WO2021177654A1 - Nouveau composé dérivé d'ester d'oxime carbazole - Google Patents

Nouveau composé dérivé d'ester d'oxime carbazole Download PDF

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Publication number
WO2021177654A1
WO2021177654A1 PCT/KR2021/002360 KR2021002360W WO2021177654A1 WO 2021177654 A1 WO2021177654 A1 WO 2021177654A1 KR 2021002360 W KR2021002360 W KR 2021002360W WO 2021177654 A1 WO2021177654 A1 WO 2021177654A1
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WO
WIPO (PCT)
Prior art keywords
compound
synthesis
meth
acrylate
oxime ester
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Application number
PCT/KR2021/002360
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English (en)
Korean (ko)
Inventor
양원기
이진주
박성준
백용구
Original Assignee
주식회사 테크늄
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Application filed by 주식회사 테크늄 filed Critical 주식회사 테크늄
Publication of WO2021177654A1 publication Critical patent/WO2021177654A1/fr

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Classifications

    • 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
    • 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

Definitions

  • a photoinitiator is a substance that absorbs light and decomposes to generate chemically active atoms or molecules, and is widely used in photosensitive compositions and the like.
  • Examples of chemically active substances include acids, bases, and radicals.
  • the photoinitiator in which radicals are generated may be used together with an acryl group that causes a polymerization reaction with the radical to improve the strength of the coated film.
  • a photoinitiator may be applied to the photosensitive resin composition for photoetching using inkjet ink or a transparent or colored protective film such as a car or mobile phone, and a phenomenon in which solubility is reduced according to a polymerization reaction by light. have.
  • Representative examples include a photopolymerization type photosensitive resin composition used for manufacturing a color filter of a liquid crystal display device, a photosensitive composition for a resin black matrix, and the like.
  • the photosensitive composition can be used to form a pattern by applying on a substrate to form a coating film, exposing a specific portion of the coating film by light irradiation using a photomask or the like, and then developing and removing the unexposed portion.
  • photoinitiator used in the photosensitive resin composition include various types of acetophenone derivatives, benzophenone derivatives, triazine derivatives, biimidazole derivatives, and acylphosphine oxide derivatives.
  • One embodiment of the present invention provides an oxime ester carbazole derivative compound useful as a photoinitiator by having excellent radical generation efficiency with a small exposure dose, excellent sensitivity, and improved solubility to sufficiently increase the concentration of the photoinitiator.
  • Another embodiment of the present invention provides a photosensitive resin comprising the novel oxime ester carbazole derivative compound as a photoinitiator.
  • an oxime ester carbazole derivative compound represented by the following formula (1).
  • R 1 and R 3 are each independently a C1-C12 aliphatic hydrocarbon
  • R 2 is C1 ⁇ C12 alkyl or C6 ⁇ C12 aryl
  • n is an integer from 1 to 5;
  • a photosensitive resin composition comprising the oxime ester carbazole derivative compound and a compound having an ethylenically unsaturated bond.
  • the novel oxime ester carbazole compound is useful as a photoinitiator with improved solubility to sufficiently increase the concentration of the photoinitiator, the novel oxime ester carbazole compound has excellent radical generation efficiency with a small exposure dose, excellent sensitivity, and sufficient concentration of the photoinitiator.
  • R 1 and R 3 are each independently a C1-C12 aliphatic hydrocarbon
  • R 2 is C1 ⁇ C12 alkyl or C6 ⁇ C12 aryl
  • n is an integer from 1 to 5;
  • R 1 and R 3 may further improve solubility as the number of carbon atoms increases.
  • the number of carbon atoms of R 1 and R 3 may be appropriately selected in consideration of both solubility and sensitivity to be implemented.
  • R 1 and R 3 may each independently be a C7 ⁇ C12 aliphatic hydrocarbon.
  • solubility may be further improved as n is larger.
  • n may be an integer of 2 to 5.
  • n may be an integer of 3 to 5.
  • R 1 and R 3 when R 1 and R 3 are branched chain alkyl rather than straight chain alkyl, solubility may be further improved.
  • R 1 and R 3 since R 1 and R 3 may be disadvantageous in terms of sensitivity when they are branched-chain alkyl rather than straight-chain alkyl, consider whether to introduce branched-chain alkyl as R 1 or R 3 in consideration of solubility and sensitivity to be implemented. can be appropriately selected.
  • R 1 and R 3 may each independently be a straight-chain alkyl.
  • R 2 may improve sensitivity as the number of carbon atoms decreases.
  • R 2 may be methyl.
  • the oxime ester carbazole derivative compound may be any one of the following compounds.
  • a photosensitive resin composition comprising the photoinitiator, and the photoinitiator comprises the oxime ester carbazole derivative compound.
