KR101991903B1 - Carbazole oxime ester derivative compounds and, photopolymerization initiator and photosensitive composition containing the same - Google Patents

Abstract

상기 화학식 1 및 2에서, A 및 R₁ 내지 R₄는 각각 발명의 상세한 설명에서 정의한 바와 같다.The present invention relates to a carbazole oxime ester derivative compound represented by the following formula (1) or (2), a photopolymerization initiator and a photosensitive composition comprising the same.
[Formula 1] [Formula 2]

In Formulas 1 and 2, A and R ₁ to R ₄ are as defined in the detailed description of the invention, respectively.

Description

Carbazole oxime ester derivative compounds and photopolymerization initiator and photosensitive composition containing the same

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

Common examples of the photopolymerization initiator used in the photosensitive composition include acetophenone derivatives, benzophenone derivatives, triazine derivatives, biimidazole derivatives, acylphosphine oxide derivatives and oxime ester derivatives. Absorbs and exhibits almost no color, has a high radical generating efficiency, and has excellent compatibility and stability with photosensitive composition materials. However, the earlier developed oxime derivative compounds have a low photoinitiation efficiency, in particular, a low sensitivity in the pattern exposure process, so that the exposure amount or the amount of use must be increased, thereby resulting in a decrease in the yield.

Therefore, the development of a photopolymerization initiator having excellent light sensitivity can realize sufficient sensitivity even with a small amount of the photopolymerization initiator, thereby reducing the cost and lowering the exposure amount due to the excellent sensitivity, thereby increasing production.

However, when the pattern is formed using a conventional photopolymerization initiator, the sensitivity is low during the exposure process for pattern formation, so the amount of use of the photopolymerization initiator should be increased or the exposure amount should be increased, thereby contaminating the mask in the exposure process, As a by-product generated after decomposition of the photopolymerization initiator has a disadvantage in that the yield is reduced, there is a problem that the production process is reduced by increasing the exposure process time according to the increase in the exposure amount, efforts have been made to solve this problem.

International Publication WO02 / 100903 (2002.12.19) Japanese Laid-Open Patent 2005-025169 (2005.01.27) International Publication WO07 / 071497 (2007.06.28) Korean Laid-Open Patent 2013-0124215 (2013.11.13) Korea Patent Publication 2013-0115272 (2013.10.21)

The problem to be solved by the present invention is 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.

In addition, another object of the present invention is to provide a molded article containing the cured product of the photosensitive composition.

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

According to an aspect of the present invention to achieve the above object, there is provided a carbazole oxime ester derivative compound of the following embodiments.

The first embodiment relates to a carbazole oxime ester derivative compound represented by the following general formula (1) or (2).

    <Formula 1> <Formula 2>

■

In Chemical Formulas 1 and 2,

A is oxygen or sulfur;

R ₁ and R ₄ are each independently (C ₁ -C 20) alkyl;

R ₂ is (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;

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.

The second embodiment, in the first embodiment,

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 ego;

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, hydroxy 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 It relates to a carbazole oxime ester derivative compound which is phenyl.

The third embodiment, in the first or second embodiment,

The carbazole oxime ester derivative compound relates to a carbazole oxime ester derivative compound selected from compounds represented by the following formulas 3-1 to 3-18.

<Formula 3-1 to 3-18>

■

According to another aspect of the present invention, there is provided a photopolymerization initiator of the following embodiment.

The fourth embodiment relates to a photopolymerization initiator comprising the carbazole oxime ester derivative compound of any one of the first to third embodiments.

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

A fifth embodiment comprises (a) an alkali soluble resin;

(b) a polymerizable compound having an ethylenically unsaturated bond; And

(c) relates to a photosensitive composition containing a photopolymerization initiator comprising the carbazole oxime ester derivative compound of any one of the first to third embodiments described above.

The sixth embodiment, in the fifth embodiment,

It relates to a photosensitive composition comprising 0.01 to 10% by weight of the carbazole oxime ester derivative compound relative to 100% by weight of the photosensitive composition.

The seventh embodiment, in the fifth or sixth embodiment,

The photoinitiator may be selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime ester compounds or thiol compounds. It further relates to a photosensitive composition comprising.

The eighth embodiment is any one of the fifth to seventh embodiments,

The said photosensitive composition relates to the photosensitive composition which further contains a coloring material.

According to another aspect of the present invention, there is provided a molding of the following embodiment and a display device including the same.

A ninth embodiment relates to a molding comprising a cured product of the photosensitive composition of any one of the fifth to eighth embodiments.

The tenth embodiment, in the ninth embodiment,

The molding relates to a molding which is an array planarization film, an insulating film, a color filter, a column spacer, a black column spacer, or a black matrix.

An eleventh embodiment relates to a display device comprising the molding of the ninth or tenth embodiment.

Carbazole oxime ester derivative compound according to an embodiment of the present invention exhibits very excellent sensitivity when used as a photopolymerization initiator of the photosensitive composition, excellent in physical properties such as residual film ratio, pattern stability, heat resistance, chemical resistance and ductility, TFT-LCD Outgassing from the photopolymerization initiator can be minimized in the exposure and post-bake processes during the process, thereby reducing contamination and minimizing defects.

Hereinafter, the present invention will be described in detail. Prior to this, terms or words used in the present specification and claims should not be construed as being limited to the common or dictionary meanings, and the inventors should properly explain the concept of terms in order to best explain their own invention. Based on the principle that can be defined, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention.

Therefore, the configurations shown in the embodiments described herein are only one of the most preferred embodiments of the present invention and do not represent all of the technical idea of the present invention, and various equivalents may be substituted for them at the time of the present application. It should be understood that there may be variations and variations.

Carbazole oxime ester derivative compound according to an aspect of the present invention is represented by the following formula (1) or (2).

[Formula 1] [Formula 2]

In Chemical Formulas 1 and 2,

A is oxygen or sulfur;

R ₁ and R ₄ are each independently (C ₁ -C 20) alkyl;

R ₂ is (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;

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.

Substituents including the "alkyl", "alkoxy" and other "alkyl" moieties described herein include all linear or pulverized forms, and "cycloalkyl" includes not only a single ring system but also several ring hydrocarbons.

In addition, "aryl" described herein is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, including a single or fused ring system, and even a form in which a plurality of aryls are connected by a single bond.

