JP2019003189A - Colored photosensitive resin composition and light-shielding spacer prepared therefrom - Google Patents

Abstract

To provide a colored photosensitive resin composition that prevents generation of uneven wrinkles when a cured film is formed, thereby, prevents spots which may be generated on edges of wrinkles during fabricating a display, and has a shorter developing time.SOLUTION: The colored photosensitive resin composition comprises (A) a copolymer including an epoxy group, (B) a photopolymerizable compound including a double bond, (C) a photopolymerization initiator, and (D) a colorant containing a black inorganic colorant, in which the colorant contains the black inorganic colorant by 50 to 100 wt.% based on the total weight of the solid content of the colorant; and a molar ratio of the double bond in the photopolymerizable compound (B) with respect to the epoxy group in the copolymer (A) satisfies a relationship of 4≤(a molar number of the double bond)/(a molar number of the epoxy group)≤35.SELECTED DRAWING: Figure 1

Description

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

  In recent years, spacers prepared from a photosensitive resin composition have been used to maintain a certain distance between an upper transparent substrate and a lower transparent substrate in a liquid crystal cell of a liquid crystal display (LCD). In an LCD which is 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. is there. If there is a region where the gap between the transparent substrates is not constant, the voltage applied to it and the transmittance of light transmitted through this region may change, resulting in spatially nonuniform brightness defects. With the recent demand for large LCD panels, it is even more important to maintain a constant gap between the two transparent substrates in the LCD.

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

  In recent years, black column spacers (BCS) in which column spacers and a black matrix are integrated into a single module using a colored photosensitive resin composition have attracted attention in order to simplify the process steps. The colored photosensitive resin composition used in the production of such a black column spacer is required not only to easily form a step, but also to satisfy an elastic recovery rate and at the same time have resistance to the pressure of the upper plate. The In addition, when the bezel in the display panel is formed from a colored photosensitive resin composition, if the cured film has uneven wrinkles on its surface, this is a defect in the gap between the upper and lower plates. Therefore, the amount of liquid crystal injected during their assembly can be non-uniform or can cause serious disadvantages that spots can occur on the display screen due to insufficient transmission of electrical signals.

  On the other hand, the content of the pigment added to the resin composition must 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 pigment is eluted into the spacer due to an increase in the amount of organic pigment having insufficient chemical resistance. In addition, as the amount of the pigment increases in the photosensitive resin composition for forming the spacer, the amount of the binder, the photopolymerizable compound, etc. is relatively decreased, and the elastic recovery rate of the spacer is lowered. cause.

  Therefore, the object of the present invention is to minimize the occurrence of uneven wrinkles on the surface and to increase the level difference characteristics, chemical resistance without significantly increasing the amount of pigment in the photosensitive resin composition for forming the spacer. It is to provide a colored photosensitive resin composition and a light-shielding spacer produced therefrom, which can form a cured film that simultaneously satisfies the properties, the elastic recovery rate, and the light-shielding property.

In order to achieve the above object, the present invention provides a colored photosensitive resin composition,
(A) a copolymer containing an epoxy group;
(B) a photopolymerizable compound containing a double bond;
(C) a photopolymerization initiator;
(D) a colorant containing a black inorganic colorant,
The colorant comprises 50 to 100% by weight of a black inorganic colorant, based on the total weight of the solids of the colorant;
Provided is a colored photosensitive resin composition in which the molar ratio of the double bond in the photopolymerizable compound (B) to the epoxy group in the copolymer (A) satisfies the following relationship.
4 ≦ mole number of double bond / mole number of epoxy group ≦ 35

  Furthermore, this invention provides the light-shielding spacer produced | generated from a coloring photosensitive resin composition.

  The colored photosensitive resin composition of the present invention prevents the generation of uneven wrinkles when a cured film is formed, thereby preventing spots that may occur at the edges during the formation of a display and short development. Have time. Therefore, the colored photosensitive resin composition is used for various electronic parts including liquid crystal display (LCD) panels and organic light emitting diode (OLED) display panels, protective films, interlayer insulating films, light shielding spacers such as black column spacers, etc. It 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 the step characteristics, chemical resistance, elastic recovery rate, and light-shielding properties without significantly increasing the amount of pigment.

It is a schematic diagram of an embodiment of a cross section of a light shielding spacer (that is, a black column spacer). It is the photograph of the surface of the cured film prepared from the photosensitive resin composition of Examples 6 and 7 and Comparative Examples 2 and 3 in order. It is the photograph of the surface of the cured film prepared from the photosensitive resin composition of Examples 6 and 7 and Comparative Examples 2 and 3 in order. It is the photograph of the surface of the cured film prepared from the photosensitive resin composition of Examples 6 and 7 and Comparative Examples 2 and 3 in order. It is the photograph of the surface of the cured film prepared from the photosensitive resin composition of Examples 6 and 7 and Comparative Examples 2 and 3 in order.

