JP7228340B2 - Colored photosensitive resin composition and light-shielding spacer prepared therefrom - Google Patents

Description

The present invention provides a colored photosensitive resin suitable as a material for forming protective films, interlayer insulating films, spacers, light shielding members, etc. used for liquid crystal display (LCD) panels, organic light emitting diode (OLED) display panels, etc. A composition and a light-shielding spacer produced from the composition.

In recent years, spacers prepared from photosensitive resin compositions have been used to maintain a constant distance between upper and lower transparent substrates in liquid crystal cells of liquid crystal displays (LCDs). In an LCD, an electro-optical device driven by a voltage applied to a liquid crystal material injected into a constant gap between two transparent substrates, it is very important to keep the gap between the two substrates constant. be. If there is an area where the gap between the transparent substrates is not constant, the voltage applied to it and the transmittance of light passing through this area can vary, resulting in spatially non-uniform brightness defects. Due to the recent demand for large LCD panels, it becomes even more important to maintain a constant gap between the two transparent substrates in the LCD.

Such spacers can be prepared by coating a photosensitive resin composition on a substrate, exposing the coated substrate to ultraviolet light or the like with a mask placed thereon, and then developing it. can. In recent years, efforts have been made to use light-shielding materials for the spacers, and accordingly, various colored photosensitive resin compositions have been vigorously developed.

Recently, black column spacers (BCS), in which column spacers and a black matrix are integrated into a single module using a colored photopolymer composition, have attracted attention to simplify process steps. The colored photosensitive resin composition used in the production of such black column spacers is required not only to easily form steps, but also to satisfy the elastic recovery rate and at the same time to have resistance to the pressure of the upper plate. be. Furthermore, when the bezel in the display panel is formed from the colored photosensitive resin composition, if the cured film has uneven wrinkles on its surface, this may indicate defects in the gap between the upper and lower plates. Therefore, the amount of liquid crystal injected during their assembly may be uneven, or the poor transmission of electrical signals may cause spots on the display screen, causing serious disadvantages.

On the other hand, the content of the pigment added to the resin composition should be increased in order to impart high light-shielding properties to the black column spacer (BCS). In this regard, Korean Patent No. 0814660 discloses a black photosensitive resin composition containing a black organic pigment, which has good light shielding properties and a low dielectric constant. However, when a large amount of black organic pigment is used, the increased amount of organic pigment with insufficient chemical resistance causes the pigment to leach into the spacer. In addition, as the amount of the pigment increases in the photosensitive resin composition for forming the spacer, the amount of the binder, photopolymerizable compound, etc. relatively decreases, and the elastic recovery rate of the spacer decreases. cause.

It is therefore an object of the present invention to minimize the occurrence of non-uniform wrinkles on its surface and improve step-height properties, chemical resistance, without significantly increasing the amount of pigment in the photosensitive resin composition for forming spacers. It is an object of the present invention to provide a colored photosensitive resin composition and a light-shielding spacer produced therefrom, capable of forming a cured film which simultaneously satisfies properties, elastic recovery rate and light-shielding properties.

In order to achieve the above objects, the present invention provides a colored photosensitive resin composition,
(A) a copolymer containing epoxy groups;
(B) a photopolymerizable compound containing a double bond;
(C) a photoinitiator;
(D) a colorant comprising a black inorganic colorant;
the colorant comprises 50 to 100% by weight of a black inorganic colorant, based on the total weight of solids of the colorant;
A colored photosensitive resin composition is provided wherein the molar ratio of double bonds in the photopolymerizable compound (B) to epoxy groups in the copolymer (A) satisfies the following relationship.
4 ≤ number of moles of double bond/number of moles of epoxy group ≤ 35

Additionally, the present invention provides a light-shielding spacer made from the colored photopolymer composition.

The colored photosensitive resin composition of the present invention prevents the formation of uneven wrinkles when the cured film is formed, thereby preventing mottling that can occur on the edges of the display during formation and short development. have time. Therefore, the colored photosensitive resin composition can be used in various electronic components including liquid crystal display (LCD) panels and organic light emitting diode (OLED) display panels, such as protective films, interlayer insulating films, light-shielding spacers such as black column spacers, and the like. is advantageously used as a material for forming

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

FIG. 10 is a schematic diagram of an embodiment of a cross-section of a light blocking spacer (ie black column spacer); 1 is a photograph of the surface of a cured film prepared from the photosensitive resin compositions of Examples 6 and 7 and Comparative Examples 2 and 3, respectively. 1 is a photograph of the surface of a cured film prepared from the photosensitive resin compositions of Examples 6 and 7 and Comparative Examples 2 and 3, respectively. 1 is a photograph of the surface of a cured film prepared from the photosensitive resin compositions of Examples 6 and 7 and Comparative Examples 2 and 3, respectively. 1 is a photograph of the surface of a cured film prepared from the photosensitive resin compositions of Examples 6 and 7 and Comparative Examples 2 and 3, respectively.

The colored photosensitive resin composition of the present invention includes (A) a copolymer containing an epoxy group, (B) a photopolymerizable compound containing a double bond, (C) a photopolymerization initiator, and (D) a black inorganic coloring. a coloring agent comprising an agent;
the colorant comprises 50 to 100% by weight of a black inorganic colorant, based on the total weight of solids of the colorant;
The molar ratio of double bonds in photopolymerizable compound (B) to epoxy groups in copolymer (A) satisfies the following relationship.
4 ≤ number of moles of double bond/number of moles of epoxy group ≤ 35

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

Each constituent component of the colored photosensitive resin composition will be described in detail below.

(A) a copolymer containing an epoxy group 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 ethylenically unsaturated compound containing an aromatic ring; and (a-3) a structural unit derived from an ethylenically unsaturated compound containing an epoxy group, and (a -4) The structural units (a-1), (a-2), and (a-3) may further contain structural units derived from ethylenically unsaturated compounds.

The copolymer is an alkali-soluble resin to achieve developability, and can also serve as a base for forming a film during coating and a structure for forming the final pattern.

