TW201439293A - Colored photosensitive resin composition suitable for both column spacer and black matrix - Google Patents

Abstract

A colored photosensitive resin composition comprising a copolymer, an epoxy resin compound or a compound derived therefrom, a polymerizable compound, a photopolymerization initiator, and a coloring agent including a black coloring agent and a blue coloring agent, is provided. When the colored photosensitive resin composition is formed into a cured layer, good transmittance and optical density as well as good elastic recovery ratio, resolution, chemical resistance, and thickness may be obtained. Thus, the colored photosensitive resin composition may be formed into a column spacer, a black matrix, or a black column spacer, and may be used in various electronic parts such as the panel of an organic light-emitting diode display and a liquid crystal display device.

Description

Colored photosensitive resin composition suitable for both column spacers and black matrix

The present invention relates to a colored photosensitive resin composition suitable for forming a passivation layer, an interlayer dielectric, a spacer, a light shielding member used in an organic light emitting diode (OLED) display or a liquid crystal display (LCD) panel, and from the composition The solidified layer formed by the object is, in particular, a black column spacer (BCS) in which the column spacers are integrated with the black matrix.

Recently, spacers formed from photosensitive compositions are used to maintain the distance between the upper and lower transparent substrates in the liquid crystal cell of a liquid crystal display (LCD). Since the LCD is an optoelectronic device that is driven by applying a voltage to a liquid crystal material injected into a constant gap between two transparent substrates, the maintenance of a constant gap between the two substrates is very important. If the gap between the transparent substrates is non-constant, the voltage applied thereto and the light transmittance penetrating the portion may change, resulting in a defect in spatial brightness unevenness. In view of the recent preference for large-sized LCD panels, the maintenance of a constant gap between two transparent substrates becomes even more critical.

The spacer may be formed by coating the photosensitive resin composition onto the substrate, and exposing the coated substrate having the mask thereon to ultraviolet light or the like, followed by development thereof. Recently, the company is committed to using light shielding materials for spacers. However, the development of colored photosensitive resin compositions has been actively carried out.

Korean Patent Publication No. 2006-125993 discloses a method for simultaneously forming a passivation layer of a color filter and a column spacer for an LCD, and a negative-type photoresist composition which can be used in the method, and more specifically, reveals A method of forming a color filter passivation layer (that is, an insulating layer) and a column spacer from a composition having a photopolymerization initiator mainly composed of phosphine oxide and a binder mainly composed of propylene oxide.

In addition, the method is simplified by developing a black column spacer (BSC), wherein the column spacer and the black matrix system are integrated into one module. However, the BCS must satisfy the properties of the black matrix, such as light shielding properties, as well as the properties required for the column spacers, such as elastic recovery and chemical resistance. Thus, it is further required to develop studies of colored photosensitive resin compositions suitable for such purposes.

Accordingly, it is an object of the present invention to provide a colored photosensitive resin composition which simultaneously satisfies the properties of a column spacer and a black matrix.

According to an aspect of the present invention, there is provided a colored photosensitive resin composition comprising (a) a copolymer, (b) an epoxy resin compound or a compound derived therefrom, (c) a polymerizable compound, (d) photopolymerization a starter, and (e) a colorant comprising 0 to 5% by weight of an inorganic black colorant, 10 to 40% by weight of an organic black colorant, and 1 to 1 based on the total solid content of the colored photosensitive resin composition 15% by weight blue colorant.

According to another aspect of the present invention, there is provided a column spacer, a black matrix, or a black column spacer (BCS) formed from the colored photosensitive resin composition.

According to still another aspect of the present invention, an electronic component comprising the column spacer, a black matrix, or a black column spacer (BCS) is provided.

The colored photosensitive resin composition of the present invention has a good exposure limit and development limit, and when formed into a cured layer, properties such as transmittance and optical density for a black matrix, and properties such as elastic recovery rate and resolution for a column spacer Degree, chemical resistance, and coating thickness provide equally satisfactory properties. Therefore, the composition is useful for forming colored spacers, black matrix, BCS, etc., which can be used for various electronic components such as OLED displays and panels of LCDs.

A‧‧‧ Thickness of column spacers

B‧‧‧Thickness of black matrix parts

C‧‧‧ Critical dimension of column spacers (CD)

The above and other objects and features of the present invention will become more apparent from the following description of the accompanying drawings in which <RTIgt; Schematic diagram of the example (A: thickness of the column spacer member; B: thickness of the black matrix member; and C: critical dimension (CD) for the column spacer member).

Hereinafter, the present invention will be described in further detail.

Colored photosensitive resin composition

According to a specific embodiment of the present invention, the colored photosensitive resin composition comprises (a) a copolymer, (b) an epoxy resin compound or a compound derived therefrom, (c) a polymerizable compound, (d) a photopolymerization initiator, And (e) a colorant comprising a black colorant and a blue colorant, and optionally, (f) a solvent, (g) a surfactant, and/or (h) a decane coupling agent.

In the present specification, "(meth)acryloyl" means "acryloyl" and/or "methacryloyl", and "(meth)acrylate" means "acrylate" and / or "A" Acrylate".

Hereinafter, the respective components of the colored photosensitive resin composition will be explained in detail.

(a) copolymer

The copolymer used in the present invention may comprise (a-1) a unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a mixture thereof; and (a-2) an olefin derived from an aromatic ring-containing a unit of a saturated compound; and may further comprise (a-3) a unit derived from an ethylenically unsaturated compound which is different from (a-1) and (a-2).

