (B) and the compound (E) derived from epoxy resin is the same as that in the copolymer (A) and the epoxy compound (F). The molar ratio of the epoxy group can satisfy the above relationship: 11 ≤ double bond molar number/epoxy group molar number ≤ 35. (G) Surfactant

The colored photosensitive resin composition of the present invention may further include a surfactant to improve coatability and prevent defects.

Although the type of the surfactant is not particularly limited, for example, a fluorine-based surfactant or a silicon-based surfactant having a ring structure may be used.

Commercially available silicon-based surfactants may include DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 from Dow Corning Toray Silicon, TSF-4440, TSF-4300 from GE Toshiba Silicone , TSF-4445, TSF-4446, TSF-4460 and TSF-4452, BYK-333, BYK-307, BYK-3560, BYK UV-3535, BYK-361N, BYK-354 and BYK-399 from BYK and their analog. These surfactants may be used alone or in combination of two or more.

Commercially available fluorosurfactants may include Megaface F-470, F-471, F-475, F-482, F-489 from Dainippon Ink Kagaku Kogyo Co. (DIC) and F-563.

Considering the coatability of the composition, BYK-333 and BYK-307 from BYK and F-563 from DIC are preferable among these surfactants.

Based on the total weight of the solid content of the colored photosensitive resin composition (ie, excluding the weight of the solvent), the amount of the surfactant may be 0.01 to 5% by weight, or 0.05 to 2% by weight. When the amount of the surfactant is within the above range, the colored photosensitive resin composition can be smoothly applied. (H) solvent

Preferably, the colored photosensitive resin composition of the present invention can be prepared as a liquid composition, wherein the above components are mixed with a solvent. Any solvent known in the art and used for preparing the colored photosensitive resin composition, which is compatible with but not reactive with the components of the colored photosensitive resin composition, may be used.

Examples of solvents may include glycol ethers, such as ethylene glycol monoethyl ether; glycol alkyl ether acetates, such as cellosolve ethyl acetate; esters, such as ethyl 2-hydroxypropionate; diethylene glycol, such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; and alkoxyalkyl acetates such as 3-methoxybutyl acetate ester. The solvents may be used alone or in combination of two or more.

The amount of the solvent is not particularly limited, but considering the coatability and stability of the finally obtained colored photosensitive resin composition, the total weight of the finally prepared colored photosensitive resin composition can be 50 to 90 wt. %, or 70 to 85% by weight. If the amount of the solvent is within the above-mentioned range, the resin composition is coated smoothly, and the delay margin that may occur during work is small.

In addition, the colored photosensitive resin composition of the present invention may include other additives, such as antioxidants and stabilizers, as long as they do not adversely affect the physical properties of the colored photosensitive resin composition.

The colored photosensitive resin composition of the present invention including the above-mentioned components can be prepared by a common method, for example, by the following method.

First, the colorant is pre-mixed with a solvent and dispersed therein using a bead mill until the average particle size of the colorant reaches a desired level. In such cases, surfactants and/or dispersants may be used. In addition, a part or all of the copolymers may be blended. To the dispersion liquid thus obtained, the remaining copolymer and surfactant, photopolymerizable compound and photopolymerization initiator are added. If necessary, a compound derived from an epoxy resin, an additive such as an epoxy compound, or another solvent is further blended to a certain concentration, followed by sufficiently stirring the same to obtain a desired colored photosensitive resin composition.

The cured film formed from the colored photosensitive resin composition may have an optical density of 1.0/μm to 3.0/μm. Specifically, the cured film formed from the colored photosensitive resin composition may have an optical density of 1.0/μm to 2.5/μm or 1.5/μm to 2.0/μm. When the optical density per 1 μm thickness of the cured film formed from the colored photosensitive resin composition is within the above range, it effectively prevents light leakage of the display.

The cured film formed from the colored photosensitive resin composition may have an elastic recovery rate of 80% or higher.

When a cured film formed of a colored photosensitive resin composition with a size of 3 cm × 3 cm × 3 um (width × length × thickness) is immersed in an organic solvent and treated at 100 ° C for 1 hour, the organic solvent is at 437 It can have an absorbance of 0.5 or less at nm. Specifically, when a cured film formed of a colored photosensitive resin composition having a size of 3 cm × 3 cm × 3 um (width × length × thickness) was immersed in an organic solvent and treated at 100°C for 1 hour, The organic solvent may have an absorbance at 437 nm of 0.0001 to 0.5 or 0.001 to 0.4 or 0.01 to 0.4 or 0.01 to 0.3.

The present invention also provides a light-shielding spacer made from the colored photosensitive resin composition.

