+

WO2013032190A1 - Résine insaturée photopolymérisable, composition de résine photosensible la comprenant, et espaceur protégeant de la lumière et dispositif d'affichage à cristaux liquides formés de ceux-ci - Google Patents

Résine insaturée photopolymérisable, composition de résine photosensible la comprenant, et espaceur protégeant de la lumière et dispositif d'affichage à cristaux liquides formés de ceux-ci Download PDF

Info

Publication number
WO2013032190A1
WO2013032190A1 PCT/KR2012/006802 KR2012006802W WO2013032190A1 WO 2013032190 A1 WO2013032190 A1 WO 2013032190A1 KR 2012006802 W KR2012006802 W KR 2012006802W WO 2013032190 A1 WO2013032190 A1 WO 2013032190A1
Authority
WO
WIPO (PCT)
Prior art keywords
glycidyl ether
group
anhydride
black
epoxy
Prior art date
Application number
PCT/KR2012/006802
Other languages
English (en)
Inventor
Gyung-Sik Choi
Sun Ryu
Kyung-Jae Park
Cheon-Sun PARK
Hag-Ju Lee
Hyeon-Jin YUN
Original Assignee
Rohm And Haas Electronic Materials Korea Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rohm And Haas Electronic Materials Korea Ltd. filed Critical Rohm And Haas Electronic Materials Korea Ltd.
Priority to JP2014527083A priority Critical patent/JP6093766B2/ja
Priority to CN201280052030.6A priority patent/CN103890659A/zh
Publication of WO2013032190A1 publication Critical patent/WO2013032190A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/064—Polymers containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • 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 novel photopolymerizable unsaturated resin, a photosensitive resin composition comprising the same, and a light shielding spacer and a liquid crystal display device formed therefrom.
  • a liquid crystal display (LCD) device as one type of flat panel display devices, which are currently widely being used, comprises a thin film transistor (TFT) substrate on which pixel electrodes are formed; a color filter substrate on which a common electrode is formed and which faces the TFT substrate; and a liquid crystal layer inserted between the TFT substrate and the color filter substrate.
  • TFT thin film transistor
  • Such an LCD device displays images in a manner of controlling the amount of light transmitting the liquid crystal layer by applying a voltage to the pixel electrodes and common electrode and rearranging the liquid crystal molecules of the liquid crystal layer.
  • a spacer is formed from a photosensitive composition by generally using lithography.
  • the spacer should have light-shielding properties in order to prevent malfunction of a TFT as a switching device caused by incident light.
  • carbon black be mixed with a photosensitive resin composition.
  • an electrical distortion phenomenon is generated by an electrical field applied to the upper and lower substrates, due to the high dielectric constant of carbon black. Therefore, it is required to develop a spacer that has excellent light-shielding properties and a low dielectric constant.
  • a photosensitive resin composition used in the preparation of a light-shielding spacer is generally a black composition prepared by mixing dyes having different colors or various types of dyes, wherein said dyes do not easily dissolve in a developing solution. Due to the low solubility in the developing solution, the dyes have problems that developing properties are not good, a long time is consumed in development, or a desired degree of resolution is not obtained. In particular, the importance of resolution is further increased in the case of forming colored independent dot spacer patterns.
  • Korean Patent Application Laid-Open No. 2010-0066197 discloses a black photosensitive resin composition, which has good pattern formability, and exhibits high compression displacement and a high recovery rate, as well as a low dielectric constant and superior optical density when forming a thin film.
  • said document does not take the resolution of a thin film formed from the composition into consideration, and regards a recovery rate of 70% as being proper, which does not satisfy the level of the recovery rate required by the relevant industry.
  • Japanese Patent Application Laid-Open No. 2002-040440 discloses a radiation-sensitive composition, which is capable of forming a spacer having excellent light-shielding properties and high mechanical strength and heat resistance, which is not deformed irreversibly during the sealing of panels, and which does not generate display defects due to a gap difference in liquid crystal layers.
  • the document does not take dielectric constant or resolution into consideration in a spacer formed from the composition.
  • Patent Document 1 Korean Patent Application Laid-Open No. 2010-0066197
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2002-040440
  • the first aspect of the present invention provides a photopolymerizable unsaturated resin of a novel structure to be included in a photosensitive resin composition.
  • the second aspect of the present invention provides a photosensitive resin composition which includes the novel photopolymerizable unsaturated resin, which can form dot spacer patterns of a size of 10 to 100 ⁇ m due to sufficient solubility in developing solutions before and after light exposure, and which is capable of maintaining excellent light-shielding properties while lowering the dielectric constant of the formed dot spacer patterns.
  • the third aspect of the present invention provides a light shielding spacer, which is formed from the photosensitive resin composition, and which has sufficient resolution and excellent elastic recovery ratio.
  • the fourth aspect of the present invention provides a liquid crystal display device having the light shielding spacer.
  • a photopolymerizable unsaturated resin which is a product (P1) obtained by reacting an epoxy resin(A) represented by formula I with an unsaturated basic acid (B) to form an epoxy adduct (AB), and reacting said adduct with a polybasic acid anhydride (C); or which is a product (P2) obtained by reacting an epoxy resin (A) represented by formula I with an unsaturated basic acid (B) to form an epoxy adduct (AB), reacting said adduct with a polybasic acid anhydride (C) to form a product (P1), and further reacting said product (P1) with a monofunctional or polyfunctional epoxy compound (D).
  • P1 obtained by reacting an epoxy resin(A) represented by formula I with an unsaturated basic acid (B) to form an epoxy adduct (AB), and reacting said adduct with a polybasic acid anhydride (C) to form a product (P1), and further reacting said product (P1) with a monofunctional
  • carbon labeled with * is replaced with a carbon labeled with * in one selected from the groupconsisting of , , and ;
  • L 1 is C 1-10 alkylene, C 3-20 cycloalkylene or C 1-10 alkyleneoxy;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are each independently selected from the group consisting of hydrogen, C 1-10 alkyl, C 1-10 alkoxy, C 2-10 alkenyl and C 6-14 aryl;
  • R 8 is selected from the group consisting of hydrogen, C 1-10 alkyl which is unsubstituted or substituted by halogen or hydroxy, C 2-10 alkenyl and C 6-14 aryl;
  • n is an integer of from 0 to 10.
  • a photosensitive resin composition comprising the photopolymerizable unsaturated resin; a functional monomer having at least one ethylenically unsaturated bond; a polymerization initiator; a black organic pigment; and a solvent.
  • a light shielding spacer formed from the photosensitive resin composition.
  • a liquid crystal display device having the spacer.
  • a photosensitive resin composition comprising a photopolymerizable unsaturated resin according to the present invention can form a light shielding spacer with dot spacer patterns of a size of 10 to 100 ⁇ m due to sufficient solubility in developing solutions before or after light exposure. Further, the formed light shielding spacer has a low dielectric constant of 8 or less, is excellent in light-shielding property by having an optical density per ⁇ m of 1.0 or more, and has sufficient resolution and excellent elastic recovery ratio.
  • the photopolymerizable unsaturated resin which is a product (P1) obtained by the steps of reacting an epoxy resin(A) represented by formula I with an unsaturated basic acid (B) to form an epoxy adduct (AB), and reacting said adduct with a polybasic acid anhydride (C), or a product (P2) obtained by further reacting a monofunctional or polyfunctional epoxy compound (D) with the product (P1).
  • the epoxy adduct (AB) can be obtained by reacting the epoxy resin (A) corresponding to 1 equivalent of an epoxy group with the unsaturated basic acid (B) corresponding to 0.1 to 5 equivalents, preferably 0.2 to 2 equivalents, and more preferably 0.4 to 1 equivalent of a carboxyl group according to known addition reactions.
