KR101784049B1 - Colored photosensitive resin composition and light shielding spacer prepared therefrom - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition comprising a copolymer; Polymerizable compounds; A photopolymerization initiator; coloring agent; And a surfactant having an ethylenic unsaturated group containing both a fluorine and a silicone component and capable of forming a hydrophilic coating film on a polyimide-based alignment liquid when formed into a cured film, Chemical resistance and thickness characteristics, it can be fabricated as a light-shielding spacer and used for various electronic components including panels of LCD and OLED displays.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition and a light-shielding spacer prepared therefrom. BACKGROUND ART [0002]

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

Recently, in a liquid crystal cell of a liquid crystal display (LCD), a spacer formed by using a photosensitive resin composition is applied in order to keep the interval between the upper and lower transparent substrates constant. Since such an LCD is an electro-optical element that applies a voltage to a liquid crystal material injected at a certain gap between transparent substrates to drive the liquid crystal material, it is very important to keep the two substrates at a constant interval. If the spacing between the transparent substrates is not constant, the voltage applied to that portion and the transmittance of light passing therethrough are varied, resulting in defects indicating spatially non-uniform brightness. As LCDs become increasingly larger, the importance of constant spacing between transparent substrates is increasing.

Such a spacer is produced by coating a photosensitive resin composition on a substrate, exposing it to ultraviolet rays or the like using a mask, and then developing it. Recently, efforts have been made to use a light-shielding material for a spacer, Development of a photosensitive resin composition has been actively promoted. By using such a colored photosensitive resin composition, a black column spacer (light-shielding spacer) in which a column spacer and a black matrix are integrated into a single module is manufactured, thereby simplifying the process procedure.

Japanese Patent Application Laid-Open No. 2010-250256 discloses a color resist composition for forming a high-precision pattern with excellent corrosion resistance of a coating film to an alkali developing solution, and JP-A-2010-186175 discloses a color photoresist composition The present invention provides a coloring composition containing a liquid repellent agent. However, all of these conventional compositions are focused on improving the lyophobicity when formed into a coating film. Therefore, when a light-shielding spacer or the like is formed, the polyimide- Problems such as burrs and pin holes may occur.

Japanese Patent Application Laid-Open No. 2010-250256 (Nov. 4, 2010) Japanese Laid-Open Patent Publication No. 2010-186175 (Aug. 26, 2010)

Accordingly, an object of the present invention is to provide a colored photosensitive resin composition which is excellent in coating properties and has improved lyophilicity to a polyimide-based alignment liquid when formed into a light-shielding spacer or the like.

In order to accomplish the above object, the present invention provides a thermoplastic resin composition comprising (a) a copolymer; (b) a polymerizable compound; (c) a photopolymerization initiator; (d) a colorant; And (e) a surfactant having an ethylenic unsaturated group containing both a fluorine and a silicone component.

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

The present invention also provides an electronic part including the light-shielding spacer.

INDUSTRIAL APPLICABILITY The colored photosensitive resin composition of the present invention can form a cured film with a lyophilic coating film for a polyimide-based alignment liquid at the time of production, has excellent exposure margins and developing margins, As well as the properties of the column spacer, such as the chemical resistance and the coating thickness, as well as the properties of the black matrix such as transmittance and optical density, it is possible to form a light-shielding spacer etc. used in various electronic components including panels of LCD and OLED displays . ≪ / RTI >

1 schematically shows an example of a cross-section of a light-shielding spacer (black column spacer).

Hereinafter, the present invention will be described more specifically.

Colored photosensitive resin composition

The colored photosensitive resin composition of the present invention comprises a copolymer, (b) a polymerizable compound, (c) a photopolymerization initiator, (d) a colorant, and (e) a surfactant component, ) Epoxy resin compound or a compound derived therefrom, (g) a solvent, and / or (h) a silane coupling agent.

As used herein, "(meth) acryl" means "acrylic" and / or "methacryl" and "(meth) acrylate" means "acrylate" and / or "methacrylate".

Hereinafter, the colored photosensitive resin composition will be described specifically for each component.

(a) Copolymer

The copolymer used in the present invention is a copolymer which comprises (a-1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof, and (a-2) (A-3) a structural unit derived from an ethylenically unsaturated compound different from (a-1) and (a-2) described above.

The copolymer serves as an alkali-soluble resin that realizes developability in the development step, and also serves as a base for forming a coating film after coating and realizing a final pattern.