Specifically, the present invention provides a black columnar spacer (BCS) made of a colored photosensitive resin composition, wherein the columnar spacer and the black matrix are integrated into a module.

The light-shielding spacer can be produced through a coating layer forming step, an exposure step, a development step, and a heat treatment step.

In the coating layer forming step, the colored photosensitive resin composition according to the present invention is coated to a desired thickness by spin coating, slit coating, roll coating, screen printing, coater or the like. , such as 1 to 25 μm, is coated on the pretreated substrate, and then it is precured at a temperature of 70° C. to 100° C. for 1 to 10 minutes to form a coating layer by removing the solvent therefrom.

In order to form a pattern in the coating film, a mask having a predetermined shape is placed thereon, and then irradiated with active rays of 200 to 500 nm. In such cases, in order to manufacture integrated black column spacers, a mask having patterns of different transmittances may be used to simultaneously prepare the column spacers and the black matrix. As a light source for irradiation, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon lasers, or the like can be used; if necessary, X-rays, electron rays, or the like can be used. analog. The exposure rate can vary depending on the kind and composition ratio of the components of the composition and the thickness of the dry coating. If a high-pressure mercury lamp is used, the exposure rate can be 500 mJ/cm ² or less (at a wavelength of 365 nm).

After the exposure step, an alkaline aqueous solution such as sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide or the like can be used as a developing solvent to dissolve and remove unnecessary parts so that only the exposed parts remain to form a pattern. The image pattern obtained by development is cooled to room temperature, and post-baked in a hot air circulation type drying oven at a temperature of 180° C. to 250° C. for 10 to 60 minutes, thereby obtaining a final pattern.

The thus-produced light-shielding spacers can be used in the manufacture of electronic parts for LCDs, OLED displays, and the like due to their excellent physical properties. Therefore, the present invention provides an electronic component including a light-shielding spacer.

In addition to incorporating the light-shielding spacers of the present invention, LCDs, OLED displays, and the like may include other components known to those skilled in the art. That is, LCD, OLED displays, and the like to which the light-shielding spacer of the present invention can be applied may fall within the scope of the present invention.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are set forth to illustrate the present invention, and the scope of the present invention is not limited thereto. Preparation Example 1 : Preparation of Copolymer

步驟(1)：9,9-雙[4-(縮水甘油氧基)苯基]茀之製備Feed 100 g of 51 mol% N -phenylmaleimide (PMI), 4 mol% styrene (Sty ), 10 mol % of 4-hydroxybutyl glycidyl acrylate (4-HBAGE) and 35 mol % of methacrylic acid (MAA), and 300 g of propylene glycol monomethyl ether acetate as solvent (PGMEA) and 2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator. The mixture was then heated to 70° C. and stirred for 5 hours to obtain a copolymer solution (A) with a solid content of 31% by weight. The copolymer thus prepared had an acid value of 100 mg KOH/g and a weight average molecular weight (Mw) of 20,000 g/mol when measured by gel permeation chromatography with reference to polystyrene. Preparation Example 2 : Preparation of Compounds Derived from Epoxy Resin and Having Cardo Main Chain Structure

Step (1): Preparation of 9,9-bis[4-(glycidyloxy)phenyl]terfenene

200 g of toluene, 125.4 g of 4,4'-(9-tertilylene)diphenol and 78.6 g of epichlorohydrin were fed into a 3000 ml three-necked round bottom flask, and the mixture was heated to 40°C, Stir simultaneously to dissolve. 0.1386 g of tert-butylammonium bromide and 50% aqueous NaOH (3 equiv) were mixed in a vessel, and the mixture was slowly added to the solution stirred in the flask.

The reaction mixture thus obtained was heated to 90° C. and reacted for 1 hour to completely consume 4,4′-(9-fenylene)diphenol, which was confirmed by HPLC or TLC. The reaction mixture was cooled to 30° C., and 400 ml of dichloromethane and 300 ml of 1 N HCl were added thereto with stirring. Then, the organic layer was separated, washed two or three times with 300 ml of distilled water, dried over magnesium sulfate, and distilled under reduced pressure to remove dichloromethane. The resultant was recrystallized from a mixture of dichloromethane and methanol, to thereby obtain the title compound, which is an epoxy resin compound. Step (2): (((9H-Oxime-9,9-diyl)bis(4,1-phenylene))bis(oxygen))bis(2-hydroxypropane-3,1-diyl)di Preparation of Acrylates (CAS No. 143182-97-2)

