JP2019099582A - Carbazole oxime ester derivative compound, and photopolymerization initiator and photosensitive composition containing the same - Google Patents

Abstract

To provide a carbazole oxime ester derivative compound having excellent sensitivity, heat resistance, chemical resistance and curability, and a photopolymerization initiator and a photosensitive composition containing the same.SOLUTION: The present invention provides a carbazole oxime ester derivative compound represented by formula 1: [A is O or S, Ris (C1-C20) alkyl, Ris (C1-C20) alkyl, (C6-C20) aryl, (C1-C20) alkoxy, (C6-C20) aryl (C1-C20) alkyl, hydroxy (C1-C20) alkyl, hydroxy (C1-C20) alkoxy (C1-C20) alkyl or (C3-C20) cycloalkyl, Ris (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) aryl (C1-C20) alkyl, (C3-C20) cycloalkyl or (C3-C20) cycloalkyl (C1-C20) alkyl].SELECTED DRAWING: None

Description

  The present invention relates to a carbazole oxime ester derivative compound, a photopolymerization initiator containing the same, and a photosensitive composition, and more specifically, a carbazole oxime ester derivative compound excellent in sensitivity, heat resistance, light resistance, chemical resistance and curability. And a photopolymerization initiator and a photosensitive composition containing the same.

  As general examples of photopolymerization initiators used in photosensitive compositions, many types are known such as acetophenone derivatives, benzophenone derivatives, triazine derivatives, biimidazole derivatives, acyl phosphine oxide derivatives and oxime ester derivatives. . Among them, oxime ester derivatives have the advantages of absorbing ultraviolet rays and exhibiting almost no color, high radical generation efficiency, and excellent compatibility and stability with photosensitive composition materials. However, since the conventional oxime derivative compound has low photoinitiation efficiency, particularly low sensitivity in the pattern exposure step, it is necessary to increase the exposure amount or the use amount, thereby causing a problem of decreasing the production amount.

  Therefore, the development of the photopolymerization initiator excellent in photosensitivity can reduce the cost because even a small amount of the photopolymerization initiator has sufficient sensitivity, the cost can be reduced, and the reduction of the exposure amount due to the excellent sensitivity can be expected, thereby improving the productivity. It can be done.

  However, when forming a pattern using a conventional photopolymerization initiator, during the exposure step for pattern formation, the amount of the photopolymerization initiator used may be increased because the photosensitivity of the photopolymerization initiator is low, or The exposure dose must be increased, which may result in contamination of the mask in the exposure step, and during high temperature crosslinking, the yield may be reduced due to by-products generated after decomposition of the photopolymerization initiator. Furthermore, there is a problem that the time of the exposure process is prolonged to increase the exposure amount, and the productivity is lowered, and an effort is made to solve them.

WO02 / 100903 JP, 2005-025169, A International Publication No. 07/071497 Korean Published Patent Application No. 2013-0124215 Korean Published Patent Application No. 2013-0115272

  The problem to be solved by the present invention is to provide a carbazole oxime ester derivative compound excellent in sensitivity, heat resistance, chemical resistance and curability, a photopolymerization initiator and a photosensitive composition containing the same.

  Another problem to be solved by the present invention is to provide a molded article containing a cured product of the photosensitive composition.

  In addition, still another object of the present invention is to provide a display device including the molded article.

  As one aspect of the present invention for achieving the above-mentioned subject, a carbazole oxime ester derivative compound of the following form is provided.

  The first form relates to a carbazole oxime ester derivative compound represented by the following chemical formula 1 or chemical formula 2.

化学式１及び化学式２において、
Ａは、酸素または硫黄であり；Ｒ_１及びＲ_４は、それぞれ独立して、（Ｃ１〜Ｃ２０）アルキルであり；Ｒ_２は、（Ｃ１〜Ｃ２０）アルキル、（Ｃ６〜Ｃ２０）アリール、（Ｃ１〜Ｃ２０）アルコキシ、（Ｃ６〜Ｃ２０）アリール（Ｃ１〜Ｃ２０）アルキル、ヒドロキシ（Ｃ１〜Ｃ２０）アルキル、ヒドロキシ（Ｃ１〜Ｃ２０）アルコキシ（Ｃ１〜Ｃ２０）アルキルまたは（Ｃ３〜Ｃ２０）シクロアルキルであり；Ｒ_３は、（Ｃ１〜Ｃ２０）アルキル、（Ｃ６〜Ｃ２０）アリール、（Ｃ６〜Ｃ２０）アリール（Ｃ１〜Ｃ２０）アルキル、（Ｃ３〜Ｃ２０）シクロアルキルまたは（Ｃ３〜Ｃ２０）シクロアルキル（Ｃ１〜Ｃ２０）アルキルである。

In chemical formula 1 and chemical formula 2,
A is oxygen or sulfur; _{R 1} and _{R 4} are each independently a (C1 to C20) alkyl; _{R 2} is (C1 to C20) alkyl, (C6 to C20) aryl, (C1 -C20) alkoxy, (C6-C20) aryl (C1-C20) alkyl, hydroxy (C1-C20) alkyl, hydroxy (C1-C20) alkoxy (C1-C20) alkyl or (C3-C20) cycloalkyl; R ₃ is, (C1 to C20) alkyl, (C6 to C20) aryl, (C6 to C20) aryl (C1 to C20) alkyl, (C3 to C20) cycloalkyl or (C3 to C20) cycloalkyl (C1 to C20 ) Alkyl.

In the second form, in the first form, R ₁ and R ₄ are each independently methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n -Pentyl, i-pentyl, n-hexyl or i-hexyl; R ₂ is 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, hydroxy n-propyl, hydroxy n-butyl, hydroxy i-butyl, hydroxy n-pentyl, hydroxy i-pentyl, hydroxy n-hexyl, hydroxy i-hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, Hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl; and R ₃ is methyl, ethyl, n-propyl, i-propyl, n-butyl Carba which is i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl, cyclopentyl, cyclohexyl or phenyl It relates Lumpur oxime ester derivative compound.

  A third aspect relates to the carbazole oxime ester derivative compound in which the carbazole oxime ester derivative compound is selected from the compounds represented by the following chemical formulas 3-1 to 3-18 in the first form or the second form.

  According to another aspect of the present invention, a photoinitiator of the following form is provided.

  A fourth aspect relates to a photopolymerization initiator comprising a carbazole oxime ester derivative compound according to any one of the first to third aspects.

  According to still another aspect of the present invention, a photosensitive composition of the following form is provided.