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

In the present invention, the constituent unit (a-1) is derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof. The ethylenically unsaturated carboxylic acid and the ethylenically unsaturated carboxylic acid anhydride are polymerizable unsaturated monomers having at least one carboxyl group in the molecule. Specific examples thereof include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, alpha-chloroacrylic acid, ; Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid, and anhydrides thereof; Unsaturated polycarboxylic acids of trivalent or more and their anhydrides; Mono [(meth) acryloyloxyalkyl] ester of a dicarboxylic acid having two or more carboxyl groups such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] phthalate And the like. The constituent units derived from the above exemplified compounds may be included in the copolymer alone or in combination of two or more.

The content of the structural unit (a-1) may be from 5 to 65 mol%, and preferably from 10 to 50 mol%, based on the total number of moles of the constituent units constituting the copolymer. Within this range, maintenance of developability can be made easier.

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

The structural unit (a-2) is derived from an aromatic ring-containing ethylenically unsaturated compound, and specific examples of the aromatic ring-containing ethylenically unsaturated compound include phenyl (meth) acrylate, benzyl (meth) acrylate, (Meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tribromophenyl ) Acrylate; Styrene; Styrene having alkyl substituents such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene and octylstyrene; Styrene having a halogen such as fluorostyrene, chlorostyrene, bromostyrene, and iodostyrene; Styrene having an alkoxy substituent such as methoxystyrene, ethoxystyrene or propoxystyrene; 4-hydroxystyrene, p-hydroxy-a-methylstyrene, acetyl styrene; Vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl methyl ether, - vinylbenzyl glycidyl ether, and the like.

The constituent units derived from the above exemplified compounds may be included in the copolymer alone or in combination of two or more.

Of these, styrene-based compounds are preferable from the viewpoint of polymerizability.

The content of the structural unit (a-2) may be from 2 to 70 mol%, and preferably from 3 to 60 mol%, based on the total molar amount of the constituent units constituting the copolymer. Within the above range, it may be more advantageous from the viewpoint of chemical resistance.

(a-3) a structural unit derived from an ethylenically unsaturated compound different from (a-1) and (a-2)

The copolymer used in the present invention further includes a constitutional unit derived from an ethylenically unsaturated compound different from (a-1) and (a-2) in addition to the above (a-1) and .

Specific examples of the ethylenically unsaturated compounds different from the above (a-1) and (a-2) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (Meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, tetrahydroperfuryl (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl Butyl (meth) acrylate, (Meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, tetrafluoropropyl (Meth) acrylate, hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, iso (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl Unsaturated carboxylic acid esters; Tertiary amines including N-vinyl, such as N-vinylpyrrolidone, N-vinylcarbazole and N-vinylmorpholine; Unsaturated ethers such as vinyl methyl ether and vinyl ethyl ether; (Meth) acrylate, 5,6-epoxyhexyl (meth) acrylate, 6,7-epoxy (meth) acrylate, (Meth) acrylate,? -Ethylglycidyl acrylate,? -N-propylglycidyl (meth) acrylate, Acrylate,? - n-butylglycidyl acrylate, N- (4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl) acrylamide, N- Propyloxy) -3,5-dimethylphenylpropyl) acrylamide, 4-hydroxybutyl (meth) acrylate glycidyl ether, allyl glycidyl ether and 2-methylallyl glycidyl ether. Ethylenically unsaturated compounds; And unsaturated imides such as N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide and N-cyclohexylmaleimide.

The constituent units derived from the above exemplified compounds may be included in the copolymer alone or in combination of two or more.

Among them, a structural unit derived from an ethylenically unsaturated compound and / or an unsaturated imide containing an epoxy group, more preferably a structural unit derived from glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl A structural unit derived from a cidyl ether and / or an N-substituted maleimide may be more advantageous in terms of copolymerization and strength improvement of an insulating film.

The content of the structural unit (a-3) may be 10 to 80 mol%, preferably 20 to 75 mol%, based on the total number of moles of the constituent units constituting the copolymer. Within the above range, it may be more advantageous to maintain the storage stability of the colored photosensitive resin composition and to improve the residual film ratio.

Examples of the copolymer having the above structural units (a-1) to (a-3) include (meth) acrylic acid / styrene copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, Styrene / methyl (meth) acrylate copolymers, (meth) acrylic acid / styrene / methyl (meth) acrylate / glycidyl (meth) acrylate copolymers, Styrene / methyl (meth) acrylate / glycidyl (meth) acrylate / N-cyclohexylmaleimide copolymer, (meth) acrylic acid / (Meth) acrylate / styrene / glycidyl (meth) acrylate / glycidyl (meth) acrylate / N-phenylmaleimide copolymer, (Meth) acrylic acid / styrene / 4-hydroxybutyl (meth) acrylate copolymer, And glycidyl ether / N-phenylmaleimide copolymers.

The copolymer may be contained in the colored photosensitive resin composition in one kind or in two or more kinds.