  • the photopolymerizable unsaturated resin is a product (P1) obtained by reacting the epoxy adduct (AB) corresponding to 1 equivalent of a hydroxyl group with the polybasic acid anhydride (C) corresponding to 0.1 to 5 equivalents, preferably 0.2 to 2 equivalents, and more preferably 0.4 to 1 equivalent of an acid anhydride group.
  • the photopolymerizable unsaturated resin can be obtained by reacting the epoxy adduct (AB) with the polybasic acid anhydride (C) according to known esterification reactions.
  • the photopolymerizable unsaturated resin can be obtained by additionally esterifying a monofunctional or polyfunctional epoxy compound (D) with the product (P1) in an amount of 0.1 to 5 equivalents, preferably 0.2 to 2 equivalents and more preferably 0.3 to 1 equivalent of the epoxy group in the monofunctional or polyfunctional epoxy compound with respect to 1 equivalent of the hydroxyl group of the epoxy adduct (AB).
  • the esterification between the monofunctional or polyfunctional epoxy compound (D) and a product (P1) obtained by esterifying the epoxy adduct (AB) with the polybasic acid anhydride (C) can occur between a carboxyl group derived from the polybasic acid anhydride (C) and an epoxy group of the monofunctional or polyfunctional epoxy compound (D).
  • the photopolymerizable unsaturated resin can be prepared by (i) reacting the epoxy adduct (AB) corresponding to 1 equivalent of a hydroxyl group with the polybasic acid anhydride (C) in such an amount that the sum of an acid anhydride equivalent of the polybasic acid anhydride (C) and an epoxy equivalent in the monofunctional or polyfunctional epoxy compound (D) is not less than 1.0 equivalent, preferably 1.1 to 2.0 equivalents to produce a product, and (ii) further reacting the product with the monofunctional or polyfunctional epoxy compound (D).
  • the photopolymerizable unsaturated binder resin has a weight average molecular weight (Mw) preferably ranging from 1,500 to 20,000, more preferably from 3,000 to 15,000. If a weight average molecular weight of the photopolymerizable unsaturated resin is within the above-mentioned range, handling property and pattern formability are good since the flowability of the resin is maintained within a proper range.
  • Mw weight average molecular weight
  • a photosensitive resin composition according to the present invention may include 0.5 to 50 wt% of a photopolymerizable unsaturated binder resin with respect to the total weight of the photosensitive resin composition except the residual amount of solvent. If the content of the photopolymerizable unsaturated binder resin is within the above-mentioned range, a pattern is easily formed after light exposure and developing processes, the basic physical properties of a light shielding material are satisfied, processing time, such as developing time, and sensitivity are optimized, and characteristics such as compressive properties, chemical resistance and the like are improved.
  • Epoxy resin (A) used in the present invention is a compound represented by the following formula 1 having a 9H-xanthene skeleton.
  • the 9H-xanthene skeleton structure of the epoxy resin (A) functions as a factor that improves adhesion between a cured body and a substrate, alkali resistance, formability, strength and the like, and increases the resolution of micro-patterns when developing and eliminating non-cured portions.
  • carbon labeled with * is replaced with a carbon labeled with * in one selected from the group consisting of , , and ;
  • L 1 is 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 the same as or different from one another and are each independently a hydrogen atom, 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;
  • n is an integer of from 0 to 10.
  • C 1-10 alkylene group may include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a pentylene group, an isopentylene group, a tert-pentylene group, a hexylene group, a heptylene group, an octylene group, an isooctylene group, a tert-octylene group, a 2-ethylhexylene group, a nonylene group, an isononylene group, a decylene group, and an isodecylene group.
  • C 3-20 cycloalkylene group may include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a decalinylene group, and an adamantylene group.
  • C 1-10 alkyleneoxy group may include a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, a sec-butyleneoxy group, a tert-butyleneoxy group, a pentyleneoxy group, a hexyleneoxy group, a heptyleneoxy group, an octyleneoxy group, and a 2-ethyl-hexyleneoxy group.
  • C 1-10 alkyl group may include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a tert-pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a tert-octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, and an isodecyl group.
  • C 1-10 alkoxy group may include a methoxy group, an ethoxy group, a propyloxy group, a butyloxy group, a sec-butoxy group, a tert-butoxy group, a pentoxy group, a hexyloxy group, a heptoxy group, an octyloxy group, and a 2-ethyl-hexyloxy group.
  • C 2-10 alkenyl group may include a vinyl group, an allyl group, a butenyl group, and a propenyl group.
  • C 6-14 aryl group may include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
  • An unsaturated basic acid (B) used in the present invention is used in order to improve the sensitivity of a photosensitive resin composition comprising a photopolymerizable unsaturated resin according to the present invention.
  • Specific examples of the unsaturated basic acid (B) may include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate ⁇ malate, hydroxyethyl acrylate ⁇ malate, hydroxypropyl methacrylate ⁇ malate, hydroxypropyl acrylate ⁇ malate, dicyclopentadiene ⁇ malate, and polyfunctional (meth)acrylate having a carboxyl group and two or more (meth)acryloyl groups, but not limited thereto.
  • the unsaturated basic acids can be used alone or in combinations of two or more thereof.
  • Acrylic acid, methacrylic acid, and polyfunctional (meth)acrylate having a carboxyl group and two or more (meth)acryloyl groups are preferably used as the unsaturated basic acids.
  • the polyfunctional (meth)acrylate having a carboxyl group and two or more (meth)acryloyl groups can be obtained by reacting, e.g., a dibasic acid anhydride or carbonic acid with a polyfunctional (meth)acrylate having a hydroxyl group and two or more (meth)acryloyl groups in a molecule.
  • a polybasic acid anhydride (C) used in the present invention is used in order to improve pattern formability, developing properties and developing rate by increasing the acid value of a photosensitive resin composition comprising a photopolymerizable unsaturated resin according to the present invention.
  • Examples of the polybasic acid anhydride (C) may include one or more selected from the group consisting of succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenone tetra carboxylic dianhydride, 3,3'-4,4'-benzophenone tetra carboxylic dianhydride, ethylene glycol bis(anhydrotrimellitate), glycerol tris(anhydrotrimellitate), phthalic anhydride, hexahydrophthalic anhydride, methyl hydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxy
  • a monofunctional epoxy compound used in the present invention is used in order to further improve the developing property of a photosensitive resin composition by controlling the acid value of the photopolymerizable unsaturated resin.
  • the solid contents of a photosensitive resin composition according to the present invention have an acid value ranging from 20 to 120 mg KOH/g.
  • the amount of a monofunctional epoxy compound is preferably selected to satisfy the above acid value.
  • the monofunctional epoxy compound may include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentade
  • Polyfunctional epoxy compounds used in the present invention play a role of controlling a developing rate by increasing the molecular weight of the photopolymerizable unsaturated resin.
  • polyfunctional epoxy compounds may include polyglycidyl ether of polyvalent alcohol or its alkyleneoxide adduct, polyglycidyl ether of polybasic acid, cyclohexene oxide- or cyclopentene oxide-containing compounds obtained by epoxidating cyclohexene- or cyclopentene-containing compounds with an oxidizer.