In addition, the "hydroxyalkyl" described in this specification means OH-alkyl which the hydroxy group couple | bonded with the alkyl group defined above, and "hydroxyalkoxyalkyl" means the hydroxyalkyl-O which the alkoxy group couple | bonded with the said hydroxyalkyl group. -Alkyl, alkenyl means a structure including a ketone to which an alkyl or aryl group is bonded.

In addition, "arylalkyl" described herein may be exemplified by benzyl and the like, "cycloalkyl" may be exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like, and "cycloalkylalkyl" is cyclopropylmethyl. , Cyclobutylmethyl, cyclopentylmethyl, cyclopropylethyl and the like,

In addition, '(C 1 -C 20) alkyl' as used herein means alkyl having 1 to 20 carbon atoms, which alkyl may preferably be (C 1 -C 10) alkyl, more preferably (C 1 -C 6) Alkyl).

'(C6-C20) aryl' means aryl having 6 to 20 carbon atoms, such aryl may preferably be (C6-C18) aryl, more preferably (C6-C12) aryl.

“(C 1 -C 20) alkoxy” means alkoxy having 1 to 20 carbon atoms, which alkoxy may preferably be (C 1 -C 10) alkoxy, more preferably (C 1 -C 4) alkoxy.

"(C6-C20) aryl (C1-C20) alkyl" means alkyl in which one hydrogen of C1-C20 alkyl is substituted with a C6-C20 aryl group, preferably (C6-C18) aryl ( C1-C10) alkyl, more preferably (C6-C18) aryl (C1-C6) alkyl, more preferably (C6-C12) aryl (C1-C6) alkyl.

"Hydroxy (C1-C20) alkyl" means alkyl in which one hydrogen is substituted with hydroxy at alkyl of 1 to 20 carbon atoms, preferably hydroxy (C1-C10) alkyl, more preferably May be hydroxy (C1-C6) alkyl.

'Hydroxy (C1-C20) alkoxy (C1-C20) alkyl' is one alkyl substituted with 1 to 20 carbon atoms and one hydrogen is substituted with hydroxy at alkoxy. Structure, preferably hydroxy (C1-C10) alkoxy (C1-C10) alkyl, more preferably hydroxy (C1-C4) alkoxy (C1-C6) alkyl.

"(C3-C20) cycloalkyl" means cycloalkyl having 3 to 20 carbon atoms, preferably (C3-C10) cycloalkyl.

"(C3-C20) cycloalkyl (C1-C20) alkyl" means an alkyl in which one hydrogen is substituted with 3 to 20 cycloalkyl atoms with 1 to 20 carbon atoms, preferably (C3-C10) It may be cycloalkyl (C1-C10) alkyl, more preferably (C3-C6) cycloalkyl (C1-C6) alkyl.

According to one embodiment of the present invention, in Chemical Formulas 1 and 2,

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, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxy 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.

More specifically, in Chemical Formulas 1 and 2,

A is oxygen or sulfur;

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 an embodiment of the present invention, the carbazole oxime ester derivative compound may include a compound selected from the group consisting of the following Chemical Formulas 3-1 to 3-18, but the following compounds are not intended to limit the present invention.

<Formula 3-1 to 3-18>

The carbazole oxime ester derivative compounds represented by Formula 1 or 2 according to the present invention may be prepared as shown in Schemes 1 or 2, but are not limited thereto.

[Scheme 1]

[Scheme 2]

In Scheme 1 or 2, A and R ₁ to R ₄ are the same as defined in Formula 1 or 2, and X is halogen.

In addition, the photopolymerization initiator according to another aspect of the present invention includes one or more selected from carbazole oxime ester derivative compounds represented by the formula (1) or (2).

In addition, the photosensitive composition according to another aspect of the present invention,

(a) alkali soluble resins;

(b) a polymerizable compound having an ethylenically unsaturated bond; And

(c) a photopolymerization initiator comprising at least one member selected from carbazole oxime ester derivative compounds of the general formula (1) or (2).

Here, the carbazole oxime ester derivative compound may be included as a photopolymerization initiator.

The photosensitive composition according to another aspect of the present invention has excellent thin film properties such as pattern property control and heat resistance and chemical resistance. Hereinafter, each component that may be included in the photosensitive composition of the present invention will be described in detail.

As used herein, "(meth) acrylic" means acryl and / or methacrylate, "(meth) acrylate" means acrylate and / or methacrylate, and (meth) acrylic acid is acrylic acid and / or It means 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 of an acrylic monomer (including a single polymer 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) ) Acrylic, 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) a Relates, (meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride, maleic acid monoalkyl esters, monoalkyl itaconates, monoalkyl fumaleates, glycidyl (meth) acrylates, 3,4-epoxy Butyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-methyloxetane-3-methyl (meth) acrylate, 3 Ethyl oxetane-3-methyl (meth) acrylate, styrene, α-methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N -Cyclohexyl maleimide, (meth) acrylamide, or N-methyl (meth) acrylamide, etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.

The acrylic polymer having an acrylic unsaturated bond in the side chain is a copolymer obtained by reacting an epoxy resin with an acrylic copolymer containing carboxylic acid, such as (meth) acrylic acid, itaconic acid, maleic acid or maleic acid monoalkyl ester. An acrylic monomer containing a carboxylic acid of; Alkyl (meth) acrylates, such as methyl (meth) acrylate or hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, and dicyclopentanyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, styrene, α-methyl Styrene, Acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, (meth) acrylamide or N-methyl (meth) acryl Glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 2,3-epoxycyclohexyl (acryl copolymer) containing carboxylic acid obtained by copolymerizing two or more kinds of monomers such as amide ( Meta) acrylate or 3,4-in Binder resin obtained by addition-reacting epoxy resins, such as a foxy cyclohexyl methyl (meth) acrylate, at the temperature of 40-180 degreeC can be used.

Another example of an acrylic polymer having an acrylic unsaturated bond in the side chain is a copolymer in which a carboxylic acid is added to an acrylic copolymer containing an epoxy group, such as glycidyl (meth) acrylate and 3,4-epoxybutyl (meth). An acrylic monomer 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, and dicyclopentanyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, styrene, α-methyl Styrene, Acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, (meth) acrylamide or N-methyl (meth) acryl 40 to 30 acrylic monomers containing carboxylic acid such as (meth) acrylic acid itaconic acid, maleic acid or maleic acid monoalkyl ester in an acrylic copolymer containing an epoxy group obtained by copolymerizing two or more kinds of monomers such as amide The binder resin obtained by addition reaction at the temperature of 180 degreeC can be used.