The weight average molecular weight (Mw) of the copolymer in terms of polystyrene measured by gel permeation chromatography (elution solvent: tetrahydrofuran, etc.) may be 3,000 to 50,000, preferably 5,000 to 40,000. When it is within the above range, it can be more excellent in adhesion to the substrate, physical / chemical properties, and viscosity.

The content of the copolymer in the entire colored photosensitive resin composition may be from 0.5 to 60% by weight, and preferably from 5 to 50% by weight, based on the total solid weight of the colored photosensitive resin composition (i.e., weight excluding the solvent). Within the above range, pattern development after development is favorable and characteristics such as chemical resistance can be improved.

The copolymer may be prepared by adding a molecular weight modifier, a radical polymerization initiator, a solvent, the above-mentioned structural units (a-1) to (a-3), and adding nitrogen thereto and then slowly polymerizing while stirring.

The copolymer according to the present invention can be prepared by adding a molecular weight modifier, a radical polymerization initiator, a solvent, the above-mentioned constituent units (a-1) to (a-3), and adding nitrogen and then slowly polymerizing while stirring.

The molecular weight modifier is not particularly limited, but may be a mercaptan compound such as butylmercaptan, octylmercaptan or the like or? -Methylstyrene dimer.

Examples of the radical polymerization initiator include, but are not limited to, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis Methoxy-2,4-dimethylvaleronitrile), azo compounds such as benzoyl peroxide, lauryl peroxide, t-butyl peroxypivalate, 1,1-bis (t-butylperoxy) have. These radical polymerization initiators may be used alone or in combination of two or more.

The solvent may be any solvent used in the production of the copolymer, for example, propylene glycol monomethyl ether acetate (PGMEA).

(b) a polymerizable compound

The polymerizable compound used in the present invention is a compound capable of polymerizing under the action of a polymerization initiator, and a polyfunctional monomer, oligomer or polymer generally used in a colored photosensitive resin composition can be used.

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. In particular, from the viewpoint of chemical resistance, a multifunctional compound having two or more functional groups .

The polymerizable compound may be at least one selected from the group consisting of ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri Acrylate, pentaerythritol tri (meth) acrylate and monoesters of succinic acid, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa , Monoesters of dipentaerythritol penta (meth) acrylate and succinic acid, caprolactone-modified dipentaerythritol hexa (meth) acrylate (Reactant of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol triacrylate, hexamethylene diisocyanate But are not limited to, bisphenol A epoxy acrylate, ethylene glycol monomethyl ether acrylate, and mixtures thereof.

The content of the polymerizable compound may be 1 to 60% by weight, preferably 5 to 45% by weight, based on the total weight of the solids of the colored photosensitive resin composition (i.e., weight excluding the solvent). When the thickness is within the above range, pattern formation is easy, and a problem of a pattern shape such as scum may not occur at the lower end during development.

(c) a photopolymerization initiator

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

The photopolymerization initiator may be at least one selected from the group consisting of an acetophenone-based compound, a nonimidazole-based compound, a triazine-based compound, an onium salt-based compound, a benzoin-based compound, a benzophenone-based compound, a diketone- Compounds, diazo compounds, imide sulfonate compounds, oxime compounds, carbazole compounds, sulfonium borate compounds, and mixtures thereof.

Among them, Korean Patent Publication Nos. 2004-0007700, 2005-0084149, 2008-0083650, 2008-0080208, 2007-0044062, 2007-0091110, 2007-0044753, 2009 -0009991, 2009-0093933, 2010-0097658, 2011-0059525, 2011-0091742, 2011-0026467 and 2011-0015683, and International Patent Publication No. WO 2010/102502 It is preferable to use at least one of the oxime compounds described in WO 2010/133077 from the viewpoint of high sensitivity. Commercially available products such as OXE-01 (BASF), OXE-02 (BASF), N-1919 (ADEKA), NCI-930 (ADEKA) and NCI-831 .

The photopolymerization initiator may be used in an amount of 0.1 to 10% by weight, preferably 0.2 to 5% by weight based on the total solid weight of the colored photosensitive resin composition (i.e., the weight excluding the solvent). When it is within the above-mentioned range, curing by exposure is sufficiently performed, and it can be sufficiently adhered to the substrate at the time of excellent development.

(d) colorant

The colored photosensitive resin composition of the present invention includes a colorant to impart light shielding properties.

The coloring agent used in the present invention may be a mixed coloring agent of two or more kinds of inorganic or organic, and is preferably a coloring agent having high coloring property and high heat resistance. Particularly, it is more advantageous to mix two or more organic coloring agents to prevent light leakage of the black matrix and to secure a transmittance which can be masked.

The colorant also comprises a black colorant and a blue colorant, wherein the black colorant may be a black inorganic colorant and / or a black organic colorant.