Into a 1,000 ml three-necked flask were fed 115 g of the compound obtained in step (1), 50 mg of tetramethylammonium chloride, 50 mg of 2,6-bis(1,1-dimethylethyl) -4-methylphenol and 35 g of acrylic acid. The mixture was heated to 90-100°C while blowing air at a flow rate of 25 ml/min, and further heated to 120°C for complete dissolution. The resulting reaction mixture was stirred for about 12 hours until its acid value dropped to less than 1.0 mg KOH/g, and then cooled to room temperature. Thereafter, 300 ml of dichloromethane and 300 ml of distilled water were added to the reaction mixture with stirring. The organic layer was separated, washed with 300 ml of distilled water two or three times, dried over magnesium sulfate, and distilled under reduced pressure to remove dichloromethane, thereby obtaining the title compound. Step (3): Preparation of Compounds Derived from Epoxy Resin and Having Cardo Main Chain Structure

Into a 1,000 ml three-necked flask, the compound obtained in step (2) in PGMEA was fed, and 1,2,4,5-benzenetetracarboxylic dianhydride (0.75 equivalents), 1, 2,3,6-Tetrahydrophthalic anhydride (0.5 equiv) and triphenylphosphine (0.01 equiv). The reaction mixture was heated to 120-130° C. for 2 hours with stirring, then cooled to 80-90° C., then stirred and heated for 6 hours. After the mixture was cooled to room temperature, a solution of polymer (E) with a weight average molecular weight (Mw) of 6000 g/mol and an acid value of 107 mg KOH/g (in terms of solid content) was obtained (solid content 49% by weight ). Preparation Example 3 : Preparation of Colored Dispersion- (1)

The colored dispersion liquid (D-1) was supplied by Tokushiki Co., Ltd., and the dispersion liquid was prepared as follows.

22.5 g of an acrylic copolymer solution (benzyl methacrylate, styrene and methyl acrylic acid copolymer) (Tokushiki Co., Ltd.), 8 g of an acrylic polymer dispersant with an amine value of 100 to 140 mg KOH/g (Tokushiki Co., Ltd.), 76.36 g of carbon black, and as a solvent 384 g of PGMEA were dispersed for 6 hours. This dispersion step was performed with 0.3 mm zirconia beads. After completion of the dispersion step, the beads were removed from the dispersion via a filter, whereby a colored dispersion having a solids content of 21.37% by weight was obtained. Preparation Example 4 : Preparation of Colored Dispersion- (2)

The colored dispersion (D-2) was supplied by Tokushiki Co., Ltd., except that a black organic colorant lactamyl black (Black 582, BASF) was used as the colorant, the dispersion was prepared in the same manner as in Preparation Example 3. liquid. Preparation Example 5 : Preparation of Epoxy Compounds

150 g of glycidyl methacrylate, 2 g of 2,2'-azobisisobutyronitrile and 450 g of PGMEA were fed into the flask, and the flask was purged with nitrogen for 30 minutes. Thereafter, the flask was immersed in an oil bath with stirring, and polymerization was performed for 5 hours while maintaining the reaction temperature at 80° C., thereby obtaining a compound having a solid content of 22% by weight and a weight average molecular weight (Mw) of 12,000 g/mol. Epoxy compound solution (F).

The compounds prepared in the above preparation examples were used to prepare photosensitive resin compositions as in the following examples and comparative examples.

The following additional components were used. Photopolymerizable compound (B): Hexafunctional dipentaerythritol hexaacrylate (DPHA; manufactured by Nippon Kayaku) Triazine photopolymerization initiator (C-1): ( E )-2-(4-Benzene Vinylphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine (manufacturer: PHARMASYNTHESE, trade name: TRIAZINE-Y) oxime photopolymerization initiator (C-2) : N-1919 manufactured by ADEKA Ketone photopolymerization initiator (C-3): 2-Dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl- Phenyl)-butan-1-one (manufacturer: Ciba, trade name: I-379) Surfactant (G): BYK-333 manufactured by BYK Solvent (H): Propylene glycol monomethyl ether ethyl manufactured by Chemtronics esters (PGMEA). Example 1 : Preparation of colored photosensitive resin composition

100 parts by weight of the copolymer (solid content) obtained in Preparation Example 1 as the copolymer (A), 163.2 parts by weight of the photopolymerizable compound (B), 7.1 parts by weight of the triazine photopolymerization initiator (C-1 ), 8.6 parts by weight oxime photopolymerization initiator (C-2), 8.9 parts by weight ketone photopolymerization initiator (C-3), 249.8 parts by weight colored dispersion (D-1), 175.4 parts by weight polymer ( The solution (solid content) of E) was mixed with 0.7 parts by weight of the surfactant (G), and then the solvent (H) was added thereto so that the solid content reached 19% by weight. The resultant was mixed for 2 hours using a vibrator, thereby preparing a liquid-phase colored photosensitive resin composition. Examples 2 to 10 and Comparative Examples 1 to 5 : Preparation of Colored Photosensitive Resin Composition