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

  In the present disclosure, “(meth) acryl” means “acryl” and / or “methacryl”, and “(meth) acrylate” means “acrylate” and / or “methacrylate”.

  Hereinafter, each component of the colored photosensitive resin composition will be described in detail.

(A) Copolymer containing 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, -4) A structural unit derived from an ethylenically unsaturated compound different from the structural units (a-1), (a-2), and (a-3) may be further included.

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

(A-1) Structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a combination thereof The structural unit (a-1) is an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid, Derived from saturated carboxylic anhydrides, or combinations thereof. Ethylenically unsaturated carboxylic acid and ethylenically unsaturated carboxylic acid anhydride are polymerizable unsaturated monomers containing at least one carboxyl group in the molecule. Specific examples thereof include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid, unsaturated dicarboxylic acids and anhydrides thereof 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 anhydrides, and divalent or higher monocarboxylic acid mono [ (Meth) acryloyloxyalkyl] esters such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] phthalate can be mentioned. Structural units derived from the above exemplified compounds may be included in the copolymer alone or in 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 moles of the structural units constituting the copolymer. Within the above amount range, developability may be preferred.

(A-2) Structural unit derived from an ethylenically unsaturated compound containing an aromatic ring 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 include phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxy polyethylene glycol (Meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tribromophenyl (meth) acrylate, styrene, styrene containing alkyl substituents such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, Triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, and octyl styrene, halogen-containing styrene such as fluorine Orostyrene, chlorostyrene, bromostyrene, and iodostyrene, styrene containing alkoxy substituents such as methoxystyrene, ethoxystyrene, and propoxystyrene, 4-hydroxystyrene, p-hydroxy-α-methylstyrene, acetylstyrene, and vinyl Toluene, divinylbenzene, vinylphenol, o-vinylbenzyldimethylether, m-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, p-vinylbenzylglycidylether, etc. Can be mentioned. Structural units derived from the above exemplified compounds may be included in the copolymer alone or in combination of two or more. A structural unit derived from a styrenic compound among the above compounds is preferred in view of polymerizability.

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

(A-3) Structural unit derived from an ethylenically unsaturated compound containing an 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- Dorokishibuchiru (meth) acrylate glycidyl ether, allyl glycidyl ether, and the like of 2-methyl allyl glycidyl ether. Structural units derived from the above exemplified compounds may be included in the copolymer alone or in combination of two or more. Among the above, the structural unit derived from glycidyl (meth) acrylate and / or 4-hydroxybutyl (meth) acrylate glycidyl ether is more preferable from the viewpoints of improvement in polymerizability and strength of the insulating film.

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

(A-4) Structural unit derived from an ethylenically unsaturated compound different from structural units (a-1), (a-2), and (a-3) The copolymer used in the present invention comprises structural unit (a -1) derived from an ethylenically unsaturated compound different from structural units (a-1), (a-2) and (a-3) in addition to (a-2) and (a-3) The structural unit may be further included.

  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 (meta ) 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, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate, N-vinyl group, For example, tertiary amines containing 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 exemplified compounds may be included in the copolymer alone or in combination of two or more. Among the above, the unsaturated imide, specifically, the structural unit derived from N-substituted maleimide is more preferable from the viewpoint of the polymerizability and the improvement in the strength of the insulating film.

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

  Examples of copolymers having structural units (a-1) to (a-4) include copolymers of (meth) acrylic acid / styrene / methyl (meth) acrylate / glycidyl (meth) acrylate, (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) Copolymer of acrylic acid / styrene / n-butyl (meth) acrylate / glycidyl (meth) acrylate / N-phenylmaleimide, copolymer of (meth) acrylic acid / styrene / glycidyl (meth) acrylate / N-phenylmaleimide, (meth) acrylic / Styrene / 4-hydroxybutyl (meth) acrylate glycidyl ether / N- phenylmaleimide copolymer, and the like. One, two, or more of the copolymers may be included in the colored photosensitive resin 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) based on polystyrene. It may be a range. If 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 (ie, weight excluding the solvent) of the solid content of the colored photosensitive resin composition. It may be. Within the above range, the pattern profile at the time of development can be preferable, and the development time, surface characteristics, etc. of the cured film formed from the resin composition can be improved.

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

  Radical polymerization initiators are 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, etc., but are not limited thereto. Absent. The radical polymerization initiator 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, including, for example, propylene glycol monomethyl ether acetate (PGMEA).

(B) Photopolymerizable compound containing a 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, examples of the photopolymerizable compound include a monofunctional or polyfunctional ester compound having at least one ethylenically unsaturated double bond, and preferably at least from the viewpoint of chemical resistance. Mention may be made of polyfunctional compounds having two functional groups.