  • the examples of the polyfunctional epoxy compounds may include: alkylidene bisphenol polyglycidyl ether type epoxy resins such as bisphenol A type epoxy resin, bisphenol B type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol S type epoxy resin, and bisphenol Z type epoxy resin; water-added bisphenol type diglycidyl ethers obtained by adding water to the alkylidene bisphenol polyglycidyl ether type epoxy resins; glycidyl ethers of aliphatic polyvalent alcohol such as ethyleneglycol diglycidyl ether, 1,3-propyleneglycol diglycidyl ether, 1,2-propyleneglycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol dig
  • polyfunctional epoxy compounds may include, for example, BREN-S, EPPN-201, EPPN-501N, EOCN-1020, GAN, and GOT (Nippon Kayaku Co., Ltd.); Adeka Resin EP-4000, Adeka Resin EP-4003S, Adeka Resin EP-4080, Adeka Resin EP-4085, Adeka Resin EP-4088, Adeka Resin EP-4100, Adeka Resin EP-4900, Adeka Resin ED-505, Adeka Resin ED-506, Adeka Resin KRM-2110, Adeka Resin KRM-2199, and Adeka Resin KRM-2720 (Adeka Corporation); R-508, R-531, and R-710 (Mitsui Chemicals); Epicoat 190P, Epicoat 191P, Epicoat 604, Epicoat 801, Epicoat 825, Epicoat 871, Epicoat 872, Epicoat 1031, Epicoat RXE15, Epicoat YX-4000, Epicoat YDE-205
  • the functional monomer having at least one ethylenically unsaturated bond is a reactive unsaturated compound and is a monomer or oligomer generally used in a photosensitive resin composition, and monofunctional or polyfunctional esters of acrylic acid or methacrylic acid having at least one ethylenically unsaturated double bond could be used.
  • the content of the functional monomer having at least one ethylenically unsaturated bond may be 1 to 50% by weight with respect to the total weight of the photosensitive resin composition excluding the residual amount of solvent. If the content of the functional monomer having at least one ethylenically unsaturated bond is within the above-mentioned range, patterns are formed easily, and it is beneficial in the development margin aspect since overdevelopment of a bottom part is not generated during the developing process.
  • the functional monomer having at least one ethylenically unsaturated bond is a reactive unsaturated compound, and examples of the functional monomer having at least one ethylenically unsaturated bond may include at least one selected from the group consisting of ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentacrylate, dipentaerythritol hexacrylate, bisphenol A epoxyacrylate, ethylene glycol monomethylether acrylate, ethylene glycol dimethacrylate and 1,6-hexanediol dimethacrylate, but not limited thereto.
  • Examples of commercially available functional monomers having at least one ethylenically unsaturated bond may include the following products: Aronix M-101, Aronix M-111 and Aronix M-114 (Toagosei Co., Ltd.); KAYARAD TC-110S and KAYARAD TC-120S (Nippon Kayaku Co. Ltd.); and V-158 and V-2311 (Osaka Yuki Kagaku Kogyo Kabushiki Kaisha) as commercial products of monofunctional (meth)acrylate;
  • Aronix M-210, Aronix M-240 and Aronix M-6200 (Toagosei Co., Ltd.); KAYARAD HDDA, KAYARAD HX-220 and KAYARAD R-604 (Nippon Kayaku Co. Ltd.); and V260, V312 and V335 HP (Osaka Yuki Kagaku Kogyo Kabushiki Kaisha) as commercial products of bifunctional (meth)acrylate products; and
  • Aronix M-309, Aronix M-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030 and Aronix M-8060 (Toagosei Co., Ltd.); KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 and KAYARAD DPCA-120 (Nippon Kayaku Co. Ltd.); and V-295, V-300, V-360, V-GPT, V-3PA and V-400 (Osaka Yuki Kagaku Kogyo Kabushiki Kaisha) as commercial products of tri- or higher functional (meth)acrylate products.
  • the foregoing compounds can be used alone or in a combination of two or more thereof.
  • the content of the functional monomer having at least one ethylenically unsaturated bond is ranged from 1 to 50% by weight, preferably from 1 to 20% by weight, and more preferably from 1 to 15% by weight with respect to the total photosensitive resin composition excluding a residual amount of solvent. If the content of the functional monomer having at least one ethylenically unsaturated bond is within the above-mentioned range of 1 to 50% by weight, sensitivity is improved in the presence of oxygen, patterns are formed easily, compatibility with copolymers is improved, the coat surface is not roughened after the formation of a coat, and it is beneficial in the development margin aspect since overdevelopment of a bottom part is not generated during the development.
  • a polymerization initiator in the present invention is a compound which generates active species that are capable of initiating the polymerization of the functional monomer having at least one ethylenically unsaturated bond, or the monofunctional or polyfunctional epoxy compound when exposed to radiation light such as visible rays, ultraviolet rays, far ultraviolet rays, electron rays, and X-rays.
  • photopolymerization initiator may include acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, ⁇ -acyloxime based compounds, onium salt-based compounds, benzoin-based compounds, benzophenone-based compounds, dikenone-based compounds, ⁇ -diketone based compounds, polynuclear quinone-based compounds, thioxanthone-based compounds, diazo-based compounds, imidesulfonate-based compounds, oxime-based compounds, carbazole-based compounds, and sulfonium borate-based compounds.
  • These compounds are components that generate active radicals, active acids, or both the active radicals and active acids by light exposure, and they may be used alone or in a mixture of two or more thereof.
  • acetophenone-based compounds may include 2,2’-diethoxyacetophenone, 2,2’-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloroacetophenone, p-t-butyldichloroacetophenone, 4-chloroacetophenone, 2,2’-dichloro-4-phenoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one.
  • benzophenone-based compounds may include benzophenone, benzoyl benzoate, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylized benzophenone, 4,4’-bis(dimethylamino)benzophenone, 4,4’-bis(diethylamino)benzophenone, 4,4’-dimethylaminobenzophenone, 4,4’-dichlorobenzophenone, and 3,3’-dimethyl-2-methoxybenzophenone.
  • thioxanthone-based compounds may include thioxanthone, 2-crolthioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.
  • benzoin-based compounds may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.
  • triazine-based compounds may include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3’4’-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4’-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho 1-yl)-4,6-bis(trichloromethyl)-
  • examples of the polymerization initiator may include one or more selected from the group consisting of p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzyldimethylketal, benzophenone, benzoin propyl ether, diethyl thioxanthone, 2,4-bis(trichloromethyl)-6-p-methoxyphenyl-s-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 9-phenyl acridine, 3-methyl-5-amino-((s-triazine-2-yl)amino)-3-phenylcoumarin, 2-(o-chlorophenyl)-4,5-diphenyl imidazolyl dimer, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, o-benzoyl-4'-(benzmercap
  • the content of the polymerization initiator may be 0.1 to 10% by weight with respect to the total weight of the photosensitive resin composition excluding the residual amount of solvent. If the content of the polymerization initiator is within the above-mentioned range, patterns of a colored layer are easily obtained and the formed colored layer is sufficiently adhered to the substrate during the development since curing due to exposure to light is sufficiently performed.
  • the black organic pigment means an organic pigment that has been colorized into black to represent black that is similar to carbon black that is an inorganic pigment.
  • black organic pigment may include, but are not limited to, at least one selected from aniline black, lactam black and perylene black.
  • the photosensitive resin composition according to the present invention may additionally include a black inorganic pigment along with the black organic pigment, wherein the black inorganic pigment is one or more selected from the group consisting of carbon black, chromium oxide, iron oxide, and titanium black, and its content is from 0.1 to 70 parts by weight with respect to 100 parts by weight of the black organic pigment.
  • the black inorganic pigment is one or more selected from the group consisting of carbon black, chromium oxide, iron oxide, and titanium black, and its content is from 0.1 to 70 parts by weight with respect to 100 parts by weight of the black organic pigment.
  • the melt flow phenomenon deteriorates, and thus it is difficult to form patterns on a thick film, such as a column spacer. Therefore, it is important to control a mixing ratio of the organic pigment to the inorganic pigment.