[表2]

測試實例 1 ：來自著色感光性樹脂組合物之固化膜之製備 A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the composition of the resin composition and the amounts of components were changed as shown in Tables 1 and 2 below. [Table 1]

[Table 2]

Test Example 1 : Preparation of Cured Film from Colored Photosensitive Resin Composition

Each of the colored photosensitive resin compositions obtained in Examples and Comparative Examples was coated on a glass substrate with a spinner, and prebaked at 95° C. for 150 seconds to form a coating film with a thickness of 4.8 μm. A pattern mask consisting of a 100% full-tone (F/T) columnar spacer (CS) pattern and a 30 %Halftone (H/T) black matrix (BM) pattern composition. Thereafter, based on a wavelength of 365 nm, the coating film was irradiated with light at an irradiation rate of 66 mJ/cm ² for a certain period of time using an aligner (model: MA6) emitting light with a wavelength of 200 nm to 450 nm. It was then developed at 23° C. with an aqueous solution of potassium hydroxide diluted to a concentration of 0.04% by weight until the unexposed portions were completely washed away. The pattern thus formed was post-baked in an oven at 230°C for 30 minutes to obtain a light-shielding spacer (ie, patterned part) and a cured film (ie, non-patterned part) with a thickness of 3.0 μm (± 0.1 μm) ). The results obtained in the following test examples are summarized in Table 3 below. (1) Measurement of development time change relative to pre-baking temperature

The prebaking temperature was changed to 80° C. or 100° C. during the above-mentioned preparation of the cured film, and the evaluation was performed under the same conditions as above. Then, the time to completely wash off the unexposed portion (until the stage O-ring portion of the developing device behind the substrate) was completely washed away with an aqueous potassium hydroxide solution diluted to a concentration of 0.04% by weight at 23° C. was measured. In addition, the change in development time relative to the change in prebake temperature was converted and recorded. (2) Measurement of surface features (contact thickness measurement)

Wrinkles on the surface of the cured film thus prepared were measured by using the vibration value of the vertical motion of the probe tip of the SCAN PLUS recording device as an α-step instrument (Alpha-step surface profiler), and the surface of the cured film thus prepared was measured with an optical microscope (STM6, Olympus) photographed the surface of the cured film. (3) Measurement of optical density

The transmittance at 550 nm of the cured film (ie, non-patterned portion) was measured using an optical densitometer (361T manufactured by Xlite), and the optical density was determined based on a thickness of 1 μm. (4) Measurement of elastic recovery rate

According to the method for preparing a cured film described above, a cured film having a total thickness of 3.0 μm (±0.1 μm) and a spacer dot pattern diameter of 30 to 35 μm when post-baked was prepared. Compression displacement and elastic recovery rate were measured using an elastic instrument (FISCHERSCOPE® HM2000LT, Fisher Technology) according to the following measurement conditions.

Specifically, a square-shaped 50 μm×50 μm planar Vickers indenter was used as the indenter for embossing the pattern. Measurements are performed by the load-unload method. After applying a load of 1.96 mN to the dot pattern using the above-mentioned elastic instrument, it was defined as the initial condition (H0) for measuring mechanical properties, ie, compression displacement and elastic recovery. Then, the load applied to each pattern sample was increased to 300 mN at a rate of 5 MN/s in the thickness direction and held for 5 seconds, and the distance (H1) moved by the indenter was measured. Upon completion of holding for 5 seconds, the load was released at a rate of 5 MN/sec in the thickness direction. When the force applied to the point by the indenter reaches 1.96 mN, hold the force for 5 seconds. Measure the moving distance of the indenter (H2). The elastic recovery rate was calculated according to the following formula 1. [Formula 1] Elastic recovery rate (%) = [(H1-H2)/(H1-H0) × 100] (5) Chemical resistance

Substrates with dimensions of 3 cm x 3 cm x 3 μm (width x length x thickness) were prepared according to the method described above for the preparation of cured films. The substrate was immersed in 18 g of N -methylpyrrolidone (NMP) solution, and aged at 100° C. for 1 hour. Then, the substrate was removed from the NMP solution, and the absorbance of the NMP solution at 437 nm was measured. (6) Measurement of step difference

The spacer part (A) and the black matrix part (B) were obtained according to the method for preparing the cured film as described above (see FIG. 1 ). Measure the thickness of A and B using a step difference measuring instrument (SNU (SIS-2000), SNU Precision). In this case, the step difference characteristic is expected to be excellent when the thickness difference (ie, A-B) is in the range of 1.0 to 2.0 μm.