The copolymer is an alkali-soluble resin which provides a developing function in a developing step, and serves as a base for forming a coating layer and as a structure for forming a final pattern.

(a-1) a unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a mixture thereof

In the present invention, the unit (a-1) is derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a mixture thereof. The ethylenically unsaturated carboxylic acid and the ethylenically unsaturated carboxylic anhydride are polymerizable unsaturated monomers having at least one carboxyl group in the molecule. Examples thereof include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, etc.; unsaturated dicarboxylic acids and anhydrides thereof such as maleic acid, maleic anhydride , fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, methyl fumaric acid, etc.; trivalent or higher valence unsaturated polycarboxylic acid and its anhydride; Or a monovalent [(meth) propylene decyloxyalkyl] ester of a polyvalent carboxylic acid, such as succinic acid mono [2-(methyl) propylene decyloxyethyl] ester, citric acid mono [2-(Methyl) propylene decyloxyethyl] ester or the like. The unit derived from the above exemplified compound may be contained in the copolymer in a single compound or in a combination of two or more compounds.

The unit (a-1) may be used in an amount of 5 to 65 mol%, and preferably 10 to 50 mol%, based on the total number of moles of the unit constituting the copolymer. The developing property is easily maintained within this amount range.

(a-2) Unit derived from an ethylenically unsaturated compound containing an aromatic ring

The unit (a-2) is derived from an ethylenically unsaturated compound containing an aromatic ring. Embodiment May include phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, p-nonyl phenoxy Polyethylene glycol (meth) acrylate, p-nonyl phenoxy polypropylene glycol (meth) acrylate, tribromophenyl (meth) acrylate; styrene; styrene having an alkyl substituent, such as Methylstyrene, dimethyl styrene, trimethylstyrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl Styrene, octyl styrene, etc.; styrene with halogen, such as fluorostyrene, chlorostyrene, bromostyrene, iodine styrene, etc.; styrene having an alkoxy substituent, such as methoxystyrene, Ethoxystyrene, propoxystyrene, etc.; 4-hydroxystyrene, p-hydroxy-α-methylstyrene, ethyl styrene styrene; vinyl toluene, divinyl benzene, vinyl phenol, neighbor -vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidol Ether, m - vinylbenzyl glycidyl ether, p - vinylbenzyl glycidyl ether.

The unit derived from the above exemplified compound may be contained in the copolymer in a single compound or in a combination of two or more compounds.

Among these compounds, styrene-based compounds are preferred in view of their polymerizability.

The unit (a-2) may be used in an amount of 2 to 70 mol%, and preferably 5 to 60 mol%, based on the total number of moles of the unit constituting the copolymer. The resin composition may have favorable chemical resistance within this amount range.

(a-3) A unit derived from an ethylenically unsaturated compound which is different from (a-1) and (a-2).

The copolymer used in the present invention may further contain, in addition to (a-1) and (a-2), a unit derived from an ethylenically unsaturated compound different from (a-1) and (a-2). its Examples may include unsaturated carboxylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (methyl) Isobutyl acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyl (meth)acrylate Ethyl ester, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glyceryl (meth)acrylate, α- Methyl hydroxymethyl methacrylate, ethyl α-hydroxyethyl methacrylate, propyl α-hydroxy methacrylate, butyl α-hydroxy methacrylate, 2-methoxyethyl (meth)acrylate, (methyl) ) 3-methoxybutyl acrylate, ethoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, Poly(ethylene glycol) methyl ether (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, Octafluoropentyl methacrylate, (meth) acrylate Anthracene ester, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, ( Dicyclopentenyloxyethyl methacrylate, etc.; tertiary amine having N-vinyl group, such as N-vinylpyrrolidone, N-vinylcarbazole, N-vinylmorpholine, etc.; Saturated ethers such as vinyl methyl ether and vinyl ethyl ether; ethylenically unsaturated compounds having an epoxy group such as glycidyl (meth)acrylate, 3,4-epoxy (meth)acrylate Butyl ester, 4,5-epoxypentyl (meth)acrylate, 5,6-epoxyhexyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, (A) 2,3-epoxycyclopentanyl acrylate, 3,4-epoxycyclohexyl (meth)acrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, acrylic acid --n-butyl glycidyl ester, N-(4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl)propenylamine, N-(4-(2,3) -Epoxypropoxy)-3,5-dimethylphenylpropyl)propenylamine, 4-hydroxy(meth)acrylate Butyl ester glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, etc.; unsaturated quinone imine, such as N-phenyl maleimide, N-(4-chloro Phenyl) maleimide, N-(4-hydroxyphenyl) maleimide, N-cyclohexylmethyleneimine, and the like.

The unit derived from the above exemplified compound may be contained in the copolymer in a single compound or in a combination of two or more compounds.

In view of its copolymerizability and improvement for the strength of the insulating layer, it is preferred to use a unit derived from an ethylenically unsaturated compound having an epoxy group and/or an unsaturated quinone imine, and more preferably a derivative may be used. A unit derived from glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and/or N-substituted maleimide.

The unit (a-3) may be used in an amount of 10 to 80 mol%, and preferably 20 to 75 mol%, based on the total number of moles of the unit constituting the copolymer. Within this dosage range, the stability of the binder can be maintained and the residual rate of the coating can be improved.