  • the content of the black organic pigment or both the black organic pigment and the black inorganic pigment may be 10 to 60% by weight with respect to the total weight of the photosensitive resin composition excluding the residual amount of solvent. If the content of the black inorganic pigment is within the above-mentioned range, the optical density is prevented from being too low, and processability, such as developing properties, is improved and high optical densities is achieved.
  • a dispersant may be used to disperse a pigment in the photosensitive resin composition according to the present invention.
  • the dispersant may be used by adding it to the pigment, for example, by treating the surface of the pigment with the dispersant in advance, or the dispersant may be used by directly adding it along with the pigment when preparing the photosensitive resin composition.
  • a solvent used in the present invention has compatibility with the components of the above-mentioned photosensitive resin composition, but does not react with the components.
  • the solvent may include compounds comprising: alcohols, such as methanol and ethanol; ethers, such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; glycol ethers, such as ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether; cellosolve acetates, such as methylcellosolve acetate, ethylcellosolve acetate, and diethylcellosolve acetate; carbitols, such as methylethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, and diethylene glycol diethyl ether; propylene glycol alkylether acetates, such as propylene glycol,
  • the examples of the solvent may additionally include high-boiling point solvents, such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ⁇ -butyrolactone, ethylene carbonate, propylene carbonate, and phenylcellosolve acetate.
  • high-boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N
  • preferable examples of the solvent among the above-mentioned examples may include: glycol esters, such as ethylene glycol monomethyl ether; ethylene glycol alkylether acetates, such as ethyl cellosolve acetate; esters, such as ethyl 2-hydroxy propionate; diethylene glycols, such as diethylene glycol monomethyl ether; and propylene glycol alkylether acetates, such as propylene glycol methylether acetate, and propylene glycol propylether acetate.
  • glycol esters such as ethylene glycol monomethyl ether
  • ethylene glycol alkylether acetates such as ethyl cellosolve acetate
  • esters such as ethyl 2-hydroxy propionate
  • diethylene glycols such as diethylene glycol monomethyl ether
  • propylene glycol alkylether acetates such as propylene glycol methylether acetate, and propylene glycol propylether
  • the solvent is used in a residual amount and preferably contained in an amount of 50 to 90% by weight with respect to the total content 100% by weight of a photosensitive resin composition comprising the solvent.
  • the content of the solvent is from 50 to 90% by weight, the resin composition has an appropriate viscosity and processability is improved.
  • a photosensitive resin composition of the present invention may further comprise a silane coupling agent having one or more reactive substituents selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and combinations thereof in order to improve adhesive properties to the substrate.
  • a silane coupling agent having one or more reactive substituents selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and combinations thereof in order to improve adhesive properties to the substrate.
  • silane coupling agent may include trimethoxysilyl benzoic acid, ⁇ -methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, ⁇ -isocyanatepropyl triethoxysilane, ⁇ -glycidoxy propyl trimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and they can be used alone or in combination of two or more thereof.
  • the addition amount of the silane coupling agent is preferably 0.001 to 20 parts by weight with respect to 100 parts by weight of a photopolymerizable binder resin.
  • a photosensitive resin composition of the present invention may additionally include a surfactant, if necessary, in order to improve coatability and prevent the formation of defects.
  • surfactant may include fluorine-based surfactants commercialized under the names of: BM-1000 and BM-1100 (BM Chemie); Megaface F142D, F172, F173 and F183 (Dainippon Ink & Chemicals, Inc.); Fluorad FC-135, FC-170C, FC-430 and FC-431 (Sumitomo 3M Co., Ltd.); Surflon S-112, S-113, S-131, S-141 and S-145 (Asahi Glass Co., Ltd.); and SH-28PA, SH-190, SH-193, SZ-6032 and SF-8428 (Toray Dow Corning Silicone).
  • fluorine-based surfactants commercialized under the names of: BM-1000 and BM-1100 (BM Chemie); Megaface F142D, F172, F173 and F183 (Dainippon Ink & Chemicals, Inc.); Fluorad FC-135, FC-170C, FC-430 and FC-431 (Sumitomo 3M Co
  • the addition amount of the surfactant is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the photopolymerizable binder resin.
  • the photosensitive resin composition of the present invention may include other additives such as an antioxidant and a stabilizer in certain amounts which do not deteriorate physical properties of the composition.
  • the present invention provides a light shielding spacer formed from the photosensitive resin composition.
  • the spacer is characterized in that it has a dielectric constant of 8 F/m or less and an optical density of 1.0 or more.
  • the present invention provides a liquid crystal display device comprising the spacer.
  • the solution was stirred until the solution had an acid value of less than 1.0 mg KOH/g by measuring an acid value of the solution when the solution became transparent and had a high viscosity. It required 11 hours to reach the target acid value of 0.8. After completion of the reaction, the temperature of the reactor was lowered to a room temperature to produce a colorless transparent solid.
  • the solution was stirred until the solution had an acid value of less than 1.0 mg KOH/g by measuring an acid value of the solution if the solution became transparent and had a high viscosity. It required 11 hours to reach the target acid value of 0.8. After the completion of the reaction, the temperature of the reactor was lowered to a room temperature to produce a colorless transparent solid.
  • the solution was stirred until the solution had an acid value of less than 1.0 mg KOH/g by measuring an acid value of the solution if the solution became transparent and had a high viscosity. It required 11 hours to reach the target acid value of 0.8. After the completion of the reaction, the temperature of the reactor was lowered to a room temperature to produce a colorless transparent solid.
  • the reaction product was obtained by addition-reacting compound b-1 that is component (B) with compound a-1 that is component (A) to form an epoxy adduct (AB), and esterifying the epoxy adduct (AB) with compound c-1 that is component (C) in an amount of 0.8 parts by equivalent with respect to 1 part by equivalent of a hydroxyl group of the epoxy adduct (AB), and then additionally esterifying the resulting product with compound d-2 that is component (D) in an amount of 0.3 parts by equivalent of an epoxy group of the compound d-2 with respect to 1 part by equivalent of a hydroxyl group of the epoxy adduct (AB).
  • the epoxy adduct (AB) has a structure to which a carboxyl group of compound b-1 is added at a ratio of 1.0 with respect to an epoxy group of compound a-1.
  • the reaction product was obtained by addition-reacting compound b-1 that is component (B) with compound a-2 that is component (A) to form an epoxy adduct (AB), and esterifying the epoxy adduct (AB) with compound c-2 that is component (C) in an amount of 0.8 parts by equivalent with respect to 1 part by equivalent of a hydroxyl group of the epoxy adduct (AB).
  • the epoxy adduct (AB) has a structure to which a carboxyl group of compound b-1 is added at a ratio of 1.0 with respect to an epoxy group of compound a-2.
  • the reaction product was obtained by addition-reacting compound b-1 that is component (B) with compound a-3 that is component (A) to form an epoxy adduct (AB), and esterifying the epoxy adduct (AB) with compound c-2 that is component (C) in an amount of 0.8 parts by equivalent with respect to 1 part by equivalent of a hydroxyl group of the epoxy adduct (AB).
  • the epoxy adduct (AB) has a structure to which a carboxyl group of compound b-1 is added at a ratio of 1.0 with respect to an epoxy group of compound a-2.
  • a pigment composition was prepared using the same method as in Preparation Example 4, except that 35 parts by weight of lactam black and 15 parts by weight of carbon black produced by Degussa were used, instead of 50 parts by weight of lactam black in Preparation Example 4.