The fifth form is (a) an alkali-soluble resin;
(B) a polymerizable compound having an ethylenically unsaturated bond; and (c) a photopolymerization initiator containing a carbazole oxime ester derivative compound according to any one of the first to third embodiments described above Photosensitive composition.

  A sixth aspect relates to the photosensitive composition according to the fifth aspect, wherein 0.01% to 10% by weight of the carbazole oxime ester derivative compound is contained in 100% by weight of the photosensitive composition.

  A seventh form is according to the fifth form or the sixth form, wherein the photopolymerization initiator is a thioxanthone compound, an acylphosphine oxide compound, an acetophenone compound, a biimidazole compound, a triazine compound, an O-acyloxy The present invention relates to a photosensitive composition further comprising one or more compounds selected from the group consisting of a muester compound and a thiol compound.

  An eighth aspect relates to the photosensitive composition according to any one of the fifth to seventh aspects, wherein the photosensitive composition further comprises a coloring material.

  According to still another aspect of the present invention, there is provided a molded article of the following form and a display device comprising the same.

  The ninth aspect relates to a molded article including a cured product of the photosensitive composition according to any one of the fifth to eighth aspects.

  A tenth aspect relates to the molding according to the ninth aspect, wherein the molding is an array flattening film, an insulating film, a color filter, a column spacer, an overcoat, a black column spacer or a black matrix.

  An eleventh aspect relates to a display device including the ninth aspect or the tenth aspect molding.

  When the carbazole oxime ester derivative compound according to one embodiment of the present invention is used as a photopolymerization initiator of a photosensitive composition, the sensitivity is extremely excellent, and the residual film rate, pattern stability, heat resistance, chemical resistance, ductility, etc. Because of the excellent physical properties, contamination can be reduced by minimizing the outgassing generated from the photopolymerization initiator in the exposure and postbake steps in the TFT-LCD manufacturing process. Can minimize problems that may occur.

  Hereinafter, the present invention will be described in detail, but the terms and words used in the present specification and claims should not be interpreted as being limited to general or lexical meanings, and the inventor himself In light of the principle that the concept of terms can be properly defined in order to explain in a best way, the meanings and concepts of terms and words must be interpreted based on the technical idea of the present invention.

  Accordingly, the configuration shown in the embodiments described herein is only one of the most desirable embodiments of the present invention and does not embody all of the technical ideas of the present invention. It should be understood that there may be various equivalents and variations that can be substituted for them at any given time.

  The carbazole oxime ester derivative compound according to one aspect of the present invention is represented by the following Chemical Formula 1 or Chemical Formula 2.

化学式１及び化学式２において、Ａは、酸素または硫黄であり；Ｒ_１及びＲ_４は、それぞれ独立して、（Ｃ１〜Ｃ２０）アルキルであり；Ｒ_２は、（Ｃ１〜Ｃ２０）アルキル、（Ｃ６〜Ｃ２０）アリール、（Ｃ１〜Ｃ２０）アルコキシ、（Ｃ６〜Ｃ２０）アリール（Ｃ１〜Ｃ２０）アルキル、ヒドロキシ（Ｃ１〜Ｃ２０）アルキル、ヒドロキシ（Ｃ１〜Ｃ２０）アルコキシ（Ｃ１〜Ｃ２０）アルキルまたは（Ｃ３〜Ｃ２０）シクロアルキルであり；Ｒ_３は、（Ｃ１〜Ｃ２０）アルキル、（Ｃ６〜Ｃ２０）アリール、（Ｃ６〜Ｃ２０）アリール（Ｃ１〜Ｃ２０）アルキル、（Ｃ３〜Ｃ２０）シクロアルキルまたは（Ｃ３〜Ｃ２０）シクロアルキル（Ｃ１〜Ｃ２０）アルキルである。

In Chemical Formula 1 and Chemical Formula 2, A is oxygen or sulfur; R ₁ and R ₄ are each independently (C 1 -C 20) alkyl; R ₂ is (C 1 -C 20) alkyl, (C 6 To C20) aryl, (C1 to C20) alkoxy, (C6 to C20) aryl (C1 to C20) alkyl, hydroxy (C1 to C20) alkyl, hydroxy (C1 to C20) alkoxy (C1 to C20) alkyl or (C3 to C20) C20) cycloalkyl; R ₃ is (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 6 -C 20) aryl (C 1 -C 20) alkyl, (C ₃ -C 20) cycloalkyl or (C ₃ -C 20) ) Cycloalkyl (C1-C20) alkyl.

  Substituents containing "alkyl", "alkoxy" and other "alkyl" moieties as described herein include all linear or branched structures, and "cycloalkyl" is a single ring system only. Also contains polycyclic hydrocarbons.

  In addition, “aryl” described herein is an organic radical derived by removing one hydrogen from an aromatic hydrocarbon, which includes a single or fused ring, and multiple aryls are single. It also includes structures linked by bonds.

  In addition, "hydroxyalkyl" described in the present specification means OH-alkyl having a hydroxy group bonded to the above-mentioned alkyl group, and "hydroxyalkoxyalkyl" has an alkoxy group bonded to the above hydroxyalkyl group. By hydroxyalkyl-O-alkyl, alkenyl is meant a structure comprising a ketone to which an alkyl or aryl group is attached.

  In addition, as "arylalkyl" described in the present specification, benzyl and the like can be mentioned, as "cycloalkyl", cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like can be mentioned, and as "cycloalkylalkyl", And cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclopropylethyl and the like.

  In addition, “(C1 to C20) alkyl” described in the present specification means alkyl having 1 to 20 carbon atoms, preferably (C1 to C10) alkyl, more preferably (C1 to C6). It may be alkyl.

  "(C6-C20) aryl" means aryl having 6 to 20 carbon atoms, preferably (C6-C18) aryl, more preferably (C6-C12) aryl.

  "(C1-C20) alkoxy" means alkoxy having 1 to 20 carbon atoms, preferably (C1-C10) alkoxy, more preferably (C1-C4) alkoxy.

  “(C 6 -C 20) aryl (C 1 -C 20) alkyl” means alkyl in which one hydrogen of alkyl having 1 to 20 carbons is substituted with an aryl group having 6 to 20 carbons, preferably (C6-C18) aryl (C1-C10) alkyl, more preferably (C6-C18) aryl (C1-C6) alkyl, still more preferably (C6-C12) aryl (C1-C6) alkyl obtain.

  "Hydroxy (C1-C20) alkyl" means alkyl having 1 to 20 carbon atoms substituted with 1 hydrogen substituted with hydroxy, preferably hydroxy (C1-C10) alkyl, more preferably hydroxy It may be (C1-C6) alkyl.