According to one embodiment of the present invention, the alkali-soluble resin is 3 to 50% by weight based on 100% by weight of the total photosensitive composition, in particular 5 to 45, in order to provide pattern properties, thin film properties such as heat resistance and chemical resistance. Weight percent, more specifically 8 to 40 weight percent can be used.

The weight average molecular weight (measured by polystyrene conversion by gel permeation chromatography (GPC)) of the alkali-soluble resin may be 2,000 to 300,000, preferably 4,000 to 100,000, and the degree of dispersion may be 1.0 to 10.0.

(b) a polymerizable compound having an ethylenically unsaturated bond

The polymerizable compound having an ethylenically unsaturated bond serves to form a pattern by crosslinking by photoreaction at the time of pattern formation and crosslinking at high temperature 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 photosensitive composition.

When the polymerizable compound having an ethylenically unsaturated bond is added in an excessive amount, the degree of crosslinking may be excessively high, resulting in a decrease 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) acryl Alkyl ester of (meth) acrylic acid, such as the rate, glycidyl (meth) acrylate, polyethyleneglycol mono (meth) acrylate whose number of ethylene oxide groups is 2-14, ethylene glycol di (meth) acrylate, ethylene oxide group Polyethylene glycol di (meth) acrylate having a number of from 2 to 14, propylene glycol di (meth) acrylate having a number of from 2 to 14 of propylene oxide group, trimethylolpropanedi (meth) acrylate, bisphenol A diglycidyl ether Acrylic acid adduct, phthalic acid diester of β-hydroxyethyl (meth) acrylate, toluene diisocy of β-hydroxyethyl (meth) acrylate Nate adduct, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylic A compound obtained by esterifying a polyhydric alcohol and an α, β-unsaturated carboxylic acid, such as a latent and dipentaerythritol tri (meth) acrylate, and an acrylic acid adduct of a polyvalent glycidyl compound, such as a trimethylolpropanetriglycidyl ether acrylic acid adduct. These etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.

(c) photopolymerization initiator

In the photosensitive composition of the present invention, one or more selected from the oxime ester derivative compounds of Formula 1 or 2 may be used as the photopolymerization initiator. In order to increase the transparency and minimize the exposure amount, 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 photosensitive composition.

(d) adhesive preparation

In addition, the photosensitive composition of the present invention may further include a silicone-based compound having an epoxy group or an amine group as an adhesive aid, if necessary.

The silicone-based compound having the epoxy group or the amine group may improve adhesion between the ITO electrode and the photosensitive composition, and may increase heat resistance after curing. As a silicone type compound which has the said epoxy group or an amine group, (3-glycidoxy propyl) trimethoxysilane, (3-glycidoxy propyl) triethoxy silane, (3-glycidoxy propyl) methyl dimethoxy silane 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) ethyltrie Methoxysilane, aminopropyltrimethoxysilane, and the like, and these may be used alone or in combination of two or more thereof.

The silicon-based compound having the epoxy group or the amine group may be included in 0.0001 to 3% by weight based on 100% by weight of the total photosensitive 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 characteristic of the non-exposed part may be lowered, and scum and residue may remain on the lower substrate, the ITO, or the glass substrate.

(e) other additives

The photosensitive 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 as 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 photosensitive composition. If the content is less than the above range, the effect of the addition may not be confirmed.

(f) solvent

The photosensitive composition of the present invention is coated with a solvent to form a pattern through a method of developing with an alkaline developer by irradiating ultraviolet rays using a mask.

Therefore, since the content of the solvent can be adjusted so that the total amount is 100% by weight in addition to the content of the other components of the photosensitive composition described above, it may be variously changed according to the content of the other components of the photosensitive compositions. For example, it is preferable to adjust the viscosity to be in the range of 1 to 50 cps by adding 10 to 95% by weight of solvent with respect to 100% by weight of the photosensitive composition.

The solvent may be ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethylethyl ether, methyl methoxy propionate, ethyl ethoxy prop in consideration of compatibility with alkali-soluble resins, photopolymerization initiators and other compounds. Cypionate (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 cello Solve acetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2- Pyrrolidone (NMP), γ-butylolactone, diethyl ether, ethylene glycol dimethyl ether, diglym e), tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, Solvents selected from xylene, hexane, heptane or octane can be used alone or in combination of two or more thereof.

(g) other photopolymerization initiators

As the photosensitive composition of the present invention, the above-described carbazole oxime ester derivative compounds may be used alone, and further, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyl oxime ester compounds. It can also be used further including 1 type (s) or 2 or more types chosen from the group which consists of a compound and a thiol type compound.

Such additional photopolymerization initiator may be used to be 0.01 to 5% by weight based on 100% by weight of the total photosensitive composition.

As said thioxanthone type compound, for example, thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- One or more selected from dichlorothioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone or 2,4-diisopropyl thioxanthone may be used, but is not limited thereto.

As said acetophenone type compound, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino propane- 1-one, 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 May be used, but is not limited thereto.

As said biimidazole type compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl- 1,2'-biimidazole, 2, 2'-bis (2,4-dichlorolophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis (2,4,6-trichloro One or more selected from rophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole may be used, but is not limited thereto.

Examples of the triazine-based compound 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-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-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine or 2- (4-n-butoxyphenyl) One or more selected from -4,6-bis (trichloromethyl) -s-triazine may be used, but is not limited thereto.

Examples of the O-acyl oxime ester compound 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-dioxoranyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) or 2- (acetoxyimino) -1- (9,9 ' One or more selected from -diethyl-9H-fluoro-2-yl) propan-1-one can be used, but is not limited thereto.

Pentaerythritol tetrakis (3-mercaptopropionate) or the like may be used as the thiol-based compound, but is not limited thereto.

(h) color

The photosensitive composition according to the exemplary embodiment of the present invention may further include a colorant included for application as a color filter or a resist for forming a black matrix.