The copolymer having the aforementioned units (a-1) to (a-3) may include (meth)acrylic acid/styrene copolymer, (meth)acrylic acid/benzyl (meth)acrylate copolymer, (methyl) Acrylic/styrene/methyl (meth) acrylate copolymer, (meth) acrylate / styrene / methyl (meth) acrylate / glycidyl (meth) acrylate copolymer, (meth) acrylate / benzene Ethylene/methyl (meth)acrylate/glycidyl (meth)acrylate/N-phenyl maleimide copolymer, (meth)acrylic acid/styrene/methyl (meth)acrylate/ Glycidyl (meth)acrylate/N-cyclohexylmethylene iodide copolymer, (meth)acrylic acid/styrene/n-butyl (meth)acrylate/glycidyl (meth)acrylate/ N-phenyl maleimide copolymer, (meth)acrylic acid/styrene/glycidyl (meth)acrylate/N-phenyl maleimide copolymer, and the like.

One or more kinds of the copolymer may be contained in the colored photosensitive resin composition.

The copolymer may have a weight average molecular weight (Mw) of from 3,000 to 50,000, preferably from 5,000 to 40,000, as measured by gel permeation chromatography (eluent: tetrahydrofuran, etc.) based on polystyrene. Within this range, adhesion to the substrate, physical/chemical properties, and viscosity may be desirable.

The content of the copolymer in the colored photosensitive resin composition may be from 0.5 to 60% by weight, preferably from 5 to 4, based on the total weight of the colored photosensitive resin composition excluding the solvent (i.e., based on the solid content). 50% by weight. Within the foregoing range, a pattern having a good shape can be obtained after development, and properties such as chemical resistance can be improved.

The copolymer can be prepared by placing a molecular weight controlling agent, a radical polymerization initiator, a solvent, and units (a-1) to (a-3) in a reactor; injecting nitrogen into the reactor and stirring slowly The mixture is polymerized.

The molecular weight controlling agent is not particularly limited, and may include a mercaptan such as butyl mercaptan, octyl mercaptan or the like, or an α-methylstyrene binary.

The radical polymerization initiator is not particularly limited, and may include an azo compound such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy 2,4-dimethylvaleronitrile), etc., benzamidine peroxide, laurel peroxide, third butyl peroxypivalate, 1,1 - bis (tert-butyl peroxy) cyclohexane and the like. The radical polymerization initiator may be used singly or in combination of two or more.

Further, any solvent used for the preparation of the copolymer may be used, and it may include, for example, propylene glycol monomethyl ether acetate (PGMEA).

(b) an epoxy resin compound or a compound derived therefrom

The colored photosensitive resin composition of the present invention comprises an epoxy resin compound or a compound derived therefrom, preferably an epoxy resin compound having a dienthene main chain structure or a compound derived therefrom. A compound having an average molecular weight (Mw) of 400 to 10,000 by weight as measured by gel permeation chromatography using polystyrene as a reference can be used as an epoxy resin compound, and the compound can be represented by the following formula 1 An epoxy resin compound having a benzopyran backbone structure:

The carbons marked with * are independently marked with * and included ,or The carbon substitution; the L ¹ groups are 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, C _1-10 alkoxy, C _2-10 alkenyl, or C _6-14 aryl; R ₈ is H, methyl, ethyl, CH ₃ CHCl-, CH ₃ CHOH- , CH ₂ =CHCH ₂ -, or phenyl; and n is an integer from 0 to 10.

Specific examples of the C _1-10 alkylene group may include methylene, ethyl, propyl, isopropyl, butyl, isobutyl, butyl, and butyl. , pentyl group, isoamyl group, third pentyl group, hexyl group, heptyl group, octyl group, octyl group, octyl group, 2-ethyl hexyl group, thiophene group, stretching壬 base, stretch base, stretch base, etc. Specific examples of the C _3-20 cycloalkyl group may include a cyclopropyl group, a cyclobutene butyl group, a cyclopentylene group, a cyclohexylene group, a cycloheptyl group, a decahydronaphthyl group, an adamantyl group, and the like. Specific examples of the C _1-10 alkyleneoxy group may include a methyleneoxy group, an ethyloxy group, a propyloxy group, a butyloxy group, a second butyloxy group, and a third embodiment. Butyloxy, pentyloxy, hexyloxy, heptanoyloxy, octyloxy, 2-ethyl-extended hexyloxy and the like. Specific examples of the C _1-10 alkyl group may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, t-butyl, pentyl, isopentyl, Tripentyl, hexyl, heptyl, octyl, isooctyl, trioctyl, 2-ethylhexyl, decyl, isodecyl, decyl, isodecyl and the like. Specific examples of the C _1-10 alkoxy group may include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a second butoxy group, a third butoxy group, a pentyloxy group, a hexyloxy group, and a hexylene group. Oxyl, octyloxy, 2-ethyl-hexyloxy and the like. Specific examples of the C _2-10 alkenyl group may include a vinyl group, an allyl group, a butenyl group, a propenyl group, and the like. Specific examples of the C _6-14 aryl group may include phenyl, tolyl, xylyl, naphthyl and the like.