  The "hydroxy (C1-C20) alkoxy (C1-C20) alkyl" is one in which one hydrogen is substituted with an alkyl having 1 to 20 carbons to an alkoxy having 1 to 20 carbons, and one hydrogen is selected from the above alkoxy It means a structure substituted by hydroxy, preferably hydroxy (C1-C10) alkoxy (C1-C10) alkyl, more preferably hydroxy (C1-C4) alkoxy (C1-C6) alkyl.

  The “(C 3 -C 20) cycloalkyl” means a cycloalkyl having 3 to 20 carbon atoms, which may desirably be (C 3 -C 10) cycloalkyl.

  “(C 3 -C 20) cycloalkyl (C 1 -C 20) alkyl” means alkyl having 1 to 20 carbons and one hydrogen substituted with cycloalkyl having 3 to 20 carbons, preferably It may be (C3-C10) cycloalkyl (C1-C10) alkyl, more preferably (C3-C6) cycloalkyl (C1-C6) alkyl.

According to one aspect of the invention, in Formula 1 and Formula 2, A is oxygen or sulfur; and R ₁ and R ₄ are each independently methyl, ethyl, n-propyl, i-propyl, n -Butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl or i-hexyl; R ₂ is 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- Toxy, t-butoxy, hydroxymethyl, hydroxyethyl, hydroxy n-propyl, hydroxy n-butyl, hydroxy i-butyl, hydroxy n-pentyl, hydroxy i-pentyl, hydroxy n-hexyl, hydroxy i-hexyl, hydroxymethoxymethyl , Hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl; R ₃ is methyl, ethyl, n-propyl , I-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl, cyclopentyl, cyclic It may be hexyl, or phenyl.

More specifically, in the chemical formula 1 and the chemical formula 2, said A is oxygen or sulfur; said R ₁ and R ₄ are each independently methyl, ethyl or n-propyl; R ₂ is methyl, Ethyl, n-propyl, i-propyl, n-butyl, n-pentyl, cyclohexyl, phenyl or benzyl; R ₃ may be methyl, ethyl, n-propyl or phenyl.

  According to one aspect of the present invention, examples of the carbazole oxime ester derivative compound include compounds selected from the group consisting of the following chemical formulas 3-1 to 3-18, but the present invention is not limited by the following compounds.

  Although the carbazole oxime ester derivative compound represented by said Chemical formula 1 or Chemical formula 2 of this invention can be manufactured according to following Reaction formula 1 or Reaction formula 2, it is not limited to these.

In Reaction Scheme 1 or Reaction Scheme 2, A and R _{1 to} R ₄ are the same as defined in Chemical Formula 1 or Chemical Equation 2, and X is a halogen.

  Moreover, the photoinitiator which is the other aspect of this invention contains 1 or more types selected from the carbazole oxime ester derivative compound represented by said Chemical formula 1 or Chemical formula 2.

In addition, the photosensitive composition according to still another aspect of the present invention includes (a) an alkali-soluble resin, (b) a polymerizable compound having an ethylenically unsaturated bond, and (c) a compound represented by Formula 1 or Formula 2 above. A photopolymerization initiator comprising one or more selected from carbazole oxime ester derivative compounds.
Here, the carbazole oxime ester derivative compound may be included as a photopolymerization initiator.

  The photosensitive composition which is the further another aspect of this invention is excellent in adjustment of a pattern characteristic, and excellent in thin film physical properties, such as heat resistance and chemical resistance. Hereinafter, each component contained in the photosensitive composition of this invention is demonstrated in detail.

  In the present specification, “(meth) acrylic” means acrylic and / or methacrylic, “(meth) acrylate” means acrylate and / or methacrylate, and “(meth) acrylic acid” means acrylic acid and / or Stands for methacrylic acid.

(A) Alkali-Soluble Resin As the alkali-soluble resin, an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in the side chain can be used.

  The acrylic polymer means a polymer (including a homopolymer or copolymer) of an acrylic monomer, and examples of such a monomer include methyl (meth) acrylate and ethyl (meth). Acrylate, propyl (meth) acrylate, 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 (meth) Acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride Maleic acid monoalkyl ester, monoalkyl itaconate, monoalkyl fumarate, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate, 3,4-epoxy Cyclohexylmethyl (meth) acrylate, 3-methyloxetane-3-methyl (meth) acrylate, 3-ethyloxetane-3-methyl (meth) acrylate, styrene, α-methylstyrene, acetoxystyrene, N-methylmaleate Imide, N-ethyl maleimide, N-propyl maleimide, N-butyl maleimide, N-cyclohexyl maleimide, (meth) acrylamide, N- methyl (meth) acrylamide and the like can be mentioned, and these can be used alone or in combination of two or more It can be used in combination.

  An acrylic polymer having an acrylic unsaturated bond in a side chain is a copolymer obtained by addition reaction of an epoxy resin to an acrylic copolymer containing a carboxylic acid, and (meth) acrylic acid, itaconic acid, and maleic acid And acrylic monomers containing carboxylic acids such as maleic acid monoalkyl ester, and alkyl (meth) acrylates such as methyl (meth) acrylate and 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, α-methylstyrene Copolymerizing two or more monomers such as acetoxystyrene, N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-butyl maleimide, N-cyclohexyl maleimide, (meth) acrylamide, N-methyl (meth) acrylamide and the like And acrylic copolymers containing carboxylic acid such as glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate And the like can be used at a temperature of 40 to 180 ° C.

  Another example of the acrylic polymer having an acrylic unsaturated bond in the side chain is a copolymer obtained by the addition reaction of an acrylic copolymer containing an epoxy group with a carboxylic acid, and glycidyl (meth) acrylate, 3, Acrylic monomers containing an epoxy group such as 4-epoxybutyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, methyl (meth) acrylate, hexyl (meth) acrylate ) Alkyl (meth) acrylates such as acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylic , 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, styrene, α-methylstyrene, acetoxystyrene, N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-butyl maleimide (Meth) acrylic acid itaconic acid, maleic acid, and maleic acid to an acrylic copolymer containing an epoxy group obtained by copolymerizing two or more monomers such as N-cyclohexylmaleimide, (meth) acrylamide, N-methyl (meth) acrylamide and the like A binder resin obtained by subjecting an acrylic monomer containing a carboxylic acid such as an acid monoalkyl ester to an addition reaction at a temperature of 40 to 180 ° C. can be used.

  According to one aspect of the present invention, the alkali-soluble resin is 3 to 50% by weight in 100% by weight of the photosensitive composition in order to adjust pattern characteristics and to impart thin film physical properties such as heat resistance and chemical resistance. Preferably, 5 to 45% by weight, more preferably 8 to 40% by weight can be used.