Various colorants may be used as the colorant, for example, cyan, magenta, yellow, and black pigments of red, green, blue and navy blue mixed systems, and more specifically, pigments that can be used include CI Pigment Yellow 12 , 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148, 153, 154, 166, 168, CI Pigment Orange 36, 43, 51, 55, 59, 61, CI Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226 , 227, 228, 240, CI Pigment Violet 19, 23, 29, 30, 37, 40, 50, CI Pigment Blue 15, 15: 1, 15: 4, 15: 6, 22, 60, 64, CI Pigment Green 7, 36, CI Pigment brown 23, 25, 26, CI pigment black 7, and titanium black.

The colorant may be included in 5 to 50% by weight based on 100% by weight of the total photosensitive composition. If it is less than the said range, light-shielding property will fall, and when it exceeds the said range, it may become a poor exposure or a hardening.

Photosensitive composition according to an embodiment of the present invention is a known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, immersion, soda glass, quartz glass, semiconductor substrate, metal, paper It can be applied to a supporting gas phase such as, plastic. Moreover, it can transfer to another support base body after performing it once on support bases, such as a film, and there is no restriction | limiting in the application method.

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

The molding may be an array planarization film, an insulating film, a color filter, a column spacer, an overcoat, a black column spacer, a black matrix, or the like, but is not limited thereto.

Further, according to another aspect of the present invention, various displays such as a liquid crystal display device, an OLED, and the like including the molded article are provided.

Hereinafter, for the detailed understanding of the present invention, the exemplary compounds of the present invention will be described in detail with reference to Examples and Comparative Examples. Should not be construed as limited to the embodiments described below. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

<Preparation of carbazole oxime ester derivative compound>

Example 1: Preparation of 1- (9- (4-methoxyphenyl) -9H-carbazol-3-yl) -1-propanone oxime (O-acetate) [Formula 3-1]

Step 1: Synthesis of 9- (4-methoxyphenyl) -9H-carbazole

Into the reactor triethyleneglycol dimethyl ether (40 ml) was added carbazole (30 g, 170.5 mmol), 4-iodineanisole (49.8 g, 204.3 mmol), copper in powder form (11.34 g, 180 mmol) and Potassium carbonate (58.8 g, 423.2 mmol) was added and then stirred at 200 ° C. for 20 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, ethyl acetate (300 ml) was added, and stirred for 30 minutes to crystallize. The solid obtained by filtration of this solution was again stirred in acetone (300 ml) and methylene chloride (300 ml) for 30 minutes, filtered and washed with water.

The obtained solid was an impurity and discarded. The filtrate was taken out, the organic solvent in the filtrate was distilled under reduced pressure at 40 ° C, and the product was refrigerated for one day to precipitate the product. After petroleum ether (about 200 ml) was added and filtered, and the resulting solid was recrystallized with acetone to give the target compound 9- (4-methoxyphenyl) -9H-carbazole (40.7 g, 87.4%). Got it.

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 3.93 (3H, s), 7.12 (2H, d), 7.28 (2H, t), 7.33 (2H, d), 7.41 (2H, t), 7.46 (2H, d), 8.15 (2H, d)

MS ( m / e ): 273

Step 2: Synthesis of 1- (9- (4-methoxyphenyl) -9H-carbazol-3-yl) propan-1-one

Aluminum chloride (5.91 g, 43.9 mmol) was added to methylene chloride (200 ml), cooled to −10 ° C. or lower, stirred for 10 minutes, and then 9- (4-methoxyphenyl) -9H- obtained in step 1 above. Carbazole (10.0 g, 36.3 mmol) 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, followed by stirring for 30 minutes. The reaction solution was poured into ice water consisting of ice (490 g) and water (500 ml), stirred for 30 minutes, left to remove the water layer, and the organic layer was sufficiently washed with an aqueous sodium bicarbonate solution. The organic layer was then dried over anhydrous magnesium sulfate, filtered and distilled under reduced pressure to obtain 1- (9- (4-methoxyphenyl) -9H-carbazol-3-yl) propan-1-one (11.8 g) as a target compound. , 98.9%).

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 1.31 (3H, t), 3.16 (2H, q), 3.93 (3H, s), 7.13 (2H, d), 7.32 (3H, m), 7.45 (3H, m), 8.07 (1H, d), 8.2 (1H, d), 8.81 (1H, s)

MS ( m / e ): 329

Step 3: Synthesis of 1- (9- (4-methoxyphenyl) -9H-carbazol-3-yl) -1-propanone-2-oxime

1- (9- (4-methoxyphenyl) -9H-carbazol-3-yl) propan-1-one (6.0 g, 18.2 mmol), tetrahydrofuran (132 ml) and 35 obtained in the above step 2 % Concentrated hydrochloric acid (8.7 ml) was added to the reactor and stirred for 30 minutes. A solution of isopentyl nitride (5.1 ml, 36.4 mmol) dissolved in tetrahydrofuran (10 ml) was added dropwise for 30 minutes, followed by stirring for 50 minutes. The reaction was then extracted with ethyl acetate and washed sufficiently with aqueous sodium bicarbonate solution. The extracted organic layer was dried over anhydrous magnesium sulfate, filtered and distilled under reduced pressure to obtain an impure product. The resulting impure product was washed three times with methylene chloride to give 1- (9- (4-methoxyphenyl) -9H-carbazol-3-yl) -1-propanone-2-oxime (2.03 g) as a target compound. , 31.1%).

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 2.26 (3H, s), 3.93 (3H, s), 7.13 (2H, d), 7.33 (3H, m), 7.44 (3H, m), 7.88 (1H, br), 8.07 (1H, d), 8.18 (1H, d), 8.83 (1H, 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-methoxyphenyl) -9H-carbazol-3-yl) -1-propanone-2-oxime (0.5 g, 1.4 mmol) obtained in step 3 was added to ethyl acetate- After cooling to 10 ° C. or below, 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) dissolved in ethyl acetate (1 ml) was added dropwise for 10 minutes, followed by stirring for 30 minutes. The reaction solution was extracted with methylene chloride and washed sufficiently with aqueous sodium bicarbonate solution. The extracted organic layer was dried over anhydrous magnesium sulfate, filtered and distilled under reduced pressure to obtain 1- (9- (4-methoxyphenyl) -9H-carbazol-3-yl) -1-propanone oxime (O) as a target compound. Acetate) (0.53 g, 94.3%).