  • a pigment composition was prepared using the same method as in Preparation Example 4, except that 30 parts by weight of lactam black and 20 parts by weight of carbon black produced by Degussa were used, instead of 50 parts by weight of lactam black in Preparation Example 4.
  • a pigment composition was prepared using the same method as in Preparation Example 4, except that 25 parts by weight of lactam black and 25 parts by weight of carbon black produced by Degussa were used, instead of 50 parts by weight of lactam black in Preparation Example 4.
  • a pigment composition was prepared using the same method as in Preparation Example 4, except that 15 parts by weight of lactam black and 35 parts by weight of carbon black produced by Degussa were used, instead of 50 parts by weight of lactam black in Preparation Example 4.
  • a pigment composition was prepared in the same method as in Preparation Example 4 except that 50 parts by weight of carbon black produced by Degussa were used instead of 50 parts by weight of lactam black in the Preparation Example 4.
  • a photosensitive resin composition having black alkali developing properties was obtained by well stirring 1.7538 g of a bisphenol type binder (ZFR-2041H, Nippon Kayaku Co., Ltd.), 0.7249 g of dipentaerythritol hexaacrylate, 0.0651 g of an oxime-based photoinitiator (OXE-02, Ciba-Geigy Corporation), 0.0042 g of a leveling surfactant (silicone-based surfactant BYK 333, produced by BYK Corporation), 0.0084 g of an adhesion assisting agent (KBE-9007, Shin-Etsu Chemical Co., Ltd.), and 8.9 g of a black organic pigment and inorganic pigment composition obtained in Preparation Example 6 in 8.543 g of propylene glycol-1-monomethyl ether-2-acetate.
  • a photosensitive resin composition having black alkali developing properties was obtained by well stirring 2.398 g of Cardo type binder (CBR-D07-3, Kyungin Synthetic Corporation), 0.7249 g of dipentaerythritol hexaacrylate, 0.0651 g of an oxime-based photoinitiator (OXE-02, Ciba-Geigy Corporation), 0.0042 g of a leveling surfactant (silicone-based surfactant BYK 333, BYK Corporation), 0.0084 g of an adhesion assisting agent (KBE-9007, Shin-Etsu Chemical Co., Ltd.), and 8.9 g of a black organic pigment and inorganic pigment composition obtained in Preparation Example 6 in 7.6188 g of propylene glycol-1-monomethyl ether-2-acetate.
  • a film was formed by coating a photosensitive resin composition of the present invention on a pre-treated substrate to a desired thickness, e.g., a thickness of 2 to 25 ⁇ m by a conventional coating method such as a spin or slit coating method, a roll coating method, a screen printing method and an applicator method, and heating the coating at a temperature of 70 to 90°C for 1 to 10 minutes to remove the solvent.
  • a desired thickness e.g., a thickness of 2 to 25 ⁇ m by a conventional coating method such as a spin or slit coating method, a roll coating method, a screen printing method and an applicator method, and heating the coating at a temperature of 70 to 90°C for 1 to 10 minutes to remove the solvent.
  • An active ray of 200 to 500 nm was irradiated through a mask of a predetermined shape to form required patterns on the obtained film.
  • Examples of light sources used for irradiation may include a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, and an argon gas laser, and may additionally include X-rays and electron rays, if necessary.
  • the amount of light exposure varies depending on types and mixing amounts of respective components, and the thickness of a dried film, it is not more than 500 mJ/cm 2 (when measured by a 365 nm sensor) in the case of using the high pressure mercury lamp.
  • patterns were formed by dissolving and removing unnecessary parts using an aqueous alkali solution as a developer, thereby allowing only light-exposed parts to remain.
  • the image patterns obtained by the development were cooled to room temperature, and post-baked at 230°C in a hot-air circulation type drying furnace for 20 minutes to produce image patterns.
  • the resolution of the obtained image patterns was measured by observing minimum sizes of formed colored spacers using a micro-optical microscope.
  • Absorbance is the amount of light when the luminous intensity of light becomes constant after the light of a certain wavelength passes through a certain layer, and optical density is obtained by dividing the absorbance value by thickness.
  • the optical density is defined as log 10 (I 0 /I). Luminous intensity of light in a specific wavelength band was measured using an optical density meter (361T Tabletop Transmission Densitometer manufactured by X-Lite Corporation).
  • colored spacers having a thicknesses (T) of 3.7 ( ⁇ 0.2) ⁇ m and a width (W) of 35 ( ⁇ 2) ⁇ m were prepared.
  • the compression displacement and elastic recovery ratio of the colored spacers were measured according to the following methods using an elasticity measurement apparatus (DUH-W201S) manufactured by Shimadzu Corporation in Japan.
  • a flat-surfaced perpetrator with a diameter of 50 ⁇ m was used as a penetrator for pressing the patterns, and the measuring principle used a load-unload method. Loads given in the tests were 300 mN and 400 mN. The loading rate and holding time were constantly maintained at 0.45 gf/sec and 3 seconds, respectively. The elastic recovery ratio was obtained by measuring the thicknesses of the patterns after a loading and unloading with the flat-surfaced perpetrator for 3 seconds using a three-dimensional thickness measurement apparatus.
  • the elastic recovery ratio means the ratio of a recovered distance (D 1 -D 2 ) after a recovery time of 10 minutes to a distance (D 1 ) of the pattern that is indented when a loading is given to the pattern, and is represented by the following Equation 1:
  • D 1 ( ⁇ m) is a compressed displacement
  • D 2 ( ⁇ m) a distance of the pattern that is indented after the recovery time
  • Films having final thicknesses ranging from 1.5 to 2.5 ⁇ m were prepared by coating photoresists (PR) formed from the black photosensitive resin compositions prepared in the Examples and Comparative Examples on an indium tin oxide (ITO) glass and drying the coated photoresists (PR) on a hot plate under a temperature of 90°C for 2.5 minutes.
  • a gold (Au) electrode with a diameter of 300 ⁇ m was deposited on the films to prepare samples.
  • Capacitance values were measured using an HP 4294A Precision Impedance Analyzer, and dielectric constants were obtained using the measured capacitance values and the following Equation 2.
  • C indicates an electric capacitance
  • ⁇ 0 indicates a dielectric constant in a vacuum condition
  • ⁇ indicates a relative dielectric constant of the film
  • A indicates an electrode area
  • d indicates a photoresist (PR) thickness.
  • ⁇ dielectric constant
  • ⁇ dielectric constant
  • the subject photosensitive resin compositions of Examples 1 to 6 are uniformly excellent in optical density, dielectric constant, elastic recovery ratio, and resolution.
  • Examples 1 to 5 were superior to Comparative Examples 1 and 2 in the resolution aspect, were superior to Comparative Examples 3, 4 and 5 in the dielectric constant aspect, and were superior to Comparative Examples 1 to 5 in the aspect of 300 mN and 400 mN elastic recovery ratios.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials For Photolithography (AREA)
  • Epoxy Resins (AREA)
  • Optical Filters (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention concerne une résine insaturée photopolymérisable, une composition de résine photosensible comprenant ladite résine insaturée photopolymérisable, un monomère fonctionnel comportant au moins une liaison éthyléniquement insaturée, un initiateur de polymérisation, un pigment organique noir et un solvant. La composition de résine photosensible est utile pour préparer un espaceur protégeant de la lumière ayant une faible constante diélectrique et d'excellentes propriétés de protection de la lumière, une excellente résolution et un excellent rapport de recouvrance élastique.
PCT/KR2012/006802 2011-08-26 2012-08-24 Résine insaturée photopolymérisable, composition de résine photosensible la comprenant, et espaceur protégeant de la lumière et dispositif d'affichage à cristaux liquides formés de ceux-ci WO2013032190A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2014527083A JP6093766B2 (ja) 2011-08-26 2012-08-24 光重合性不飽和樹脂、これを含む感光性樹脂組成物、並びにそれから形成された光遮蔽スペーサーおよび液晶ディスプレイデバイス
CN201280052030.6A CN103890659A (zh) 2011-08-26 2012-08-24 光可聚合不饱和树脂，含有该光可聚合不饱和树脂的光敏树脂组合物，以及由此制备的光屏蔽间隔和液晶显示器件

