WO2020139042A2 - Composé dérivé d'ester d'oxime multi-bêta de carbazole et amorceur de photopolymérisation et composition de résine photosensible comprenant ledit composé - Google Patents

Composé dérivé d'ester d'oxime multi-bêta de carbazole et amorceur de photopolymérisation et composition de résine photosensible comprenant ledit composé Download PDF

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WO2020139042A2
WO2020139042A2 PCT/KR2019/018657 KR2019018657W WO2020139042A2 WO 2020139042 A2 WO2020139042 A2 WO 2020139042A2 KR 2019018657 W KR2019018657 W KR 2019018657W WO 2020139042 A2 WO2020139042 A2 WO 2020139042A2
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Prior art keywords
photoresist composition
butyl
alkyl
meth
oxime ester
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PCT/KR2019/018657
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English (en)
Korean (ko)
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WO2020139042A3 (fr
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이원중
이득락
오천림
신승림
전근
안경룡
박활기
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주식회사 삼양사
한국화학연구원
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Priority to CN201980086476.2A priority Critical patent/CN113227050B/zh
Priority to JP2021538079A priority patent/JP7263522B2/ja
Publication of WO2020139042A2 publication Critical patent/WO2020139042A2/fr
Publication of WO2020139042A3 publication Critical patent/WO2020139042A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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 carbazole multi beta oxime ester derivative compound, and a photopolymerization initiator and photoresist composition comprising the same, more specifically, a carbazole multi beta oxime ester derivative compound excellent in sensitivity, heat resistance, chemical resistance and curability, and It relates to a photopolymerization initiator and a photoresist composition comprising the same.
  • the photopolymerization initiator used in the photoresist composition include acetophenone derivatives, benzophenone derivatives, triazine derivatives, biimidazole derivatives, acylphosphine oxide derivatives, and oxime ester derivatives. It has the advantage of absorbing ultraviolet rays, showing little color, high radical generation efficiency, and excellent compatibility and stability with photoresist composition materials.
  • the initially developed oxime derivative compound has a low photo-initiation efficiency, and in particular, it has a low sensitivity in the pattern exposure process, so that the exposure amount or the amount of use must be increased, thereby reducing production.
  • outgassing occurs during hard baking due to low stability to heat.
  • the development of a photopolymerization initiator with excellent light sensitivity and heat resistance can realize sufficient sensitivity even with a small amount of photopolymerization initiator, thereby reducing the cost, and due to the excellent sensitivity, the exposure amount can be lowered, thereby increasing the production amount and outgassing. The resulting contamination can be reduced.
  • Patent Document 1 International Publication Patent WO02/100903 (2002.12.19)
  • Patent Document 2 Japanese Patent Publication 2005-025169 (2005.01.27)
  • Patent Document 3 International Publication Patent WO07/071497 (2007.06.28)
  • Patent Document 4 Korean Patent Publication 2013-0124215 (2013.11.13)
  • Patent Document 5 Korean Patent Publication 2013-0115272 (2013.10.21)
  • the problem to be solved by the present invention is to provide a carbazole multi beta oxime ester derivative compound excellent in sensitivity, heat resistance, chemical resistance and curability, and a photopolymerization initiator and photoresist composition containing the same.
  • Another problem to be solved of the present invention is to provide a molded article comprising a cured product of the photoresist composition.
  • Another problem to be solved of the present invention is to provide a display device including the molding.
  • the first embodiment relates to a carbazole multi beta oxime ester derivative compound represented by Formula 1 below:
  • A is oxygen or sulfur
  • R 1 is (C1-C12)alkyl
  • R 2 and R '2 are each independently (C1-C12) alkyl, (C6-C20) aryl, (C1-C12) alkoxy, (C6-C12) aryl (C1-C12) alkyl, hydroxy (C1-C12 )Alkyl, hydroxy(C1-C12)alkoxy(C1-C12)alkyl or (C3-C8)cycloalkyl;
  • R 3 is (C1-C20)alkyl, (C6-C20)aryl, (C6-C20)aryl(C1-C20)alkyl, (C3-C20)cycloalkyl or (C3-C20)cycloalkyl(C1-C20) Alkyl.