  The weight average molecular weight of the alkali-soluble resin (as measured by polystyrene conversion by gel permeation chromatography (GPC)) may be 2,000 to 300,000, preferably 4,000 to 100,000, and the dispersion degree may be 1. It may be from 0 to 10.0.

(B) Polymerizable compound having an ethylenically unsaturated bond The polymerizable compound having an ethylenically unsaturated bond plays a role of being cross-linked by light reaction during pattern formation to form a pattern, and being cross-linked during high temperature heating Provide chemical resistance and heat resistance.

  The polymerizable compound having an ethylenically unsaturated bond is 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 in 100% by weight of the photosensitive composition. It can be done.

  If the addition amount of the polymerizable compound having an ethylenically unsaturated bond is too large, there is a possibility that the degree of crosslinking may be excessively increased to decrease the ductility of the pattern.

  Specifically, examples of the polymerizable compound having an ethylenically unsaturated bond include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate and the like. Alkyl esters of (meth) acrylic acid, glycidyl (meth) acrylates, polyethylene glycol mono (meth) acrylates having 2 to 14 ethylene oxide groups, ethylene glycol di (meth) acrylates, 2 to 14 ethylene oxide groups Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, trimethylolpropane di (meth) acrylate, bisphenol A diglycidyl ether with acrylic acid , Phthalic acid diester of β-hydroxyethyl (meth) acrylate, toluene diisocyanate adduct of β-hydroxyethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( Esterify polyhydric alcohol with α, β-unsaturated carboxylic acid like meta) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol tri (meth) acrylate And acrylic acid adducts of polyvalent glycidyl compounds such as trimethylolpropane triglycidyl ether acrylic acid adduct, and the like, and these may be used alone or in combination of two or more. The above can be used in combination.

(C) Photoinitiator In the photosensitive composition of the present invention, one or more selected from carbazole oxime ester derivative compounds represented by the above Chemical Formula 1 or Chemical Formula 2 can be used as a photopolymerization initiator. The photopolymerization initiator is contained in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, in 100% by weight of the photosensitive composition in order to enhance the transparency and minimize the exposure amount. Is more effective.

(D) Adhesion Aid Also, the photosensitive composition of the present invention may further contain a silicone compound having an epoxy group or an amine group as an adhesion aide, if necessary.

  The silicone type compound which has the said epoxy group or an amine group can improve the adhesive force of an ITO electrode and a photosensitive composition, and can increase the heat resistant characteristic after hardening. Examples of the silicone compound having an epoxy group or an amine group include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, and (3-glycidoxypropyl) methyldimethoxysilane. (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4 Epoxy-butyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltrimethoxysilane and the like. Alone or two or more Combined and can be used.

  The silicone compound having an epoxy group or an amine group may be contained in an amount of 0.0001 to 3% by weight in 100% by weight of the photosensitive composition. Below the above range, the additive effect can not be obtained, and above the above range, the development characteristics of the non-exposed area are degraded, and scum and residue on the lower substrate, ITO or glass substrate It may remain.

(E) Other Additives The photosensitive composition of the present invention may further contain one or more compatible additives selected from photosensitizers, thermal polymerization inhibitors, antifoaming agents and leveling agents as required. Can be included.

  The above-mentioned other additives may be contained in an amount of 0.1 to 10% by weight in 100% by weight of the photosensitive composition, and the addition effect can not be obtained below the above range, and the foam It may occur in excess.

(F) Solvent The photosensitive composition of the present invention is coated with a solvent and coated on a substrate, and then irradiated with ultraviolet rays using a mask to form a pattern by development with an alkaline developer.

  Therefore, since the solvent content can be adjusted so that the total amount of the composition becomes 100% by weight by combining the solvent with the content of components other than the solvent in the photosensitive composition described above, Depending on the content of components other than the solvent, the content of the solvent may be variously changed. For example, it is desirable to adjust the content of the solvent to 10 to 95% by weight in 100% by weight of the photosensitive composition and to adjust the viscosity to be in the range of 1 to 50 cps.

  As the solvent, ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propionate, in consideration of compatibility with an alkali soluble resin, a photo polymerization initiator and other compounds (EEP), ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol methyl ether propionate (PGMEP), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, diethylene glycol Ethyl acetate, acetone, methyl isobutyl ketone, syrup Hexanone, dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ-butyl lactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (THF) A solvent selected from methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane and octane alone; Alternatively, two or more kinds can be mixed and used.

(G) Other Photopolymerization Initiators The photosensitive composition of the present invention may use the carbazole oxime ester derivative compound described above as the photopolymerization initiator alone, and may use thioxanthone compounds, acylphosphine oxide compounds, acetophenone compounds. One or more selected from the group consisting of a compound, a biimidazole compound, a triazine compound, an O-acyl oxime ester compound and a thiol compound can also be used.

  These further usable photoinitiators can be contained in an amount of 0.01 to 5% by weight in 100% by weight of the photosensitive composition.

  Examples of the thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-dichloro thioxanthone, 2,4- dimethyl thioxanthone, 2,4- diethyl One or more selected from thioxanthone and 2,4-diisopropyl thioxanthone can be used, but is not limited thereto.

  As the acyl phosphine oxide compound, for example, diphenyl (2,4,6-trimethyl benzoyl) phosphine oxide, phenyl bis (2, 4, 6- trimethyl benzoyl) phosphine oxide or a combination of these can be used. It is not limited.

  Examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl). One or more selected from butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one can be used, but is not limited thereto I will not.

  Examples of the biimidazole compounds include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 2,2′-bis 2,4-Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis (2,4,6-trichlorophenyl) -4,4', One or more selected from 5,5'-tetraphenyl-1,2'-biimidazole can be used, but is not limited thereto.

  Examples of the triazine compounds include 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-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl ] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy) Use one or more selected from tyryl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Although it can be, it is not limited to these.

  Examples of the O-acyloxime ester compounds 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) methoxy Benzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) and 2- (acetoxyimino) -1- (9,9'-diethyl-9H-ful) B-2-yl) but more than one can be used which is selected from propan-1-one, and the like.

  Although the pentaerythritol tetrakis (3-mercapto propionate) etc. can be used as said thiol type compound, It is not limited to these.

(H) Color material The photosensitive composition which is one form of the present invention can further contain a color material contained for use as a color filter or a resist for forming a black matrix.