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 2.31 (3H, s), 2.37 (3H, s), 3.93 (3H, s), 7.13 (2H, d), 7.34 (3H, q), 7.45 (3H, q), 8.19 (2H, t), 8.99 (1H, s)

MS ( m / e ): 400

Decomposition Point: 241.8 ℃

Examples 2-12

Carbazole oxime ester derivative compounds were synthesized in the composition of Table 1 under the same conditions as in Example 1.

Example Chemical formula A R ₁ R ₂ R ₃ ¹ H NMR (δ ppm; CDCl ₃ ) Decomposition point 2 3-2 O C ₂ H ₅ CH ₃ CH ₃ 2.31 (3H, s), 2.37 (3H, s), 3.12 (3H, t), 3.90 (2H, q), 7.13 (2H, d), 7.34 (3H, q), 7.45 (3H, q), 8.19 (2H, t), 8.99 (1H, s) 242.1 ℃ 3 3-3 O CH ₃ CH ₃

2.5 (3H, s), 3.93 (3H, s), 7.13 (2H, d), 7.34 (3H, q), 7.45 (3H, t), 7.53 (2H, t), 7.65 (1H, t), 8.17 (2H, d), 8.27 (2H, d, d), 9.1 (1H, s) 247.3 ℃ 4 3-4 O CH ₃ C ₂ H ₅ CH ₃ 2.10 (3H, t), 2.31 (3H, s), 2.35 (2H, q), 3.92 (3H, s), 7.13 (2H, d), 7.34 (3H, q), 7.45 (3H, q), 8.19 (2H, t), 8.99 (1H, s) 241.6 ℃ 5 3-5 O CH ₃ CH ₃ C ₂ H ₅ 1.72 (3H, t), 2.28 (2H, q), 2.37 (3H, s), 3.93 (3H, s), 7.13 (2H, d), 7.34 (3H, q), 7.45 (3H, q), 8.19 (2H, t), 8.99 (1H, s) 240.7 ℃ 6 3-6 O CH ₃

CH ₃ 2.31 (3H, s), 3.93 (3H, s), 7.13-7.65 (13H, m), 8.19 (2H, t), 8.99 (1H, s) 246.3 ℃ 7 3-7 S CH ₃ CH ₃ CH ₃ 2.31 (3H, s), 2.37 (3H, s), 2.59 (3H, s), 7.36 (3H, m), 7.47 (5H, m), 8.2 (2H, m), 8.99 (1H, s) 242.3 ℃ 8 3-8 S C ₂ H ₅ CH ₃ CH ₃ 2.31 (3H, s), 2.35 (3H, s), 3.16 (3H, t), 3.96 (2H, q), 7.13 (2H, d), 7.34 (3H, q), 7.45 (3H, q), 8.19 (2H, t), 8.99 (1H, s) 242.5 ℃ 9 3-9 S CH ₃ CH ₃

2.5 (3H, s), 2.6 (3H, s), 7.38 (3H, m), 7.46 (5H, m), 7.54 (2H, t), 7.66 (1H, t), 8.17 (2H, d), 8.24 (1H, d), 8.29 (1H, d), 9.09 (1H, s) 246.6 ℃ 10 3-10 S CH ₃ C ₂ H ₅ CH ₃ 2.09 (3H, t), 2.33 (3H, s), 2.37 (2H, q), 3.95 (3H, s), 7.13 (2H, d), 7.34 (3H, q), 7.46 (3H, q), 8.19 (2H, t), 9.01 (1H, s) 244.6 ℃ 11 3-11 S CH ₃ CH ₃ C ₂ H ₅ 1.73 (3H, t), 2.31 (2H, q), 2.38 (3H, s), 3.93 (3H, s), 7.12 (2H, d), 7.34 (3H, q), 7.46 (3H, q), 8.20 (2H, t), 8.99 (1H, s) 243.1 ℃ 12 3-12 S CH ₃ C ₃ H ₇ CH ₃ 1.62 (3H, t), 2.01-2.25 (7H, m), 2.33 (3H, s), 2.37 (2H, q), 3.95 (3H, s), 7.13 (2H, d), 7.34 (3H, q) , 7.46 (3H, q), 8.19 (2H, t), 9.01 (1H, s) 243.5 ℃

Example 13: 2 -( Hydroxyimino ) -1- (6- Methoxy -9- (4- Methoxyphenyl ) -9H- Carbazole -3-yl) propan-1-one (O-acetate) Preparation of [Formula 3-13]

Step 1: Synthesis of 3-methoxy-9H-carbazole

3-bromo-9H-carbazole (19.8 g, 78.8 mmol), iodine (8.0 g, 41.76 mmol), sodium methoxide 25% methanol solution (750 ml), ethyl acetate (15 ml) and toluene under nitrogen atmosphere (15 ml) each was placed in a reactor and refluxed at 90 ° C. for 4 days. After the reaction was completed, the mixture was cooled to room temperature. Subsequently, the reaction solution was transferred to a beaker, water (300 ml) and methylene chloride (300 ml) were added to the beaker, followed by stirring for 1 hour. The beaker solution was filtered through a filter coated with 2 to 3 cm silica gel (40 to 400 mesh) to remove impurities that did not dissolve. Subsequently, the filtrate was extracted three times with methylene chloride (300 ml), the organic layer was dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure, and then recrystallized (methylene chloride: hexane = 1: 1) to obtain a target compound. 3-methoxy-9H-carbazole (10.3 g, 66.4%) was obtained.

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 3.93 (3H, s), 7.12 (2H, d), 7.28 (2H, t), 7.33 (2H, d), 7.41 (2H, t), 7.46 (2H, d), 8.15 (2H, d)

MS ( m / e ): 197

Step 2: Synthesis of 3-methoxy-9- (4-methoxyphenyl) -9H-carbazole

3-methoxy-9H-carbazole (3.0 g, 15.2 mmol), 4-iodine anisole (4.34 g, 17.8 mmol) obtained in step 1, copper in powder form (1.01 g, 15.8 mmol), and potassium carbonate (5.28 g, 38 mmol) and triethylene glycol dimethyl ether (5.3 ml, 29.3 mmol) were added to the reactor and stirred at 200 ° C. for 24 hours. After the reaction was cooled to room temperature and methylene chloride (60 ml) was added and stirred for 1 hour. The reaction solution was filtered through a filter coated with 2 to 3 cm silica gel (40 to 400 mesh). Subsequently, the methylene chloride and triethylene glycol dimethyl ether present in the filtrate were removed by distillation under reduced pressure, and the column (methylene chloride: hexane = 1: 5) was separated to separate 3-methoxy-9- (4-methoxyphenyl as a target compound. ) -9H-carbazole (4.05 g, 88.2%) was obtained.