(a-1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof The structural unit (a-1) is an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated derived from saturated carboxylic acid anhydrides, or combinations thereof. Ethylenically unsaturated carboxylic acids and ethylenically unsaturated carboxylic acid anhydrides are polymerizable unsaturated monomers containing at least one carboxyl group in the molecule. Particular examples thereof 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 anhydride. acids, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid, trivalent or higher unsaturated polycarboxylic acids and their anhydrides, and divalent or higher polycarboxylic acids mono[ (Meth)acryloyloxyalkyl] esters such as mono[2-(meth)acryloyloxyethyl]succinate, mono[2-(meth)acryloyloxyethyl]phthalate and the like. Structural units derived from the above exemplified compounds may be included in the copolymer singly or in combination of two or more.

The amount of structural unit (a-1) may be from 5 to 65 mol %, or from 10 to 50 mol %, based on the total moles of structural units that make up the copolymer. Within the above amounts, developability can be favorable.

(a-2) Structural Unit Derived from Ethylenically Unsaturated Compound Containing Aromatic Ring The structural unit (a-2) is derived from an ethylenically unsaturated compound containing an aromatic ring. Particular examples of ethylenically unsaturated compounds containing aromatic rings include phenyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, phenoxydiethyleneglycol (meth)acrylate, p-nonylphenoxypolyethylene glycol. (meth)acrylates, p-nonylphenoxypolypropylene glycol (meth)acrylates, tribromophenyl (meth)acrylates, styrene, styrenes containing alkyl substituents such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene and octylstyrene, halogen-containing styrenes such as fluorostyrene, chlorostyrene, bromostyrene and iodostyrene, styrenes containing alkoxy substituents such as methoxystyrene , ethoxystyrene and propoxystyrene, 4-hydroxystyrene, p-hydroxy-α-methylstyrene, acetylstyrene and vinyltoluene, divinylbenzene, vinylphenol, o-vinylbenzyldimethylether, m-vinylbenzylmethylether, 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 exemplified compounds may be included in the copolymer singly or in combination of two or more. Structural units derived from styrenic compounds among the above compounds are preferred in consideration of polymerizability.

The amount of structural unit (a-2) may be from 2 to 70 mol %, or from 3 to 60 mol %, based on the total moles of structural units that make up the copolymer. Within the above amounts, chemical resistance can be more favorable.

(a-3) Structural Unit Derived from Ethylenically Unsaturated Compound Containing Epoxy Group The structural unit (a-3) is derived from an ethylenically unsaturated compound containing an epoxy group. Specific examples of ethylenically unsaturated compounds containing epoxy groups include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 5,6-epoxy Hexyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 2,3-epoxycyclopentyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, α-ethylglycidyl acrylate, 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, 4-hydroxybutyl (meth)acrylate glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether and the like. Structural units derived from the above exemplified compounds may be included in the copolymer singly or in combination of two or more. Structural units derived from glycidyl (meth)acrylate and/or 4-hydroxybutyl (meth)acrylate glycidyl ether among the above are more preferable from the viewpoint of improvement in polymerizability and strength of the insulating film.

The amount of structural unit (a-3) may be 1 to 40 mol %, or 5 to 20 mol %, based on the total moles of structural units making up the copolymer. Within the above amounts, the residue during the process and the margin at the time of pre-baking are more favorable.

(a-4) Structural units derived from structural units (a-1), (a-2), and (a-3) and derived from an ethylenically unsaturated compound different from the structural unit (a-3). -1), (a-2), and (a-3), and derived from an ethylenically unsaturated compound different from the structural units (a-1), (a-2), and (a-3) may further include a structural unit.

Specific examples of structural units derived from ethylenically unsaturated compounds different from structural units (a-1), (a-2), and (a-3) include unsaturated carboxylic acid esters such as methyl (meth ) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, tetrahydro Furfuryl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate , methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethoxydiethylene glycol ( meth) acrylate, 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, heptadecafluorodecyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate Tertiary containing acrylates, dicyclopentanyloxyethyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate, N-vinyl groups such as N-vinylpyrrolidone, N-vinylcarbazole, and N-vinylmorpholine amines, 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; can be mentioned. Structural units derived from the above exemplified compounds may be included in the copolymer singly or in combination of two or more. Among the unsaturated imides described above, structural units derived from N-substituted maleimides are more preferable from the viewpoint of improvement in polymerizability and strength of the insulating film.

The amount of structural unit (a-4) may be from 0 to 80 mol%, or from 30 to 70 mol%, based on the total moles of structural units that make up 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 improved more advantageously.

Examples of copolymers having structural units (a-1) to (a-4) include (meth)acrylic acid/styrene/methyl (meth)acrylate/glycidyl (meth)acrylate copolymers, (meth)acrylic acid/styrene /methyl (meth)acrylate/glycidyl (meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/styrene/methyl (meth)acrylate/glycidyl (meth)acrylate/N-cyclohexylmaleimide copolymer, (meth) Acrylic acid/styrene/n-butyl (meth)acrylate/glycidyl (meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/styrene/glycidyl (meth)acrylate/N-phenylmaleimide copolymer, (meth) Copolymers of acrylic acid/styrene/4-hydroxybutyl (meth)acrylate glycidyl ether/N-phenylmaleimide and the like can be mentioned. One, two, or more of the copolymers may be included in the colored photopolymer composition.

The weight average molecular weight (Mw) of the copolymer is 5,000 to 30,000 g/mol, or 10,000 to 20,000 g/mol as determined by gel permeation chromatography (eluent: tetrahydrofuran) on a polystyrene basis. It can be a range. When the weight average molecular weight of the copolymer is within the above range, the step due to the lower pattern can be advantageously improved, and the pattern profile during development can be favorable.

The amount of the copolymer in the colored photosensitive resin composition is 5 to 60% by weight, or 8 to 45% by weight, based on the total weight of solids (i.e., weight excluding solvent) of the colored photosensitive resin composition. may be Within the above range, the pattern profile during development can be favorable, and the development time, surface properties, etc. of the cured film formed from the resin composition can be improved.

The copolymer is obtained by charging a radical polymerization initiator, solvent, and structural units (a-1) to (a-4) into a reactor, then nitrogen is charged therein, and the mixture for polymerization is slowly It may be prepared by stirring.

Radical polymerization initiators include azo compounds such as 2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), and 2,2′-azobis(4-methoxy- 2,4-dimethylvaleronitrile), or benzoyl peroxide, lauryl peroxide, t-butylperoxypivalate, 1,1-bis(t-butylperoxy)cyclohexane, and the like, but are not limited thereto. do not have. Radical polymerization initiators may be used alone or in combination of two or more.

