WO2017126795A1 - Composition de résine photosensible noire et élément d'espacement de colonne noir préparé à partir de cette dernière - Google Patents

Composition de résine photosensible noire et élément d'espacement de colonne noir préparé à partir de cette dernière Download PDF

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Publication number
WO2017126795A1
WO2017126795A1 PCT/KR2016/013396 KR2016013396W WO2017126795A1 WO 2017126795 A1 WO2017126795 A1 WO 2017126795A1 KR 2016013396 W KR2016013396 W KR 2016013396W WO 2017126795 A1 WO2017126795 A1 WO 2017126795A1
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Prior art keywords
black
meth
resin composition
photosensitive resin
acrylate
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PCT/KR2016/013396
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English (en)
Inventor
Hyung Gu Jeong
Seok-Bong Park
Ji Ung Kim
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Rohm And Haas Electronic Materials Korea Ltd.
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Priority claimed from KR1020160154303A external-priority patent/KR102674718B1/ko
Application filed by Rohm And Haas Electronic Materials Korea Ltd. filed Critical Rohm And Haas Electronic Materials Korea Ltd.
Priority to CN201680076438.5A priority Critical patent/CN108475013B/zh
Priority to US16/066,475 priority patent/US10884335B2/en
Priority to JP2018533178A priority patent/JP7079198B2/ja
Publication of WO2017126795A1 publication Critical patent/WO2017126795A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Definitions

  • the present invention relates to a black photosensitive resin composition and a black column spacer prepared therefrom, in particular, a black photosensitive resin composition which is appropriate as a material for the formation of a spacer, a light shielding part, etc., which are used in a panel of a liquid crystal display (LCD) or an organic light-emitting diode (OLED) display, and a cured film, particularly, a black column spacer (BCS) prepared therefrom.
  • a black photosensitive resin composition which is appropriate as a material for the formation of a spacer, a light shielding part, etc.
  • LCD liquid crystal display
  • OLED organic light-emitting diode
  • BCS black column spacer
  • a spacer formed using a photosensitive resin composition is employed to maintain a constant distance between upper and lower transparent substrates.
  • an electro-optic device driven by a voltage applied to a liquid crystal material injected into a constant gap between two transparent substrates it is very crucial to maintain the gap between the two substrates even. If the gap between the transparent substrates is not constant, the voltage applied thereto as well as the transmittance of light penetrating this area may vary, resulting in defects of spatially non-uniform luminance. According to a recent demand for large LCD panels in size, it is even more crucial to maintain a constant gap between two transparent substrates.
  • a spacer may be formed by coating a photosensitive resin composition onto a substrate and exposing the coated substrate to ultraviolet light, etc., using a mask, followed by development thereof.
  • a photosensitive resin composition onto a substrate and exposing the coated substrate to ultraviolet light, etc., using a mask, followed by development thereof.
  • Recently, efforts of using a light shielding material for a spacer have been made; accordingly, various colored photosensitive resin compositions have been actively developed.
  • Korean Patent No. 10-0814660 discloses a method of using a black organic pigment having good light shielding property and low dielectric constant. However, when a black organic pigment is used, a large amount of black organic pigment is required in comparison with carbon black to accomplish high optical density.
  • An object of the present invention is to provide a black photosensitive resin composition which may produce a cured film that satisfies good adhesion, surface roughness and high light shielding property (optical density), particularly a black column spacer having good height difference property, and a cured film prepared therefrom.
  • a black photosensitive resin composition which comprises (A) an acrylic copolymer; (B) an epoxy resin or a compound derived therefrom; (C) an epoxy compound different from (A) and (B); (D) a photopolymerizable compound; (E) a photoinitiator; and (F) a black colorant.
  • the black photosensitive resin composition of the present invention may form a cured film exhibiting good adhesion, good height difference property, good surface roughness and high light shielding property (optical density) and may be effectively used for the formation of a cured film, particularly a black column spacer of a liquid crystal display (LCD) or an organic light-emitting diode (OLED) display.
  • LCD liquid crystal display
  • OLED organic light-emitting diode
  • Fig. 1 is a schematic diagram showing each shape and height difference (step) of a main column spacer (Main CS) and a sub column spacer (Sub CS) formed in Experimental Example 1.
  • Fig. 2 is a schematic diagram showing each of a mask of a 100% full tone (F/T) column spacer pattern and a mask of a 30% half tone (H/T) column spacer pattern, which are used in Experimental Example 1.
  • the black photosensitive resin composition according to the present invention may comprise (A) an acrylic copolymer; (B) an epoxy resin or a compound derived therefrom; (C) an epoxy compound different from (A) and (B); (D) a photopolymerizable compound; (E) a photoinitiator; and (F) a black colorant, and may further comprise (G) a solvent, and (H) a surfactant and/or (I) a silane coupling agent as additives, if desired.