  As the coloring material, various pigments can be used, and examples thereof include additive mixed red, green and blue, and color-reduced mixed cyan, magenta, yellow and black pigments, and the like. As pigments usable for C.I. I. Pigment yellow 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 147, 148, 153, 154, 166, 168, C.I. I. Pigment orange 36, 43, 51, 55, 59, 61, C.I. I. Pigment red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment blue 15, 15: 1, 15: 4, 15: 6, 22, 60, 64, C.I. I. Pigment green 7, 36, C.I. I. Pigment browns 23, 25, 26, C.I. I. Pigment black 7 and titanium black.

  The colorant may be contained in an amount of 5 to 50% by weight in 100% by weight of the photosensitive composition. If it is less than the above range, the light shielding property is lowered, and if it is more than the above range, there is a possibility that exposure failure or curing failure may occur.

  The photosensitive composition which is one form of the present invention may be soda glass, quartz glass, semiconductor substrate, metal by known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, immersion and the like. , Paper, plastic and the like. Moreover, after applying on a support | carrier, such as a film first, it can also be transcribe | transferred on another support | carrier, and there is no restriction | limiting in the application method.

  According to still another aspect of the present invention, there is provided a molded article comprising the cured product of the photosensitive composition described above.

  Examples of the molded product include, but are not limited to, an array planarization film, an insulating film, a color filter, a column spacer, an overcoat, a black column spacer, a black matrix, and the like.

  Moreover, according to the further another aspect of this invention, various displays, such as a liquid crystal display element containing the said molding, and OLED, are provided.

  Hereinafter, in order to aid the understanding of the present invention, representative compounds of the present invention will be described in detail by way of examples and comparative examples. However, the embodiments of the present invention can be modified in many other forms, and the scope of the present invention is not limited to the embodiments described below. Examples of the present invention are provided to those skilled in the art to describe the present invention in more detail.

<Production of Carbazole Oxime Ester Derivative Compound>
Example 1: Preparation of 1- (9- (4-methoxyphenyl) -9H-carbazol-3-yl) -1-propanone oxime (O-acetate) [Chemical formula 3-1]

Step 1: Synthesis of 9- (4-methoxyphenyl) -9H-carbazole Into a reactor was placed triethylene glycol dimethyl ether (40 ml), into which carbazole (30 g, 170.5 mmol), 4-iodoanisole (49. After adding 8 g (204.3 mmol), powdered copper (11.34 g, 180 mmol) and potassium carbonate (58.8 g, 423.2 mmol), the mixture was stirred at 200 ° C. for 20 hours. After completion of the reaction, the reaction solution was cooled to normal temperature and ethyl acetate (300 ml) was added and then stirred for 30 minutes to crystallize. The solution was filtered and the solid obtained was again stirred for 30 minutes each in acetone (300 ml) and methylene chloride (300 ml) and then filtered and washed with water.

  The solid obtained was discarded because it was an impurity, the filtrate was collected, the organic solvent in the filtrate was distilled at 40 ° C. under reduced pressure, and the liquid containing the product was kept refrigerated for one day to precipitate the product. Subsequently, petroleum ether (about 200 ml) is added and filtered, and the resulting solid is recrystallized with acetone to obtain the target compound 9- (4-methoxyphenyl) -9H-carbazole (40.7 g, 87). .4%).

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 3.93 (3 H, s), 7.12 (2 H, d), 7. 28 (2 H, t), 7.33 (2 H, d), 7. 41 (2H, t), 7.46 (2H, d), 8.15 (2H, d)
MS (m / e): 273

Two steps: Synthesis of 1- (9- (4-methoxyphenyl) -9H-carbazol-3-yl) propan-1-one Aluminum chloride (5.91 g, 43.9 mmol) is added to methylene chloride (200 ml), After cooling to −10 ° C. or less and stirring for 10 minutes, 9- (4-methoxyphenyl) -9H-carbazole (10.0 g, 36.3 mmol) obtained in the first step was added and stirred for 30 minutes. A solution of propionyl chloride (3.89 ml, 43.9 mmol) in methylene chloride (25 ml) was added dropwise for 50 minutes and then stirred for 30 minutes. The reaction solution was stirred in ice water consisting of ice (490 g) and water (500 ml) for 30 minutes and allowed to stand to remove the aqueous layer, and the organic layer was thoroughly washed with aqueous sodium bicarbonate solution. Subsequently, the organic layer is dried using anhydrous magnesium sulfate, filtered and distilled under reduced pressure to obtain the target compound 1- (9- (4-methoxyphenyl) -9H-carbazol-3-yl) propane-1 -Obtained on (11.8 g, 98.9%).

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 1.31 (3 H, t), 3.16 (2 H, q), 3.93 (3 H, s), 7.13 (2 H, d), 7. 32 (3 H, m), 7. 45 (3 H, m), 8.07 (1 H, d), 8.2 (1 H, d), 8.8 1 (1 H, s)
MS (m / e): 329

Three steps: Synthesis of 1- (9- (4-methoxyphenyl) -9H-carbazol-3-yl) -1-propanone-2-oxime 1- (9- (4-methoxy) obtained in the above two steps Phenyl) -9H-carbazol-3-yl) propan-1-one (6.0 g, 18.2 mmol), tetrahydrofuran (132 ml) and 35% concentrated hydrochloric acid (8.7 ml) were placed in a reactor and stirred for 30 minutes did. A solution of isopentyl nitrite (5.1 ml, 36.4 mmol) in tetrahydrofuran (10 ml) was added dropwise for 30 minutes and then stirred for 50 minutes. Subsequently, the reaction was extracted with ethyl acetate and thoroughly washed with aqueous sodium bicarbonate. The extracted organic layer was dried over anhydrous magnesium sulfate, filtered and distilled under reduced pressure to obtain an impurity-containing product. The resulting impurity-containing product is washed three times with methylene chloride to give the target compound 1- (9- (4-methoxyphenyl) -9H-carbazol-3-yl) -1-propanone-. 2-Oxime (2.03 g, 31.1%) was obtained.

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 2.26 (3 H, s), 3.93 (3 H, s), 7.13 (2 H, d), 7.33 (3 H, m), 7. 44 (3H, m), 7.88 (1 H, br), 8.07 (1 H, d), 8. 18 (1 H, d), 8.83 (1 H, s)
MS (m / e): 358

Step 4: Synthesis of 1- (9- (4-methoxyphenyl) -9H-carbazol-3-yl) -1-propanone oxime (O-acetate) 1- (9- (4 ) obtained in the above step -Methoxyphenyl) -9H-carbazol-3-yl) -1-propanone-2-oxime (0.5 g, 1.4 mmol) is added to ethyl acetate and cooled to -10 ° C. or less, triethylamine (0.39 ml) , 2.8 mmol) was added dropwise and stirred for 10 minutes. Subsequently, a solution of acetyl chloride (0.22 ml, 3.08 mmol) in ethyl acetate (1 ml) was added dropwise for 10 minutes and stirred for 30 minutes. The reaction solution was extracted with methylene chloride and thoroughly washed with aqueous sodium bicarbonate solution. The extracted organic layer is dried over anhydrous magnesium sulfate, filtered and distilled under reduced pressure to obtain the target compound 1- (9- (4-methoxyphenyl) -9H-carbazol-3-yl) -1-propane On oxime (O-acetate) (0.53 g, 94.3%) was obtained.