The results obtained in the above test examples are summarized in Table 3 below, and photographs of the cured film surfaces are shown in FIGS. 2 to 5 . [table 3]

As shown in Table 3 and Figures 2 to 5, the compositions of the examples falling within the scope of the present invention not only provide cured films with minimized uneven wrinkles on the surface, but also have excellent elastic recovery and excellent chemical resistance Sex, and can also be developed in a short time. In contrast, the compositions of the comparative examples, which do not fall within the scope of the present invention, showed at least one unfavorable result.

A‧‧‧thickness of the column spacer part B‧‧‧thickness of the black matrix part C‧‧‧critical dimension (CD) of the columnar spacer part

FIG. 1 is a schematic diagram of an embodiment of a cross-section of a light-shielding spacer (or a black column spacer). 2 to 5 are photographs of the surfaces of cured films prepared from the photosensitive resin compositions of Examples 6 and 7 and Comparative Examples 2 and 3, respectively.

A‧‧‧Thickness of columnar spacer

B‧‧‧Thickness of the black matrix part

C‧‧‧Critical Dimension (CD) of Column Spacer

Claims (12)

A colored photosensitive resin composition comprising: (A) a copolymer including an epoxy group; (B) a photopolymerizable compound including a double bond; (C) a photopolymerization initiator; and (D) a colorant including a black Inorganic colorant, wherein the colored photosensitive resin composition further includes (F) an epoxy compound, based on the total weight of the solid content of the colored photosensitive resin composition, the amount of the epoxy compound is 0 to 10% by weight, wherein The copolymer has a weight average molecular weight in the range of 5,000 to 30,000 g/mol when determined by gel permeation chromatography with reference to polystyrene. Wherein, based on the total weight of the solid content of the colorant, the colorant includes 50 to 100% by weight of the black inorganic colorant, and the double bond in the photopolymerizable compound (B) and the The mol ratio of the epoxy group in the above-mentioned copolymer (A) satisfies the following relationship: 4

Moles of Double Bonds/Moles of Epoxy Groups

35. The colored photosensitive resin composition as described in item 1 of the patent application, wherein the black inorganic colorant includes at least one selected from the group consisting of carbon black, titanium black, copper-iron-manganese oxides and metal oxides. The colored photosensitive resin composition as described in claim 1 of the patent application, wherein the colorant includes a black organic colorant. The colored photosensitive resin composition as described in claim 1, wherein the colorant includes a dispersion resin, and the dispersion resin has an amine value of 3 mg KOH/g or less, and the total molar weight of the constituent units is Contains 50 mole % or less of maleimide monomer in terms of ears. The colored photosensitive resin composition as described in item 1 of the patent scope, wherein by The cured film formed from the colored photosensitive resin composition has an optical density of 1.0/μm to 3.0/μm. The colored photosensitive resin composition described in claim 1 of the patent application further includes (E) a compound derived from an epoxy resin and having a double bond. The colored photosensitive resin composition as described in claim 6 of the patent application, wherein the double bond in the photopolymerizable compound (B) and the compound (E) derived from epoxy resin is copolymerized with the The mol ratio of the epoxy group in the thing (A) satisfies the following relationship: 4

Moles of Double Bonds/Moles of Epoxy Groups

35. The colored photosensitive resin composition as described in claim 1, wherein the double bond in the photopolymerizable compound (B) is compatible with the copolymer (A) and the epoxy compound (F) Among them, the mol ratio of the epoxy group satisfies the following relationship: 4

Moles of Double Bonds/Moles of Epoxy Groups

35. The colored photosensitive resin composition as described in claim 6 of the patent application, wherein the double bond in the photopolymerizable compound (B) and the compound (E) derived from epoxy resin is copolymerized with the The mol ratio of the epoxy group in the thing (A) and the epoxy compound (F) satisfies the following relationship: 4

Moles of Double Bonds/Moles of Epoxy Groups

35. The colored photosensitive resin composition as described in claim 1, wherein the cured film formed from the colored photosensitive resin composition has an elastic recovery rate of 80% or higher. The colored photosensitive resin composition as described in item 1 of the patent scope of the application, wherein when the cured film formed by the colored photosensitive resin composition with a size of 3cm×3cm×3μm (width×length×thickness) is immersed in When treated in an organic solvent at 100° C. for 1 hour, the organic solvent has an absorbance of 0.5 or less at 437 nm. A light-shielding spacer, prepared from the colored photosensitive resin composition described in item 1 of the patent application.

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