A compound derived from an epoxy resin having a dibenzopyran main chain structure of Formula 1 can be obtained by allowing an epoxy resin having a dibenzopyran main chain structure of Formula 1 and an unsaturated base. The epoxy acid adduct is produced by an acid reaction, and the epoxy adduct thus obtained is reacted with a polybasic acid anhydride; or the compound thus obtained is additionally reacted with a monofunctional or polyfunctional epoxy compound. Any of the unsaturated basic acid acids known in the art to which the invention pertains, such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, and the like, can be used in the present invention. Any polybasic acid anhydride known in the art to which the invention pertains, such as succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like, can be used in the present invention. Any of the monofunctional or polyfunctional epoxy compounds known in the art to which the invention pertains, such as methacryl Acid glycidyl ester, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, bisphenol Z glycidyl ether, etc. Both can be used in the present invention.

When a compound derived from an epoxy resin having a dibenzopyran backbone structure of Formula 1 is used, the dibenzopyran backbone structure can improve the adhesion, alkali resistance, processability, and adhesion of the cured material to the substrate. The strength and the like, and once the uncured portion is removed by development, a pattern having a fine resolution image can be formed.

The epoxy resin compound or the compound derived therefrom may be used in an amount of from 1 to 70% by weight, preferably from 5 to 50, based on the total amount of the photosensitive resin composition excluding the solvent (i.e., based on the solid content). weight%. Within this range, the resolution and chemical resistance can be improved, the pattern shape can be well maintained, and a step difference between patterns having a desired boundary width (i.e., allowable width) can be advantageously obtained. .

(c) polymerizable compound

The polymerizable compound used in the present invention may be any compound which can be polymerized by a polymerization initiator, and may be a polyfunctional monomer, oligomer or polymer which is commonly used for a colored photosensitive resin composition.

More specifically, the polymerizable compound may include a monofunctional or polyfunctional ester compound of acrylic acid or methacrylic acid having at least one ethylenically unsaturated double bond, and may have at least two functional groups to obtain a desired chemical resistance. a polyfunctional compound.

The polymerizable compound may be selected from the group consisting of ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol. Alcohol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerol (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate and succinic acid monoester, pentaerythritol tetra (methyl ) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and succinic acid monoester, caprolactone modified dipentaerythritol Hexa(meth)acrylate, pentaerythritol triacrylate hexamethylene diisocyanate (reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol hepta (meth) acrylate, tripentaerythritol VIII (a) Acrylate, bisphenol A epoxy acrylate, ethylene glycol monomethyl ether acrylate, and mixtures thereof, but are not limited thereto.

The polymerizable compound may be used in an amount of 1 to 60% by weight, preferably 5 to 45% by weight based on the total amount of the photosensitive resin composition excluding the solvent (i.e., based on the solid content). Within this range, it is easy to generate a pattern, and it is possible to prevent defects in the shape of the pattern during development, such as scum at the bottom.

(d) Photopolymerization initiator

Any known polymerization initiator can be used as the photopolymerization initiator of the present invention.

The photopolymerization initiator may be selected from the group consisting of acetophenones, non-imidazoles, and tri- Classes, strontium salts, benzoin, benzophenones, diketones, α-diketones, polynuclear steroids, thioxanthones, diazonium compounds, sulfhydrazine sulfonates , terpenoids, oxazoles, bismuth borate, and mixtures thereof.

Among the foregoing compounds, preferred are disclosed in Korean Patent Publication No. 2004-7700, 2005-84149, 2008-83650, 2008-80208, 2007-44062, 2007-91110, 2007-44753, 2009-9991, 2009-93933. No. 2010-97658 or 2011-59525, or PCT publication WO 2010/102502, or WO 2010/133077. In addition, it is preferable to use commercially available materials such as Ou Xi (OXE)-01 and Ou Xi -02 (Ciba Co.), N-1919 (ADEKA Co.), etc., and preferably used to obtain high sensitivity and resolution.

The polymerization initiator may be used in an amount of from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, based on the total amount of the photosensitive resin composition excluding the solvent (i.e., based on the solid content). Within this range, curing by transmission exposure can be sufficiently performed, whereby the spacer pattern can be easily formed, and the spacer thus formed can be sufficiently adhered to the substrate during development.

(e) colorant

A colorant is included in the colored photosensitive resin composition of the present invention to provide light shielding properties.

The coloring agent used in the present invention may be a mixture of two or more of an inorganic coloring agent or an organic coloring agent, preferably a coloring agent having high coloring properties and heat resistance. In particular, the use of a mixture of two or more organic colorants can be beneficial to prevent light leakage from escaping from the black matrix and to ensure transmittance for mask alignment.

Further, the colorant contains a black colorant and a blue colorant. The black colorant can be a black inorganic colorant and/or a black organic colorant.

Any of the black inorganic colorants, black organic colorants, and blue colorants known in the art can be used, for example, in color index (printed by The Society of Dyers and Colourists). Compounds classified as pigments and any of the dyes known in the art to which the invention pertains can be used.

Specific examples of the black inorganic colorant may include carbon black, titanium black, a metal oxide such as an oxide mainly composed of Cu-Fe-Mn, synthetic iron black, and the like. Preferred among these are carbon blacks for obtaining desired pattern properties and chemical resistance.

Further, specific examples of the black organic colorant may include nigrosine, indoleamine black, indigo, and the like. Among them, mesamine black (for example, black 582 of FASF Corporation) for obtaining desired optical density, penetrability, transmittance, and the like is preferable.

Specific examples of the blue colorant may include C.I. Pigment Blue 15:6, C.I. Pigment Blue 15:4, C.I. Pigment Blue 60, C.I. Pigment Blue 16, and the like. Preferred among them are C.I. Pigment Blue 15:6 for preventing light from escaping.