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 2.31 (3 H, s), 2.37 (3 H, s), 3.93 (3 H, s), 7.13 (2 H, d), 34 (3 H, q), 7. 45 (3 H, q), 8. 19 (2 H, t), 8.99 (1 H, s)
MS (m / e): 400
Decomposition point: 241.8 ° C

Example 2 to Example 12
Under the same conditions as in Example 1, carbazole oxime ester derivative compounds having the compositions in Table 1 below were synthesized.

Example 13: 2- (hydroxyimino) -1- (6-methoxy-9- (4-methoxyphenyl) -9H-carbazol-3-yl) propan-1-one (O-acetate) [chemical formula 3-13 ]Manufacturing of

Step 1: Synthesis of 3-methoxy-9H-carbazole 3-bromo-9H-carbazole (19.8 g, 78.8 mmol), copper iodide (8.0 g, 41.76 mmol), sodium methoxide 25 under nitrogen atmosphere % Methanol solution (750 ml), ethyl acetate (15 ml) and toluene (15 ml) were put into a reactor and reacted under reflux at 90 ° C. for 4 days. It cooled to normal temperature after reaction completion. Subsequently, the reaction solution was transferred to a beaker, water (300 ml) and methylene chloride (300 ml) were added, and the mixture was stirred for 1 hour. The solution of the beaker was passed through a filter filled with 2-3 cm sized silica gel (40-400 mesh) and filtered to remove undissolved impurities. Subsequently, the filtrate is extracted three times with methylene chloride (300 ml), the organic layer is dried using anhydrous magnesium sulfate, filtered and distilled under reduced pressure to recrystallize (methylene chloride: hexane = 1: 1). The target compound 3-methoxy-9H-carbazole (10.3 g, 66.4%) was obtained.

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 3.93 (3 H, s), 7.12 (2 H, d), 7. 28 (2 H, t), 7.33 (2 H, d), 7. 41 (2H, t), 7.46 (2H, d), 8.15 (2H, d)
MS (m / e): 197

Two steps: Synthesis of 3-methoxy-9- (4-methoxyphenyl) -9H-carbazole 3-methoxy-9H-carbazole (3.0 g, 15.2 mmol) obtained in the above one step, 4-iodoanisole ( 4.34 g (17.8 mmol), powdered copper (1.01 g, 15.8 mmol), potassium carbonate (5.28 g, 38 mmol) and triethylene glycol dimethyl ether (5.3 ml, 29.3 mmol) in the reactor Then, it was stirred at 200 ° C. for 24 hours. After completion of the reaction, the reaction solution was cooled to room temperature, methylene chloride (60 ml) was added, and the mixture was stirred for 1 hour. The reaction solution was passed through a filter filled with 2-3 cm sized silica gel (40-400 mesh) and filtered. Subsequently, methylene chloride and triethylene glycol dimethyl ether in the filtrate are removed by distillation under reduced pressure and column separation (methylene chloride: hexane = 1: 5) is carried out to obtain the target compound 3-methoxy-9- (4-methoxy Phenyl) -9H-carbazole (4.05 g, 88.2%) was obtained.

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 3.91 (3 H, s), 3.95 (3 H, s), 7.04 (1 H, dd), 7.10 (2 H, dd), 24 (2H, m), 7.32 (1 H, d), 7. 38 (1 H, m), 7.44 (2 H, dd), 7.61 (1 H, d), 8.09 (1 H, d) )
MS (m / e): 303

Three steps: Synthesis of 1- (6-methoxy-9- (4-methoxyphenyl) -9H-carbazol-3-yl) propan-1-one Aluminum chloride (2.32 g, 17.2 mmol) in methylene chloride (40 ml) ) And cooled to -10 ° C or less. After dropping 3-methoxy-9- (4-methoxyphenyl) -9H-carbazole (4.0 g, 13.2 mmol) obtained in the above two steps into the above methylene chloride (5 ml), it is stirred for about 20 minutes did. Propionyl chloride (1.52 ml, 17.2 mmol) was added dropwise for 30 minutes and then stirred for 20 minutes. After completion of the reaction, the reaction solution was poured into water (200 ml) and stirred for 1 hour, then methylene chloride (100 ml) was added to extract the organic layer, and the extracted organic layer was thoroughly washed with an aqueous sodium bicarbonate solution. The extracted organic layer is dried using anhydrous magnesium sulfate, filtered and distilled under reduced pressure to obtain the target compound 1- (6-methoxy-9- (4-methoxyphenyl) -9H-carbazol-3-yl). Propan-1-one (4.5 g, 94.7%) was obtained.

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 1.30 (3H, t), 3.15 (2H, q), 3.91 (3H, s), 3.95 (3H, s), 7. 07 (1H, dd), 7.11 (2H, dd), 7.24 (1H, d), 7.29 (1H, d), 7.42 (2H, dd), 7.66 (1H, d) ), 8.04 (1 H, dd), 8.76 (1 H, d)
MS (m / e): 359

Four steps: Synthesis of 2- (hydroxyimino) -1- (6-methoxy-9- (4-methoxyphenyl) -9H-carbazol-3-yl) propan-1-one 1- obtained in the above three steps (6-Methoxy-9- (4-methoxyphenyl) -9H-carbazol-3-yl) propan-1-one (4.91 g, 13.7 mmol) and 35% concentrated hydrochloric acid (2.4 ml, 27.4 mmol) Was added to tetrahydrofuran (40 ml) and stirred for 30 minutes. Subsequently, a solution of isopentyl nitrite (3.83 ml, 27.4 mmol) in tetrahydrofuran (8 ml) was added dropwise for 20 minutes and stirred for 5 hours. After completion of the reaction, ethyl acetate (100 ml) was added to extract the organic layer, and the extracted organic layer was thoroughly washed with an aqueous sodium bicarbonate solution. The extracted organic layer was dried using anhydrous magnesium sulfate and filtered. Then, after distillation under reduced pressure, column separation (ethyl acetate: hexane = 1: 4) is carried out to obtain the target compound 2- (hydroxyimino) -1- (6-methoxy-9- (4-methoxyphenyl) -9H-. Carbazol-3-yl) propan-1-one (1.63 g, 30.7%) was obtained.