According to one example, the colored photosensitive resin composition may include a black organic colorant as a colorant, and may further include a black inorganic colorant and a blue colorant.

Any of the above-mentioned black inorganic coloring agents, black organic coloring agents, and blue coloring agents may be used and may include, for example, a compound classified as a pigment in the color index (The Society of Dyers and Colourists) And may include known dyes.

Specific examples of the black inorganic colorant include carbon black, titanium black, metal oxides such as Cu-Fe-Mn-based oxides and synthetic iron black, and among them, use of carbon black is advantageous in terms of pattern characteristics and chemical resistance .

Specific examples of the black organic coloring agent include aniline black, lactam black and perylene black. Among them, lactam black (for example, Black 582 from BASF) is used in view of optical density, dielectric constant, desirable.

Specific examples of the blue colorant include CI Pigment Blue 15: 6, CI Pigment Blue 15: 4, CI Pigment Blue 60, CI Pigment Blue 16, and the like. Among them, it is preferable to use C.I. Pigment Blue 15: 6 in order to prevent light leakage.

The content of the black inorganic colorant, the black organic colorant and the blue colorant is 0 to 20% by weight, 10 to 40% by weight and 0 to 15% by weight, respectively, based on the total weight of the colored photosensitive resin composition excluding the solvent %, Preferably from greater than 0 to 20 weight percent, from 10 to 40 weight percent, and from greater than 0 to 15 weight percent, more preferably from greater than 0 to 10 weight percent, from 10 to 40 weight percent, and 1 to 15% by weight. In the above range, it is advantageous to achieve a high optical density capable of preventing light leakage, and the required transmittance for mask alignment can be realized.

Meanwhile, a dispersant may be used to disperse the coloring agent in the colored photosensitive resin composition of the present invention. Examples of the dispersing agent include any of those known as coloring agent dispersing agents. Specific examples thereof include a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a silicone surfactant, a fluorinated surfactant, etc. . Commercially available dispersing agents include Disperbyk-182, -183, -184, -185, -2000, -2150, -2155, -2163, and -2164 available from BYK. These may be used alone or in combination of two or more. The dispersant may be added to the colorant internally in advance by surface treatment with a colorant, or may be used in combination with a colorant in the production of the colored photosensitive resin composition.

Further, after the colorant is mixed with the binder, it may be used in the production of the colored photosensitive resin composition. The binder used herein may be the copolymer (a) described in the present invention, a known copolymer, or a mixture thereof.

Therefore, the colorant used in the present invention may be added to the colored photosensitive resin composition in the form of a colored dispersion (mill base) mixed with a dispersant, a binder, a solvent and the like.

(e) Surfactant

The colored photosensitive resin composition of the present invention further includes a surfactant for improving coatability and preventing defect formation.

As the surfactant, a surfactant containing an ethylenic unsaturated group containing both fluorine (F) and silicon (Si) is used.

Specific examples of commercially available products of the surfactants include Megaface RS-55 manufactured by Dainippon Ink and Chemicals, Inc. (DIC).

The surfactant is added in an amount of 0.0001 to 0.01% by weight, more preferably 0.001 to 0.01% by weight based on the total weight of the colored photosensitive resin composition. Here, the weight of the colored photosensitive resin composition as a reference for the content may be the total weight including the solvent. In the above range, the coating properties and the lyophilicity for the polyimide-based alignment liquid can be maintained in a more preferable range.

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

The colored photosensitive resin composition of the present invention may further comprise an epoxy resin compound or a compound derived therefrom.

The epoxy resin compounding may be a compound having a weight average molecular weight (Mw) of 400 to 10,000 as measured by gel permeation chromatography in terms of polystyrene.

For example, the epoxy resin compound may be an epoxy resin compound having a xanthene skeleton structure, preferably an epoxy resin compound having a xanthene skeleton structure represented by the following formula (1)

[Chemical Formula 1]

In Formula 1,

,

,

또는

에 포함된 *로 라벨링된 탄소로 대체되고;Each carbon labeled * is independently < RTI ID = 0.0 >

,

,

or

Lt; RTI ID = 0.0 > * < / RTI >

L ¹ each independently represents a C _1-10 alkylene group, a C _3-20 cycloalkylene group or a C _1-10 alkyleneoxy group;

R ₁ to R ₇ Are each 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;

R ₈ Is H, a methyl group, an ethyl group, CH ₃ CHCl-, CH ₃ CHOH-, CH ₂ = CHCH ₂ - or a phenyl group;

n is an integer of 0 to 10;