The amount of the black inorganic colorant, the black organic colorant, and the blue colorant may be 0 to 5% by weight, respectively, based on the total amount of the photosensitive resin composition excluding the solvent (that is, based on the solid content). 10 to 40% by weight and 1 to 15% by weight. Within this range, it is possible to have a high optical density, thereby preventing light from escaping, and the transmittance required for the mask alignment is also desirable, for example, less than 15% at 730 nm and less than 15% at 900 nm.

Meanwhile, a dispersant for dispersing a colorant can be used for the colored photosensitive resin composition of the present invention. Examples of the dispersing agent may include any of the known dispersing agents of the coloring agent. Specific examples may include a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a quinone-based surfactant, a fluorine-based surfactant, and the like. Commercially available dispersants may be from Disperbyk-182, -183, -184, -185, -2000, -2150, -2150, -2155, -2163 from BYK Co. Or -2164. These compounds may be used singly or in combination of two or more. The dispersing agent may be added to the coloring agent by surface treatment of the coloring agent using a dispersing agent, or may be added together with the coloring agent during preparation of the colored photosensitive resin composition.

Alternatively, the colorant may be mixed with a binder for the preparation of a colored photosensitive resin composition. In this case, the binder may be the copolymer (a) described in the present invention, known a copolymer, or a mixture thereof.

Therefore, the color former used in the present invention can be added to the colored photosensitive resin composition in the form of a colored dispersion (colored abrasive base) obtained by mixing a colorant with a dispersant, a binder, a solvent, or the like.

(f) solvent

The colored photosensitive resin composition of the present invention is preferably prepared into a liquid composition by mixing the above components with a solvent. Any of the solvents known in the art to which the invention pertains can be used for the colored photosensitive resin composition which is compatible with the components of the colored photosensitive resin composition, but is non-reactive.

Examples of the solvent may include glycol ethers such as ethylene glycol monoethyl ether or the like; ethylene glycol alkyl ether acetate such as ethyl cellosolve acetate; and the like; esters such as ethyl 2-hydroxypropionate and the like; Diethylene glycols such as diethylene glycol monomethyl ether; and propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate; propylene glycol propyl ether acetate. The solvent may be used singly or in combination of two or more.

The amount of the solvent to be used is not particularly limited, but may be determined so that the total concentration of each component excluding the solvent in the composition (that is, based on the solid content) is usually 5 to 70% by weight, preferably 10 to 55% by weight. In order to finally obtain the dispersibility and stability of the colored photosensitive resin composition.

(g) surfactant

If desired, the colored photosensitive resin composition of the present invention may further comprise a surfactant to improve coating properties and prevent generation of defects.

The type of the surfactant is not particularly limited, and for example, a fluorine-based surfactant or a ruthenium-based surfactant can be used.

Commercially available 界面-based surfactant is obtained from Dow Corning Dongli Poly Oxygen Company (Dow Corning Toray Silicone Co.) DC3PA, DC7PA, SH11PA, SH21PA and SH8400, TSF-4440, TSF-4300, TSF-4445, TSF-4446 from GE Toshiba Silicones Co. , TSF-4460 and TSF-4452, from the BAK 333 of the BAK company. These compounds may be used singly or in combination of two or more. Commercially available fluorine-based surfactants are Megafac F-470, F-471, F-475, F-482, F from Dainippon Ink Kagaku Kogyo Co. -489 and so on. Among them, the BAK 333 from the BAK company can be preferably used for obtaining dispersibility.

The surfactant may be used in an amount of from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, based on the total amount of the photosensitive resin composition excluding the solvent (i.e., based on the solid content). Within this range, the colored photosensitive resin composition is easily applied.

(h) decane coupling agent

If desired, the colored photosensitive resin composition of the present invention may further comprise a decane coupling agent having a selected from the group consisting of a carboxyl group, a (meth) acrylonitrile group, an isocyanate group, an amine group, a decyl group, a vinyl group, and a ring. A reactive substituent of the group consisting of an oxy group and a combination thereof improves the adhesion to the substrate.

The type of the decane coupling agent is not particularly limited, but is preferably selected from the group consisting of trimethoxydecylbenzoic acid, γ-methylacryloxypropyltrimethoxydecane, and vinyl. Triethoxydecane, vinyltrimethoxydecane, γ-isocyanatopropyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyl Ethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, phenylaminotrimethoxydecane, and mixtures thereof. Among them, γ-isocyanatopropyltriethoxydecane having an isocyanate group (for example, KBE-9007 from Shin-Etsu Co.) or phenylaminotrimethoxydecane For comparison Preferably, it has good chemical resistance and adhesion to the substrate.

The decane coupling agent may be used in an amount of from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight based on the total amount of the photosensitive resin composition excluding the solvent (i.e., based on the solid content). Within this range, the adhesion of the colored photosensitive resin composition can be improved.

Further, other additives such as an antioxidant, a stabilizer, and the like may be included only when the physical properties of the colored photosensitive resin composition are not deteriorated.