The solvent may be any conventional solvent commonly used in preparing copolymers and may include, for example, propylene glycol monomethyl ether acetate (PGMEA).

(B) Photopolymerizable Compound Containing Double Bond The photopolymerizable compound used in the present invention is a compound having a double bond and can be polymerized by the action of a polymerization initiator. Specifically, the photopolymerizable compound includes a monofunctional or polyfunctional ester compound having at least one ethylenically unsaturated double bond. Polyfunctional compounds with two functional groups may be mentioned.

Photopolymerizable compounds include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, Polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate and succinic acid monoesters of pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate and monoesters of succinic acid, pentaerythritol triacrylate- Hexamethylene diisocyanate (reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, bisphenol A epoxy acrylate, and ethylene glycol monomethyl ether acrylate, and their may be selected from the group consisting of, but not limited to, mixtures of

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

The amount of the photopolymerizable compound may be 5 to 50% by weight, or 10 to 40% by weight, based on the total solid weight (i.e., weight excluding solvent) of the colored photosensitive resin composition. . If the amount of the photopolymerizable compound is within the above range, it is possible to extend the development time and prevent the problem that the process and residue are affected by it, and also the pattern resolution is insufficient. The pattern can be easily developed because it is possible to prevent the problem of becoming uneven and the problem of wrinkles being generated on the surface.

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

If the cured film for the display bezel has uneven wrinkles on its surface, this is due to imperfections in the gap between the upper and lower plates, which reduces the amount of liquid crystal injected during their assembly. It may be non-uniform, or the poor transmission of the electrical signal may cause the disadvantage that speckles may occur on the display screen. However, when the colored photosensitive resin composition of the present invention satisfies the molar ratio defined by the above relationship, the formation of non-uniform wrinkles on the surface of the cured film is minimized, resulting in steps and high-resolution patterns. It is possible to form

When the number of moles of double bonds is increased, if the molar ratio exceeds 35, hardening of the surface of the coated film occurs strongly during exposure to light, while materials with unreacted double bonds remains within it, which enhances the fluidity (ie, mobility) of such unreacted material in the subsequent thermal curing process. As a result, the polymer near the surface and the polymer deep inside the pattern have different mobilities during thermal curing, resulting in non-uniform wrinkles on the surface of the cured film. In addition, when the molar ratio is less than 4, the number of moles of epoxy groups is relatively larger than the number of moles of double bonds, so it is difficult to control the degree of cross-linking by changing the temperature, and the temperature changes during the process. , the development margin becomes insufficient, resulting in a decrease in resolution.

Specifically, the molar ratio of double bonds in photopolymerizable compound (B) to epoxy groups in copolymer (A) can satisfy the following relationship.
11 ≤ number of moles of double bonds/number of moles of epoxy groups ≤ 35

(C) Photoinitiator The photoinitiator used in the present invention can be any known polymerization initiator.

Photopolymerization initiators include acetophenone compounds, non-imidazole compounds, triazine compounds, onium salt compounds, benzoin compounds, benzophenone compounds, polynuclear quinone compounds, thioxanthone compounds, diazo compounds, imidosulfonate compounds, It may be selected from the group consisting of oxime-based compounds, carbazole-based compounds, sulfonium borate-based compounds, ketone-based compounds, and mixtures thereof. Specifically, the photopolymerization initiator may be at least one selected from the group consisting of oxime-based compounds, triazine-based compounds, and ketone-based compounds. More specifically, combinations of oxime-based compounds, triazine-based compounds, and ketone-based compounds can be used.

Specific examples of photoinitiators include 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, Lauryl peroxide, t-butyl peroxypivalate, 1,1-bis(t-butylperoxy)cyclohexane, p-dimethylaminoacetophenone, 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-oxodiazole, 9-phenylacridine, 3-methyl-5-amino-((s-triazin-2-yl ) amino)-3-phenylcoumarin, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-[4 -(Phenylthio)phenyl]-octane-l,2-dione-2-(o-benzoyloxime), o-enzoyl-4′-(benzmercapto)benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl -diphenylphosphonyl oxide, hexafluorophosphoro-trialkylphenyl sulfonium salt, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl disulfide, (E)-2-(4-styrylphenyl)-4,6 -bis(trichloromethyl)-1,3,5-triazine, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one, and them can include, but are not limited to, mixtures of

For reference, 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 is 0.1 to 15% by weight, or 0.1 to 10% by weight, based on the total weight of the solid content (that is, the weight excluding the solvent) of the colored photosensitive resin composition. may be used. Specifically, based on the total weight of the solid content (that is, the weight excluding the solvent) of the colored photosensitive resin composition, 0.1 to 2% by weight of the oxime compound, 0.1 to 2% by weight of the Triazine-based compounds and 0.1-2% by weight of ketone-based compounds may be used as photoinitiators. More specifically, 0.5 to 1.5% by weight of an oxime compound, 0.5 to 1 0.5% by weight of triazine-based compounds and 0.5-1.5% by weight of ketone-based compounds may be used as photoinitiators. When the oxime compound is used within the above amount range, development and coating properties can be improved with high sensitivity. In addition, when the triazine-based compound is used within the above amount range, a coated film having excellent chemical resistance and taper angle can be obtained during pattern formation. Furthermore, when the ketone-based compound is used within the above amount range, the colored photosensitive resin composition thus prepared is a coating having excellent chemical resistance due to the deep inner curing of the coated film. can form a thin film.

(D) Colorant The colored photosensitive resin composition of the present invention contains a colorant for imparting light-shielding properties to it. A colorant may be a mixture of two or more inorganic or organic colorants. The colorant preferably has high pigment productivity and high heat resistance.

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

Any black inorganic colorant and any 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 Colorists) and any dye known in the art may be used.

The black inorganic colorant may contain at least one selected from the group consisting of carbon black, titanium black, Cu—Fe—Μn-based oxides, and metal oxides. Specifically, it is preferable to use carbon black as the black inorganic colorant from the viewpoint of pattern properties and chemical resistance.

Cu—Fe—Mn-based oxides include, for example, Cu _1.5 Mn _1.5 O ₄ , CuFeMnO ₄ , MnO ₂ and FeMn ₂ O ₄ .

The metal oxide may be a metal oxide such as _synthetic black iron, examples of _which include FeO, _Fe2O3 , _Fe3O4 , and the like.