  The photopolymerizable compound includes 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 Monoester, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( ) Acrylate, dipentaerythritol penta (meth) acrylate and monoester 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 mixtures thereof, but are not limited thereto.

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

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

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.
4 ≦ mole number of double bond / mole number of epoxy group ≦ 35

  If the cured film for the display bezel has uneven wrinkles on its surface, this is due to defects in the gap between the upper and lower plates, and the amount of liquid crystal injected during their assembly. It can be non-uniform, or can cause the disadvantage that spots can occur on the display screen due to insufficient transmission of electrical signals. However, when the colored photosensitive resin composition of the present invention satisfies the molar ratio defined by the above relationship, the generation of uneven 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, the surface of the coated film is strongly cured during exposure to light, while the material having unreacted double bonds Remains within it, which increases the fluidity (ie, mobility) of such unreacted material in the subsequent thermosetting process. As a result, the polymer near the surface and the polymer deep inside the pattern have different mobilities during thermal curing, resulting in uneven wrinkles on the surface of the cured film. In addition, when the molar ratio is less than 4, since the number of moles of epoxy groups is relatively larger than the number of moles of double bonds, it is difficult to control the degree of cross-linking by changing the temperature. The development margin due to becomes insufficient, and the resolution is lowered.

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 ≦ mole number of double bond / mole number of epoxy group ≦ 35

(C) Photopolymerization initiator The photopolymerization initiator used in the present invention may 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, imide sulfonate compounds, It can be selected from the group consisting of oxime compounds, carbazole compounds, sulfonium borate compounds, ketone compounds, and mixtures thereof. Specifically, the photopolymerization initiator may be at least one selected from the group consisting of an oxime compound, a triazine compound, and a ketone compound. More specifically, a combination of an oxime compound, a triazine compound, and a ketone compound can be used.

  Specific examples of photopolymerization initiators include 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, Lauryl peroxide, t-butylperoxypivalate, 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, benzyldimethyl ketal, benzophenone, benzoinpropyl ether, diethylthioxanthone, 2,4-bis (trichloromethyl) -6 p-methoxyphenyl-s-triazine, 2-trichloromethyl- -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-1,2-dione- 2- (o-benzoyloxime), o-enzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophosphoro-trialkylphenylsulfonium Salt, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl Sulfide, (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 mixtures thereof may be mentioned, but are not limited thereto.

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

  The photopolymerization initiator is 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 (that is, the weight excluding the solvent). May be used. Specifically, based on the total weight of the solid content of the colored photosensitive resin composition (that is, the weight excluding the solvent), 0.1 to 2% by weight of the oxime compound, 0.1 to 2% by weight Triazine-based compounds and 0.1-2% by weight of ketone-based compounds may be used as photopolymerization initiators. More specifically, based on the total weight of the solid content (that is, the weight excluding the solvent) of the colored photosensitive resin composition, 0.5 to 1.5% by weight of the oxime compound, 0.5 to 1 .5% by weight of a triazine compound and 0.5 to 1.5% by weight of a ketone compound may be used as a photopolymerization initiator. When oxime-based compounds are used within the above ranges, development and coating properties can be improved with high sensitivity. In addition, when the triazine-based compound is used within the above range, a coated film having excellent chemical resistance and taper angle can be obtained when forming a pattern. Further, when the ketone compound is used within the above range, the colored photosensitive resin composition prepared in this way is a coating having excellent chemical resistance by curing of the inner deep part of the coated film. Formed film can be formed.

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

  The colorant includes a black inorganic colorant. In addition, the colorant can include a black organic colorant. In addition, the colorant may include a colored colorant other than black, such as blue or purple.

  Any black inorganic colorant and any black organic colorant known in the art can be used. For example, any compound classified as a pigment in 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 include at least one selected from the group consisting of carbon black, titanium black, Cu—Fe—Μn-based oxide, and metal oxide. Specifically, it is preferable to use carbon black as a black inorganic colorant from the viewpoint of pattern characteristics and chemical resistance.

Cu-FeMn-based oxide include, for _{example, Cu 1.5 Mn 1.5 O 4,} CuFeMnO 4, MnO 2, and FeMn ₂ O _4, and the like.

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

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

  The colorant includes 50 to 100% by weight of a black inorganic colorant based on the total weight of the colorant solids. Specifically, the colorant may include 50-100% by weight black inorganic colorant and 0-50% by weight black organic colorant, based on the total weight of the solids of the colorant. More specifically, the colorant may comprise 80-100% by weight black inorganic colorant and 0-20% by weight black organic colorant, based on the total weight of the colorant solids. 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 capable of preventing light leakage in the visible light 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 kneaded pigment mixed with a dispersion resin, a solvent or the like.