When a cured layer is formed from the colored photosensitive resin composition of the present invention, properties of the black matrix such as transmittance and optical density, and columnar spacer properties such as elastic recovery, resolution, chemical resistance, and coating thickness are the same Satisfactory. As such, both the exposure limit and the development limit are desirable. In particular, when a cured layer having a thickness of 1 μm is formed from the colored photosensitive resin composition of the present invention, an optical density of 0.6 to 1.5, more precisely, an optical density of 0.6 to 1.4 can be achieved. In addition, when a cured layer having a thickness of 1.5 to 2.5 μm is formed, a transmittance of less than 15% can be achieved at a wavelength of 730 nm; and when a cured layer having a thickness of 3.5 to 4.5 μm is formed, less than 15 can be achieved at a wavelength of 900 nm. % transmittance. Therefore, the colored photosensitive resin composition of the present invention can simultaneously form a columnar spacer and a black matrix, thereby shortening the processing time.

Method for preparing colored photosensitive resin composition

The colored photosensitive resin composition containing the aforementioned components according to the present invention can be produced by a conventional method, and a specific embodiment thereof will be explained below.

First, the colorant and the solvent are mixed in advance, and dispersed in a ball mill or the like until the average diameter of the colorant becomes a desired size. At this stage, a surfactant may be added if desired, and some or all of the copolymer may be added. The copolymer, the epoxy resin compound or a compound derived therefrom, a polymerizable compound, and a photopolymerization initiator are added to the dispersion. Additives such as decane coupling if desired Or an additional solvent to adjust the concentration of the mixture. The mixture is then thoroughly stirred to obtain the desired colored photosensitive resin composition.

Column spacers, black matrix, and BCS

According to the present invention, a columnar spacer and a black matrix formed from a colored photosensitive resin composition are provided. In particular, the present invention provides an integrated black column spacer (BCS) formed from a colored photosensitive resin composition. Specific embodiments of the BCS pattern are illustrated in Figure 1.

The column spacers, black matrix or BCS can be formed by steps of forming a coating, exposure, development, and heat treatment.

In the coating forming step, the colored photosensitive resin composition of the present invention is applied to the pretreated substrate to a desired thickness by spin coating or slit coating, roll coating, screen printing, applicator method, or the like. For example, 2 to 25 microns, and then pre-cured at 70 to 100 ° C for 1 to 10 minutes to remove the solvent and form a coating.

In order to form the pattern of the coating thus obtained, 200 to 500 nm of activating light is irradiated after a mask having a certain shape has been placed thereon. At this stage, in order to obtain an integrated BCS, a mask having a pattern of different transmittances can be used to simultaneously form a column spacer and a black matrix. As the light source for exposure, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, an argon laser or the like can be used; and if necessary, X-rays, electron beams, or the like can also be used. The dose may vary depending on the kind and mixing ratio of the components of the composition and the thickness of the dried layer. When a high pressure mercury lamp is used, the dose may be 500 millijoules per square centimeter (mJ/cm ² ) or less (at a wavelength of 365 nanometers).

After the exposure step, a development step using an alkaline aqueous solution such as sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide or the like is performed to remove the unnecessary portion by dissolving the unnecessary portion, thereby allowing the exposure to be left behind. Partially patterned. Obtained by development The image pattern was cooled to room temperature and baked in a hot air circulating type drying oven at 180 to 250 ° C for 10 to 60 minutes, thereby obtaining a final pattern.

The column spacer, black matrix or BCS thus manufactured can be usefully used for electronic components such as an OLED display, an LCD, etc. due to its good physical properties. As such, electronic components including the column spacer, black matrix, or BCS can be provided in the present invention.

In addition to the spacers in accordance with the present invention, OLED displays, LCDs, and the like can include elements known to those skilled in the art to which the invention pertains. In other words, an OLED display, an LCD or the like in which a columnar spacer, a black matrix or a BCS of the present invention can be employed can be included in the present invention.

Hereinafter, the present invention will be more specifically described by the following examples, but these examples are for illustrative purposes only, and the invention is not limited thereto.

Preparation Example 1: Preparation of Copolymer

100 g of a monomer mixture having the amount shown in Table 1 below, 300 g (g) of PGMEA as a solvent, and 2 g of 2,2'-azo (2,4-dimethyl) as a radical polymerization initiator The valeronitrile was placed in a 500 ml round bottom bottle equipped with a reflux condenser and a stirrer. The temperature was raised to 70 ° C, and the mixture was stirred for 5 hours to carry out polymerization to produce a copolymer. The copolymer thus produced had an acid value of 80 mg of potassium hydroxide per gram (mgKOH/g) and a weight average molecular weight (Mw) of 11,000 as measured by gel permeation chromatography using polystyrene as a reference.

The amounts of the constituent units of the copolymer and the weight average molecular weight of the copolymer are exemplified in Table 1 below.

Preparation Example 2: A compound derived from an epoxy resin having a dibenzopyran main chain structure

125.4 g of spiro[茀-9,9'-dibenzopyran]-3',6'-diol and 0.1386 g of t-butylammonium bromide were placed in a 3000 ml round bottom flask and mixed. An additional 78.6 g of epichlorohydrin was added thereto, and the mixture was heated to 90 ° C to carry out a reaction. After using liquid chromatography to ensure that the snail [茀-9,9'-dibenzopyran]-3',6'-diol is completely consumed, the reaction is cooled to 30 ° C, and slowly added 50 % aqueous sodium hydroxide (3 equivalents). After ensuring complete elution of epichlorohydrin using liquid chromatography, the reaction was extracted with dichloromethane and washed three times. The organic layer was dried over magnesium sulfate, and dichloromethane was evaporated under reduced pressure. The crude product was recrystallized from a dichloromethane/methanol mixture solvent (50:50, v/v).