Specific examples of black organic colorants include aniline black, lactam black, perylene black, and the like. Among these, lactam black (eg, Black 582 from BASF) is preferred from the viewpoint of optical density, dielectric properties, and the like.

The colorant comprises 50-100% by weight of a black inorganic colorant, based on the total solids weight of the colorant. Specifically, the colorant may comprise 50-100% by weight black inorganic colorant and 0-50% by weight black organic colorant, based on the total solids weight of the colorant. More specifically, the colorant may comprise 80 to 100 weight percent black inorganic colorant and 0 to 20 weight percent black organic colorant, based on the total solids weight of the colorant. When the amount of the black inorganic colorant and/or the black organic colorant in the colorant is within the above range, it is possible to achieve a high optical density that can prevent light leakage in the visible and infrared light regions. more advantageous.

The amount of the black colorant is 10 to 60% by weight, 20 to 50% by weight, 20 to 45% by weight, based on the total weight of the solid content of the colored photosensitive resin composition (that is, the weight excluding the solvent). It may be 25-50% by weight, or 30-50% by weight. Within the above range, it is more advantageous to achieve a high optical density that can prevent light leakage.

On the other hand, 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 dispersing resin, solvent and the like.

The dispersing resin serves to uniformly disperse the pigment in the solvent, and specifically can be at least one selected from the group consisting of dispersants and dispersion binders.

Examples of dispersants can include any known dispersant for colorants. Specific examples thereof include cationic surfactants, anionic surfactants, nonionic surfactants, zwitterionic surfactants, silicon surfactants, fluorine surfactants, polyester compounds, Polycarboxylic acids represented by polycarboxylic acid ester compounds, unsaturated polyamide compounds, polycarboxylic acid compounds, polycarboxylic acid alkyl salt compounds, polyacrylic compounds, polyethyleneimine compounds, polyurethane compounds, polyurethanes, and polyacrylates esters, unsaturated polyamides, polycarboxylic acids, amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-substituted poly Esters of carboxylic acids and modifications thereof, amides or salts thereof formed by reaction of polyesters having free carboxyl groups with poly(lower alkylene imines), (meth)acrylic acid styrene copolymers, (meth)acrylic acid (meth) Acrylate ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, water-soluble resins or water-soluble polymeric compounds such as polyvinylpyrrolidone, modified polyacrylates, adducts of ethylene oxide/propylene oxide, phosphate esters, and the like. Commercially available dispersants include Disperbyk-182, Disperbyk-183, Disperbyk-184, Disperbyk-185, Disperbyk-2000, Disperbyk-2150, Disperbyk-2155, Disperbyk-2163, and Disperbyk-2164 from BYK Co. can be done. These compounds may be used alone or in combination of two or more. The dispersants may have amine groups and/or acid groups as pigment affinity groups and may optionally be ammonium salt based.

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

The amine value of the dispersant can be 10-200 mg KOH/g, 40-200 mg KOH/g, or 50-150 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.

Dispersants may be used in amounts of 1 to 20 wt%, or 2 to 15 wt%, based on the total weight of the colored dispersion. When the amount of dispersant is within the above range, the colorant is efficiently dispersed to improve dispersion stability, and by maintaining a suitable viscosity when it is applied, the colorant is optically and physically , and improved chemical properties. This is desirable in terms of a good balance between dispersion stability and viscosity.

Further, the colorant may comprise a dispersing resin, the dispersing resin having an amine value of 3 mg KOH/g or less and containing 50 mol % or less maleimide monomer, based on the total moles of constituent units. In such events, the dispersing resin can be the dispersion binder.

If the dispersion binder has an acid value, it may contain monomers with carboxyl groups and unsaturated bonds. Particular 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. and mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends such as ω-carboxypolycaprolactone mono(meth)acrylate. Acrylic acid and methacrylic acid are preferred.

In addition, the dispersion binder may contain monomers having carboxyl groups and unsaturation as well as monomers having copolymerizable unsaturation. Examples of monomers having copolymerizable unsaturated bonds include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinyl aromatic vinyl compounds such as benzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether; ) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, and Alkyl (meth)acrylates such as t-butyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ] Alicyclic (meth)acrylates such as decan-8-yl (meth)acrylate, 2-dicyclopentanyloxyethyl (meth)acrylate, and isobornyl (meth)acrylate, phenyl (meth)acrylate and benzyl (meth)acrylate aryl (meth)acrylates such as acrylates, hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenyl maleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, N-substituted maleimide compounds such as No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide, such as (meth)acrylamide and N,N-dimethyl(meth)acrylamide unsaturated amide compounds, as well as 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, Unsaturated oxetane compounds such as 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, and 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane can be mentioned, May be used alone or in combination of two or more.

The dispersion binder may contain up to 50 mole percent maleimide monomer, based on total moles of constitutional units.

The dispersion binder can have an acid number of 30-200 mg KOH/g. Specifically, the dispersion binder may have an acid number of 50-150 mg KOH/g. When the acid number of the dispersion binder is within the above range, the effect of the dispersant surrounding the pigment on the amine number is reduced, thereby resulting in excellent stability and uniform particle size of the pigmented dispersion. produce.

Additionally, 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, thereby adversely affecting the storage stability of the overall resin composition. For this reason, the amine value of the dispersion binder is preferably 3 mg KOH/g or less. When the amine value of the dispersion binder is within the above range, the non-exposed portions can be easily developed in the development process and problems such as residue formation can be ameliorated.

Dispersion binders may be used in amounts of 1 to 20 weight percent, or 2 to 15 weight percent, based on the total weight of the pigmented dispersion. When the dispersion binder is used in the above amount range, the resin composition can maintain an appropriate viscosity level, which is preferable from the standpoint of dispersion stability and developability.

The colored dispersion may be used in an amount of 10 to 80 wt%, or 20 to 60 wt%, based on the total solid weight of the colored photosensitive resin composition.

(E) Compound derived from epoxy resin and having double bond The colored photosensitive resin composition of the present invention may further contain a compound derived from an epoxy resin and having a double bond. Compounds derived from epoxy resins have at least one double bond and may have a cardo backbone structure, may be novolac resins, or may be acrylic resins containing double bonds in their side chains. could be.

The weight average molecular weight (Mw) of the compounds derived from epoxy resins ranges from 3,000 to 18,000 g/mol, or from 5,000 to 10,000 g/mol as determined by gel permeation chromatography relative to polystyrene. It can be a range. When the weight-average molecular weight of the compound derived from the epoxy resin is within the above range, the pattern profile during development can be favorable, and the step due to the lower pattern can be advantageously improved.