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 2.27 (3 H, s), 3.92 (3 H, s), 3.95 (3 H, s), 7.07 (1 H, dd), 7. 12 (2H, dd), 7.23 (1 H, d), 7.29 (1 H, d), 7.42 (2 H, dd), 7.65 (1 H, d), 7.68 (1 H, s) ), 8.06 (1 H, dd), 8.79 (1 H, d)
MS (m / e): 388

Step 5: Synthesis of 2- (hydroxyimino) -1- (6-methoxy-9- (4-methoxyphenyl) -9H-carbazol-3-yl) propan-1-one (O-acetate) The obtained 2- (hydroxyimino) -1- (6-methoxy-9- (4-methoxyphenyl) -9H-carbazol-3-yl) propan-1-one (0.76 g, 1.96 mmol) in ethyl The reaction solution was added to acetate (15 ml) and cooled to -10 ° C or lower, and triethylamine (0.55 ml, 3.92 mmol) was further added and stirred for 10 minutes. Subsequently, a solution of acetyl chloride (0.29 ml, 3.92 mmol) in ethyl acetate (2 ml) was added dropwise for 5 minutes and stirred for 20 minutes. After completion of the reaction, methylene chloride (50 ml) was added to extract the organic layer, and the extracted organic layer was thoroughly washed with an aqueous sodium bicarbonate solution. The extracted organic layer is dried over anhydrous magnesium sulfate and distilled under reduced pressure to give the target compound 2- (hydroxyimino) -1- (6-methoxy-9- (4-methoxyphenyl) -9H-carbazole-3. -Yl) propan-1-one (O-acetate) (0.77 g, 91.3%) was obtained.

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 2.30 (3H, s), 2.37 (3H, s), 3.92 (3H, s), 3.96 (3H, s), 7. 08 (1 H, dd), 7.12 (2 H, dd), 7.24 (1 H, d), 7.31 (1 H, d), 7.42 (2 H, dd), 7.67 (1 H, d) ), 8.16 (1 H, dd), 8.93 (1 H, d)
MS (m / e): 430
Decomposition point: 248.3 ° C

Example 14 to Example 18
Under the same conditions as in Example 13, carbazole oxime ester derivative compounds having the compositions shown in Table 2 below were synthesized.

<Production of alkali-soluble resin>
Production Example 1 Production of Acrylic Polymer (a-1) After adding 200 mL of propylene glycol methyl ether acetate (PGMEA) and 1.5 g of azobisisobutyronitrile (AIBN) to a 500 mL polymerization vessel, methacrylic acid, glycidyl After adding methacrylic acid, methyl methacrylic acid and dicyclopentanyl acrylic acid in a molar ratio of 20: 20: 40: 20, respectively, so that the solid content of the acrylic monomer is 40% by weight, under a nitrogen atmosphere, at 70 ° C. The mixture was stirred for 5 hours to polymerize to produce an acrylic polymer (a-1). The weight average molecular weight of the polymer (a-1) thus produced was 25,000, and the degree of dispersion was 1.9.

Production Example 2 Production of Acrylic Polymer (a-2) After adding 200 mL of PGMEA and 1.0 g of AIBN to a 500 mL polymerization vessel, methacrylic acid, styrene, methyl methacrylic acid and cyclohexyl methacrylic acid were each 40: 20: 20. After adding so that solid content of an acryl monomer might be 40 weight% by molar ratio of: 20, it stirred for 5 hours at 70 degreeC under nitrogen atmosphere, was polymerized, and the copolymer was synthesize | combined. 0.3 g of N, N-dimethylaniline and 20 mol of glycidyl methacrylic acid based on 100 mol of total monomer solids were added to this reactor, and then stirred at 100 ° C. for 10 hours for acrylic on the side chain An acrylic polymer (a-2) having unsaturated bonds was produced. The weight average molecular weight of the acrylic polymer (a-2) thus produced was 20,000, and the degree of dispersion was 2.0.

Production Example 3 Production of Acrylic Polymer (a-3) After adding 200 mL of PGMEA and 1.0 g of AIBN to a 500 mL polymerization vessel, 40:20 each of glycidyl methacrylic acid, styrene, methyl methacrylic acid and cyclohexyl methacrylic acid: After adding so that the solid content of an acrylic monomer might be 40 weight% by molar ratio of 20:20, it stirred for 5 hours at 70 degreeC under nitrogen atmosphere, was polymerized, and the copolymer was synthesize | combined. After adding 0.3 g of N, N-dimethylaniline and 20 mol of acrylic acid based on 100 mol of total monomer solids to this reactor, the side chain is stirred for 10 hours at 100 ° C. An acrylic polymer (a-3) having a saturated bond was produced. The weight average molecular weight of the acrylic polymer (a-3) thus produced was 18,000, and the degree of dispersion was 1.8.

<Production of Photosensitive Composition>
Examples 19 to 34 Preparation of Photosensitive Composition Alkali-Soluble Resin According to the Components and Content Described in the Following Table 3 in a Reaction-mixing Tank Equipped with an Ultraviolet Blocking Film and a Stirrer; Polymerization Having an Ethylenically Unsaturated Bond Compound; the photopolymerization initiator of the present invention; and FC-430 (leveling agent manufactured by 3M) are sequentially added, and after stirring at normal temperature (23 ° C.), the total amount of the composition becomes 100% by weight Photosensitive compositions of Examples 19 to 34 were produced by adding PGMEA as a solvent.

<Production of Colored Photosensitive Composition>
Examples 35 to 36: Preparation of a colored photosensitive composition As described in Table 3 below, except that 50% by weight of a carbon black dispersion dispersed in PGMEA at 25% by weight solids was added, The colored photosensitive composition of Example 35 was produced in the same manner as in Example 19. Also, the color photosensitivity of Example 36 was the same as Example 19 except that 50% by weight of a dispersion of Pigment Red 177 (PR 177) dispersed in PGMEA at a solid content of 25% was added. The composition was manufactured.

Example 37
As described in Table 3 below, a photosensitive composition was prepared in the same manner as Example 19, except that the compound represented by the following Chemical Formula 4 was used in combination with the compound of Example 1 as a photopolymerization initiator. Manufactured.