  • R 1 is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, or i-hexyl;
  • R 2 and R '2 is methyl, ethyl, each independently, n- propyl, i- propyl, n- butyl, i- butyl, t- butyl, n- pentyl, i- pentyl, n- hexyl, i- hexyl, n- octyl , n-decyl, i-decyl, n-dodecyl, cyclopentyl, cyclohexyl, phenyl, benzyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl, methoxy, ethoxy, n- Propyloxy, i-propyloxy, n-butoxy, i-butoxy, t-butoxy, hydroxymethyl, hydroxyethyl, hydroxyn-propyl, hydroxyn-butyl,
  • R 3 is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl, cyclopentyl, cyclohexyl, or It relates to a phenylin carbazole multi beta oxime ester derivative compound.
  • the carbazole multi beta oxime ester derivative compound relates to a carbazole multi beta oxime ester derivative compound selected from compounds represented by the following Chemical Formulas 2-1 to 2-14.
  • a photopolymerization initiator of the following embodiments is provided.
  • the fourth embodiment relates to a photopolymerization initiator comprising the carbazole multi beta oxime ester derivative compound of any one of the first to third embodiments.
  • a photoresist composition of the following embodiment is provided.
  • the photoresist composition relates to a photoresist composition containing 0.01 to 10% by weight of the carbazole multi beta oxime ester derivative compound, based on 100% by weight.
  • the photoresist composition relates to a photoresist composition further comprising a color material.
  • a molded article of the following embodiment and a display device including the same are provided.
  • the ninth embodiment relates to a molded article comprising a cured product of the photoresist composition of any one of the fifth to eighth embodiments.
  • the tenth embodiment is the ninth embodiment
  • the molded article relates to a molded article that is an array planarization film, an insulating film, a color filter, a column spacer, a black column spacer, or a black matrix.
  • the eleventh embodiment relates to a display device comprising the molded article of the ninth or tenth embodiment.
  • the carbazole multi beta oxime ester derivative compound according to an embodiment of the present invention When used as a photopolymerization initiator of a photoresist composition, it exhibits very good sensitivity, and has excellent physical properties such as residual film rate, pattern stability, heat resistance, chemical resistance, and ductility. -It is possible to minimize the outgassing generated from the photopolymerization initiator in the exposure and post-baking process during the LCD manufacturing process, thereby reducing contamination and thereby minimizing defects that may occur.
  • the carbazole multi beta oxime ester derivative compound according to an aspect of the present invention is represented by the following Chemical Formula 1.
  • A is oxygen or sulfur
  • R 1 is (C1-C12)alkyl
  • R 2 and R '2 are each independently (C1-C12) alkyl, (C6-C20) aryl, (C1-C12) alkoxy, (C6-C12) aryl (C1-C12) alkyl, hydroxy (C1-C12 )Alkyl, hydroxy(C1-C12)alkoxy(C1-C12)alkyl or (C3-C8)cycloalkyl;
  • R 3 is (C1-C12)alkyl, (C6-C12)aryl, (C6-C12)aryl(C1-C12)alkyl, (C3-C20)cycloalkyl or (C3-C20)cycloalkyl(C1-C20) Alkyl.
  • Substituents containing "alkyl”, “alkoxy” and other “alkyl” portions described herein include both straight-chain or pulverized forms, and "cycloalkyl” includes not only a single ring system but also a plurality of ring-based hydrocarbons. .
  • aryl is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, including a single or fused ring system, and includes a form in which a plurality of aryls are connected by a single bond.
  • hydroxyalkyl described herein means OH-alkyl in which a hydroxy group is bonded to an alkyl group as defined above, and "hydroxyalkoxyalkyl” is hydroxyalkyl-O in which an alkoxy group is bonded to the hydroxyalkyl group.
  • -Means alkyl, and alkenyl means a structure including a ketone to which an alkyl or aryl group is bonded.
  • arylalkyl described herein may be exemplified by benzyl, etc.
  • cycloalkyl may be exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • cycloalkylalkyl may be cyclopropylmethyl.
  • alkyl having 1 to 12 carbon atoms means alkyl having 1 to 12 carbon atoms, and such alkyl may preferably be (C1-C10)alkyl, and more preferably (C1-C6). )Alkyl.
  • '(C6-C20)aryl means aryl having 6 to 20 carbon atoms, and such aryl may preferably be (C6-C18)aryl, more preferably (C6-C12)aryl.