Specifically, the epoxy resin may be a compound having a cardo backbone structure as represented by Formula 1 below.

In Formula 1 above, each X is independently

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

Particular examples of C _1-10 alkylene groups are methylene, ethylene, propylene, isopropylene, butylene, isobutylene, sec-butylene, t-butylene, pentylene, isopentylene, t-pentylene, hexylene, heptylene, octylene, isooctylene, Examples include t-octylene, 2-ethylhexylene, nonylene, isononylene, decylene, and isodecylene. Particular examples of C _3-20 cycloalkylene groups include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, decalinylene, adamantylene, and the like. Particular examples of C _1-10 alkyleneoxy groups are methyleneoxy, ethyleneoxy, propyleneoxy, butyleneoxy, sec-butyleneoxy, t-butyleneoxy, pentyleneoxy, hexyleneoxy, heptyleneoxy, octyleneoxy, 2-ethyl-hexyleneoxy and the like can be mentioned. Particular examples of C _1-10 alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, t-pentyl, hexyl, heptyl, octyl, isooctyl, t -octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl and the like. Particular examples of C _1-10 alkoxy groups include methoxy, ethoxy, propoxy, butyloxy, sec-butoxy, t-butoxy, pentoxy, hexyloxy, heptoxy, octyloxy, 2-ethyl-hexyloxy and the like. can. Particular examples of C _2-10 alkenyl groups include vinyl, allyl, butenyl, propenyl and the like. Particular examples of C _6-14 aryl groups include phenyl, tolyl, xylyl, naphthyl and the like.

As an example, an epoxy resin having a cardo backbone structure may be prepared by the following synthetic routes.

In Reaction Scheme 1 above, 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 backbone structure is prepared by reacting the epoxy resin having a cardo backbone structure with an unsaturated basic acid to form an epoxy adduct, and then the epoxy adduct thus obtained. may be obtained by reacting the product with a polybasic acid anhydride, or by further reacting the product thus obtained with a monofunctional or polyfunctional epoxy compound. 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 such as succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hexahydro Phthalic anhydride and the like may also be used. Any monofunctional or multifunctional epoxy compound known in the art 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 Ethers and the like may also be used.

As an example, compounds derived from epoxy resins having a cardo backbone structure may be prepared by the following synthetic route.

In Reaction Scheme 2 above, each R ₉ is independently H, a C _1-10 alkyl group, a C _1-10 alkoxy group, a C _2-10 alkenyl group, or a C _6-14 aryl group, and R ₁₀ and R ₁₁ are each independently a saturated or _unsaturated C ₆ aliphatic or _aromatic ring; n is an integer from 1 to ₁₀ ; is the same as defined in

When compounds derived from epoxy resins with a cardo backbone structure are used, the cardo backbone structure can improve the adhesion, alkali resistance, processability, strength, etc. of the cured material to the substrate. Further, when the uncured portions are removed during development, a fine resolution image may be formed in the pattern.

The amount of the epoxy resin-derived compound is from 0 to 40% by weight, or from 0 to 30% by weight, based on the total weight of the solid content of the colored photosensitive resin composition (that is, the weight excluding the solvent). may When a compound derived from an epoxy resin is used, the pattern profile during development may be favorable within the above range, and the development time and surface properties of a cured film formed from the resin composition may be improved.

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

(F) Epoxy compound The colored photosensitive resin composition of the present invention may further comprise an epoxy compound to increase the internal density of the resin, thereby improving the chemical resistance of cured films prepared therefrom. .

Epoxy compounds can be unsaturated monomers containing at least one epoxy group, or homo- or hetero-oligomers thereof. Examples of unsaturated monomers containing at least one epoxy group are 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-epoxycyclopentyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, α-ethylglycidyl acrylates, α-n-propylglycidyl acrylate, α-n-butylglycidyl 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 their Mixtures may be mentioned. Specifically, glycidyl (meth)acrylate can be used.

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

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

Specific examples include any structural unit derived from styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene. styrenes with alkyl substituents such as styrene, styrenes with halogens such as fluorostyrene, chlorostyrene, bromostyrene, and iodostyrene, styrenes with alkoxy substituents such as methoxystyrene, ethoxystyrene, and propoxystyrene, p- Ethylenically unsaturated compounds having an aromatic ring such as hydroxy-α-methylstyrene, acetylstyrene, divinylbenzene, vinylphenol, o-vinylbenzyldimethylether, m-vinylbenzylmethylether, and p-vinylbenzylmethylether, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate , tetrahydrofurfuryl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate ) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethoxy Diethylene 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-nonylphenoxypolyethylene glycol (meth)acrylate, p-nonylphenoxypolypropylene glycol (meth)acrylate , tetrafluoropropyl (meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, tribromophenyl ( such as meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate unsaturated carboxylic acid esters, tertiary amines having an N-vinyl group such as N-vinylpyrrolidone, N-vinylcarbazole, and N-vinylmorpholine, unsaturated ethers such as vinylmethyl ether and vinylethyl ether, 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) singly or in combination of two or more thereof.

Epoxy compound (F) may have a weight average molecular weight of 100 to 30,000 g/mol. Specifically, epoxy compound (F) may have a weight average molecular weight of 100 to 15,000 g/mol. When the weight average molecular weight of the epoxy compound is 100 g/mol or more, the thin film can have better hardness. When the weight average molecular weight of the epoxy compound is 30,000 g/mol or less, the thickness of the thin film becomes uniform with smaller steps, which is more suitable for planarization. The weight average molecular weight is determined by gel permeation chromatography (eluent: tetrahydrofuran) on the basis of polystyrene.

The amount of epoxy compound may be from 0 to 10% by weight, or from 0 to 8% by weight, based on the total solid weight (ie, weight exclusive of solvent) of the colored photosensitive resin composition. When the amount of the epoxy compound is within the above amount range, the pattern profile during development may be favorable, properties such as chemical resistance and elastic restoring force may be improved, and the problem of peeling occurring in the development process or composition may be improved. It is possible to prevent the problem that the storage stability of the product is lowered.

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

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

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

(G) Surfactant The colored photosensitive resin composition of the present invention may further contain a surfactant to improve coatability and prevent defects.