¹ H NMR (δ ppm, CDCl 3, 500 MHz): 3.91 (3H, s), 3.95 (3H, s), 7.04 (1H, dd), 7.10 (2H, dd), 7.24 (2H, m), 7.32 ( 1H, d), 7.38 (1H, m), 7.44 (2H, dd), 7.61 (1H, d), 8.09 (1H, d)

MS (m / e): 303

Step 3: Synthesis of 1- (6-methoxy-9- (4-methoxyphenyl) -9H-carbazol-3-yl) propan-1-one

Aluminum chloride (2.32 g, 17.2 mmol) was added to methylene chloride (40 ml) and cooled to −10 ° C. or lower. 3-methoxy-9- (4-methoxyphenyl) -9H-carbazole (4.0 g, 13.2 mmol) obtained in step 2 was added dropwise to methylene chloride (5 ml), followed by stirring for about 20 minutes. Propionyl chloride (1.52 ml, 17.2 mmol) was added dropwise for 30 minutes and stirred for 20 minutes. After completion of the reaction, the reaction solution was poured into water (200 ml), stirred for 1 hour, methylene chloride (100 ml) was added to extract the organic layer, and the extracted organic layer was sufficiently washed with an aqueous solution of sodium bicarbonate. The extracted organic layer was dried over anhydrous magnesium sulfate, filtered and distilled under reduced pressure to obtain 1- (6-methoxy-9- (4-methoxyphenyl) -9H-carbazol-3-yl) propane- as a target compound. 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 (1H, dd), 8.76 (1H, d)

MS ( m / e ): 359

Step 4: Synthesis of 2- (hydroxyimino) -1- (6-methoxy-9- (4-methoxyphenyl) -9H-carbazol-3-yl) propan-1-one

1- (6-methoxy-9- (4-methoxyphenyl) -9H-carbazol-3-yl) propan-1-one (4.91 g, 13.7 mmol) and 35% concentrated hydrochloric acid obtained in step 3 above (2.4 ml, 27.4 mmol) was added to tetrahydrofuran (40 ml) and stirred for 30 minutes. Subsequently, a solution of isopentylnitrite (3.83 ml, 27.4 mmol) dissolved in tetrahydrofuran (8 ml) was added dropwise for 20 minutes, followed by stirring 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 sufficiently washed with an aqueous sodium bicarbonate solution. The extracted organic layer was dried over anhydrous magnesium sulfate and filtered. After distillation under reduced pressure, the column (ethyl acetate: hexane = 1: 4) was separated, and then 2- (hydroxyimino) -1- (6-methoxy-9- (4-methoxyphenyl) -9H-carbazole was a target compound. 3-yl) propan-1-one (1.63 g, 30.7%) was obtained.

¹ H NMR (δ ppm, CDCl 3, 500 MHz): 2.27 (3H, s), 3.92 (3H, s), 3.95 (3H, s), 7.07 (1H, dd), 7.12 (2H, dd), 7.23 ( 1H, d), 7.29 (1H, d), 7.42 (2H, dd), 7.65 (1H, d), 7.68 (1H, s), 8.06 (1H, dd), 8.79 (1H, d)

MS ( m / e ): 388

5 steps : 2-( Hydroxyimino ) -1- (6- Methoxy -9- (4- Methoxyphenyl ) -9H- Carbazole Synthesis of -3-yl) propan-1-one (O-acetate)

2- (hydroxyimino) -1- (6-methoxy-9- (4-methoxyphenyl) -9H-carbazol-3-yl) propan-1-one obtained in step 4 (0.76 g, 1.96 mmol) was added to ethyl acetate (15 ml), cooled to −10 ° C. or less, triethylamine (0.55 ml, 3.92 mmol) was added thereto, followed by stirring for 10 minutes. Subsequently, a solution of acetyl chloride (0.29 ml, 3.92 mmol) dissolved in ethyl acetate (2 ml) was added dropwise for 5 minutes, followed by stirring 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 sufficiently washed with an aqueous sodium bicarbonate solution. The extracted organic layer was dried using anhydrous magnesium sulfate, distilled under reduced pressure, and then 2- (hydroxyimino) -1- (6-methoxy-9- (4-methoxyphenyl) -9H-carbazole-3 as a target compound. -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 (1H, dd), 7.12 ( 2H, dd), 7.24 (1H, d), 7.31 (1H, d), 7.42 (2H, dd), 7.67 (1H, d), 8.16 (1H, dd), 8.93 (1H, d)

MS ( m / e ): 430

Decomposition point: 248.3 ℃

Examples 14-18

Carbazole oxime ester derivative compounds were synthesized in the compositions shown in Table 2 under the same conditions as in Example 13.

Example Chemical formula A R ₁ R ₂ R ₃ R ₄ ¹ H NMR (δ ppm; CDCl ₃ ) Decomposition point 14 3-14 O C ₂ H ₅ C ₂ H ₅ CH ₃ CH ₃ 2.30 (3H, s), 2.35-2.86 (6H, m), 3.21 (3H, t), 3.92 (2H, q), 3.96 (3H, s), 7.08 (1H, dd), 7.12 (2H, dd) , 7.24 (1H, d), 7.31 (1H, d), 7.42 (2H, dd), 7.67 (1H, d), 8.16 (1H, dd), 8.93 (1H, d) 248.3 ℃ 15 3-15 O CH ₃ CH ₃

CH ₃ 2.5 (3H, s), 3.92 (3H, s), 3.96 (3H, s), 7.08 (1H, dd), 7.12 (2H, dd), 7.25 (1H, d), 7.34 (1H, d), 7.44 (2H, dd), 7.54 (2H, t), 7.66 (1H, t), 7.70 (1H, d), 8.17 (2H, d), 8.27 (1H, dd), 9.03 (1H, d) 248.7 ℃ 16 3-16 S CH ₃ CH ₃ CH ₃ CH ₃ 2.30 (3H, s), 2.37 (3H, s), 2.58 (3H, s), 3.96 (3H, s), 7.08 (1H, dd), 7.28 (1H, d), 7.35 (1H, d), 7.45 (4H, m), 7.66 (1H, d), 8.47 (1H, d), 8.93 (1H, s) 247.3 ℃ 17 3-17 S C ₂ H ₅