<Component>
(A) Alkali-soluble resin: Acrylic polymers (a-1) to (a-3) of Production Examples 1 to 3
(B) Polymerizable compound having an ethylenically unsaturated bond b-1: dipentaerythritol hexaacrylate b-2: dipentaerythritol pentaacrylate b-3: pentaerythritol triacrylate b-4: pentaerythritol trimethacrylate b-5 : Trimethylolpropane triacrylate b-6: ethylene glycol diacrylate b-7: bisphenol-A diglycidyl ether acrylic acid adduct b-8: trimethylolpropane triglycidyl ether acrylic acid adduct (c) photopolymerization initiator: Carbazole oxime ester derivative compound produced in Examples 1 to 18 (e) Leveling agent: FC-430 (leveling agent manufactured by 3M)
(H) Color material h-1: carbon black (solid content 25% by weight)
h-2: pigment red 177 (PR 177) (solid content 25% by weight)

Comparative Example 1
A photosensitive composition was manufactured in the same manner as Example 19, except that a compound represented by the following Chemical Formula 5 was used instead of the compound represented by Chemical Formula 3-1 of Example 1 as a photopolymerization initiator. .

Comparative example 2
A photosensitive composition was manufactured in the same manner as Example 19, except that a compound represented by the following Chemical Formula 6 was used instead of the compound represented by Chemical Formula 3-1 of Example 1 as a photopolymerization initiator. .

<Evaluation of photosensitive composition>
The photosensitive compositions produced in Examples 19 to 37 and Comparative Examples 1 and 2 were evaluated on a glass substrate, and the sensitivity, residual film ratio, pattern stability, chemical resistance, and the like of the photosensitive composition were evaluated. The performances such as ductility were measured, and the results are shown in Table 4 below.

1) Sensitivity A 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 developed with a 0.04% aqueous KOH solution. The exposure amount at which the step mask pattern maintained a thickness of 80% with respect to the initial thickness was evaluated as sensitivity.

2) Residual film ratio After the photosensitive composition is coated on a substrate by a spin coater, it is prebaked at 100 ° C. for 1 minute, exposed at 365 nm, and postbaked at 230 ° C. for 20 minutes. The thickness ratio (%) before and after post-baking of the resist film was measured.

3) Pattern stability The silicon wafer in which the photoresist pattern was formed was cut from the perpendicular direction of a hole pattern, and the section direction of the pattern was observed with the electron microscope. The side walls of the pattern stood at an angle of 55 ° or more with respect to the substrate, and those having no decrease in the resist film were regarded as “good”, and those in which the decrease in the resist film was recognized were judged as “film loss”.

4) Chemical resistance After the photosensitive composition is applied onto the substrate using a spin coater, the resist film formed through steps such as prebaking and postbaking is immersed in a stripper solution at 40 ° C. for 10 minutes. The presence or absence of the change of the transmittance and thickness of the resist film was observed. When the change of the transmittance and the thickness was 2% or less was regarded as “good”, and when the change of the transmittance and the thickness exceeded 2%, it was determined as “defect”.

5) Ductility After spin-coating the photosensitive composition on a substrate, it was prebaked at 100 ° C. for 1 minute, exposed with the sensitivity of a photoresist, and then developed with an aqueous solution of KOH to form a 20 μm × 20 μm pattern. The formed pattern was post-baked at 230 ° C. for 20 minutes to crosslink, and the ductility of the pattern was measured using a nano indentor. The measurement with a nano indenter was performed with a load of 5 gf, and it was determined as "good" if the total displacement amount is 500 nm or more and "poor" if less than 500 nm.

  From Table 4, when the carbazole oxime ester derivative compound of the present invention is used as a photopolymerization initiator of a photosensitive composition, the sensitivity is remarkably excellent even in a small amount, and the residual film rate, pattern stability, chemical resistance, ductility, etc. It was also confirmed that the physical properties of were excellent. Therefore, in the exposure and post-baking steps in the TFT-LCD manufacturing process, the contamination can be reduced by minimizing the outgassing generated from the photopolymerization initiator, thereby minimizing the problems that may occur. Be

Claims (12)

Carbazole oxime ester derivative compounds represented by the following chemical formula 1 or chemical formula 2:

In chemical formula 1 and chemical formula 2,
A is oxygen or sulfur;
R ₁ and R ₄ are each independently (C ₁ -C 20) alkyl;
R ₂ is, (C1 to C20) alkyl, (C6 to C20) aryl, (C1 to C20) alkoxy, (C6 to C20) aryl (C1 to C20) alkyl, hydroxy (C1 to C20) alkyl, hydroxy (C1 to C20) alkoxy (C 1 -C 20) alkyl or (C 3 -C 20) cycloalkyl;
R ₃ is, (C1 to C20) alkyl, (C6 to C20) aryl, (C6 to C20) aryl (C1 to C20) alkyl, (C3 to C20) cycloalkyl or (C3 to C20) cycloalkyl (C1 to C20 ) Alkyl. Said A is oxygen or sulfur;
R ₁ and R ₄ are each independently methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl or i -Hexyl;
R ₂ is 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, hydroxy n-propyl, hydroxy n-butyl, hydroxy i-butyl, hydroxy n-pentyl, hydroxy i-pentyl, hydroxy n-hexyl, hydroxy i-hexyl, hydroxy Methoxymethyl, hydroxy Methoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl;
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 The carbazole oxime ester derivative compound according to claim 1, which is The carbazole oxime ester derivative compound according to claim 1, wherein the carbazole oxime ester derivative compound is one or more selected from compounds represented by the following chemical formulas 3-1 to 3-18.

  A photopolymerization initiator comprising the carbazole oxime ester derivative compound according to any one of claims 1 to 3. (A) alkali-soluble resin;
(B) A polymerizable compound having an ethylenically unsaturated bond; and (c) a photopolymerization initiator containing a photopolymerization initiator containing the carbazole oxime ester derivative compound according to any one of claims 1 to 3. Composition.   The photosensitive composition according to claim 5, wherein the content of the carbazole oxime ester derivative compound is 0.01 to 10 wt% in 100 wt% of the photosensitive composition.   The photopolymerization initiator is selected from the group consisting of thioxanthone compounds, acyl phosphine oxide compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime ester compounds and thiol compounds. Or the photosensitive composition of Claim 5 which further contains 2 or more types.   The photosensitive composition according to claim 5, wherein the photosensitive composition further comprises a colorant.   The photosensitive composition according to claim 7, wherein the photosensitive composition further comprises a colorant.   A molded article comprising the cured product of the photosensitive composition according to claim 5.   The molded article according to claim 10, wherein the molded article is an array flattening film, an insulating film, a color filter, a column spacer, an overcoat, a black column spacer or a black matrix.   A display device comprising the molding according to claim 10.