  • (meth)acryl means acryl and/or methacryl
  • (meth)acrylate means acrylate and/or methacrylate
  • the black photosensitive resin composition of the present invention may include an acrylic copolymer, which may be a random copolymer.
  • the copolymer of the present invention includes (A-1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride or a combination thereof, and (A-2) a structural unit derived from an ethylenically unsaturated compound containing an aromatic ring, and may additionally include (A-3) a structural unit derived from an ethylenically unsaturated compound different from the structural units (A-1) and (A-2).
  • the copolymer is an alkali-soluble resin for achieving desired developability during a development step and may function as both of a basic support for forming a film after coating and a structure for accomplishing final patterns.
  • the structural unit (A-1) is derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a combination thereof.
  • the ethylenically unsaturated carboxylic acid or the ethylenically unsaturated carboxylic anhydride is a polymerizable unsaturated monomer having at least one carboxyl group in the molecule.
  • ethylenically unsaturated carboxylic acid and the ethylenically unsaturated carboxylic anhydride may include an unsaturated monocarboxylic acid such as (meth)acrylic acid, crotonic acid, ⁇ -chloroacrylic acid, and cinnamic acid; an unsaturated dicarboxylic acid and an anhydride thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; an unsaturated polycarboxylic acid of trivalence or more and an anhydride thereof; and a mono[(meth)acryloyloxyalkyl] ester of a polycarboxylic acid of divalence or more such as mono[2-(meth)acryloyloxyethyl] succinate, and mono[2-(meth)acryloyloxyethyl] phthalate.
  • the structural unit derived from the above-exemplified compounds may be included in a copolymer alone or as a combination of two or more thereof.
  • the amount of the structural unit (A-1) may be 5 to 65 mole%, preferably 10 to 50 mole% based on the total number of moles of the structural units constituting the copolymer to easily maintain developability.
  • the structural unit (A-2) is derived from an ethylenically unsaturated compound containing an aromatic ring.
  • ethylenically unsaturated compound containing an aromatic ring may include phenyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, phenoxy diethylene glycol (meth)acrylate, p -nonylphenoxy polyethylene glycol (meth)acrylate, p -nonylphenoxy polypropylene glycol (meth)acrylate, tribromophenyl (meth)acrylate; styrene; styrene containing an alkyl substituent such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and oct
  • the structural unit derived from the above-exemplified compounds may be included in a copolymer alone or as a combination of two or more thereof.
  • the styrene compounds are preferred in consideration of polymerization properties.
  • the amount of the structural unit (A-2) may be 2 to 70 mole%, preferably 5 to 60 mole% in consideration of chemical resistance, based on the total number of moles of the structural units constituting the copolymer.
  • (A-3) Structural unit derived from an ethylenically unsaturated compound different from the structural units (A-1) and (A-2)
  • the copolymer of the present invention may further include a structural unit (A-3) derived from an ethylenically unsaturated compound different from the structural units (A-1) and (A-2) in addition to the structural units (A-1) and (A-2).
  • ethylenically unsaturated compound different from the structural units (A-1) and (A-2) may include an unsaturated carboxylic acid ester such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, isobutyl (meth)acrylate, t -butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, methyl ⁇ -hydroxymethylacrylate, ethyl ⁇ -hydroxymethylacrylate, propyl (
  • the structural unit derived from the above-exemplified compounds may be included in a copolymer alone or as a combination of two or more thereof.
  • the structural unit (A-3) may be derived from an ethylenically unsaturated compound containing an epoxy group and/or an unsaturated imide, preferably, glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and/or N- substituted maleimide may be used in consideration of the improvement of copolymerization property and the strength of an insulating film.
  • the amount of the structural unit (A-3) may be 10 to 80 mole%, preferably 20 to 75 mole%, based on the total number of moles of the structural units constituting the copolymer. Within this amount range, the storage stability of a black photosensitive resin composition may be maintained and the retention rate may be improved.
  • Examples of the copolymer having the structural units (A-1) to (A-3) may include a (meth)acrylic acid/styrene copolymer, a (meth)acrylic acid/benzyl (meth)acrylate copolymer, a (meth)acrylic acid/styrene/methyl (meth)acrylate copolymer, a (meth)acrylic acid/styrene/methyl (meth)acrylate/glycidyl (meth)acrylate copolymer, a (meth)acrylic acid/styrene/methyl (meth)acrylate/glycidyl (meth)acrylate/ N -phenyl maleimide copolymer, a (meth)acrylic acid/styrene/methyl (meth)acrylate/glycidyl (meth)acrylate/ N -cyclohexyl maleimide copolymer, a (meth)acrylic acid/styrene/n
  • One or more copolymers may be included in the black photosensitive resin composition.