  • '(C1-C12)alkoxy means alkoxy having 1 to 12 carbon atoms, and such alkoxy may preferably be (C1-C10)alkoxy, and more preferably (C1-C4)alkoxy.
  • '(C6-C12)aryl(C1-C12)alkyl means alkyl in which one of the alkyls having 1 to 12 carbons is substituted with an aryl group having 6 to 12 carbons, preferably (C6-C10)aryl( C1-C10)alkyl, and more preferably (C6-C8)aryl(C1-C6)alkyl.
  • 'Hydroxy(C1-C12)alkyl means alkyl in which one hydrogen is substituted with hydroxy in alkyl having 1 to 12 carbon atoms, preferably hydroxy(C1-C10)alkyl, and more preferably Can be hydroxy(C1-C6)alkyl.
  • In'hydroxy(C1-C12)alkoxy(C1-C12)alkyl' one hydrogen in 1 to 12 carbon atoms is substituted with alkoxy having 1 to 12 carbon atoms, and one hydrogen in alkoxy is substituted with hydroxy.
  • Means a structure and may preferably be hydroxy (C1-C10) alkoxy (C1-C10) alkyl, more preferably hydroxy (C1-C4) alkoxy (C1-C6) alkyl.
  • '(C3-C20)cycloalkyl' means a cycloalkyl having 3 to 20 carbon atoms, preferably (C3-C10)cycloalkyl, more preferably (C3-C8)cycloalkyl, even more preferably (C3) -C6) cycloalkyl.
  • A is oxygen or sulfur
  • R 1 is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, or i-hexyl;
  • R 2 and R '2 are each independently methyl, ethyl, n- propyl, i- propyl, n- butyl, i- butyl, t- butyl, n- pentyl, i- pentyl, n- hexyl, i- hexyl, n-octyl, n-decyl, i-decyl, n-dodecyl, cyclopentyl, cyclohexyl, phenyl, benzyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl, methoxy, ethoxy , n-propyloxy, i-propyloxy, n-butoxy, i-butoxy, t-butoxy, hydroxymethyl, hydroxyethyl, hydroxyn-propyl, hydroxyn-butyl, hydroxyi
  • R 3 is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl, cyclopentyl, cyclohexyl, or Phenyl.
  • A is oxygen or sulfur
  • R 1 is methyl, ethyl, or n-propyl
  • R 2 and R '2 are each independently methyl, ethyl, n- propyl, i- propyl, n- butyl, n- pentyl, cyclohexyl, phenyl, or benzyl;
  • R 3 may be methyl, ethyl, n-propyl, or phenyl.
  • the carbazole multi beta oxime ester derivative compound may include a compound selected from the group consisting of the following Chemical Formulas 2-1 to 2-14, but the following compounds limit the present invention no.
  • the carbazole multi beta oxime ester derivative compound represented by Formula 1 according to the present invention may be prepared as shown in Scheme 1 or Scheme 2 below, but is not limited thereto.
  • the photopolymerization initiator according to another aspect of the present invention includes at least one selected from carbazole multi beta oxime ester derivative compounds represented by Chemical Formula 1.
  • a photopolymerization initiator comprising at least one selected from carbazole multi beta oxime ester derivatives of Formula 1 above.
  • carbazole multi beta oxime ester derivative compound may be included as a photopolymerization initiator.
  • the photoresist composition according to another aspect of the present invention has excellent thin film properties such as control of pattern characteristics and heat resistance and chemical resistance.
  • each component that may be included in the photoresist composition of the present invention will be described in detail.
  • (meth)acrylic means acrylic and/or methacryl
  • (meth)acrylate means acrylate and/or methacrylate
  • (meth)acrylic acid is acrylic acid and/or Means methacrylic acid.
  • an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in the side chain can be used as the alkali-soluble resin.
  • the acrylic polymer means a polymer of an acrylic monomer (including a homopolymer or a copolymer), and examples of such monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth) )Acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth) )Acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth) Acrylate, dicyclopentanyl (
  • the acrylic polymer having an acrylic unsaturated bond in the side chain is a copolymer in which an epoxy resin is added to an acrylic copolymer containing a carboxylic acid, (meth)acrylic acid, itaconic acid, maleic acid or maleic acid monoalkyl ester, etc.