To 1 equivalent of the epoxy group-based compound thus obtained, 0.004 equivalent of butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalents of acrylic acid were added. Then, 8.29 g of PGMEA solvent was added thereto, followed by mixing the solutions. Air was blown at 25 ml/min to the solution thus prepared, and the solution was heated to 90 to 100 ° C to dissolve the reactant. When the solution was white turbid, the temperature was raised to 120 ° C to completely dissolve the reactants. The acid value was measured as the solution became clear and the viscosity increased, and the solution was stirred until the acid value reached less than 1.0 mgKOH/g. Stirring was continued for 11 hours until the acid value reached the target value (0.8). After the reaction is completed, the reactor temperature is raised. The temperature was lowered to room temperature, and a colorless transparent solid was obtained.

43 g of the solid product thus obtained, 33.6 g of acrylic acid, 0.04 g of 2,6-di-t-butyl-p-cresol, 0.21 g of tetrabutylammonium acetate, and 18 g of PGMEA were placed in the reaction flask, and The mixture was stirred at 120 ° C for 13 hours. Thereafter, the reactant was cooled to room temperature, and 24 g of PGMEA and 10 g of succinic anhydride were added thereto, followed by stirring the mixture at 100 ° C for 3 hours. To the mixture, 8 g of bisphenol Z glycidyl ether was additionally added, and the mixture was stirred at 120 ° C for 4 hours, at 90 ° C for 3 hours, at 60 ° C for 2 hours, and at 40 ° C for 5 hours. Reprecipitation is carried out in water and alcohol to obtain a final resin in a powder state. Then, PGMEA was added to make the solid content 48%. The acid value of the resin thus obtained was 105 mgKOH/g, and the weight average molecular weight (Mw) measured by gel permeation chromatography using polystyrene as a reference was 5,500.

Preparation Example 3: Preparation of Colored Dispersion

The ingredients in the amounts shown in Table 2 below are mixed. In this case, the copolymer obtained in Preparation Example 1 was used as a copolymer, and the indole amine black (black 582) of BASF Co. was used as the organic black, and the polymer dispersant was used (Dissbike-2000). As a dispersing agent, and using PGMEA as a solvent. The mixture thus obtained was dispersed in a paint shaker at 25 to 60 ° C for 6 hours. The dispersion step was carried out using 0.3 mm zirconia beads. After the dispersion step is completed, the beads and the dispersion are separated, whereby the colored dispersions A to C are separately produced.

Examples 1 to 6 and Comparative Examples 1 to 3: Preparation of colored photosensitive resin composition

Copolymer A having a solid content of 31% obtained in Preparation Example 1, a compound derived from an epoxy resin having a dibenzopyran structure obtained in Preparation Example 2, and dipentaerythritol hexaacrylate as a polymerizable compound (DPHA, Nippon Chemical Co., Ltd.) The company (Nippon Kayaku Co.), and the colored dispersions A to C obtained in Preparation Example 3 were mixed in the amounts described in Table 3 below. In addition, 0.04 g of a photoinitiator-based photoinitiator (Ou Xi (OXE)-02, Ciba), 0.0082 g of a surfactant (Bik-333) was mixed by a conventional method. , BC 176, and 7.5176 g of PGMEA as a solvent, and stirring for 5 hours to prepare respective colored photosensitive resin compositions (Examples 1 to 6 and Comparative Examples 1 to 3).

The amounts of the components of the compositions thus prepared in the examples and comparative examples are illustrated in Table 3 below.

Experimental Example 1: Measurement of physical properties of a cured layer formed from a colored photosensitive resin composition

On the glass substrate, various colored photosensitive resin compositions prepared in the examples and the comparative examples were applied by using a spin coater, and pre-cured at 100 ° C for 150 seconds to form a coating layer. A pattern mask having a 100% fully tuned column spacer (CS) pattern and a 30% halftone black matrix pattern was placed on the coating thus obtained, and then exposed to 365 by 40 mJ/cm 2 The light of the nanometer wavelength. Then, the break point time (BP) was examined by using an aqueous solution diluted with 1% by weight of potassium hydroxide at 23 ° C, and additionally developed for 15 seconds. After washing with pure water for 1 minute, the pattern thus formed was post-cured in an oven at 230 ° C for 30 minutes to obtain a cured layer.

(1) Measurement of elastic recovery rate

Forming a cured layer having a total thickness of 4.0 (±0.2) μm and a pattern width of 35 (±1) μm after post-curing according to the method of forming a cured layer, and setting the cured layer to measure physical properties, That is, the basic reference shape of the compression displacement and the elastic recovery rate. The compression displacement and the elastic recovery rate are based on the following measurement conditions. The measuring device (DUH-W201S, Japan Shimadzu Co.) measured.

As a damper of the compression pattern, a flat damper having a diameter of 50 μm is used in a weight load-unloading manner. The elastic recovery rate is measured at 300 millinewtons (mN) to transfer load measurements and to obtain distinguishable results between the comparison groups. Constantly maintain a load rate of 3 gram force per second (gf/sec) and a dwell time of 3 seconds. As for the elastic recovery rate, the constant load flat damper lasted for 3 seconds, and then the actual elastic recovery rate of the pattern before and after the load was measured by using a three-dimensional thickness measuring device. The elastic recovery rate indicates the ratio of the recovery distance to the compression distance (compression displacement) after a 10 minute recovery time when a constant force is applied, which is expressed by the following Equation 1.