  The dispersion-type resin serves 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 dispersants can include any known dispersant for colorants. Specific examples thereof include cationic surfactants, anionic surfactants, nonionic surfactants, zwitterionic surfactants, silicon surfactants, fluorosurfactants, 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 group-substituted poly Esters of carboxylic acids and modified products thereof, Amide formed by reaction of polyester having free carboxyl group with (lower alkyleneimine) or salt thereof, (meth) acrylic acid styrene copolymer, (meth) acrylic acid (meth) acrylate ester copolymer, styrene maleic acid copolymer, polyvinyl Examples include alcohols, water-soluble resins or water-soluble polymer compounds such as polyvinyl pyrrolidone, modified polyacrylates, adducts of ethylene oxide / propylene oxide, and phosphate esters. Commercially available dispersants include Disperbyk-182, Disperbyk-183, Disperbyk-184, Disperbyk-185, Disperbyk-2000, Disperbyk-2150, Disperbyk-2155, Disperbyk-2163, Disperbyk-2163, and Disperbyk-2163 from BYK Co. Can do. 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 an affinity group of the pigment, and may optionally be an ammonium salt system.

  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.

  The dispersant may be used in an amount of 1-20 wt%, or 2-15 wt%, based on the total weight of the colored dispersion. When the amount of dispersant is within the above range, the colorant is optically and physically dispersed by effectively dispersing to improve dispersion stability and maintaining proper viscosity when it is applied. And chemical properties are improved. For this reason, it is desirable from the viewpoint of an excellent balance between dispersion stability and viscosity.

  Further, the colorant may include a dispersion resin, the dispersion resin may have an amine value of 3 mg KOH / g or less, and may contain 50 mol% or less of maleimide monomer based on the total number of moles of the structural units. In such an event, the dispersed resin can be a dispersion binder.

  When the dispersion binder has an acid value, it may contain a monomer having a carboxyl group and an unsaturated bond. Specific examples of monomers having carboxyl groups and unsaturated bonds 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 Anhydrous anhydride, and mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate. 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 the monomer having a copolymerizable unsaturated bond include, for example, styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinyl. Aromatic vinyl compounds such as benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether, methyl (meta ) 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 - butyl (meth) alkyl (meth) acrylates such as acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6]} decane Cycloaliphatic (meth) acrylates such as -8-yl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate, phenyl (meth) acrylate and benzyl (meth) acrylate Aryl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and hydroxyalkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, N-cyclohexylmaleimide, N-benzylmale N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, Nm-methylphenylmaleimide, Np N-substituted maleimide compounds such as -methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide, (meth) acrylamide and N, N-dimethyl (meta ) Unsaturated amide compounds such as acrylamide, and 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3 And unsaturated oxetane compounds such as (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, and 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane , Or a combination of two or more.

  The dispersion binder may contain up to 50 mole% maleimide monomer, based on the total number of moles of building blocks.

  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. When the acid value of the dispersion binder is within the above range, the influence of the dispersant surrounding the pigment on the amine value is reduced, thereby improving the stability of the colored dispersion and the effect of uniform particle size. produce.

  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, thereby adversely affecting the storage stability of the overall resin composition. For this reason, the amine value of the dispersion binder is preferably 3 mgKOH / g or less. If the amine value of the dispersion binder is within the above range, the unexposed parts can be easily developed in the development process and problems such as residue formation can be improved.

  The dispersion binder may be used in an amount of 1-20% by weight, or 2-15% by weight, based on the total weight of the colored dispersion. When the dispersion binder is used in the above range, the resin composition can maintain an appropriate viscosity level, which is preferable from the viewpoint of dispersion stability and developability.

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

  The weight average molecular weight (Mw) of the compound derived from the epoxy resin is 3,000-18,000 g / mol, or 5,000-10,000 g / mol as determined by gel permeation chromatography based on polystyrene. It may 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 preferable, and the step difference due to the lower pattern can be advantageously improved.

  Specifically, the epoxy resin may be a compound having a cardo main chain structure as represented by the following formula 1.

  In the above formula 1, each X is independently

L ¹ is each 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, R ₈ is H, methyl, ethyl, CH ₃ CHCl—, CH ₃ CHOH—, CH ₂ ═CHCH ₂ —, or phenyl, and n is an integer of 0-10.