  • Alkyl (meth)acrylates such as methyl (meth)acrylate or hexyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (Meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, styrene, ⁇ -methyl Styrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, (meth)acrylamide or N-methyl(meth)acrylic Glycidyl (meth)acrylate, 3,4-
  • an acrylic polymer having an acrylic unsaturated bond in the side chain is a copolymer obtained by addition reaction of a carboxylic acid to an acrylic copolymer containing an epoxy group, glycidyl (meth)acrylate, 3,4-epoxybutyl (meth) )
  • Acrylic monomers containing an epoxy group such as acrylate, 2,3-epoxycyclohexyl (meth)acrylate or 3,4-epoxycyclohexylmethyl (meth)acrylate
  • Alkyl (meth)acrylates such as methyl (meth)acrylate or hexyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (Meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-
  • acrylic monomers containing carboxylic acids such as (meth)acrylic itaconic acid, maleic acid or maleic acid monoalkyl ester in an acrylic copolymer containing an epoxy group obtained by copolymerizing two or more monomers such as amides.
  • the binder resin obtained by addition reaction at the temperature of can be used.
  • the alkali-soluble resin is 3 to 50% by weight, specifically 5 to 5% with respect to 100% by weight of the total photoresist composition in order to impart thin film properties such as control of pattern characteristics and heat resistance and chemical resistance 45% by weight, more specifically 8 to 40% by weight can be used.
  • the weight average molecular weight of the alkali-soluble resin (measured by polystyrene conversion by gel permeation chromatography (GPC)) may be 2,000 to 300,000, preferably 4,000 to 100,000, and dispersion degree may be 1.0 to 10.0.
  • the polymerizable compound having an ethylenically unsaturated bond serves to form a pattern by crosslinking by photoreaction when forming a pattern, and crosslinks upon high temperature heating to impart chemical resistance and heat resistance.
  • the polymerizable compound having an ethylenically unsaturated bond may be included in an amount of 0.001 to 40% by weight, preferably 0.1 to 30% by weight, and more preferably 1 to 20% by weight based on 100% by weight of the photoresist composition.
  • a crosslinking degree may be excessively high, resulting in a deterioration in ductility of the pattern.
  • the polymerizable compound having an ethylenically unsaturated bond is specifically methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate or lauryl (meth)acrylic.
  • Alkyl ester of (meth)acrylic acid such as rate, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate having 2 to 14 ethylene oxide groups, ethylene glycol di(meth)acrylate, ethylene oxide group
  • one or more selected from carbazole multi beta oxime ester derivatives of Formula 1 may be used as a photopolymerization initiator.
  • the photopolymerization initiator is more effective to use 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on 100% by weight of the total photoresist composition.
  • the photoresist composition of the present invention may further include a silicone-based compound having an epoxy group or an amine group as an adhesive as needed.
  • the silicone-based compound having an epoxy group or an amine group may improve adhesion between the ITO electrode and the photoresist composition, and may increase heat resistance after curing.
  • examples of the silicone-based compound having an epoxy group or an amine group include (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, and (3-glycidoxypropyl)methyldimethoxysilane Phosphorus, (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, 3,4-epoxybutyl Trimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)
  • the silicone-based compound having an epoxy group or an amine group may be included in 0.0001 to 3% by weight based on 100% by weight of the total photoresist composition. If it is less than the above range, the effect of the addition cannot be confirmed, and if it exceeds the above range, the developing characteristics of the non-exposed portion may be lowered, and scum and residue may remain on the lower substrate, ITO or glass substrate.
  • the photoresist composition of the present invention may further include one or more compatible additives selected from a photosensitizer, a thermal polymerization inhibitor, an antifoaming agent or a leveling agent, if necessary.
  • the other additives may be included in an amount of 0.1 to 10% by weight based on 100% by weight of the total photoresist composition, and if it is less than the above range, the effect of the addition cannot be confirmed, and if it exceeds the above range, bubbles may be excessively generated.
  • the photoresist composition of the present invention is coated on a substrate by adding a solvent, and then a pattern is formed through a method of irradiating ultraviolet rays using a mask to develop with an alkali developer.
  • the content of the solvent can be adjusted such that the total amount is 100% by weight in addition to the contents of the other components of the photoresist composition described above, it can be variously changed according to the contents of other components of the photoresist compositions.
  • the viscosity it is preferable to adjust the viscosity to be in the range of 1 to 50 cps by adding a solvent of 10 to 95% by weight relative to 100% by weight of the photoresist composition.