  • the amount of the copolymer in the entire black photosensitive resin composition may be 5 to 60 wt%, preferably, 7 to 50 wt%, more preferably, 10 to 40 wt% based on the total amount of the black photosensitive resin composition excluding solvents ( i.e. , based on solid content). Within this range, the composition would produce a coating film having a good profile after development and improved chemical resistance.
  • the weight average molecular weight (Mw) of the copolymer thus prepared with reference to polystyrene may be in the range of 3,000 to 50,000, preferably, 5,000 to 40,000, when determined by gel permeation chromatography (GPC, using tetrahydrofuran as eluent). Within this range, the composition would have good adhesion to a substrate, physical/chemical properties, and viscosity.
  • the copolymer may be prepared by charging a molecular weight regulator, a radical polymerization initiator, a solvent, and respective compounds that provide the structural units (A-1) to (A-3), introducing nitrogen, and subjecting the mixture to polymerization with slow agitation.
  • the molecular weight regulator may be a mercaptan compound such as butyl mercaptan and octyl mercaptan, or an ⁇ - methylstyrene dimer, but is not limited thereto.
  • the radical polymerization initiator may be an azo compound such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl peroxide, t -butyl peroxypivalate and 1,1-bis( t -butylperoxy)cyclohexane, but is not limited thereto.
  • the radical polymerization initiator may be used alone or as a mixture of two or more thereof.
  • the solvent may be any solvent commonly used in the preparation of a copolymer and may include, e.g. , propylene glycol monomethyl ether acetate (PGMEA).
  • PGMEA propylene glycol monomethyl ether acetate
  • the black photosensitive resin composition of the present invention includes an epoxy resin or a compound derived therefrom.
  • the epoxy resin or the compound derived therefrom may have a cado backbone structure.
  • the epoxy resin or the compound derived therefrom may have a weight average molecular weight when determined by gel permeation chromatography, with reference to polystyrene, of 3,000 to 18,000, preferably, 5,000 to 10,000. Within this range, the resin composition would produce a coating film having a good height difference property and a good pattern profile after development.
  • the epoxy resin having a cado backbone structure may be represented by the following Formula 1:
  • X is each independently , , , or ;
  • L 1 is each independently C 1-10 alkylene, C 3-20 cycloalkylene, or C 1-10 alkyleneoxy;
  • 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;
  • n is an integer of 0 to 10.
  • C 1-10 alkylene may include methylene, ethylene, propylene, isopropylene, butylenes, isobutylene, sec -butylene, t- butylene, pentylene, isopentylene, t- pentylene, hexylene, heptylene, octylene, isooctylene, t- octylene, 2-ethylhexylene, nonylene, isononylene, decylene, isodecylene, or the like.
  • C 3-20 cycloalkylene may include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, decalinylene, adamantylene, or the like.
  • C 1-10 alkyleneoxy may include methyleneoxy, ethyleneoxy, propyleneoxy, butyleneoxy, sec- butyleneoxy, t- butyleneoxy, pentyleneoxy, hexyleneoxy, heptyleneoxy, octyleneoxy, 2-ethyl-hexyleneoxy, or the like.
  • C 1-10 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec -butyl, t- butyl, pentyl, isopentyl, t- pentyl, hexyl, heptyl, octyl, isooctyl, t- octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, or the like.
  • C 1-10 alkoxy may include methoxy, ethoxy, propoxy, butyloxy, sec -butoxy, t- butoxy, pentoxy, hexyloxy, heptoxy, octyloxy, 2-ethyl-hexyloxy, or the like.
  • C 2-10 alkenyl may include vinyl, allyl, butenyl, propenyl, or the like.
  • C 6-14 aryl may include phenyl, tolyl, xylyl, naphthyl, or the like.
  • the epoxy resin having the cardo backbone structure may be prepared through the synthesis route of below:
  • Hal is halogen; and X, R 1 , R 2 and L 1 are the same as defined in Formula 1.
  • the compound derived from an epoxy resin having a cado backbone structure may be a compound obtained by reacting an epoxy resin having a cado backbone structure with an unsaturated basic acid to produce an epoxy adduct and then reacting the epoxy adduct with a polybasic anhydride, or by further reacting the product thus obtained with a monofunctional or polyfunctional epoxy compound.
  • the unsaturated basic acid may use well-known acids including acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, or the like.
  • the polybasic anhydride may use well-known compounds including succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, hexahydrophthalic anhydride, or the like.
  • the monofunctional or polyfunctional epoxy compound may use well-known compounds including glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, bisphenol Z glycidyl ether, or the like.
  • the compound derived from the epoxy resin having the cardo backbone structure may be prepared through the synthesis route of below:
  • R 9 is 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 10 and R 11 are each independently a saturated or unsaturated C 6 aliphatic ring, or a benzene ring;
  • n is an integer from 1 to 10;
  • X, R 1 , R 2 and L 1 are the same as defined in Formula 1.