Specific examples of C _1-10 alkylene groups include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, sec-butylene, t-butylene, pentylene, isopentylene, t-pentylene, hexylene, heptylene, octylene, isooctylene, Examples thereof include t-octylene, 2-ethylhexylene, nonylene, isononylene, decylene, and isodecylene. Specific examples of the C _3-20 cycloalkylene group include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, decalinylene, adamantylene and the like. Specific examples of C _1-10 alkyleneoxy groups include methyleneoxy, ethyleneoxy, propyleneoxy, butyleneoxy, sec-butyleneoxy, t-butyleneoxy, pentyleneoxy, hexyleneoxy, heptyleneoxy, octyleneoxy, 2-ethyl-hexyleneoxy and the like can be mentioned. Specific examples of C _1-10 alkyl groups include 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 can be mentioned. Specific 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. it can. Specific examples of C _2-10 alkenyl groups include vinyl, allyl, butenyl, propenyl and the like. Specific examples of C _6-14 aryl groups include phenyl, tolyl, xylyl, naphthyl and the like.

  As an example, an epoxy resin having a cardo main chain structure may be prepared by the following synthetic route.

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 reacts an epoxy resin having a cardo backbone structure with an unsaturated basic acid to produce an epoxy adduct, and then the resulting epoxy addition It 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 acid anhydride known in the art, such as succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hexahydro Phthalic anhydride or the like may be used. Any monofunctional or polyfunctional 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 Ether or the like may be used.

  As an example, a compound derived from an epoxy resin 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 ring or aromatic ring, n is an integer from 1 to 10, and X, R ₁ , R ₂ , and L ₁ are represented by the formula 1 Is the same as defined in.

  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, alkali resistance, workability, strength, etc. of the cured material to the substrate. Furthermore, if uncured portions are removed during development, a fine resolution image may be formed in the pattern.

  The amount of the compound derived from the epoxy resin was 0 to 40% by weight, or 0 to 30% by weight, based on the total solid content of the colored photosensitive resin composition (ie, the weight excluding the solvent). May be. When a compound derived from an epoxy resin is used, the pattern profile at the time of development can be preferable within the above amount range, and the development time and surface characteristics of the cured film formed from the resin composition can 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 the epoxy resin to the epoxy group in the copolymer (A) is as follows. Satisfy the relationship.
4 ≦ mole number of double bond / mole number of epoxy group ≦ 35

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

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

  The epoxy compound can be an unsaturated monomer containing at least one epoxy group, or a homo- or hetero-oligomer thereof. Examples of unsaturated monomers containing at least one epoxy group 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-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, allyl glycidyl ether, 2-methylallyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, or mixtures thereof. Can do. Specifically, glycidyl (meth) acrylate may 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) can further include the following structural units.

  Specific examples include any structural unit derived from styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, and octyl styrene. Styrenes having such alkyl substituents, styrenes having halogens such as fluorostyrene, chlorostyrene, bromostyrene, and iodostyrene, styrenes having alkoxy substituents such as methoxystyrene, ethoxystyrene, and propoxystyrene, p- Hydroxy-α-methyl styrene, acetyl styrene, divinyl benzene, vinyl phenol, o-vinyl benzyl dimethyl ether, m-vinyl benzyl methyl ether, and p-bi Ethylenically unsaturated compounds having an aromatic ring such as rubenzyl methyl ether, 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-chloro Propyl (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, methoxy Tripropylene 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, Trifluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) ) Acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate Unsaturated carboxylic acid esters, N-vinyl pyrrolidone, N-vinyl carbazole, and tertiary amines having N-vinyl groups such as N-vinyl morpholine, unsaturated such as vinyl methyl ether and vinyl ethyl ether Mention may be made of unsaturated imides such as ether, N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, and N-cyclohexylmaleimide. The structural unit 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. 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) based on polystyrene.

  The amount of the epoxy compound may be 0 to 10% by weight, or 0 to 8% by weight based on the total weight of the solid content of the colored photosensitive resin composition (that is, the weight excluding the solvent). When the amount of the epoxy compound is within the above range, the pattern profile at the time of development can be preferable, characteristics such as chemical resistance and elastic resilience can be improved, and the problem or composition of peeling that occurs in the development process The problem that the storage stability of a thing falls can be prevented.

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) satisfies the following relationship. obtain.
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 compound (E) derived from the photopolymerizable compound (B) and the epoxy resin with respect to the epoxy group in the copolymer (A) and the epoxy compound (F). The molar ratio of the double bonds 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) has the following relationship: Can meet. In addition, in the colored photosensitive resin composition of the present invention, the compound (E) derived from the photopolymerizable compound (B) and the epoxy resin with respect to the epoxy group in the copolymer (A) and the epoxy compound (F). The molar ratio of the double bonds can satisfy the above relationship.
11 ≦ mole number of double bond / mole number of epoxy group ≦ 35

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

  Although the kind of surfactant is not specifically limited, For example, the fluorine-type surfactant or silicon-type surfactant which has a cyclic structure may be used.