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2011-0086025 2011-08-26
KR1020110086025A KR101349622B1 (ko) 2011-08-26 2011-08-26 광중합성 불포화 수지, 이를 포함하는 감광성 수지 조성물 및 이로부터 형성되는 차광성 스페이서와 액정 디스플레이 장치

Publications (1)

Publication Number Publication Date
WO2013032190A1 true WO2013032190A1 (fr) 2013-03-07

Family

ID=47756578

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2012/006802 WO2013032190A1 (fr) 2011-08-26 2012-08-24 Résine insaturée photopolymérisable, composition de résine photosensible la comprenant, et espaceur protégeant de la lumière et dispositif d'affichage à cristaux liquides formés de ceux-ci

Country Status (5)

Country Link
JP (1) JP6093766B2 (fr)
KR (1) KR101349622B1 (fr)
CN (2) CN103890659A (fr)
TW (1) TWI477526B (fr)
WO (1) WO2013032190A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140319097A1 (en) * 2011-11-02 2014-10-30 Dongjin Semichem Co., Ltd Phenol monomer, polymer for forming a resist underlayer film including same, and composition for a resist underlayer film including same
JP2015093986A (ja) * 2013-11-14 2015-05-18 東京応化工業株式会社 ブラックカラムスペーサ形成用感光性樹脂組成物
WO2015087973A1 (fr) * 2013-12-12 2015-06-18 日本化薬株式会社 Résine phénolique, résine époxy, composition de résine époxy et produit durci à base de celle-ci
US10106643B2 (en) * 2015-03-31 2018-10-23 3M Innovative Properties Company Dual-cure nanostructure transfer film
KR20200021043A (ko) 2017-06-20 2020-02-27 가부시키가이샤 아데카 중합성 조성물, 블랙 매트릭스용 감광성 조성물 및 블랙 칼럼 스페이서용 감광성 조성물
TWI722038B (zh) * 2015-11-20 2021-03-21 南韓商東進世美肯股份有限公司 感光性樹脂組合物
TWI731989B (zh) * 2016-06-30 2021-07-01 日商東京應化工業股份有限公司 感光性樹脂組成物、硬化膜、有機ｅｌ元件中之發光層之分區用之隔排、有機ｅｌ元件用之基板、有機ｅｌ元件、硬化膜之製造方法、隔排之製造方法、及有機ｅｌ元件之製造方法
TWI736601B (zh) * 2016-03-31 2021-08-21 日商日鐵化學材料股份有限公司 遮光膜用感光性樹脂組合物、顯示器用基板及其製造方法