  • the oxime ester carbazole derivative compound absorbs ultraviolet light and shows almost no color, has high radical generation efficiency, has excellent compatibility and stability with other components mixed in the photosensitive resin composition, and improves photopolymerization initiation efficiency do.
  • the sensitivity during the pattern exposure process of the photosensitive resin composition to which the oxime ester carbazole derivative compound is applied as a photoinitiator is high, the exposure amount may not be increased, and thus the production amount may be increased.
  • the photoinitiator has excellent radical generation efficiency with a small exposure amount, has excellent sensitivity, and exhibits improved solubility to sufficiently increase the concentration of the photoinitiator.
  • the photosensitive resin composition may be manufactured for use in forming liquid crystal display devices such as TVs and monitors, in addition to uses such as laptops and mobiles, in response to the increasing and diversifying uses of LCDs.
  • the photosensitive resin composition can quickly respond to light and mechanically implement excellent physical properties, thereby improving the productivity and durability of the applied product.
  • the photosensitive resin composition may form a pattern by, for example, a photo-lithography method, or an insulating protective film may be formed through exposure of the entire surface.
  • a property of rapidly reacting to light ie, photosensitivity
  • the photoinitiator has excellent photosensitivity, excellent quality may be realized by a process by a photolithography method.
  • a column spacer serving as a support or an overcoat and passivation film serving as a protective film may be formed by the photosensitive resin composition.
  • Such column spacers, overcoats and passivation films should have excellent mechanical properties.
  • the photoinitiator since the photoinitiator has excellent photosensitivity, it can be suitably applied to applications requiring excellent mechanical properties.
  • the photosensitive resin composition may include a developable binder resin.
  • the developable binder resin may include one selected from the group consisting of an acrylic acid-containing acrylic copolymer, a novolak-based phenol resin, a polyhydroxystyrene resin, a copolymer of hydroxystyrene and an acrylate, and combinations thereof.
  • the compound having the ethylenically unsaturated bond is, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylic Alkyl esters of (meth)acrylic acid such as lactate, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate having 2 to 14 ethylene oxide groups, ethylene glycol di(meth)acrylate, ethylene oxide group Polyethylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, propylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, trimethylolpropane di (meth) acrylate, bisphenol A diglycidyl ether Acrylic acid adduct, phthalic acid diester of ⁇ -hydroxyethyl (meth)acrylate, toluene diisocyan
  • the photosensitive resin may include a photopolymerizable compound.
  • the photopolymerizable compound is a component for supplementing light efficiency, and the type thereof is not particularly limited, but may include an acrylic binder resin having an ethylenically unsaturated bond.
  • the acrylic binder resin having an ethylenically unsaturated bond is a photocurable acrylic oligomer configured to enable a UV curing reaction by a chemical reaction between an acrylic oligomer precursor and a monomer for introducing an ethylenically unsaturated bond.
  • the acrylic oligomer precursor may be a copolymer of a (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms and a polymerizable monomer.
  • the method for preparing the acrylic oligomer precursor is not particularly limited, and it can be prepared using methods such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization commonly used in the art, and bulk polymerization is preferred.
  • the alkyl group of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms includes an aliphatic alkyl group and an aromatic alkyl group, and these monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) Acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) Acrylate, ethylhexyl (meth) acrylate, ethylbutyl (meth) acrylate, n-oct
  • polymerizable monomer for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate, 2-hydroxypropylene glycol (meth)acrylate and 4-hydroxybutyl vinyl ether a monomer having a hydroxyl group; and monomers having a carboxyl group such as (meth)acrylic acid, crotonic acid, maleic acid, itaconic acid, and fumaric acid.
  • the polymerizable monomers may be used alone or in combination of two or more.
  • the kind of monomer for introducing the said ethylenically unsaturated bond is not specifically limited.
  • an isocyanate-based monomer having an isocyanate group and a double bond in one molecule is used, for example, 2-isocyanatoethyl (meth)acrylate.
  • a method for producing a photocurable acrylic oligomer preferably used as the photopolymerizable compound is not particularly limited. Specifically, for example, after preparing the acrylic oligomer precursor, 0.5 to 20 parts by weight of the isocyanate-based monomer and 0.001 to 0.5 parts by weight of the catalyst are added and reacted with respect to 100 parts by weight of the prepared acrylic oligomer precursor.