Specific examples of the C _1-10 alkylene group include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, sec-butylene, A pentylene group, a hexylene group, a heptylene group, an octylene group, an isooctylene group, a t-octylene group, a 2-ethylhexylene group, a nonylene group, an isononylene group, a decylene group and an isodecylene group. Specific examples of the C _3-20 cycloalkylene group include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, decalinylene and adamantylene. Specific examples of the C _1-10 alkyleneoxy group include methyleneoxy, ethyleneoxy, propyleneoxy, butyleneoxy, sec-butyleneoxy, t-butyleneoxy, pentyleneoxy, An octyloxy group, a 2-ethyl-hexylenoxy group and the like. Specific examples of the C _1-10 alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, Hexyl group, heptyl group, octyl group, isooctyl group, t-octyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group and isodecyl group. Specific examples of the C _1-10 alkoxy group include methoxy, ethoxy, propoxy, butyloxy, sec-butoxy, t-butoxy, pentoxy, hexyloxy, heptoxy, octyloxy, -Ethyl-hexyloxy group and the like. Specific examples of the C _2-10 alkenyl group include a vinyl group, an allyl group, a butenyl group, and a propenyl group. Specific examples of the C _6-14 aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

The compound derived from the epoxy resin having the zetene skeleton structure of Formula 1 can be obtained by reacting an epoxy resin having a zetene skeleton structure of Formula 1 with an unsaturated basic acid to obtain an epoxy adduct and then reacting it with a polybasic acid anhydride Compound, or a compound obtained by reacting it with a further monofunctional or polyfunctional epoxy compound. As the unsaturated basic acid, known ones such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and sorbic acid can be used. Examples of the polybasic acid anhydride include succinic acid anhydride, maleic anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, hexa And a known material such as hexahydrophthalic anhydride may be used. The monofunctional or polyfunctional epoxy compound may be selected from the group consisting of glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, Epoxycyclohexyl glycidyl ether, cy- idyl ether, and bisphenol Z glycidyl ether.

When a compound derived from an epoxy resin having a zetene skeleton structure of Formula 1 is used, the zeta-system skeleton structure improves the adhesiveness, alkali resistance, workability, and strength between the cured product and the substrate, It is possible to form an image in a fine pattern more precisely.

The epoxy resin compound or a compound derived therefrom may be contained in an amount of 1 to 70% by weight, preferably 5 to 50% by weight, based on the total solid weight (i.e., weight of the solvent) of the colored photosensitive resin composition. When the thickness is within the above range, resolution and chemical resistance can be further improved, and it is more advantageous to realize a desired step width between patterns while maintaining a pattern shape with a desired margin width (allowable width).

(g) Solvent

The colored photosensitive resin composition of the present invention may preferably be prepared from a liquid composition in which the above-mentioned components are mixed with a solvent. The solvent is compatible with the above-mentioned colored photosensitive resin composition components and does not react with the above-mentioned colored photosensitive resin composition components, and any of known solvents used in the colored photosensitive resin composition can be used.

Examples of such solvents include glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Diethylene glycol such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; And alkoxyalkyl acetates such as 3-methoxybutyl acetate. These solvents may be used alone or in combination of two or more.

The content of the solvent is not particularly limited. However, from the viewpoints of coatability, stability, etc. of the final colored photosensitive resin composition, the solid content of the composition excluding the solvent may be an amount such that the solid content concentration is usually 5 to 70% by weight, By weight to 55% by weight.

(h) Silane coupling agent

The colored photosensitive resin composition of the present invention may contain a carboxyl group, a (meth) acryloyl group, an isocyanate group, an amino group, a mercapto group, a vinyl group, an epoxy group, and a combination thereof in order to improve adhesion with a substrate A silane coupling agent having a reactive substituent selected from the group consisting of R < 1 >

The type of the silane coupling agent is not particularly limited, and examples thereof include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltri Glycidoxypropyltrimethoxysilane,? - glycidoxypropyltriethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, phenylaminotrimethoxysilane, and? ≪ / RTI > and mixtures thereof. Of these, γ-isocyanatopropyltriethoxysilane (eg KBE-9007, Shin-Etsu) or phenylaminotrimethoxysilane having an isocyanate group with good adhesion to a substrate while maintaining chemical resistance is preferable .

The silane coupling agent may be contained in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight based on the total solid weight of the colored photosensitive resin composition (i.e., the weight excluding the solvent). Within the above range, the adhesiveness of the colored photosensitive resin composition can be improved.

In addition, the colored photosensitive resin composition of the present invention may contain other additives such as an antioxidant, a stabilizer and the like within a range not lowering the physical properties.

The above-mentioned colored photosensitive resin composition of the present invention can form a curable film with a lyophilic coating film for a polyimide-based alignment liquid at the time of production. Specifically, the cured film formed using the colored photosensitive resin composition of the present invention and the polyimide-based alignment liquid can have a contact angle of less than 10 °, and preferably a contact angle of less than 8 °. Accordingly, the colored photosensitive resin composition of the present invention may form a light-shielding spacer and may not cause problems such as scratching and pinholes in a polyimide coating process in a subsequent step.