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

Commercially available silicone surfactants include DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 from Dow Corning Toray Silicone; 4460, and TSF-4452, and BYK-333, BYK-307, BYK-3560, BYK UV-3535, BYK-361N, BYK-354, and BYK-399 from BYK. The surfactants may be used alone or in combination of two or more.

Dainippon Ink Kagaku Kogyo Co., Ltd. has commercially available fluorine-based surfactants. (DIC) Megaface F-470, F-471, F-475, F-482, F-489, and F-563.

Among these surfactants, BYK-333 and BYK-307 from BYK and F-563 from DIC may be preferred from the viewpoint of coatability of the composition.

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

(H) Solvent The colored photosensitive resin composition of the present invention may preferably be prepared as a liquid composition in which a solvent and the above components are mixed. Any solvent known in the art and used in the preparation of colored photopolymer compositions that is compatible with, but not reactive with, the components of the colored photopolymer compositions may be used. .

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

The amount of the solvent is not specifically limited, but based on the total weight of the finally prepared colored photosensitive resin composition, from the viewpoint of coatability and finally obtained colored photosensitive resin composition , 50-90% by weight, or 70-85% by weight. When the amount of solvent is within the above range, the resin composition is coated smoothly and the possible delay margin in the working process is small.

In addition, the colored photopolymer composition of the present invention may contain other additives, such as antioxidants, and stabilizers, so long as the physical properties of the colored photopolymer composition are not adversely affected.

The colored photosensitive resin composition of the present invention containing the above components may be prepared by a general method, for example, by the following method.

First, the colorant is premixed with and dispersed in a solvent using a bead mill until the average particle size of the colorant reaches the desired level. Surfactants and/or dispersants may be used in such events. Additionally, some or all of the copolymers can be blended. To the dispersion thus obtained is added the remainder of the copolymer and surfactant, the photopolymerizable compound and the photoinitiator. Compounds derived from epoxy resins, additives such as epoxy compounds, or additional solvents are optionally further mixed to a certain concentration, after which they are thoroughly stirred to obtain the desired colored photosensitivity. A resin composition is obtained.

A cured film formed from the colored photosensitive resin composition may have an optical density of 1.0/μm to 3.0/μm. Specifically, a 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 light density per 1 μm in the thickness of the cured film formed from the colored photosensitive resin composition is within the above range, it is effective in preventing light leakage from the display.

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

When a cured film formed from a colored photosensitive resin composition having a size of 3 cm × 3 cm × 3 µm (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 0.5 or less. Specifically, a cured film formed from a colored photosensitive resin composition having a size of 3 cm × 3 cm × 3 µm (width × length × thickness) is 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 light-shielding spacers made from the colored photopolymer composition.

Specifically, the present invention provides a black column spacer (BCS) made from a colored photopolymer composition, wherein the column spacer and black matrix are integrated into one module.

Light-shielding spacers may be prepared by coating formation, exposure, development, and heat treatment steps.

In the coating formation step, the colored photosensitive resin composition according to the present invention is applied to a desired thickness, for example, 1 to 25 μm, by a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, or the like. It is coated onto the treated substrate and then pre-cured at a temperature of 70-100° C. for 1-10 minutes to remove the solvent therefrom to form the coating.

In order to form a pattern on the coated film, a mask with a predetermined shape is placed thereon and then irradiated with actinic radiation having 200-500 nm. In such an event, the column spacers and the black matrix may be prepared simultaneously using masks with patterns with different transmittances to produce integrated black column spacers. As a light source used for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. may be used, and if necessary, X-rays, electron beams, etc. may also be used. may The exposure rate may vary depending on the type and composition ratio of the constituents of the composition and the thickness of the dried coating. If a high pressure mercury lamp is used, the exposure rate may be 500 mJ/cm ² or less (wavelength of 365 nm).

Following the exposure step, alkaline aqueous solutions such as sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, etc. can be used as developing solvents to dissolve and remove unwanted moieties, here. , leaving only the exposed portion to form a pattern. The image pattern obtained by development is cooled to room temperature and post-baked in a hot air circulating drying oven at a temperature of 180-250° C. for 10-60 minutes, thereby obtaining a final pattern.

The light shielding spacers thus produced may be used in the manufacture of electronic components such as LCD, OLED displays due to their excellent physical properties. Accordingly, the present invention provides an electronic component that includes a light shielding spacer.

LCDs, OLED displays, etc. may include other components known to those skilled in the art, except provided with the light-shielding spacers of the present invention. That is, LCDs, OLED displays, etc. to which the light-shielding spacers of the present invention can be applied can be included within the scope of the present invention.

The invention will now be described in more detail with reference to the following examples. However, these examples are provided to illustrate the invention and the scope of the invention is not limited thereto.

Preparation Example 1: Preparation of Copolymer In a 500 ml round bottom flask equipped with a reflux condenser and stirrer, 300 g of propylene glycol monomethyl ether acetate (PGMEA) as solvent and 2 g of 2,2'-azobis as radical polymerization initiator. (2,4-dimethylvaleronitrile) plus 51 mol% N-phenylmaleimide (PMI), 4 mol% styrene (Sty), 10 mol% 4-hydroxybutyl acrylate glycidyl ether (4-HBAGE) , and 35 mol % methacrylic acid (MAA) were charged. The mixture was then heated to 70° C. and stirred for 5 hours to obtain a copolymer solution (A) having a solids content of 31% by weight. The copolymer thus prepared had an acid number of 100 mg KOH/g and a weight average molecular weight (Mw) of 20,000 g/mol as measured by gel permeation chromatography and based on polystyrene.

Preparation Example 2: Preparation of a compound derived from an epoxy resin and having a cardo backbone structure

Step (1): Preparation of 9,9-bis[4-(glycidyloxy)phenyl]fluorene In a 3,000 ml 3-necked round bottom flask, add 200 g of toluene, fluorenylidene)diphenol, and 78.6 g of epichlorohydrin were charged and the mixture was heated to 40° C. with stirring until dissolved. 0.1386 g of t-butylammonium bromide and 50% aqueous NaOH (3 equivalents) were mixed in a vessel and the mixture was slowly added to the solution while stirring in the flask.