  • the type of the catalyst is not particularly limited as long as it can promote the reaction between the hydroxyl group or the carboxyl group and the isocyanate group contained in the acrylic oligomer precursor, and for example, an organotin-based compound, an organic silver-based compound, or a mixture thereof may be used.
  • the photopolymerizable compound may have a weight average molecular weight (in terms of polystyrene, Mw) of 200,000 to 1,000,000 measured by gel permeation chromatography (GPC).
  • the photopolymerization initiator is included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the solid content of the photopolymerizable compound. If the content is less than 0.01 parts by weight, the overall degree of curing of the photopolymerizable composition is lowered, and when it exceeds 10 parts by weight, the transmittance of ultraviolet rays is lowered and the degree of curing in the deep part is lowered.
  • the photosensitive composition may be polymerized and cured by irradiating light.
  • the photosensitive composition can be applied to applications that can utilize these properties.
  • the photosensitive composition may be applied to a photocurable ink, a photosensitive printing plate, various photoresists, a color filter photoresist for LCD, a photoresist for a resin black matrix, or a transparent photosensitive material.
  • the photosensitive composition may further include a solvent.
  • the solvent used in the conventional photopolymerizable composition is not particularly limited.
  • ethers aromatic hydrocarbons, ketones, alcohols, esters or amides are preferable.
  • the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; and alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate
  • esters examples include esters such as ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate; and cyclic esters such as ⁇ -butyrolactone.
  • an organic solvent having a boiling point of 100°C to 200°C in terms of applicability and drying properties, and examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, and ethyl lactate. , butalactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate.
  • the photosensitive composition may further include other components such as additives suitable for its specific use.
  • the additive may be, for example, a silane coupling agent for improving glass adhesion, or a leveling agent for improving flatness.
  • Step 2 (4-( turt Synthesis of -butyl)phenyl)(9-ethyl-6-nitro-9H-carbazol-3-yl)methanone (Compound 2-2)
  • the reactant is naturally heated to room temperature (20-25 °C) and stirred for at least 8 hours. After completion of the reaction, cold water is added to the reaction mixture and extracted with MC (x 3). The extracted organic layer was dried over anhydrous MgSO 4 , concentrated under reduced pressure, and purified by column with ethyl acetate (EA)/hexane to obtain a pale yellow solid 2.2 (27.3 g, 82 % yield).
  • EA ethyl acetate
  • step 3 compound 3-1 was obtained by synthesis in the same manner except that compound 3-2 was used instead of compound 2-2 used in Scheme 1. (19.3 g, 70% yield)
  • step 4 compound 3 was obtained by synthesis in the same manner except that compound 3-1 was used instead of compound 2-1 used in Scheme 1. (15.4 g, 72% yield)
  • step 2 compound 4-2 was obtained in the same manner except that compound c was used instead of compound a used in Scheme 1. (28.3 g, 83% yield)
  • step 4 compound 4 was obtained by synthesis in the same manner except that compound 4-1 was used instead of compound 2-1 used in Scheme 1. (16.5 g, 74% yield)
  • step 2 compound 4-2 was obtained in the same manner except that compound d was used instead of compound a used in Scheme 1. (29.7 g, 84% yield)
  • step 3 compound 5-1 was obtained by synthesizing in the same manner except that compound 5-2 was used instead of compound 2-2 used in Scheme 1. (21.8 g, 71% yield)
  • step 4 compound 5 was obtained by synthesis in the same manner except that compound 5-1 was used instead of compound 2-1 used in Scheme 1. (19.6 g, 72% yield)
  • step 2 compound 6-2 was obtained in the same manner except that compound e was used instead of compound a used in Scheme 1. (28.5 g, 78% yield)
  • step 3 compound 6-1 was obtained by synthesis in the same manner except that compound 6-2 was used instead of compound 2-2 used in Scheme 1. (20.7 g, 70% yield)
  • step 3 compound 7-1 was obtained by synthesizing in the same manner except that compound 7-2 was used instead of compound 2-2 used in Scheme 1. (23.1 g, 72% yield)
  • step 4 compound 7 was obtained by synthesis in the same manner except that compound 7-1 was used instead of compound 2-1 used in Scheme 1. (19.0 g, 75% yield)
  • PMEA Propylene glycol methyl ether acetate
  • PHS polyhydroxystyrene resin
  • DPHA dipentaerythritol hexaacrylate
  • the coating was coated to have a film thickness of 5 ⁇ m, dried at 120° C. for 2 minutes to volatilize the solvent, and a fusion lamp was used. Exposure, development in 0.045wt% KOH aqueous solution at 23 °C, and the thickness was evaluated based on the exposure amount maintaining 80% compared to the initial thickness using a non-contact thickness measuring instrument.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)