In addition, the colored photosensitive resin composition of the present invention can satisfactorily satisfy the properties of a black matrix such as transmittance and optical density, as well as the properties of a column spacer such as elastic recovery rate, resolution, chemical resistance and coating thickness at the time of manufacturing a light- Thus, both the exposure margin and the developing margin are excellent.

Method for producing colored photosensitive resin composition

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

First, the colorant is mixed with the solvent in advance and dispersed using a bead mill or the like until the average particle diameter of the colorant becomes a desired level. At this time, a surfactant may be used, and some or all of the copolymer may be blended. To the dispersion is added the remainder of the copolymer and the surfactant, the epoxy resin compound or a compound derived therefrom, a polymerizable compound and a photopolymerization initiator, and if necessary, an additive such as a silane coupling agent or an additional solvent is added to a predetermined concentration After further blending, the mixture is sufficiently stirred to obtain a desired colored photosensitive resin composition.

Light-blocking spacer

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

In particular, the present invention provides a black column spacer (BCS) which is manufactured using the colored photosensitive resin composition and in which a column spacer and a black matrix are integrally formed. An example of the black column spacer pattern is shown in Fig.

The column spacer, the black matrix or the black column spacer may be manufactured through a film forming step, an exposure step, a development step, and a heat treatment step.

In the coating film forming step, the colored photosensitive resin composition according to the present invention is coated on a predetermined pretreated substrate by a method such as a spin or slit coating method, a roll coating method, a screen printing method, an applicator method, In a thickness of 2 to 25 탆, and then preliminarily cured at a temperature of 70 to 100 캜 for 1 to 10 minutes to remove the solvent, whereby a coating film can be formed.

In order to form a pattern on the obtained coating film, a mask of a predetermined type is interposed, and an active line of 200 to 500 nm is irradiated. At this time, in order to manufacture an integrated black column spacer, a mask having a pattern with a different transmittance can be used so that a column spacer and a black matrix can be simultaneously realized. As the light source used for the irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, and the like can be used. The exposure dose varies depending on the kind of each component of the composition, the blending amount and the dried film thickness, but may be 500 mJ / cm 2 (at a wavelength of 365 nm) or less when a high-pressure mercury lamp is used.

Following the above exposure step, an unnecessary portion is dissolved and removed by using an alkaline aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, or the like as a developer, so that only the exposed portion is left to form a pattern. After the image pattern obtained by the development is cooled to room temperature, it is post-baked at 180 ° C to 250 ° C for 10 to 60 minutes in a hot air circulation type drying furnace to obtain a desired final pattern.

The light-shielding spacer thus produced can be advantageously used for electronic parts such as LCD and OLED display due to its excellent physical properties. Accordingly, the present invention provides an electronic part including the light-shielding spacer.

The LCD, OLED display, and the like may include configurations known to those skilled in the art, except for having a light-shielding spacer of the present invention. That is, an LCD, an OLED display, and the like, to which the light-shielding spacer of the present invention can be applied, may all be included in the present invention.

Hereinafter, the present invention will be described in more detail with reference to the following examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Preparation Example 1: Preparation of Copolymer

100 g of the monomer mixture having the content ratio shown in the following Table 1, 300 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and 300 g of 2,2'-azobisisobutyronitrile as a radical polymerization initiator were placed in a 500 ml round bottom flask equipped with a reflux condenser and a stirrer (2,4-dimethylvaleronitrile) were added, and the mixture was heated to 70 ° C and stirred for 5 hours to polymerize a copolymer having a solid content of 31% by weight. The acid value of the resulting copolymer was 100 mgKOH / g, and the polystyrene-reduced weight average molecular weight (Mw) as measured by gel permeation chromatography was 20,000.

The monomer (mol%) constituting the copolymer Methacrylic acid Styrene Glycidyl methacrylate N-phenylmaleimide 35 4 10 51

Production Example 2: Compound derived from an epoxy resin having a zettenoid skeleton

160 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent was placed in a flask equipped with a stirrer, a thermometer, a nitrogen purging device and a reflux condenser, and 3,3 '- (spiro [fluorene-9,9'- -3 ', 6'-diylbis (oxy)) bis (2-hydroxypropane-3,1-diyl) diacrylate (3,3'- (spiro [fluorene-9,9'-xanthene] -3 100 g of 6'-diylbis (oxy) bis (2-hydroxypropane-3,1-diyl) diacrylate and 0.1 g of chloroplatinic acid. To this, 47.6 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was diluted in 80 g of PGMEA, and the mixture was slowly dropped. The mixture was heated to 100 DEG C and reacted for 2 hours. After cooling to room temperature (25 캜), 0.3 g of pyridinium sulfonate pyridinium salt was added. As a result, a polymer compound having a weight average molecular weight (Mw) of 6,000, an acid value of 107 mgKOH / g and a solid content of 50% by weight was obtained.