CH ₃ C ₂ H ₅ 0.96 (3H, t) 1.11 (3H, t), 1.20-1.46 (2H, m), 2.32 (3H, s), 4.40 (2H, s), 7.05-7.55 (11H, m), 8.50 (2H, d ), 8.82 (2H, s) 246.8 ℃ 18 3-18 S CH ₃ CH ₃

CH ₃ 2.50 (3H, s), 2.59 (3H, s), 3.96 (3H, s), 7.09 (1H, dd), 7.29 (1H, d), 7.39 (1H, d), 7.47 (4H, m), 7.54 (2H, t), 7.66 (1H, t), 7.70 (1H, d), 8.17 (2H, dd), 8.28 (1H, dd), 9.04 (1H, s) 247.2 ℃

<Production of Alkali Soluble Resin>

Preparation Example 1 Preparation of Acrylic Polymer (a-1)

To a 500 mL polymerization vessel was added 200 mL of propylene glycol methyl ether acetate (PGMEA) and 1.5 g of azobisisobutyronitrile (AIBN), followed by methacrylic acid, glycidylmethacrylic acid, methylmethacrylic acid and Dicyclopentanylacrylic acid was added to the solid content of the acrylic monomer in 40% by weight in a molar ratio of 20: 20: 40: 20, respectively, and polymerized by stirring with stirring at 70 ° C. for 5 hours under a nitrogen atmosphere. Prepared. The prepared polymer (a-1) had a weight average molecular weight of 25,000 and a dispersion degree of 1.9.

Preparation Example 2 Preparation of Acrylic Polymer (a-2)

After adding 200 mL of propylene glycol methyl ether acetate and 1.0 g of AIBN to a 500 mL polymerization vessel, methacrylic acid, styrene, methylmethacrylic acid and cyclohexylmethacrylic acid were each acrylic in a molar ratio of 40: 20: 20: 20. A solid content of the monomer was added at 40% by weight, and then polymerized by stirring with stirring at 70 ° C. for 5 hours under a nitrogen atmosphere. Subsequently, based on 0.3 g of N, N-dimethylaniline and 100 mol of the total monomer, 20 mol of glycidylmethacrylic acid was added to the reactor, followed by stirring at 100 ° C. for 10 hours to form an acrylic polymer having an acrylic unsaturated bond in the side chain. (a-2) was prepared. The weight average molecular weight of the prepared acrylic polymer (a-2) was 20,000, and the degree of dispersion was found to be 2.0.

Production Example  3: acrylic polymer (a- 3)  Produce

After adding 200 mL of propylene glycol methyl ether acetate and 1.0 g of AIBN to a 500 mL polymerization vessel, glycidyl methacrylic acid, styrene, methylmethacrylic acid and cyclohexyl methacrylic acid were respectively added in an amount of 40: 20: 20: 20. The copolymer was synthesized by adding 40% by weight of the solid content of the acrylic monomer in a molar ratio, followed by polymerization with stirring at 70 ° C. for 5 hours under a nitrogen atmosphere. Subsequently, based on 0.3 g of N, N-dimethylaniline and 100 moles of solids of the total monomers, 20 moles of acrylic acid was added thereto, followed by stirring at 100 ° C. for 10 hours to form an acrylic polymer having an acrylic unsaturated bond in the side chain (a-3). Was prepared. The weight average molecular weight of the prepared acrylic polymer (a-2) was 18,000, and the degree of dispersion was found to be 1.8.

<Production of Photosensitive Composition>

Examples 19-34 Preparation of Photosensitive Compositions

Alkali-soluble resin according to the component and content of following Table 3 in the reaction mixing tank equipped with the ultraviolet shielding film and the stirrer; Polymerizable compounds having an ethylenically unsaturated bond; Photopolymerization initiator of the present invention; And FC-430 (a 3M leveling agent) were added sequentially, stirred at room temperature (23 ° C.), and PGMEA was added to the solvent so that the composition was 100% by weight in total, thereby preparing the photosensitive compositions of Examples 19 to 34. It was.

<Production of Colored Photosensitive Composition>

Examples 35-36 Preparation of Colored Photosensitive Compositions

As described in Table 3 below, the colored photosensitive composition of Example 35 was prepared in the same manner as in Example 19, except that 50% by weight of the carbon black dispersion dispersed in the PGMEA of 25% by weight of solids was added. The colored photosensitive composition of Example 36 was prepared in the same manner as in Example 19, except that 50% by weight of the dispersion of Pigment Red 177 (PR 177) dispersed in 25% by weight of PGMEA was added.

Example 37

As shown in Table 3, a photosensitive composition was prepared in the same manner as in Example 19, except that the following Chemical Formula 4 was mixed with the compound of Example 1 as a photopolymerization initiator.

<Formula 4>

<Ingredients>

(a) Alkali-soluble resin: Acrylic polymers of Production Examples 1 to 3 (a-1 to a-3)

(b) a 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) Photoinitiator: Carbazole oxime ester derivative compounds prepared in Examples 1 to 18

(e) Leveling agent: FC-430 (3M leveling agent)

(h) color

h-1: carbon black (solid weight 25weight%)

h-2: Pigment Red 177 (P.R. 177) (solid content 25% by weight)