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101349622B1 (ko) * 2011-08-26 2014-01-10 롬엔드하스전자재료코리아유한회사 광중합성 불포화 수지, 이를 포함하는 감광성 수지 조성물 및 이로부터 형성되는 차광성 스페이서와 액정 디스플레이 장치
JP5916373B2 (ja) * 2011-12-22 2016-05-11 東京応化工業株式会社 ブラックカラムスペーサ用感光性樹脂組成物、ブラックカラムスペーサ、表示装置、及びブラックカラムスペーサの形成方法
KR101861067B1 (ko) * 2013-08-30 2018-05-28 동우 화인켐 주식회사 흑색 감광성 수지 조성물
KR102002134B1 (ko) * 2013-09-05 2019-07-19 동우 화인켐 주식회사 흑색 감광성 수지 조성물, 이를 이용한 블랙매트릭스 및 이를 구비한 화상 표시 장치
JP6556735B2 (ja) * 2014-08-26 2019-08-07 日本化薬株式会社 反応性ポリエステル化合物、それを用いた活性エネルギー線硬化型樹脂組成物
CN113608408A (zh) * 2015-03-11 2021-11-05 三菱化学株式会社 着色间隔物形成用感光性着色组合物、固化物、着色间隔物、图像显示装置
KR102437844B1 (ko) * 2015-04-02 2022-08-31 롬엔드하스전자재료코리아유한회사 착색 감광성 수지 조성물 및 이를 이용한 블랙 컬럼 스페이서
JP6521448B2 (ja) * 2015-08-19 2019-05-29 田岡化学工業株式会社 ビスフェノールフルオレン骨格を有するエポキシ樹脂
JP6713746B2 (ja) * 2015-10-08 2020-06-24 日鉄ケミカル＆マテリアル株式会社 スペーサー機能を有する遮光膜用の感光性樹脂組成物、遮光膜、液晶表示装置、スペーサー機能を有する遮光膜用の感光性樹脂組成物の製造方法、遮光膜の製造方法、および液晶表示装置の製造方法
WO2017110689A1 (fr) * 2015-12-25 2017-06-29 東レ株式会社 Composition de résine photosensible, film durci, stratifié, élément pour panneau tactile, et procédé de fabrication de film durci
TWI766941B (zh) * 2017-03-31 2022-06-11 南韓商東友精細化工有限公司 藍色感光性樹脂組成物以及利用彼製造之彩色濾光片與影像顯示裝置
KR102565582B1 (ko) * 2017-06-12 2023-08-11 롬엔드하스전자재료코리아유한회사 착색 감광성 수지 조성물 및 이로부터 제조된 차광성 스페이서
KR102361604B1 (ko) 2017-08-07 2022-02-10 동우 화인켐 주식회사 착색 감광성 수지 조성물, 이를 포함하는 컬러필터 및 이를 포함하는 표시장치
CN107459634B (zh) * 2017-08-07 2019-05-21 南方医科大学 一种不饱和脂肪族聚酯及其制备方法和应用
KR102312785B1 (ko) 2017-08-10 2021-10-14 동우 화인켐 주식회사 광중합성 불포화 수지, 이를 포함하는 감광성 수지 조성물 및 이로부터 형성되는 차광성 스페이서와 액정 디스플레이 장치
KR102377266B1 (ko) 2018-01-10 2022-03-22 동우 화인켐 주식회사 바인더 수지, 착색 감광성 수지 조성물, 이를 포함하는 디스플레이 격벽 구조물 및 이를 포함하는 자발광 표시장치
KR102377269B1 (ko) 2018-01-10 2022-03-22 동우 화인켐 주식회사 바인더 수지, 착색 감광성 수지 조성물, 이를 포함하는 디스플레이 격벽 구조물 및 이를 포함하는 표시장치
WO2019230539A1 (fr) * 2018-05-31 2019-12-05 東洋インキＳｃホールディングス株式会社 Composition colorante et procédé de production de filtre coloré destiné à une utilisation dans un élément d'imagerie à semi-conducteurs
JP7484459B2 (ja) 2020-06-11 2024-05-16 Dic株式会社 エポキシ（メタ）アクリレート樹脂、硬化性樹脂組成物、硬化物及び物品
JP7484460B2 (ja) 2020-06-11 2024-05-16 Dic株式会社 酸基含有エポキシ（メタ）アクリレート樹脂、硬化性樹脂組成物、ソルダーレジスト用樹脂材料、硬化物、絶縁材料及びレジスト部材

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004231790A (ja) * 2003-01-30 2004-08-19 Dainippon Ink & Chem Inc エポキシ樹脂組成物及びその硬化物
JP2006003860A (ja) * 2003-11-26 2006-01-05 Nippon Steel Chem Co Ltd 感光性樹脂組成物及びそれを用いたカラーフィルター
JP2006251007A (ja) * 2005-03-08 2006-09-21 Dainippon Ink & Chem Inc アルカリ現像型感光性樹脂組成物及びプリント配線基板。
KR20090046101A (ko) * 2007-11-05 2009-05-11 타코마테크놀러지 주식회사 플루오렌 유도체 화합물, 이를 포함하는 감광성 수지조성물 및 광학 시트

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4247658B2 (ja) 2001-07-12 2009-04-02 Ｄｉｃ株式会社 新規エポキシ樹脂、エポキシ樹脂組成物及びその硬化物
JP2005126674A (ja) * 2003-09-30 2005-05-19 Mitsubishi Chemicals Corp 着色樹脂組成物、カラーフィルタ、及び液晶表示装置
JP4684293B2 (ja) * 2005-06-20 2011-05-18 凸版印刷株式会社 着色アルカリ現像型感光性樹脂組成物、及び該着色アルカリ現像型感光性樹脂組成物を用いたカラーフィルタ
US20080176169A1 (en) * 2007-01-22 2008-07-24 Icf Technology Limited. Binder composition and photosensitive composition including the same
CN101542393B (zh) * 2007-04-20 2012-12-12 三菱化学株式会社 着色树脂组合物、滤色器、液晶显示装置以及有机电致发光显示屏
JP5177503B2 (ja) 2008-02-04 2013-04-03 Ｄｉｃ株式会社 感光性樹脂組成物、及び新規酸基含有ビニルエステル樹脂
JP5161032B2 (ja) * 2008-10-27 2013-03-13 昭和電工株式会社 感光性樹脂組成物、それに用いる感光性樹脂の製造方法及び硬化塗膜の製造方法
JP2010108615A (ja) 2008-10-28 2010-05-13 Kyocera Chemical Corp 導電性樹脂ペースト
KR20100066197A (ko) * 2008-12-09 2010-06-17 제일모직주식회사 흑색 감광성 수지 조성물, 및 이를 이용한 차광층 및 칼럼 스페이서
TW201113303A (en) * 2009-10-07 2011-04-16 Sumitomo Chemical Co Colored photosensitive resin compositions
KR101068622B1 (ko) * 2009-12-22 2011-09-28 주식회사 엘지화학 기판접착력이 향상된 고차광성 블랙매트릭스 조성물
KR101349622B1 (ko) * 2011-08-26 2014-01-10 롬엔드하스전자재료코리아유한회사 광중합성 불포화 수지, 이를 포함하는 감광성 수지 조성물 및 이로부터 형성되는 차광성 스페이서와 액정 디스플레이 장치