Production Example 3: Preparation of colored dispersion

8 g of the copolymer prepared in Preparation Example 1, 8 g of a polymer dispersant (DISPERBYK-2000, manufactured by BYK), 12 g of carbon black, 53 g of lactam black (Black 582, BASF Corp.) as an organic black, 15 g of CI Pigment Blue 15 : 6 and 384 g of PGMEA as a solvent were dispersed for 6 hours at 25 to 60 ° C using a paint shaker. Dispersion was performed using 0.3 mm zirconia beads. After dispersion was completed, the beads and the dispersion were separated by a filter to prepare a colored dispersion.

Example 1 To 4 and Comparative Examples 1 to 8: Preparation of colored photosensitive resin composition

The copolymer obtained in Preparation Example 1, the compound derived from the epoxy resin having the residual skeleton structure obtained in Preparation Example 2, the polymerizable compound dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku), the photopolymerization initiator c- (Triazine initiator, TY, PHARMASYNTEHSE) represented by the following formula (1), (e-1) to (e-6) described in Table 2 below as a surfactant, The colored dispersion obtained in Preparative Example 3 was compounded in 44.0 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent in a blending amount shown in Table 3 according to a conventional method and stirred for 5 hours to prepare a colored photosensitive resin composition.

Brand name manufacturer Explanation e-1 Megaface RS-55 DIC Contains fluorine and silicon and has double bonds e-2 Megaface F-563 DIC Fluoric surfactant e-3 BYK-307 BYK Silicone surfactant e-4 Megaface RS-72-K DIC Reactive fluorinated surfactant e-5 Rad-2010 TEGO Reactive silicone surfactant e-6 Rad-2250 TEGO Reactive silicone surfactant

division Production Example 1
Copolymer Preparation Example 2 Compound Polymerizable
compound Photoinitiator
(c-1) Photoinitiator
(c-2) coloring
Dispersion Surfactants menstruum Example 1 12.4g 6.6 g 3.8 g 0.1 g 0.5 g 32.5 g (e-1) 0.009 g 44.0 g Example 2 12.4g 6.6 g 3.8 g 0.1 g 0.5 g 32.5 g (e-1) 0.006 g 44.0 g Example 3 12.4g 6.6 g 3.8 g 0.1 g 0.5 g 32.5 g 0.004 g (e-1) 44.0 g Example 4 10.7 g 8.3 g 3.8 g 0.1 g 0.5 g 32.5 g (e-1) 0.006 g 44.0 g Comparative Example 1 12.4g 6.6 g 3.8 g 0.1 g 0.5 g 32.5 g 0.015 g (e-1) 44.0 g Comparative Example 2 12.4g 6.6 g 3.8 g 0.1 g 0.5 g 32.5 g (e-2) 0.026 g 44.0 g Comparative Example 3 12.4g 6.6 g 3.8 g 0.1 g 0.5 g 32.5 g (e-2) 0.009 g 44.0 g Comparative Example 4 12.4g 6.6 g 3.8 g 0.1 g 0.5 g 32.5 g (e-3) 0.026 g 44.0 g Comparative Example 5 12.4g 6.6 g 3.8 g 0.1 g 0.5 g 32.5 g (e-3) 0.009 g 44.0 g Comparative Example 6 12.4g 6.6 g 3.8 g 0.1 g 0.5 g 32.5 g (e-4) 0.038 g 44.0 g Comparative Example 7 12.4g 6.6 g 3.8 g 0.1 g 0.5 g 32.5 g (e-5) 0.038 g 44.0 g Comparative Example 8 12.4g 6.6 g 3.8 g 0.1 g 0.5 g 32.5 g (e-6) 0.038 g 44.0 g

Test Example 1: Evaluation of coating properties

The color photosensitive resin compositions of the above Examples and Comparative Examples were spin-coated on a glass substrate of 10 cm x 10 cm in an amount of 3 mg to evaluate the applicability.

Bernard cells or interference fringes can not be seen and can be said to be excellent when a coating film having no unevenness is obtained.