  • the cado backbone structure may improve adhesion between a cured product and a substrate, alkaline resistance, processability, strength, etc., and may produce more accurate images from minute patterns after removing uncured parts by development.
  • the amount of the epoxy resin or the compound derived therefrom may be 5 to 50 wt%, preferably, 7 to 40 wt%, more preferably, 10 to 35 wt% based on the total weight of a black photosensitive resin composition excluding solvents ( i.e. , based on solid content). Within the range, resolution and chemical resistance may be improved, and pattern profile maintaining pattern shape with a constant height difference to a desired margin width (allowed width) between patterns may be favorably attained.
  • the black photosensitive resin composition of the present invention may include 10 to 40 wt% of the acrylic copolymer (A) based on the total weight of the black photosensitive resin composition (based on solid content) and may include 10 to 40 wt% of the epoxy resin or the compound derived therefrom (B) based on the total weight of the black photosensitive resin composition (based on solid content).
  • the weight ratio of acrylic copolymer (A) : the epoxy resin or the compound derived therefrom (B) may be 40 to 80 : 60 to 20, and particularly, 40 to 75 : 60 to 25.
  • the black photosensitive resin composition of the present invention includes an epoxy compound other than (A) and (B), and such epoxy compound may be a homopolymer or copolymer having a structural unit derived from a monomer having an epoxy group and an unsaturated double bond.
  • Examples of the monomer having an epoxy group and an unsaturated double bond may include glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 5,6-epoxyhexyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 2,3-epoxycyclopentylmethyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, ⁇ -ethyl glycidyl acrylate, ⁇ -n -propyl glycidyl acrylate, ⁇ -n -butyl glycidyl acrylate, N- (4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl)acrylamide, N -(4-(2,3- epoxypropoxy)-3,
  • Other monomers copolymerizable with the monomer having an epoxy group and an unsaturated double bond include at least one selected from the group consisting of an unsaturated carboxylic acid ester such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, isobutyl (meth)acrylate, t -butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, methyl- ⁇ -hydroxymethylacrylate, ethyl- ⁇
  • the epoxy compound used in the present invention may be synthesized by a conventional method.
  • an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a mixture thereof may be added to a (co)polymer derived from a monomer having an epoxy group and an unsaturated double bond and may be polymerized, to produce a copolymer having an epoxy group and a double bond in a side chain.
  • the ethylenically unsaturated carboxylic acid, the ethylenically unsaturated carboxylic anhydride, or a mixture thereof may be at least one selected from the group consisting of an unsaturated monocarboxylic acid such as (meth)acrylic acid, crotonic acid, alpha-chloroacrylic acid and cinnamic acid; an unsaturated dicarboxylic acid and an anhydride thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; an unsaturated polycarboxylic acid of trivalence or more and an anhydride thereof; and a mono[(meth)acryloyloxyalkyl] ester of a polycarboxylic acid of divalence or more such as mono[2-(meth)acryloyloxyethyl] succinate, and mono[2-(meth)acryloy
  • the copolymer having an epoxy group and a double bond in a side chain is preferable in consideration of retention rate.
  • the amount of the epoxy compound may be 0.1 to 10 wt%, preferably, 0.1 to 5 wt% based on the total weight of the photosensitive resin composition excluding solvents (based on solid content). Within this range, adhesion after development or adhesion after immersing in an NMP solvent may be improved.
  • the weight average molecular weight of the epoxy compound ((co)polymer derived from a monomer having an epoxy group and an unsaturated double bond) may be in the range of 1,000 to 9,000, preferably, 1,000 to 7,000, more preferably, 2,000 to 5,000 when determined by gel permeation chromatography with reference to polystyrene. With the weight average molecular weight, adhesion may be improved and good chemical resistance may be attained.
  • the photopolymerizable compound of the present invention is a compound capable of being polymerized by the function of a photoinitiator and may include a polyfunctional monomer, oligomer, or polymer, which is generally used in a black photosensitive resin composition.
  • the photopolymerizable compound may include a monofunctional or polyfunctional ester compound of acrylic acid or methacrylic acid having at least one ethylenically unsaturated group.
  • a polyfunctional compound having at least two functional groups may be preferable in consideration of chemical resistance.
  • the photopolymerizable compound may be selected from the group consisting of ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, monoester of pentaerythritol tri(meth)acrylate and succinic acid, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, monoester of dipentaerythritol
  • the amount of the photopolymerizable compound may be 1 to 50 wt%, preferably 5 to 40 wt% on the basis of the total weight of the black photosensitive resin composition excluding solvents (i.e., based on solid content). Within this range, the resin composition would readily form a pattern without generating defects of pattern profile such as scum at the bottom part during development.
  • the photopolymerization initiator used in the present invention may be any known polymerization initiator.