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004231790A (ja) * 2003-01-30 2004-08-19 Dainippon Ink & Chem Inc エポキシ樹脂組成物及びその硬化物
JP2006003860A (ja) * 2003-11-26 2006-01-05 Nippon Steel Chem Co Ltd 感光性樹脂組成物及びそれを用いたカラーフィルター
JP2006251007A (ja) * 2005-03-08 2006-09-21 Dainippon Ink & Chem Inc アルカリ現像型感光性樹脂組成物及びプリント配線基板。
KR20090046101A (ko) * 2007-11-05 2009-05-11 타코마테크놀러지 주식회사 플루오렌 유도체 화합물, 이를 포함하는 감광성 수지조성물 및 광학 시트

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140319097A1 (en) * 2011-11-02 2014-10-30 Dongjin Semichem Co., Ltd Phenol monomer, polymer for forming a resist underlayer film including same, and composition for a resist underlayer film including same
US9170495B2 (en) * 2011-11-02 2015-10-27 Dongjin Semichem Co., Ltd. Phenol monomer, polymer for forming a resist underlayer film including same, and composition for a resist underlayer film including same
JP2015093986A (ja) * 2013-11-14 2015-05-18 東京応化工業株式会社 ブラックカラムスペーサ形成用感光性樹脂組成物
WO2015087973A1 (fr) * 2013-12-12 2015-06-18 日本化薬株式会社 Résine phénolique, résine époxy, composition de résine époxy et produit durci à base de celle-ci
JPWO2015087973A1 (ja) * 2013-12-12 2017-03-16 日本化薬株式会社 フェノール樹脂、エポキシ樹脂、エポキシ樹脂組成物およびそれらの硬化物
US10106643B2 (en) * 2015-03-31 2018-10-23 3M Innovative Properties Company Dual-cure nanostructure transfer film
TWI722038B (zh) * 2015-11-20 2021-03-21 南韓商東進世美肯股份有限公司 感光性樹脂組合物
TWI736601B (zh) * 2016-03-31 2021-08-21 日商日鐵化學材料股份有限公司 遮光膜用感光性樹脂組合物、顯示器用基板及其製造方法
TWI731989B (zh) * 2016-06-30 2021-07-01 日商東京應化工業股份有限公司 感光性樹脂組成物、硬化膜、有機ｅｌ元件中之發光層之分區用之隔排、有機ｅｌ元件用之基板、有機ｅｌ元件、硬化膜之製造方法、隔排之製造方法、及有機ｅｌ元件之製造方法
KR20200021043A (ko) 2017-06-20 2020-02-27 가부시키가이샤 아데카 중합성 조성물, 블랙 매트릭스용 감광성 조성물 및 블랙 칼럼 스페이서용 감광성 조성물

Also Published As

Publication number Publication date
KR101349622B1 (ko) 2014-01-10
KR20130022955A (ko) 2013-03-07
JP6093766B2 (ja) 2017-03-08
TW201326244A (zh) 2013-07-01
CN110007562A (zh) 2019-07-12
TWI477526B (zh) 2015-03-21
JP2014529652A (ja) 2014-11-13
CN103890659A (zh) 2014-06-25

Similar Documents

Publication Publication Date Title
WO2013032190A1 (fr) Résine insaturée photopolymérisable, composition de résine photosensible la comprenant, et espaceur protégeant de la lumière et dispositif d'affichage à cristaux liquides formés de ceux-ci
KR101746607B1 (ko) 블랙 레지스트용 감광성 수지 조성물 및 컬러필터 차광막
WO2015108386A1 (fr) Nouveau composé de β-ester d'oxime fluorène, amorceur de photopolymérisation comprenant ce composé et composition de résine photosensible
JP6713746B2 (ja) スペーサー機能を有する遮光膜用の感光性樹脂組成物、遮光膜、液晶表示装置、スペーサー機能を有する遮光膜用の感光性樹脂組成物の製造方法、遮光膜の製造方法、および液晶表示装置の製造方法
KR20200078476A (ko) 화합물, 조성물, 경화물 및 경화물의 제조 방법
US8758654B1 (en) Photosensitive resin composition for color filter and color filter using the same
KR20190039858A (ko) 감광성 수지 조성물 및 수지막이 형성된 기판의 제조 방법
WO2015005546A1 (fr) Composition de résine photosensible noire et couche de blocage de la lumière utilisant celle-ci
JP7664682B2 (ja) 感光性樹脂組成物、感光性樹脂組成物を硬化してなる硬化膜、硬化膜付き基板および硬化膜付き基板の製造方法
KR20170113390A (ko) 차광막용 감광성 수지 조성물, 이것을 경화시킨 차광막을 구비한 디스플레이용 기판, 및 디스플레이용 기판의 제조 방법
WO2018182133A1 (fr) Composition de résine photosensible bleue, filtre coloré fabriqué en l'utilisant, et dispositif d'affichage d'image
KR101832097B1 (ko) 착색 감광성 수지 조성물 및 이로부터 제조된 차광성 스페이서
WO2015122567A1 (fr) Nouveau composé de colorant, composé de résine photosensible, et filtre de couleur comprenant le composé de colorant
JPH08278629A (ja) 遮光性薄膜形成用組成物及びこれを用いて形成された遮光膜
JP2014126663A (ja) 活性エネルギー線硬化型樹脂組成物、表示素子用着色スペーサー及びブラックマトリックス
JP6075763B2 (ja) 活性エネルギー線硬化型樹脂組成物、及びそれを用いた表示素子用着色スペーサー及び／またはブラックマトリックス
KR102312785B1 (ko) 광중합성 불포화 수지, 이를 포함하는 감광성 수지 조성물 및 이로부터 형성되는 차광성 스페이서와 액정 디스플레이 장치
WO2017086590A1 (fr) Procédé de préparation d'élément d'espacement de colonne
TWI544279B (zh) 光敏樹脂組成物、低介電常數光屏蔽層及使用該光屏蔽層之液晶顯示器設備
KR20060101339A (ko) 감방사선성 수지 조성물, 이것으로부터 형성된 돌기 및스페이서, 및 이들을 구비하는 액정 표시 소자
JP7536481B2 (ja) 感光性樹脂組成物、感光性樹脂組成物を硬化してなる硬化膜、硬化膜付き基板および硬化膜付き基板の製造方法
KR20180135403A (ko) 착색 감광성 수지 조성물 및 이로부터 제조된 차광성 스페이서
WO2021125821A1 (fr) Composé, résine liante, composition de résine photosensible de type négatif et dispositif d'affichage comprenant un masque noir formé en faisant appel à ceux-ci
WO2010090406A2 (fr) Composition de résine photosensible colorée, et filtre de couleur et afficheur à cristaux liquides la comprenant
JP7568413B2 (ja) 感光性樹脂組成物、それを硬化してなる硬化膜、およびその硬化膜を有する表示装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12828346

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014527083

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12828346

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载