Test Example 2: Measurement of black column spacer thickness

The colored photosensitive resin compositions prepared in the above Examples and Comparative Examples were respectively coated on a glass substrate using a spin coater and preliminarily cured at 80 DEG C for 150 seconds to form a coated film. A pattern mask composed of a 100% full-tone column spacer (CS) pattern and a 20% half-tone black matrix pattern was applied to the thus obtained coating film, and light having a wavelength of 365 nm was irradiated at 40 mJ / Respectively. After confirming the break point (BP) time at 23 DEG C with an aqueous solution diluted with 1 wt% of potassium hydroxide, the solution was further developed for 15 seconds and then washed with pure water for 1 minute. The formed pattern was cured in an oven at 230 캜 for 30 minutes to obtain a cured film.

As a result, a black column spacer pattern (see FIG. 1) in which the black matrix and the column spacer were integrally formed was obtained, and then the column spacer portion thickness A and the black matrix spacer portion were formed using a step difference measuring instrument (SIS- The thickness (B) was measured. At this time, when the thickness (B) of the black matrix portion is 2.0 ± 0.5 μm, excellent light shielding property can be expected.

Test Example 3: Evaluation of contact angle of polyimide

A cured film was prepared according to the procedure of Test Example 2, and a cured film having a thickness of 2.0 (+/- 0.2) 占 퐉 after the post-curing was prepared by carrying out a mask comprising a 20% half-tone having a 3 x 3 cm area .

Thereafter, 6 mg of pure polyimide (PI) was dropped onto the remaining pattern portion of the exposed area, and the contact angle was measured using a contact type contact angle meter (MD300, manufactured by KYOWA). The contact angle is the angle between the tangent to the liquid surface and the solid surface at the point where the solid and the liquid are in contact, and the PI contact angle is defined as the angle containing the liquid. The lower the PI contact angle, the better the PI application.

The measurement results are summarized in Table 4 below.

division
Application Characteristics Black column spacer
PI contact angle
(°) Column spacer thickness
(탆) Black Matrix Thickness
(탆) Example 1 Good 3.00 2.01 5.4 Example 2 Good 3.05 2.02 4.1 Example 3 Good 3.04 1.98 3.0 Example 4 Good 3.03 2.12 4.2 Comparative Example 1 Good 3.01 2.02 16.5 Comparative Example 2 Good 3.08 1.98 17.3 Comparative Example 3 Bad Not measurable Not measurable Not measurable Comparative Example 4 Good 3.02 2.05 9.4 Comparative Example 5 Bad Not measurable Not measurable Not measurable Comparative Example 6 Good 3.07 2.08 23.5 Comparative Example 7 Good 3.03 2.02 26.2 Comparative Example 8 Good 2.98 1.95 27.5

As shown in Table 4, the colored photosensitive resin compositions of Examples 1 to 4 and the cured films prepared therefrom, for example, the column spacer and the black matrix, were uniformly excellent in terms of coating properties, thickness and PI contact angle. Therefore, the colored photosensitive resin composition according to the present invention can be usefully used for manufacturing various electronic parts including LCD, OLED display and the like.

On the other hand, it can be seen that the colored photosensitive resin compositions of Comparative Examples 1 to 8 and the cured film prepared therefrom had poor characteristics of at least one of them. In particular, the PI contact angles of Comparative Examples 1 to 8 were all measured to be high, and the PI rubbing resistance was low.

A: the thickness of the column spacer,
B: thickness of black matrix portion,
C: Line width of the column spacer (CD).

Claims (7)

(a) a copolymer;
(b) a polymerizable compound;
(c) a photopolymerization initiator;
(d) a colorant; And
(e) a surfactant containing a fluorine and silicon component and having an ethylenic unsaturated group
Wherein the coloring photosensitive resin composition comprises:
And 0.0001 to 0.01% by weight of the surfactant relative to the total weight of the colored photosensitive resin composition,
Wherein the colored photosensitive resin composition has a contact angle of not less than 0 DEG and less than 10 DEG between the cured film formed by using the colored photosensitive resin composition and the polyimide system oriented liquid.
delete The method according to claim 1,
Wherein the colored photosensitive resin composition has a contact angle of between 0 DEG and less than 8 DEG between the cured film formed using the colored photosensitive resin composition and the polyimide based alignment liquid.
The method according to claim 1,
(F) an epoxy resin compound or a compound derived therefrom.
5. The method of claim 4,
Wherein the epoxy resin compound is an epoxy resin compound having a zetene skeleton structure.
The method according to claim 1,
Wherein the colored photosensitive resin composition contains 10 to 40% by weight of a black organic coloring agent as the coloring agent with respect to the total solid content of the colored photosensitive resin composition.
The method according to claim 6,
Characterized in that the colored photosensitive resin composition further contains, as the coloring agent, from 0 to 20% by weight of a black inorganic coloring agent in an amount of more than 0 to 20% by weight based on the total solid content of the colored photosensitive resin composition, and more than 0 to 15% by weight of a blue coloring agent. Sensitive resin composition.

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