The reaction mixture thus obtained was heated to 90° C. and allowed to react for 1 hour until complete consumption of 4,4′-(9-fluorenylidene)diphenol was confirmed by HPLC or TLC. The reaction mixture was cooled to 30° C. and 400 ml of dichloromethane and 300 ml of 1N HCl were added to it while stirring. The organic layer was then separated, washed twice or three times with 300 ml of distilled water, dried over magnesium sulfate, and distilled under reduced pressure to remove dichloromethane. The compound was recrystallized using a mixture of dichloromethane and methanol, thereby obtaining the title compound, an epoxy resin compound.

Step (2): (((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(2-hydroxypropane-3,1-diyl)diacrylate (CAS No. 143182-97-2) In a 1,000 ml three-necked flask, 115 g of the compound obtained in step (1), 50 mg of tetramethylammonium chloride, 50 mg of 2,6-bis(1,1-dimethyl Ethyl)-4-methylphenol and 35 g of acrylic acid were charged. The mixture was heated to 90-100° C. and further heated to 120° C. with air at a flow rate of 25 ml/min for complete dissolution. The reaction mixture was stirred for about 12 hours until the acid number dropped below 1.0 mg KOH/g and then cooled to room temperature. 300 ml of dichloromethane and 300 ml of distilled water were then added to the reaction mixture with stirring. The organic layer was separated, washed with 300 ml of distilled water twice or three times, dried over magnesium sulfate and distilled under reduced pressure to remove dichloromethane, thereby obtaining the title compound.

Step (3): Preparation of compound derived from epoxy resin and having cardo backbone structure. , 4,5-benzenetetracarboxylic dianhydride (0.75 equivalents), 1,2,3,6-tetrahydrophthalic anhydride (0.5 equivalents), and triphenylphosphine (0.01 equivalents). Added more to it. The reaction mixture was heated with stirring to 120-130° C. for 2 hours, cooled to 80-90° C. and then stirred and heated for 6 hours. After cooling the mixture to room temperature, a solution (49 wt. Obtained.

Preparation Example 3: Preparation of Colored Dispersion-(1)
Colored Dispersion (D-1) is available from Tokushiki Co.; Co., Ltd., and the dispersion was prepared as follows.

22.5 g acrylic acid copolymer solution (a copolymer of benzyl methacrylate, styrene, and methacrylic acid) having a weight average molecular weight of 12,000-20,000 g/mol and an acid value of 80-150 mg KOH/g (Tokushiki Co., Ltd. .), 8 g acrylic acid polymer dispersant (Tokushiki Co., Ltd.) with an amine value of 100-140 mg KOH/g, 76.36 g carbon black, and 384 g PGMEA as solvent for 6 hours at 25°C. Dispersed using a shaker. This dispersion step was performed with 0.3 mm zirconia beads. After the dispersing step was completed, the beads were removed from the dispersion through a filter, resulting in a colored dispersion with 21.37% solids by weight.

Preparation Example 4: Preparation of Colored Dispersion-(2)
The colored dispersion (D-2) was prepared in the same manner as in Preparation Example 3, except that a black organic colorant, lactam black (Black 582, BASF) was used as the colorant. Co. , Ltd. supplied from.

Preparation 5: Preparation of Epoxy Compound A flask was charged with 150 g of glycidyl methacrylate, 2 g of 2,2'-azobisisobutyronitrile, and 450 g of PGMEA, and the flask was purged with nitrogen for 30 minutes. The flask was then immersed in an oil bath with stirring and the polymerization was carried out for 5 hours while maintaining the reaction temperature at 80° C., resulting in a solids content of 22% by weight and a weight average molecular weight (Mw) of 12,000 g/mol. ) to obtain an epoxy compound solution (F) having

Using the compounds prepared in the above preparation examples, photosensitive resin compositions were prepared in the following examples and comparative examples.

We used the following additional components:

Photopolymerizable compound (B): Hexafunctional dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku)

Triazine-based photopolymerization initiator (C-1): (E)-2-(4-styrylphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine (manufacturer: PHARMASYNTHESE, trademark: TRIAZIN-Y)

Oxime photoinitiator (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 , Trademark: I-379)

Surfactant (G): BYK-333 manufactured by BYK

Solvent (H): Propylene glycol monomethyl ether acetate (PGMEA) manufactured by Chemtronics

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 part by weight of triazine-based photopolymerization initiator (C-1), 8.6 parts by weight of oxime-based photopolymerization initiator (C-2), 8.9 parts by weight of ketone-based photopolymerization initiator (C-3 ), 249.8 parts by weight of colored dispersion (D-1), 175.4 parts by weight of solution (solid content) of polymer (E), and 0.7 parts by weight of surfactant (G) are mixed. , and then the solvent (H) was added thereto so that the solids content reached 19% by weight. The composition was mixed for 2 hours using a shaker, thereby preparing a liquid phase colored photopolymer composition.

Examples 2-10 and Comparative Examples 1-5 Preparation of Colored Photosensitive Resin Composition A resin composition was prepared in the same manner as in Example 1.

Test Example 1: Preparation of Cured Film from Colored Photosensitive Resin Composition The colored photosensitive resin compositions obtained in Examples and Comparative Examples were each coated on a glass substrate using a spin coater, and cured at 95°C for 150°C. Seconds pre-bake to form a 4.8 μm thick coated film. A pattern mask is placed on the coated film thus formed, the substrate gap is maintained at 50 μm, the pattern mask is 100% full tone (F/T) column spacer (CS) pattern and 30% halftone ( H/T) to include a black matrix (BM) pattern. Then, using an aligner (trade name: MA6) that emits light with a wavelength of 200 nm to 450 nm, the coated film is subjected to an irradiation dose of 66 mJ/cm ² based on a wavelength of 365 nm for a certain period of time. illuminated with a constant light. 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 areas were completely washed out. The pattern thus formed was post-baked in an oven at 230° C. for 30 minutes to remove light-shielding spacers (i.e., patterned portions) and a 3.0 μm (±0.1 μm) thick cured film (i.e., , unpatterned part). The results obtained in the following test examples are summarized in Table 3 below.

(1) Measurement of change in development time for each prebake temperature In the above process for preparing a cured film, the prebake temperature was changed to 80°C or 100°C, and evaluation was performed under the same conditions as above. The unexposed areas were then thoroughly washed with an aqueous solution of potassium hydroxide diluted to a concentration of 0.04 wt. time was measured. In addition, the change in development time for each change in prebake temperature was converted and recorded.