  • the solvent examples include ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, and ethyl ethoxy pro considering compatibility with alkali-soluble resins, photopolymerization initiators, and other compounds.
  • the photoresist composition of the present invention may also use the above-mentioned carbazole multi beta oxime ester derivative compound alone as a photopolymerization initiator, and also a thioxanthone-based compound, an acylphosphine oxide-based compound, an acetophenone-based compound, a biimidazole-based compound, Triazine-based compounds, O-acyl oxime ester-based compounds and thiol-based compounds may be used further comprising one or two or more selected from the group consisting of.
  • the added photopolymerization initiator may be used in an amount of 0.01 to 5% by weight based on 100% by weight of the total photoresist composition.
  • thioxanthone-based compound examples include, for example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- Dichloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone or one or more selected from 2,4-diisopropyl thioxanthone may be used, but is not limited thereto.
  • acylphosphine oxide-based compound examples include diphenyl (2,4,6-trimethyl benzoyl) phosphine oxide, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, or combinations thereof. It can be used, but is not limited thereto.
  • Examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- At least one selected from (4-morpholinophenyl)butan-1-one or 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one It can be used, but is not limited thereto.
  • biimidazole-based compound for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2, 2'-bis(2,4-dichlororophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis(2,4,6-triclo Rophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole may be used, but is not limited thereto.
  • triazine-based compound for example, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2 -[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]- 4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-tri Azine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6- Bis(trichloromethyl)-s-triazine, 2-(4-meth
  • O-acyl oxime ester-based compound examples include 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) and ethanone-1-[9 -Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4- Tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6- ⁇ 2-methyl-4-(2,2) -Dimethyl-1,3-dioxolanyl)methoxybenzoyl ⁇ -9H-carbazol-3-yl]-1-(O-acetyloxime) or 2-(acetoxyimino)-1-(9,9' One or more selected from -diethyl
  • thiol-based compound pentaerythritol tetrakis (3-mercaptopropionate) or the like can be used, but is not limited thereto.
  • the photoresist composition according to an embodiment of the present invention may further include a color filter or a color material included for application as a black matrix forming resist.
  • Various pigments may be used as the color material, for example, cyan, magenta, yellow, and black pigments of red, green, blue, and navy blue mixed systems, and CI pigment yellow 12 may be more specifically used as a pigment.
  • CI pigment yellow 12 may be more specifically used as a pigment.
  • the color material may be included in 5 to 50% by weight based on 100% by weight of the total photoresist composition. If it is less than the above range, the light-shielding property decreases, and if it is above the above range, exposure failure or curing failure may occur.
  • the photoresist composition according to an embodiment of the present invention is a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, a variety of printing, dipping, or other known means, soda glass, quartz glass, semiconductor substrate, metal, It can be applied to supporting gas phases such as paper and plastic. In addition, once carried out on a supporting base such as a film, it can be transferred onto another supporting base, and the application method is not limited.
  • a molded article comprising a cured product of the photoresist composition described above is provided.
  • the molded article may be an array planarization film, an insulating film, a color filter, a column spacer, an overcoat, a black column spacer, or a black matrix, but is not limited thereto.
  • various displays such as a liquid crystal display device and the OLED, including the molding are provided.
  • Step 2 Synthesis of 1,1'-(9-(4-methoxyphenyl)-carbazole-3,6-diyl)bis(propan-1-one)
  • the reaction solution was placed in ice water consisting of ice (300 g) and water (300 ml), stirred for 30 minutes and then left to remove the water layer, and the organic layer was sufficiently washed with a sodium bicarbonate aqueous solution. Then, the organic layer was dried over anhydrous magnesium sulfate, filtered, and then distilled under reduced pressure to obtain the target compound, 1,1'-(9-(4-methoxyphenyl)-9H-carbazole-3,6-yl)bis(propane). -1-one) (9.7 g, 94.3%).
  • Step 3 Synthesis of 1,1'-(9-(4-methoxyphenyl)-carbazole-3,6-diyl)bis(propan-1-one)-2,2'-bisoxime
  • the extracted organic layer was dried using anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to obtain an impure product.
  • -3,6-Diyl)bis(propan-1-one)-2,2'-bisoxime (1.81g, 26.3%) was obtained.