  • the photopolymerization initiator may be selected from the group consisting of an acetophenone compound, a non-imidazole compound, a triazine compound, an onium compound, a benzoin compound, a benzophenone compound, a diketone compound, an ⁇ -diketone compound, a polynuclear quinone compound, a thioxanthene compound, a diazo compound, an imidesulfonate compound, an oxime compound, a carbazole compound, a sulfonium borate compound, and a mixture thereof.
  • Preferred for high sensitivity are one or more oxime compounds disclosed in Korean Laid-open 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 Publication Nos. WO 2010/102502, and WO 2010/133077.
  • Preferred for high sensitivity and resolution are commercially available photopolymerization initiators such as OXE-01 (BASF Co. Ltd.), OXE-02 (BASF Co. Ltd.), OXE-03 (BASF Co. Ltd.), N-1919 (ADEKA Co. Ltd.), NCI-930 (ADEKA Co. Ltd.) and NCI-831 (ADEKA Co. Ltd.).
  • the photopolymerization initiator may be included in an amount of 0.01 to 15 wt%, preferably 0.1 to 10 wt%, based on the total solid content (excluding solvents) of the photosensitive resin composition. Within this range, curing by exposure may be sufficiently attained, and a column spacer having good elasticity recovery ratio may be manufactured.
  • the black photosensitive resin composition of the present invention includes a black colorant for imparting light shielding properties.
  • the black colorant used in the present invention may be a black inorganic colorant, a black organic colorant, or a mixture thereof.
  • the black inorganic colorant and the black organic colorant may be any known material and may include any compound, for example, classified as a pigment by color index (The Society of Dyers and Colourists printed), and any known dye may be included.
  • any colorant with a chromatic color such as blue may be optionally included in addition to the black colorant.
  • the black inorganic colorant may include carbon black, titanium black, Cu-Fe-Mn-based oxides, and metal oxides such as synthetic iron black.
  • carbon black is preferable in consideration of pattern properties and chemical resistance.
  • black organic colorant may include aniline black, lactam black, perylene black, etc.
  • lactam black for example, Black 582 of BASF
  • the black colorant may include 90 wt% or more of the black inorganic colorant on the basis of the total weight of the colorant (based on solid content), and may additionally include 0 to 10 wt% of the black organic colorant. Within this range, high optical density capable of preventing the leakage of light in visible and infrared regions may be favorably attained.
  • the amount of the black colorant may be 10 to 60 wt%, 20 to 50 wt%, 20 to 45 wt%, 25 to 50 wt%, or 25 to 45 wt% based on the total weight of the black photosensitive resin composition excluding solvents ( i.e. , based on solid content).
  • optical density of 0.5 to 2.5, preferably, 0.8 to 2.0, more preferably, 1.0 to 2.3, more preferably, 1.0 to 2.0, may be attained.
  • the prevention of light leakage may be effectively accomplished.
  • a dispersant may be used.
  • Such dispersant may be any known dispersant of a colorant.
  • the dispersant may include a cationic surfactant, an anionic surfactant, a nonionic surfactant, a zwitterionic surfactant, a silicone-based surfactant, a fluorine-based surfactant, or the like.
  • Commercially available dispersant may include Disperbyk-182, -183, -184, -185, -2000, -2150, -2155, -2163, -2164, etc. of BYK Co. Ltd.
  • the materials may be used alone or as a combination of two or more thereof.
  • the dispersant may be used by adding to a colorant by a method treating the surface of the colorant in advance, or may be used by adding together with a colorant in the process of preparing a black photosensitive resin composition.
  • the mixture may be used for the preparation of a black photosensitive resin composition.
  • a binder may be the copolymer (A) described above, a known copolymer, or a mixture thereof.
  • the colorant used in the present invention may be added to a black photosensitive resin composition in the form of a colorant mill base obtained by mixing the colorant with a dispersant, a binder, a solvent, etc.
  • the black photosensitive resin composition of the present invention may preferably be prepared as a liquid composition mixing the above components with a solvent.
  • the solvent may be any known solvent used in a black photosensitive resin composition, as long as the solvent has compatibility but not reactivity with the components of the black photosensitive resin composition.
  • solvent examples 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 glycols 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.
  • 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 glycols such as diethylene glycol monomethyl ether
  • propylene glycol alkyl ether acetates such as propylene glycol
  • the amount of the solvent is not particularly limited, and may be an amount such that the total concentration of each component of the composition excluding solvents ( i.e. , based on solid content) may be 5 to 70 wt%, preferably, 10 to 55 wt%, in consideration of the coatability and stability of a final black photosensitive resin composition.
  • the black photosensitive resin composition of the present invention may further include a surfactant, if desired, to enhance its coatability and to prevent the generation of defects.