(2) Measurement of surface properties (contact thickness measurement)
The wrinkles on the surface of the cured film prepared in this way are recorded using the SCAN PLUS, which is an α-step instrument (alpha-step surface profilometer), and the vibration value of the vertical movement of the equipped probe is recorded. The surface of the cured film was photographed with an optical microscope (STM6, Olympus).

(3) Measurement of Optical Density The transmittance at 550 nm of the cured film (i.e., unpatterned portion) thus prepared was measured using an optical densitometer (361T manufactured by Xlite), The optical density based on 1 μm thickness was determined.

(4) Measurement of elastic recovery rate 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 at the time of post-baking was prepared by the method for preparing the cured film described above. prepared. Using an elastic instrument (FISCHERSCOPE (registered trademark) HM2000LT, Fisher Technology), compression displacement and elastic recovery rate were measured under the following measurement conditions.

Specifically, a square 50 μm×50 μm planar Vickers indenter was used as the indenter for pressing the pattern. Measurements were made by the load/unload method. After applying a load of 1.96 mN on the dot pattern using the elastic device described above, it is defined as the initial state (H0) in order to measure the mechanical properties of compressive displacement and elastic recovery. The load applied on each pattern sample was then increased at a rate of 5 mN/sec, increased by 300 mN in the thickness direction, maintained for 5 sec, and the distance traveled by the indenter (H1) was measured. At the completion of the 5 second hold, the load was released in the thickness direction at a rate of 5 mN/s. When the force applied to the dot by the indenter reached 1.96 mN, the force was maintained for 5 seconds. The distance traveled by the indenter (H2) was measured. Elastic recovery was calculated according to Equation 1 below.
[equation 1]
Elastic recovery rate (%) = [(H1-H2) / (H1-H0) × 100]

(5) Chemical Resistance A substrate with a size of 3 cm×3 cm×3 μm (width×length×thickness) was prepared according to the method for preparing a cured film as described above. The substrate was immersed in 18 g of N-methylpyrrolidone (NMP) solution and aged at 100° C. for 1 hour. After that, the substrate was removed from the NMP solution and the absorbance of the NMP solution was measured at 437 nm.

(6) Step difference measurement A spacer part (A) and a black matrix part (B) were obtained according to the method for preparing a cured film as described above (see Fig. 1). The thickness of A and B was measured using a step measuring instrument (SNU (SIS-2000), SNU Precision). In such an event, the step performance is expected to be excellent when the thickness difference (ie, AB) is within the range of 1.0-2.0 μm.

The results obtained in the above test examples are summarized in Table 3 below, and photographs of the surfaces of the cured films are shown in Figures 2-5.

As shown in Table 3 and Figures 2-5, the compositions of the examples falling within the scope of the present invention had minimized uneven wrinkles on their surfaces, excellent elastic recovery and excellent In addition to providing a cured film with excellent chemical resistance, development in a short time is also possible. In contrast, comparative compositions not within the scope of the present invention exhibited at least one adverse result.

Drawing reference numbers A: Thickness of column spacer portion B: Thickness of black matrix portion C: Critical dimension (CD) of column spacer portion

Claims (14)

A colored photosensitive resin composition,
(A) a copolymer containing an epoxy group, wherein the copolymer (A) is (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 ethylenically unsaturated compound containing an aromatic ring, (a-3) a structural unit derived from an ethylenically unsaturated compound containing an epoxy group, and (a-4) an unsaturated a copolymer comprising structural units derived from a saturated imide ;
(B) a photopolymerizable compound containing a double bond;
(C) a photoinitiator;
(D) a colorant comprising a black inorganic colorant;
wherein the colorant comprises 50 to 100% by weight of the black inorganic colorant, based on the total weight of solids of the colorant;
A colored photosensitive resin composition wherein the molar ratio of said double bonds in said photopolymerizable compound (B) to said epoxy groups in said copolymer (A) satisfies the following relationship:
4 ≤ number of moles of double bond/number of moles of epoxy group ≤ 35 The colored photosensitive resin composition according to claim 1, wherein the black inorganic colorant contains at least one selected from the group consisting of carbon black, titanium black, Cu-Fe-Μn-based oxides, and metal oxides. thing. 2. The colored photosensitive resin composition of claim 1, wherein the colorant comprises a black organic colorant. Claim 1, wherein the colorant comprises a dispersing resin, the dispersing resin having an amine value of 3 mg KOH/g or less and comprising 50 mol% or less of a maleimide monomer, based on the total number of moles of structural units. The colored photosensitive resin composition according to . 2. The colored photosensitive resin composition according to claim 1, wherein a cured film formed from said colored photosensitive resin composition has an optical density of 1.0/μm to 3.0/μm. 2. The colored photosensitive resin composition according to claim 1, further comprising (E) a compound derived from an epoxy resin and having a double bond. The molar ratio of the double bonds in the photopolymerizable compound (B) and in the compound (E) derived from the epoxy resin to the epoxy groups in the copolymer (A) satisfies the following relationship: The colored photosensitive resin composition according to claim 6.
4 ≤ number of moles of double bond/number of moles of epoxy group ≤ 35 2. The colored photosensitive resin composition according to claim 1, further comprising (F) an epoxy compound. 9. Claim 8, wherein the molar ratio of the double bonds in the photopolymerizable compound (B) to the epoxy groups in the copolymer (A) and in the epoxy compound (F) satisfies the following relationship: A colored photosensitive resin composition.
4 ≤ number of moles of double bond/number of moles of epoxy group ≤ 35 7. The colored photosensitive resin composition according to claim 6, further comprising (F) an epoxy compound. molar ratio of the double bonds in the photopolymerizable compound (B) and in the compound (E) derived from the epoxy resin to the epoxy groups in the copolymer (A) and the epoxy compound (F) satisfies the following relationship: The colored photosensitive resin composition according to claim 10.
4 ≤ number of moles of double bond/number of moles of epoxy group ≤ 35 2. The colored photosensitive resin composition according to claim 1, wherein a cured film formed from said colored photosensitive resin composition has an elastic recovery rate of 80% or more. When a cured film formed from the colored photosensitive resin composition having a size of 3 cm × 3 cm × 3 µm (width × length × thickness) was immersed in an organic solvent and treated at 100 ° C. for 1 hour, the above 2. The colored photosensitive resin composition of claim 1, wherein the organic solvent has an absorbance at 437 nm of 0.5 or less. A light-shielding spacer produced from the colored photosensitive resin composition according to claim 1 .

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