  • Step 4 Synthesis of 1,1'-(9-(4-methoxyphenyl)-carbazole-3,6-diyl)bis(propan-1-one)2,2'-bisoxime (O-acetate)
  • 1,1'-(9-(4-methoxyphenyl)-9H-carbazole-3,6-diyl)bis(propan-1-one)-2,2'-bisoxime obtained in step 3 above ( 0.5 g, 1.4 mmol) was added to ethyl acetate, cooled to -10°C or lower, and triethylamine (0.31 ml, 2.8 mmol) was added dropwise and stirred for 10 minutes. Subsequently, a solution of acetyl chloride (0.16 ml, 2.8 mmol) dissolved in ethyl acetate (1 ml) was added dropwise for 10 minutes, followed by stirring for 30 minutes.
  • reaction solution was extracted with methylene chloride and washed sufficiently with aqueous sodium bicarbonate solution.
  • the extracted organic layer was dried using anhydrous magnesium sulfate, filtered, and then distilled under reduced pressure to separate the product by column (MC:Acetone 200:1) and target compound 1,1'-(9-(4-methoxyphenyl)-9H.
  • -Carbazole-3,6-diyl)bis(propan-1-one)-2,2'-bisoxime (O-acetate) (0.16g, 28.1%) was obtained.
  • Triethylene glycol dimethyl ether (40 ml) was added under a nitrogen atmosphere, and carbazole (30 g, 170.5 mmol), 4-iodothioanisole (53.8 g, 204.3 mmol), and copper in powder form (11.34 g, 180 mmol) ) And potassium carbonate (58.8 g, 423.2 mmol) were put in a reactor and reacted at reflux at 90° C. for 4 days. After the reaction was completed, it was cooled to room temperature. Subsequently, the reaction solution was transferred to a beaker and water (300 ml) and methylene chloride (300 ml) were added to the beaker, followed by stirring for 1 hour.
  • Step 2 to Step 3 Synthesis of 1-(9-(4-(methylthio)phenyl)-6-propionyl-carbazol-3-yl)pentan-1-one
  • the extracted organic layer was dried using anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to obtain an impure product.
  • the reaction solution was extracted with methylene chloride and washed sufficiently with aqueous sodium bicarbonate solution.
  • the extracted organic layer was dried using anhydrous magnesium sulfate, filtered, and then distilled under reduced pressure to separate the product from the column (MC:Acetone 200:1) to separate the target compound, 2-(acetoxyimino)-1-(6-(2-( Acetoxyimino)propanoyl)-9-(4-(methylthio)phenyl)-carbazol-3-yl)pentan-1-one (0.15g, 26.1%) was obtained.
  • Carbazole multi beta oxime ester derivative compounds were synthesized under the same conditions as in Example 1 or 2, respectively, in the compositions shown in Tables 1 and 2 below.
  • the prepared polymer (a-1) had a weight average molecular weight of 25,000 and a dispersion degree of 1.8.
  • methacrylic acid, styrene, methyl methacrylic acid, and cyclohexyl methacrylic acid were each acrylic at a molar ratio of 40:20:20:20.
  • the solid content of the monomer was added at 40% by weight, and then polymerized with stirring under nitrogen atmosphere at 70° C. for 5 hours to synthesize a copolymer.
  • the prepared acrylic polymer (a-2) had a weight average molecular weight of 18,000 and a dispersion degree of 1.9.
  • Alkali-soluble resin according to the components and contents shown in Table 3 below in the reaction mixing tank in which the sunscreen and the stirrer are installed; Polymerizable compounds having ethylenically unsaturated bonds; The photopolymerization initiator of the present invention; And FC-430 (leveling agent of 3M company) was sequentially added, stirred at room temperature (23° C.), and then PGMEA was added as a solvent so that the composition was 100% by weight, to obtain the photoresist compositions of Examples 15 to 30 . It was prepared.
  • Example 31 a colored photoresist composition of Example 31 was prepared in the same manner as in Example 15 , except that 50% by weight of the carbon black dispersion dispersed in PGMEA of 25% by weight of solid content was added.
  • the colored photoresist composition of Example 32 was prepared in the same manner as in Example 15, except that 50% by weight of a dispersion of Pigment Red 177 (PR 177) dispersed in PGMEA of 25% by weight of solid content was added.
  • PR 177 50% by weight of a dispersion of Pigment Red 177
  • a photoresist composition was prepared in the same manner as in Example 15, except that the following Formula 3 was mixed with the compound of Example 1 as a photopolymerization initiator.