  • the type of surfactants is not particularly limited, but preferred are fluorine-based surfactants, silicon-based surfactants, and the like.
  • silicon-based surfactant may include DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 manufactured by Dow Corning Toray Silicon, TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, and TSF-4452 manufactured by GE Toshiba Silicon, and BYK-333, BYK 307, BYK 3560, BYK UV 3535, BYK 361N, BYK 354, and BYK 399 manufactured by BYK. These surfactants may be used alone or in combination of two or more thereof.
  • fluorine-based surfactant may include Megaface F-470, F-471, F-475, F-482, F-489, F-563, RS-55, etc. manufactured by Dai Nippon Ink Kagaku Kogyo (DIC). Among them, BYK 333, and BYK 307 of BYK, F-563 of DIC, and Megaface RS-55 of Dai Nippon Ink Kagaku Kogyo may be used.
  • the amount of the surfactant may be 0.01 to 10 wt%, preferably, 0.05 to 5 wt%, based on the total weight of the black photosensitive resin composition excluding solvents ( i.e. , based on solid content). Within the amount range, the black photosensitive resin composition can be readily coated.
  • the black photosensitive resin composition of the present invention may additionally include a silane coupling agent containing a reactive substituent selected from the group consisting of carboxyl, (meth)acryloyl, isocyanate, amino, mercapto, vinyl, epoxy, and a combination thereof, as an adhesion assisting agent to improve the adhesion of a coating to a substrate.
  • a silane coupling agent containing a reactive substituent selected from the group consisting of carboxyl, (meth)acryloyl, isocyanate, amino, mercapto, vinyl, epoxy, and a combination thereof, as an adhesion assisting agent to improve the adhesion of a coating to a substrate.
  • the kind of the silane coupling agent is not particularly limited and may be selected from the group consisting of trimethoxysilyl benzoic acid, ⁇ -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, ⁇ - isocyanatopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - glycidoxypropyltriethoxysilane, ⁇ - (3,4-epoxycyclohexyl)ethyltrimethoxysilane, phenylaminotrimethoxysilane, and a mixture thereof.
  • ⁇ -isocyanatopropyltriethoxysilane containing an isocyanate group e.g. , KBE-9007 manufactured by Shin-Etsu
  • phenylaminotrimethoxysilane which can maintain chemical resistance and have good adhesion of a coating to a substrate.
  • the amount of the silane coupling agent may be 0.01 to 10 wt%, preferably, 0.05 to 5 wt% based on the total weight of the black photosensitive resin composition excluding solvents ( i.e. , based on solid content). Within this amount range, the adhesion of the black photosensitive resin composition may be further improved.
  • the black photosensitive resin composition of the present invention may further include other additives such as an antioxidant and a stabilizer as long as the physical properties of the composition are not adversely affected.
  • the black photosensitive resin composition of the present invention includes a large amount of a black colorant (pigment), a cured film prepared therefrom shows good adhesion, height difference, surface roughness, and light shielding properties.
  • a black photosensitive resin composition including the above-described components according to the present invention may be prepared by a conventional method, and an embodiment thereof is as follows.
  • a black colorant is mixed with a solvent in advance and then is dispersed using a bead mill, etc. until a desired average particle diameter of the black colorant is obtained.
  • a surfactant may be used, and part of or the entire copolymer may be mixed.
  • an epoxy resin or a compound derived therefrom, an epoxy compound, a photopolymerization compound and a photoinitiator are added, and if desired, an additive such as a surfactant and a silane coupling agent is added, or an additional solvent is mixed to attain a certain concentration.
  • the mixture is sufficiently agitated to produce a black photosensitive resin composition of the present invention.
  • the present invention provides a black column spacer (BCS) formed using the black photosensitive resin composition.
  • An embodiment of a black column spacer pattern is shown in Fig. 1.
  • the black column spacer may be manufactured via the steps of forming a coating film, exposing, developing, and heating.
  • a black photosensitive resin composition according to the present invention is coated by a spin or slit coating method, a roll coating method, a screen printing method, an applicator method, etc. in a thickness of, for example, 1 to 25 ⁇ m, on a pre-treated substrate and then is pre-cured to remove solvents at a temperature of 70°C to 100°C for 1 to 10 minutes to form a coating film.
  • a mask having a certain shape is disposed, and an activation beam of 200 to 500nm is irradiated.
  • a mask having a pattern with different light transmittances may be used to accomplish a main column spacer and a sub column spacer at the same time.
  • a light source used for irradiation a low pressure mercury lamp, a high pressure mercury lamp, a ultra-high pressure mercury lamp, a metal halogenide lamp, an argon gas laser, or the like may be used, and X-rays, electron beams, etc. may be used if necessary.
  • Exposure intensity varies with the kind, and the mixing ratio of each component in the composition and the thickness of a dried film, and may be 500mJ/cm 2 or less (at a wavelength of 365nm) for a high pressure mercury lamp.