  Commercially available silicon surfactants include DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 from Dow Corning Toray Silicon, TSF-4440, TSF-4300, TSF-4446, TSF-4446, TSF-4446 from GE Toshiba Silicone. 4460, and TSF-4442, and BYK-333, BYK-307, BYK-3560, BYK UV-3535, BYK-361N, BYK-354, and BYK-399 from BYK. This surfactant may be used alone or in combination of two or more.

  Examples of commercially available fluorosurfactants include Dainippon Ink Kagaku Kogyo Co. Mention may be made of Megaface F-470, F-471, F-475, F-482, F-487, and F-563 from (DIC).

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

  The amount of the surfactant was 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 (ie, the weight excluding the solvent). May be. When the amount of the surfactant is within the above range, the colored photosensitive resin composition can be smoothly coated.

(H) Solvent The colored photosensitive resin composition of the present invention may be preferably 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 photosensitive resin compositions and compatible with the components of the colored photosensitive resin composition, but not reactive 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 acetate. Mention may be made, for example, of propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate, and alkoxyalkyl acetates such as 3-methoxybutyl acetate. Solvents may be used alone or in combination of two or more.

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

  In addition, the colored photosensitive resin composition of the present invention may contain other additives such as antioxidants and stabilizers as long as the physical properties of the colored photosensitive resin 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 a solvent using a bead mill and dispersed therein until the average particle size of the colorant reaches the desired level. In such events, surfactants and / or dispersants can be used. Furthermore, some or all of the copolymer can be mixed. The remainder of the copolymer and surfactant, the photopolymerizable compound, and the photopolymerization initiator are added to the dispersion thus obtained. Compounds derived from epoxy resins, additives such as epoxy compounds, or additional solvents, if necessary, are further mixed to a certain concentration, after which they are thoroughly stirred to achieve the desired color sensitivity. A resin composition is obtained.

  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 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 to prevent light leakage of the display.

  The 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 Can 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 can have an absorbance at 437 nm of 0.0001-0.5, or 0.001-0.4, or 0.01-0.4, or 0.01-0.3.

  The present invention also provides a light shielding spacer produced from a colored photosensitive resin composition.

  Specifically, the present invention provides a black column spacer (BCS) produced from a colored photosensitive resin composition, and the column spacer and the black matrix are integrated in one module.

  The light shielding spacer may be prepared by a coating formation step, an exposure step, a development step, and a heat treatment step.

  In the coating formation step, the colored photosensitive resin composition according to the present invention may be applied at 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 on the treated substrate and then precured at a temperature of 70-100 ° C. for 1-10 minutes to form the coating by removing the solvent therefrom.

In order to form a pattern on the coated film, a mask having a predetermined shape is placed thereon and then irradiated with actinic light having a wavelength of 200-500 nm. In such an event, the column spacer and black matrix may be prepared simultaneously using a mask having a pattern with different transmittance to produce an integrated black column spacer. As a light source used for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like may be used, and an X-ray, an electron beam, or the like is also used as necessary. May be. The exposure rate may vary depending on the type and composition ratio of the components of the composition and the thickness of the dry coating. When 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, an aqueous alkaline solution, such as sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, etc., can be used as a developing solvent to dissolve and remove unwanted portions, where Thus, only the exposed portion remains and forms 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 to 250 ° C. for 10 to 60 minutes, thereby obtaining a final pattern.

  The light-shielding spacer generated in this way may be used in the manufacture of electronic components such as LCDs and OLED displays due to its excellent physical properties. For this reason, this invention provides the electronic component containing a light-shielding spacer.

  LCDs, OLED displays, etc. may include other components known to those skilled in the art, except that they include the light blocking spacers of the present invention. That is, LCDs, OLED displays, and the like to which the light shielding spacer of the present invention can be applied can be included 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 described to illustrate the present invention and the scope of the present invention is not limited thereto.

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

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

Step (1): Preparation of 9,9-bis [4- (glycidyloxy) phenyl] fluorene In a 3,000 ml 3-neck round bottom flask, 200 g of toluene, 125.4 g of 4,4 ′-(9- Fluorenylidene) diphenol and 78.6 g epichlorohydrin were charged and the mixture was heated to 40 ° C. with stirring to dissolve. 0.1386 g of t-butylammonium bromide and 50% aqueous NaOH (3 eq) were mixed into the vessel and the mixture was slowly added to the solution with stirring in the flask.

  The reaction mixture thus obtained was heated to 90 ° C. and reacted for 1 hour to completely consume 4,4 ′-(9-fluorenylidene) diphenol and 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 with stirring. The organic layer was then separated, washed 2 or 3 times with 300 ml distilled water, dried over magnesium sulfate and distilled under reduced pressure to remove dichloromethane. The mixture was recrystallized using a mixture of dichloromethane and methanol to give the title compound, the epoxy resin compound.