  • Alkali-soluble resin acrylic polymers (a-1 to a-3) of Preparation Examples 1 to 3
  • Example 1 (0.5) FC-430 (0.1) - 16 a-1 (40) b-3 (20)
  • Example 3 (0.5) FC-430 (0.1) - 17 a-1 (40) b-5 (10) b-6 (10)
  • Example 6 (0.5) FC-430 (0.1) - 19 a-1 (40) b-1 (20)
  • Example 8 (0.5) FC-430 (0.1) - 20 a-1 (40) b-3 (20)
  • Example 9 (0.5) FC-430 (0.1) - 21 a-1 (40) b-5 (10) b-6 (10)
  • Example 11 (0.5) FC-430 (0.1) - 22 a-1 (40) b-1 (20
  • a photoresist composition was prepared in the same manner as in Example 15, except that the compound of Formula 4 below was used instead of the compound of Formula 2-1 of Example 1 as a photopolymerization initiator.
  • a photoresist composition was prepared in the same manner as in Example 15, except that the compound of Formula 5 below was used instead of the compound of Formula 2-1 of Example 1 as the photopolymerization initiator.
  • the photoresist was spin-coated on a glass substrate, dried on a hot plate at 100° C. for 1 minute, exposed using a step mask, and then developed in a 0.04% KOH aqueous solution.
  • the exposure amount at which the step mask pattern maintains 80% thickness compared to the initial thickness was evaluated by sensitivity.
  • the photoresist composition After coating the photoresist composition on a substrate with a spin coater, it is pre-baked at 100°C for 1 minute, exposed at 365 nm, and then post-baked at 230°C for 20 minutes to post-bake the resist film. The thickness ratio (%) before and after was measured.
  • the silicon wafer on which the photoresist pattern was formed was cut from the vertical direction of the hole pattern, and the results observed with an electron microscope were shown in the cross-sectional direction of the pattern. It was judged that the pattern side wall was erected at an angle of 55 degrees or more with respect to the substrate, and that the film was not reduced was regarded as'good', and that the reduction of the film was recognized as'film'.
  • a resist film formed through processes such as prebake and postbake is soaked in a stripper solution at 40°C for 10 minutes, and then the resist film We examined whether there is a change in transmittance and thickness. If the change in transmittance and thickness was 2% or less, it was determined as'good', and if the change in transmittance and thickness was more than 2%, it was determined as'bad'.
  • the photoresist composition After spin coating the photoresist composition on a substrate, it was prebaked at 100° C. for 1 minute, exposed with the sensitivity of the photoresist, and then developed with a KOH aqueous solution to form a pattern of 20 ⁇ m ⁇ 20 ⁇ m.
  • the formed pattern was crosslinked by post-baking at 230° C. for 20 minutes, and the pattern was measured for ductility using a nano indentor.
  • the measurement of the nanoindenter was determined to be'good' when the total variation was 500 nm or more and'bad' when it was less than 500 nm by 5 g.f loading.
  • the carbazole multi beta oxime ester derivative compound according to the present invention has a high thermal stability with a decomposition point of at most 240°C or higher, and is excellent in sensitivity even when used in a small amount when used as a photopolymerization initiator of a photoresist composition. It was confirmed that the physical properties such as residual film rate, pattern stability, chemical resistance and ductility are excellent. Accordingly, it was confirmed that the outgassing generated from the photopolymerization initiator in the exposure and post-baking process during the TFT-LCD manufacturing process can be minimized, thereby reducing contamination and minimizing defects that may occur.

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Abstract

La présente invention concerne un composé dérivé d'ester d'oxime multi-bêta de carbazole représenté par la formule chimique 1 ainsi qu'un amorceur de photopolymérisation et une composition de résine photosensible, comprenant chacun ledit composé. [formule chimique 1] Dans la formule chimique 1, A et R 1 à R 3 sont chacun définis dans la description détaillée de l'invention.