Abstract

L'invention concerne un nouveau composé dérivé d'ester d'oxime carbazole.
PCT/KR2021/002360 2020-03-03 2021-02-25 Nouveau composé dérivé d'ester d'oxime carbazole WO2021177654A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20200026271 2020-03-03
KR10-2020-0026271 2020-03-03

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Publication Number Publication Date
WO2021177654A1 true WO2021177654A1 (fr) 2021-09-10

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WO (1) WO2021177654A1 (fr)

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Publication number Priority date Publication date Assignee Title
CN115745867B (zh) * 2022-12-08 2024-10-15 阜阳欣奕华新材料科技股份有限公司 含咔唑并茚酮基团的化合物和肟酯类光引发剂、光固化涂料和固化膜

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010015025A (ja) * 2008-07-04 2010-01-21 Adeka Corp 特定の光重合開始剤を含有する感光性組成物
JP2012008205A (ja) * 2010-06-22 2012-01-12 Tokyo Ohka Kogyo Co Ltd 樹脂パターンの製造方法
US20170235224A1 (en) * 2014-10-15 2017-08-17 Chi Mei Corporation Photosensitive resin composition, color filter, and liquid crystal display element thereof
WO2018235664A1 (fr) * 2017-06-20 2018-12-27 株式会社Adeka Composition polymérisable, composition photosensible pour matrices noires, et composition photosensible pour entretoises en colonne noire
WO2019087985A1 (fr) * 2017-10-31 2019-05-09 東レ株式会社 Composition de résine photosensible de type négatif, film durci, et écran d'affichage électroluminescent organique et son procédé de fabrication

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010015025A (ja) * 2008-07-04 2010-01-21 Adeka Corp 特定の光重合開始剤を含有する感光性組成物
JP2012008205A (ja) * 2010-06-22 2012-01-12 Tokyo Ohka Kogyo Co Ltd 樹脂パターンの製造方法
US20170235224A1 (en) * 2014-10-15 2017-08-17 Chi Mei Corporation Photosensitive resin composition, color filter, and liquid crystal display element thereof
WO2018235664A1 (fr) * 2017-06-20 2018-12-27 株式会社Adeka Composition polymérisable, composition photosensible pour matrices noires, et composition photosensible pour entretoises en colonne noire
WO2019087985A1 (fr) * 2017-10-31 2019-05-09 東レ株式会社 Composition de résine photosensible de type négatif, film durci, et écran d'affichage électroluminescent organique et son procédé de fabrication

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