Step (2): (((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy)) bis (2-hydroxypropane-3,1-diyl) diacrylate (CAS number Preparation of 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. While sending air at a flow rate of 25 ml / min, the mixture was heated to 90-100 ° C. and further heated to 120 ° C. to completely dissolve. The reaction mixture was stirred for about 12 hours until the acid value dropped below 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 2 or 3 times with 300 ml of distilled water, dried over magnesium sulfate and distilled under reduced pressure to remove dichloromethane, thereby yielding the title compound.

Step (3): Preparation of Compound Derived from Epoxy Resin and having Cardo Main Chain Structure The compound obtained in step (2) in PGMEA was charged into a 1,000 ml three-necked flask, , 4,5-benzenetetracarboxylic dianhydride (0.75 equivalent), 1,2,3,6-tetrahydrophthalic anhydride (0.5 equivalent), and triphenylphosphine (0.01 equivalent). It was further charged. The reaction mixture was heated to 120-130 ° C. with stirring for 2 hours, cooled to 80-90 ° C., and then stirred and heated for 6 hours. After the mixture was cooled to room temperature, a solution of polymer (E) (49 wt% solids) having a weight average molecular weight (Mw) of 6,000 g / mol and an acid number of 107 mg KOH / g (based on solids) was obtained. Obtained.

Preparation Example 3: Preparation of colored dispersion-(1)
The colored dispersion (D-1) is manufactured by Tokushiki Co. , Ltd. and the dispersion was prepared as follows.

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

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

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

  Using the compounds prepared in the above preparation examples, photosensitive resin compositions were prepared 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-based photopolymerization initiator (C-1): (E) -2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine (manufacturer: PHARMASYNTHESE, trademark: TRIAZIN-Y)

  Oxime-based photopolymerization initiator (C-2): N-1919 produced by ADEKA

  Ketone-based 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 As copolymer (A), 100 parts by weight of the copolymer obtained in Preparation Example 1 (solid content), 163.2 parts by weight of photopolymerizable compound (B), 7. 1 part by weight of triazine photopolymerization initiator (C-1), 8.6 parts by weight of oxime photopolymerization initiator (C-2), 8.9 parts by weight of ketone photopolymerization initiator (C-3) ) 249.8 parts by weight of the colored dispersion (D-1), 175.4 parts by weight of the polymer (E) of the solution (solid content), and 0.7 parts by weight of the surfactant (G). Thereafter, a solvent (H) was added thereto so that the solid content reached 19% by weight. The composite was mixed for 2 hours using a shaker, thereby preparing a liquid phase colored photosensitive resin composition.

Examples 2 to 10 and Comparative Examples 1 to 5 Preparation of Colored Photosensitive Resin Compositions Colored photosensitivity except that the composition of the resin composition and the amount of the composition were changed as shown in Tables 1 and 2 below. 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 Each of the colored photosensitive resin compositions obtained in Examples and Comparative Examples was coated on a glass substrate using a spin coater, and 150 ° C at 95 ° C. Pre-baked for 2 seconds 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, and the pattern mask is 100% full tone (F / T) column spacer (CS) pattern and 30% halftone ( H / T) Black matrix (BM) pattern was included. Thereafter, using an aligner (trade name: MA6) that emits light having a wavelength of 200 nm to 450 nm, the coated film is irradiated at a dose of 66 mJ / cm ² based on a wavelength of 365 nm for a certain period of time. Irradiated with rate light. It was then developed at 23 ° C. with an aqueous potassium hydroxide solution diluted to a concentration of 0.04% by weight until the unexposed areas were thoroughly washed. The pattern formed in this way is post-baked in an oven at 230 ° C. for 30 minutes, a light-shielding spacer (ie, a patterned portion), and a cured film having a thickness of 3.0 μm (± 0.1 μm) (ie, , 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 pre-baking temperature In the above process for preparing a cured film, the pre-baking temperature was changed to 80 ° C. or 100 ° C., and evaluation was performed under the same conditions as described above. Next, the non-exposed portion was thoroughly cleaned with an aqueous potassium hydroxide solution diluted to a concentration of 0.04% by weight at 23 ° C. (until the O-ring portion of the developing device stage was completely visible behind the substrate). Time was measured. In addition, changes in development time for each change in prebake temperature were converted and recorded.

(2) Measurement of surface characteristics (contact type thickness measurement)
Using the SCAN PLUS, which is an α-step instrument (alpha-step surface profile measuring device), the vibration value of the vertical movement of the equipped probe is recorded on the surface of the cured film thus prepared. 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 thus prepared (ie, the unpatterned portion) was measured using an optical densitometer (361T manufactured by Xlite), The optical density based on a thickness of 1 μm was determined.