  • aqueous alkaline solution such as sodium carbonate, sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide, as a developing solution to maintain exposed parts only to form a pattern.
  • an aqueous alkaline solution such as sodium carbonate, sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide
  • the black column spacer thus manufactured may be useful as electronic parts of an LCD, OLED display, or the like.
  • the LCD, OLED display, or the like may include well-known parts to a person skilled in the art in addition to the spacer of the present invention. That is, an LCD, OLED display, or the like in which the black column spacer of the present invention may be applied, may be encompassed by in the present invention.
  • the weight average molecular weight is determined by gel permeation chromatography (GPC) using a polystyrene standard.
  • the reaction mixture thus obtained was heated to 90°C for 1 hour to remove 4,4'-(9-fluorenylidene)diphenol completely, which was confirmed by HPLC or TLC.
  • the reaction mixture was cooled to 30°C, and 400mL of dichloromethane and 300mL of 1N HCl were added thereto with stirring. Then, the organic layer was separated, washed with 300mL of distilled water twice or three times, dried over magnesium sulfate, and distilled under a reduced pressure to remove dichloromethane.
  • the resultant was recrystallized using a mixture of dichloromethane and methanol to obtain the title compound, an epoxy resin compound.
  • Step (2) Preparation of (((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(2-hydroxypropane-3,1-diyl) diacrylate (CAS No. 143182-97-2)
  • step (1) To a 1,000mL three-neck flask, 115g of the compound obtained in step (1), 50mg of tetramethylammonium chloride, 50mg of 2,6-bis(1,1-dimethylethyl)-4-methylphenol and 35g of acrylic acid were added. The mixture was heated to 90 to 100°C while blowing air at a flow rate of 25mL/min and further heated to 120°C to obtain a solution. The resulting solution was stirred for about 12 hours until its acid value dropped to less than 1.0 mg KOH/g and then cooled to room temperature. 300mL of dichloromethane and 300mL of distilled water were added to the reaction mixture with stirring. Then, the organic layer was separated, washed with 300mL of distilled water twice or three times, dried over magnesium sulfate, and distilled under a reduced pressure to remove dichloromethane, thereby providing the title compound.
  • Step (3) Preparation of a compound derived from an epoxy resin having a cardo backbone structure
  • step (2) The compound obtained in step (2) in PGMEA was placed into a 1,000mL three-neck flask, and 1,2,4,5-benzenetetracarboxylic dianhydride(0.75eq), 1,2,3,6-tetrahydrophthalic anhydride(0.5eq) and triphenylphosphine(0.01eq) were further added thereto.
  • the reaction mixture was heated to 120 to 130°C for 2 hours with stirring and then cooled to 80 to 90°C, followed by stirring for 6 hours. After cooling to room temperature, a solution (solid content of 49wt%) of polymer having a weight average molecular weight (Mw) of 6,000 and an acid value of 107mg KOH/g (based on solid content) was obtained.
  • the colored dispersion (F-1) was supplied from Tokushiki Co., which was prepared by the following method;
  • 8g of an acrylic copolymer solution (Tokushiki Co.) having a weight average molecular weight of 12,000 to 20,000 g/mol and an acid value of 80 to 150 mgKOH/g, 8g of an acrylic polymer dispersion (Tokushiki Co.) having an amine value of 100 to 140 mgKOH/g, 80g of carbon black as inorganic black, and 384g of PGMEA as a solvent were dispersed using a paint shaker at 25°C for 6 hours. The dispersion was carried out using 0.3mm zirconia beads. After dispersion was finished, beads and a dispersed solution were separated using a filter to prepare a colored dispersion having a solid content of 23wt%.
  • the colored dispersion (F-2) was supplied from Tokushiki Co., which was prepared by the following method;
  • Black photosensitive resin compositions were prepared by carrying out the same procedure described in Example 1 except for changing the kind and/or amount of each component as listed in Table 1 below.
  • Each of the black photosensitive resin compositions prepared in the examples and the comparative examples was coated on a glass substrate using a spin coater, and was pre-baked at 100°C for 100 seconds to form a coating film.
  • a pattern mask of a 100% full-tone (F/T) column spacer (CS) and a pattern mask of a 30% half-tone (H/T) column spacer (CS) were applied, respectively, and a light having a wavelength of 365nm was irradiated with the intensity of 42mJ/cm 2 with the gap of 150 ⁇ m between the cured film and the mask.
  • the coating film was developed at 23°C for 15 seconds using a diluted aqueous solution having 0.04wt% of potassium hydroxide, and washed with pure water for 1 minute.
  • the pattern thus formed was post-baked at 230°C for 30 minutes in an oven to obtain a cured film.
  • each of thickness A and thickness B was measured using a height difference measuring apparatus (SNU(SIS-2000), SNU Precision).