Example (a) Component (% by weight) (b) Component (% by weight) (c) Component (% by weight) (e) Component (% by weight) (h) Component (% by weight) 19 a-1 (40)  b-1 (20) Example 1 (0.5) FC-430 (0.1) - 20 a-1 (40) b-3 (20) Example 2 (0.5) FC-430 (0.1) - 21 a-1 (40) b-5 (10)
b-6 (10) Example 3 (0.5) FC-430 (0.1) - 22 a-1 (40) b-2 (20) Example 5 (0.5) FC-430 (0.1) - 23 a-1 (40) b-1 (20) Example 6 (0.5) FC-430 (0.1) - 24 a-1 (40) b-3 (20) Example 7 (0.5) FC-430 (0.1) - 25 a-1 (40) b-5 (10)
b-6 (10) Example 10 (0.5) FC-430 (0.1) - 26 a-1 (40) b-1 (20) Example 11 (0.5) FC-430 (0.1) - 27 a-1 (40) b-3 (20) Example 13 (0.5) FC-430 (0.1) - 28 a-1 (40) b-5 (10)
b-6 (10) Example 16 (0.5) FC-430 (0.1) - 29 a-2 (40) b-7 (20) Example 1 (0.5) FC-430 (0.1) - 30 a-2 (40) b-8 (20) Example 9 (0.5) FC-430 (0.1) - 31 a-3 (40) b-3 (20) Example 1 (0.5) FC-430 (0.1) - 32 a-3 (40) b-4 (20) Example 9 (0.5) FC-430 (0.1) - 33 a-1 (20)
a-2 (20) b-1 (20) Example 1 (0.5) FC-430 (0.1) - 34 a-1 (20)
a-3 (20) b-1 (20) Example 1 (0.5) FC-430 (0.1) - 35 a-1 (20) b-1 (10) Example 1 (0.5) FC-430 (0.1) h-1 (50) 36 a-1 (20) b-1 (10) Example 1 (0.5) FC-430 (0.1) h-2 (50) 37 a-1 (40) b-1 (20) Example 1 (0.4)
Formula 4 (0.1) FC-430 (0.1) -

Comparative example  One

A photosensitive composition was prepared in the same manner as in Example 19, except that the compound of Formula 5 was used instead of the compound of Formula 3-1 of Example 1 as a photopolymerization initiator.

<Formula 5>

Comparative Example 2

A photosensitive composition was prepared in the same manner as in Example 19, except that the compound of Formula 6 was used instead of the compound of Formula 3-1 of Example 1 as a photopolymerization initiator.

<Formula 6>

<Evaluation of the photosensitive composition>

Evaluation of the photosensitive composition prepared in Examples 19 to 37 and Comparative Examples 1 and 2 was carried out on a glass substrate, the performance of the sensitivity, residual film ratio, pattern stability, chemical resistance and ductility of the photosensitive composition was measured and the results Table 4 below.

1) Sensitivity

The photoresist was spin coated onto 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. Sensitivity was evaluated for the exposure amount in which the step mask pattern maintains 80% of the initial thickness.

2) Residual rate

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

3) pattern stability

The silicon wafer on which the photoresist pattern was formed was cut from the vertical direction of the hole pattern, and the result of observing with an electron microscope in the cross-sectional direction of the pattern was shown. The pattern side wall was erected at an angle of 55 degrees or more with respect to the substrate, the film was not reduced, and it was determined as 'good', and the reduction of the film was judged as 'film'.

4) Chemical resistance

After the photosensitive composition was applied onto the substrate using a spin coater, the resist film formed through a process such as prebake and postbake was immersed in a stripper solution at 40 ° C. for 10 minutes, and then the transmittance of the resist film. And the change in thickness was examined. When the change in transmittance and thickness is 2% or less, it is set as 'good', and when the change in transmittance and thickness is more than 2%, it is determined as 'poor'.

5) Ductile

After spin-coating the photosensitive composition on the substrate, it was prebaked at 100 ° C. for 1 minute, exposed with the sensitivity of the photoresist, and developed with an aqueous KOH solution to form a pattern of 20 μm × 20 μm. The formed pattern was crosslinked by postbake at 230 ° C. for 20 minutes, and the ductility thereof was measured using a nano indentor. The measurement of the nanoindenter was determined to be 'good' if the total variation was more than 500 nm with 5 g.f loading, and 'bad' if it was less than 500 nm.

division Sensitivity (mJ / cm ² ) Residual Rate (%) Pattern stability Chemical resistance ductility Example 19 85 91 Good Good Good 20 85 90 Good Good Good 21 100 90 Good Good Good 22 85 89 Good Good Good 23 95 92 Good Good Good 24 90 91 Good Good Good 25 85 90 Good Good Good 26 85 90 Good Good Good 27 100 92 Good Good Good 28 85 92 Good Good Good 29 95 90 Good Good Good 30 80 91 Good Good Good 31 80 92 Good Good Good 32 90 91 Good Good Good 33 80 91 Good Good Good 34 80 89 Good Good Good 35 95 88 Good Good Good 36 90 91 Good Good Good 37 95 90 Good Good Good Comparative example One 200 82 Film Bad Bad 2 120 85 Film Bad Good

The carbazole oxime ester derivative compounds according to the present invention from Table 4 have excellent sensitivity even when used in small amounts when used as a photopolymerization initiator of the photosensitive composition, and have excellent physical properties such as residual film ratio, pattern stability, chemical resistance and ductility. Confirmed. Therefore, it was confirmed that the outgassing generated from the photopolymerization initiator in the exposure and the post-baking process during the TFT-LCD manufacturing process can be minimized, thereby reducing the contamination and minimizing the defects that may occur.

Claims (12)

Carbazole oxime ester derivative compounds represented by the following formula (1) or (2):
<Formula 1><Formula2>

In Chemical Formulas 1 and 2,
A is oxygen or sulfur;
R ₁ and R ₄ are each independently (C ₁ -C 20) alkyl;
R ₂ is (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;
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. The method of claim 1,
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, hydroxy 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 Carbazole oxime ester derivative compound which is phenyl. The method of claim 1,
The carbazole oxime ester derivative compound wherein the carbazole oxime ester derivative compound is at least one selected from compounds represented by the following formulas 3-1 to 3-18.
<Formula 3-1 to 3-18>

The photoinitiator containing the carbazole oxime ester derivative compound of any one of Claims 1-3. (a) alkali soluble resins;
(b) a polymerizable compound having an ethylenically unsaturated bond; And
(c) Photosensitive composition containing the photoinitiator containing the carbazole oxime ester derivative compound of any one of Claims 1-3. The method of claim 5,
The content of the carbazole oxime ester derivative compound is 0.01 to 10% by weight based on 100% by weight of the total photosensitive composition. The method of claim 5,
The photoinitiator further comprises one or two or more selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, an O-acyl oxime ester compound or a thiol compound. Photosensitive composition comprising. The method of claim 5,
The photosensitive composition wherein the photosensitive composition further comprises a colorant. The method of claim 7, wherein
The photosensitive composition wherein the photosensitive composition further comprises a colorant. Molded article containing the hardened | cured material of the photosensitive composition of Claim 5. The method of claim 10,
And wherein the molding is an array planarization 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 of claim 10.