[Equation 1] Elastic recovery rate (%) = [(return distance / compression displacement) x 100]

(2) Measurement of resolution

According to the method of forming a cured layer, a pre-cured layer having a thickness of 3.5 (±0.2) μm is formed, and then exposed to a photomask (having a pattern size of 8, 10, 12, 14 μm, etc.) under the same conditions as those used to develop the cured layer. And development. The critical dimension of the pattern of the cured layer is measured, and the resolution (micron) is evaluated.

(3) Measurement of chemical resistance

A cured layer having a thickness of 3.0 (±0.2) μm after post-curing was prepared by a method of forming a cured layer without using a barrier, and the initial thickness of the cured layer thus prepared was measured. Then, the sample was immersed in 1 gram of 100% N-methylpyrrolidone (NMP), boiled at 100 ° C for 5 minutes in a thermostat, and baked in an oven at 100 ° C for 2 minutes, and measured. Two thicknesses. The sample was finally baked in an oven at 230 ° C for 20 minutes and the final thickness was measured. Based on the values thus measured, chemical resistance was calculated by the following Equation 2. The lower the chemical resistance (%), the better the properties of the cured layer.

[Equation 2] Chemical resistance (%) = [(final thickness / initial thickness) x 100] - 100

(4) Measurement of thickness of BCS

Similar to the measurement method of elastic recovery rate, a BCS pattern (refer to FIG. 1) is prepared in which a black matrix is integrated with a column spacer. The total thickness of the BCS (A+B), the thickness of the columnar spacer (A), and the thickness of the black matrix portion (B) were measured using a height measuring device (Heath (SIS)-2000, Seoul National University). When the black matrix portion thickness (A) is in the range of 2.0 ± 0.5 μm, light shielding properties are desirable.

(5) Measurement of transmittance at different wavelengths

A cured layer having a thickness of 2.0 μm and 4.0 μm after post-cure was prepared by using a mask to form a cured layer, and a spectrophotometer (Cary 100, Agilent Co.) was used. The transmittance at a wavelength of 730 nm and the transmittance at a wavelength of 900 nm were measured for a cured layer having a specific thickness. When the thickness is 2.0 (±0.5) microns and the transmittance of 730 nm is less than 15% and the lowest transmittance (which does not cause any defects in alignment) is 4.0 (±0.5) microns thickness and 900 nm wavelength is At least 15% prevents light from escaping.

(6) Measurement of optical density

A cured layer having a thickness of 3.0 μm after post-curing was prepared by a method of forming a cured layer without using a barrier. The transmittance of the cured layer at 550 nm was measured by using an optical density system (361T, X-lite Co.), and an optical density of 1 μm thickness was obtained.

The measurement results obtained as above are illustrated in Tables 4 and 5 below.

As shown in Tables 4 and 5, the cured layers prepared from the colored photosensitive resin compositions according to Examples 1 to 6, such as column spacers, black matrix, and BCS display Such as good elastic recovery, resolution, chemical resistance, thickness, transmittance and optical density. In contrast, at least one of the aforementioned properties of the cured layer formed from the colored photosensitive resin compositions according to Comparative Examples 1 to 3 showed unsatisfactory results. More specifically, the cured layers of Comparative Examples 1 to 3 have a high transmittance measured at a wavelength of 730 nm at a thickness of 2 μm, and are not suitable for use as BCS. Meanwhile, the cured layer of Comparative Example 2 had a low transmittance measured at a wavelength of 900 nm at a thickness of 4 μm, and was not suitable for use as BCS. Therefore, the colored photosensitive resin composition according to the present invention can be used as a spacer and/or a black matrix including various electronic components of an LCD.

A‧‧‧ Thickness of column spacers

B‧‧‧Thickness of black matrix parts

C‧‧‧ Critical dimension of column spacers (CD)

Claims (6)

A colored photosensitive resin composition comprising: (a) a copolymer; (b) an epoxy resin compound or a compound derived therefrom; (c) a polymerizable compound; (d) a photopolymerization initiator; and (e) a colorant comprising 0 to 5% by weight of an inorganic black colorant, 10 to 40% by weight of an organic black colorant, and 1 to 15% by weight based on the total solid content of the colored photosensitive resin composition Blue colorant. The colored photosensitive resin composition according to claim 1, wherein the copolymer comprises: (a-1) a unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a mixture thereof. (a-2) a unit derived from an aromatic unsaturated compound containing an aromatic ring; and (a-3) a unit derived from an ethylenically unsaturated compound different from (a-1) and (a-2) . The colored photosensitive resin composition according to claim 1, wherein the epoxy resin compound comprises a dibenzopyran main chain structure. The colored photosensitive resin composition according to claim 1, wherein the blue colorant is C.I. Pigment Blue 15:6. The colored photosensitive resin composition as described in claim 1, wherein when formed into a cured layer having a thickness of 1 μm, it has an optical density of 0.6 to 1.4. The colored photosensitive resin composition according to claim 1, wherein when formed into a cured layer having a thickness of 1.5 to 2.5 μm, it has a light transmittance of less than 15% at 730 nm, and is formed at 3.5 when formed. When cured to a thickness of 4.5 microns, it has a light transmission of at least 15% at 900 nanometers (nm).