  • SNU height difference measuring apparatus
  • thickness difference A-B is 0.3 to 0.5 ⁇ m, good height difference property may be expected.
  • an exposure intensity for reproducing a constant dot pattern using a 30% H/T pattern mask with a diameter of 20 ⁇ m was obtained, and a pattern capable of being developed was checked. If a dot pattern had a minimum pattern size of 10 ⁇ m or less and was not exfoliated after immersing the pattern in 100% N- methyl pyrrolidone (NMP) solution at 80°C for 10 minutes, the adhesion was evaluated as ⁇ . On the other hand, if a dot pattern had a size greater than 10 ⁇ m or was exfoliated after immersing the pattern in an NMP solution at 80°C for 10 minutes, the adhesion was evaluated as ⁇ .
  • NMP N- methyl pyrrolidone
  • each surface was observed using a scanning electron microscope (SEM, S-4300, Hitachi). If surface particles were found to be aggregated, the surface properties were evaluated as bad( ⁇ ), and if surface particles were found to be smooth, the surface properties were evaluated as good( ⁇ ).
  • the manufacture of a cured film was carried out without using a mask, to form a cured film having a thickness of 3.0 ⁇ m after post-baking.
  • transmittance at 550nm was measured using an optical density system (361T, Xlite), and optical density with respect to a thickness of 1 ⁇ m was obtained.
  • the cured films (Main CS and Sub CS) manufactured from the black photosensitive resin compositions of Examples 1 to 7 had good coatability, height difference, adhesion to a substrate, surface roughness and optical density.
  • the cured films of the examples showed height difference of 0.3 to 0.5 ⁇ m, and good surface roughness, coatability and adhesion. Accordingly, both pattern forming properties and developability were good.
  • the cured films manufactured from the photosensitive resin compositions of Comparative Examples 1 to 3, which do not contain any one of a copolymer, an epoxy resin or a compound derived therefrom and an epoxy compound had poor surface roughness.
  • Comparative Examples 1 and 2 had inferior height difference properties, and Comparative Example 3 exhibited inferior adhesion to a substrate.
  • the black photosensitive resin composition according to the present invention can be effectively used as a black column spacer in various electronic devices such as an LCD and OLED display.

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Abstract

L'invention concerne une composition de résine photosensible noire et un élément d'espacement de colonne noir préparé à partir de cette dernière. La composition de résine photosensible noire peut former un film durci présentant une bonne adhérence à un substrat, une bonne propriété de différence de hauteur, une bonne rugosité de surface et des propriétés pare-lumière élevées (densité optique), et peut être utilisée efficacement pour la formation d'un film durci, en particulier un élément d'espacement de colonne noir, d'un écran à cristaux liquides (LCD) ou d'un écran à diode électroluminescente organique (DELO).
PCT/KR2016/013396 2016-01-18 2016-11-21 Composition de résine photosensible noire et élément d'espacement de colonne noir préparé à partir de cette dernière WO2017126795A1 (fr)

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CN201680076438.5A CN108475013B (zh) 2016-01-18 2016-11-21 黑色感光性树脂组合物和由其制备的黑色柱状间隔物
US16/066,475 US10884335B2 (en) 2016-01-18 2016-11-21 Black photosensitive resin composition and black column spacer prepared therefrom
JP2018533178A JP7079198B2 (ja) 2016-01-18 2016-11-21 黒色感光性樹脂組成物及びそれから調製される黒色カラムスペーサ

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KR10-2016-0006040 2016-01-18
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KR1020160154303A KR102674718B1 (ko) 2016-01-18 2016-11-18 흑색 감광성 수지 조성물 및 이로부터 제조된 블랙 컬럼 스페이서

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JP2019032512A (ja) * 2017-08-07 2019-02-28 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． 着色感光性樹脂組成物、これを含むカラーフィルタおよびこれを含む表示装置

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JP2010237488A (ja) * 2009-03-31 2010-10-21 Toppan Printing Co Ltd 感光性樹脂組成物、カラーフィルタ及びカラーフィルタの製造方法。
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JP2015084086A (ja) * 2013-09-20 2015-04-30 三菱化学株式会社 感光性樹脂組成物、それを硬化させてなる硬化物、ブラックマトリックス及び画像表示装置
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KR20070036816A (ko) * 2005-09-30 2007-04-04 주식회사 동진쎄미켐 감광성 수지 조성물
JP2010237488A (ja) * 2009-03-31 2010-10-21 Toppan Printing Co Ltd 感光性樹脂組成物、カラーフィルタ及びカラーフィルタの製造方法。
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JP2019032512A (ja) * 2017-08-07 2019-02-28 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． 着色感光性樹脂組成物、これを含むカラーフィルタおよびこれを含む表示装置

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