PCT/KR2019/018657 2018-12-28 2019-12-27 Composé dérivé d'ester d'oxime multi-bêta de carbazole et amorceur de photopolymérisation et composition de résine photosensible comprenant ledit composé WO2020139042A2 (fr)

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CN201980086476.2A CN113227050B (zh) 2018-12-28 2019-12-27 咔唑多β-肟酯衍生化合物以及包含该咔唑多β-肟酯衍生化合物的光聚合引发剂及光刻胶组合物
JP2021538079A JP7263522B2 (ja) 2018-12-28 2019-12-27 カルバゾールマルチβ－オキシムエステル誘導体化合物、それを含む光重合開始剤、及びフォトレジスト組成物

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JP7267532B1 (ja) 2022-04-20 2023-05-02 東洋インキＳｃホールディングス株式会社 感光性組成物、光学フィルタ、画像表示装置、及び固体撮像素子
JP7267533B1 (ja) 2022-04-20 2023-05-02 東洋インキＳｃホールディングス株式会社 感光性組成物、光学フィルタ、画像表示装置、及び固体撮像素子
JP7274078B1 (ja) 2022-04-20 2023-05-16 東洋インキＳｃホールディングス株式会社 感光性着色組成物、及びその用途
CN117348340A (zh) * 2022-06-24 2024-01-05 常州强力先端电子材料有限公司 负型感光性树脂组合物、固化膜及其制备方法、el元件和显示装置
CN117510396A (zh) * 2022-07-27 2024-02-06 常州强力电子新材料股份有限公司 肟酯光引发剂、其制备方法及应用

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1395615B1 (fr) 2001-06-11 2009-10-21 Basf Se Photoamorceurs d'oxime ester possedant une structure combinee
TW200714651A (en) 2002-10-28 2007-04-16 Mitsubishi Chem Corp Photopolymerization composition and color filter using the same
JP4484482B2 (ja) * 2003-09-25 2010-06-16 東洋インキ製造株式会社 感光性着色組成物およびカラーフィルタ
JP4736328B2 (ja) 2004-02-09 2011-07-27 コニカミノルタホールディングス株式会社 インクジェット記録方法
JP4631594B2 (ja) * 2005-08-16 2011-02-16 Ｊｓｒ株式会社 感光性樹脂組成物、表示パネル用スペーサーおよび表示パネル
JP5680274B2 (ja) * 2005-12-01 2015-03-04 チバ ホールディング インコーポレーテッドＣｉｂａ Ｈｏｌｄｉｎｇ Ｉｎｃ． オキシムエステル光開始剤
EP1963374B1 (fr) 2005-12-20 2010-02-17 Basf Se Photoinitiateurs de type ester d'oxime
JP5481856B2 (ja) * 2008-12-26 2014-04-23 東洋インキＳｃホールディングス株式会社 光重合開始剤、重合性組成物、および重合物の製造方法
CN102459171B (zh) 2009-06-17 2014-07-09 东洋油墨Sc控股株式会社 肟酯化合物、自由基聚合引发剂、聚合性组合物、负型抗蚀剂以及图像图案
TWI438570B (zh) * 2010-03-11 2014-05-21 Toyo Ink Mfg Co 感光性著色組合物及濾色器
EP4372742A2 (fr) 2010-07-08 2024-05-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Codeur utilisant une annulation de repliement vers l'avant
RU2707251C2 (ru) 2011-10-03 2019-11-25 Модерна Терапьютикс, Инк. Модифицированные нуклеозиды, нуклеотиды и нуклеиновые кислоты и их применение
JP2015138133A (ja) * 2014-01-22 2015-07-30 東洋インキＳｃホールディングス株式会社 感光性着色組成物およびカラーフィルタ
CN103833872B (zh) 2014-03-18 2016-04-06 常州强力先端电子材料有限公司 一种双肟酯类光引发剂及其制备方法和应用
JP6762739B2 (ja) 2016-03-17 2020-09-30 株式会社Ｄｎｐファインケミカル カラーフィルタ用感光性着色樹脂組成物、カラーフィルタ、表示装置
TWI635079B (zh) * 2016-07-08 2018-09-11 韓國化學研究院 高敏感肟酯光聚合起始劑以及包含該起始劑的光聚合組合物

Cited By (2)

* Cited by examiner, † Cited by third party
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JP2023026377A (ja) * 2021-08-13 2023-02-24 達興材料股▲ふん▼有限公司 感光性樹脂組成物及びそれを応用する装置
JP7358583B2 (ja) 2021-08-13 2023-10-10 達興材料股▲ふん▼有限公司 感光性樹脂組成物及びそれを応用する装置

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