(4) Measurement of elastic recovery rate A cured film having a total thickness of 3.0 [mu] m (± 0.1 [mu] m) and a spacer dot pattern diameter of 30 to 35 [mu] m during post-baking by the method for preparing the cured film described above. Prepared. Using an elastic instrument (FISCHERSCOPE (registered trademark) HM2000LT, Fisher Technology), the compression displacement and the elastic recovery rate were measured under the following measurement conditions.

Specifically, a square 50 μm × 50 μm planar Vickers indenter was used as an indenter for pressing the pattern. Measurements were made by the load / unload method. After applying a 1.96 mN load on the dot pattern using the elastic instrument described above, we will define it as the initial state (H0) in order to measure the mechanical properties of compression displacement and elastic recovery. Next, the load applied on each pattern sample was increased at a speed of 5 mN / second, increased by 300 mN in the thickness direction, maintained for 5 seconds, and the distance (H1) moved by the indenter was measured. Upon completion of the 5 second hold, the load was released at a rate of 5 mN / sec in the thickness direction. When the force applied to the dots 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 having 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. Thereafter, the substrate was removed from the NMP solution, and the absorbance of the NMP solution was measured at 437 nm.

(6) Measurement of level difference According to the method for preparing a cured film as described above, a spacer part (A) and a black matrix part (B) were obtained (see FIG. 1). The thicknesses of A and B were measured using a step measuring instrument (SNU (SIS-2000), SNU Precision). In such an event, when the difference in thickness (i.e., AB) is in the range of 1.0 to 2.0 [mu] m, the step characteristics are expected to be excellent.

  The results obtained in the above test examples are summarized in Table 3 below, and photographs of the surface of the cured film are shown in FIGS.

  As shown in Table 3 and FIGS. 2-5, the compositions of the examples falling within the scope of the present invention have minimized uneven wrinkles on their surface, excellent elastic recovery and excellent In addition to providing a cured film having high chemical resistance, development in a short period of time is also possible. In contrast, comparative compositions that were not within the scope of the present invention showed at least one adverse result.

Reference number of drawing A: Thickness of column spacer part B: Thickness of black matrix part C: Critical dimension (CD) of column spacer part

Claims (14)

A colored photosensitive resin composition comprising:
(A) a copolymer containing an epoxy group;
(B) a photopolymerizable compound containing a double bond;
(C) a photopolymerization initiator;
(D) a colorant containing a black inorganic colorant,
The colorant comprises 50 to 100% by weight of the black inorganic colorant, based on the total weight of the solids of the colorant;
A colored photosensitive resin composition, wherein a molar ratio of the double bond in the photopolymerizable compound (B) to the epoxy group in the copolymer (A) satisfies the following relationship.
4 ≦ mole number of double bond / mole number of epoxy group ≦ 35   The colored photosensitive resin composition according to claim 1, wherein the black inorganic colorant includes at least one selected from the group consisting of carbon black, titanium black, Cu—Fe—−n-based oxide, and metal oxide. object.   The colored photosensitive resin composition according to claim 1, wherein the colorant contains a black organic colorant.   The colorant includes a dispersion resin, and the dispersion resin has an amine value of 3 mgKOH / g or less and includes 50 mol% or less of a maleimide monomer based on the total number of moles of structural units. The colored photosensitive resin composition described in 1.   The colored photosensitive resin composition according to claim 1, wherein the cured film formed from the colored photosensitive resin composition has an optical density of 1.0 / μm to 3.0 / μm.   (E) The colored photosensitive resin composition according to claim 1, further comprising a compound derived from an epoxy resin and having a double bond. The molar ratio of the double bond in the photopolymerizable compound (B) and in the compound (E) derived from the epoxy resin with respect to the epoxy group in the copolymer (A) satisfies the following relationship: The colored photosensitive resin composition according to claim 6.
4 ≦ mole number of double bond / mole number of epoxy group ≦ 35   The colored photosensitive resin composition according to claim 1, further comprising (F) an epoxy compound. 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) satisfies the following relationship. Colored photosensitive resin composition.
4 ≦ mole number of double bond / mole number of epoxy group ≦ 35   The colored photosensitive resin composition according to claim 6, further comprising (F) an epoxy compound. The molar ratio of the double bond in the photopolymerizable compound (B) and in the compound (E) derived from the epoxy resin to the epoxy group in the copolymer (A) and the epoxy compound (F). The colored photosensitive resin composition according to claim 10, wherein the following relationship is satisfied.
4 ≦ mole number of double bond / mole number of epoxy group ≦ 35   The colored photosensitive resin composition according to claim 1, wherein the cured film formed from the 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 colored photosensitive resin composition according to claim 1, wherein the organic solvent has an absorbance at 437 nm of 0.5 or less.   The light-shielding spacer produced | generated from the colored photosensitive resin composition of Claim 1.