KR20190067602A - Carbazole oxime ester derivative compounds and, photopolymerization initiator and photosensitive composition containing the same - Google Patents

Abstract

The present invention relates to a carbazole oxime ester derivative compound expressed by chemical formula 1 or 2, and a photopolymerization initiator and a photosensitive composition containing the same. In chemical formula 1 and 2, A and R_1 to R_4 are as defined respectively in the description of the invention. According to the present invention, the carbazole oxime ester derivative has excellent sensitivity, heat resistance, chemical resistance, and hardenability.

Description

[Technical Field] The present invention relates to a carbazole oxime ester derivative compound, a photopolymerization initiator containing the same, and a photosensitive composition containing the carbazole oxime ester derivative compound and a photopolymerization initiator,

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

As typical examples of the photopolymerization initiator used in the photosensitive composition, various kinds of acetophenone derivatives, benzophenone derivatives, triazine derivatives, nonimidazole derivatives, acylphosphine oxide derivatives and oxime ester derivatives are known, and oxime ester derivatives include ultraviolet Exhibits almost no color, has a high radical generation efficiency, and is excellent in compatibility with a photosensitive composition and in stability. However, the initially developed oxime derivative compounds have a low photoinitiator efficiency, and in particular, the sensitivity is low in the pattern exposure process, so that the exposure dose or the usage amount must be increased, thereby causing a problem that the production amount is reduced.

Therefore, the development of a photopolymerization initiator having excellent photosensitivity can realize a sufficient sensitivity even with a small amount of a photopolymerization initiator, so that a cost can be reduced and an exposure amount can be lowered due to excellent sensitivity, thereby increasing the production amount.

However, when a conventional photopolymerization initiator is used to form a pattern, sensitivity in the exposure process for pattern formation is low, so that the amount of photopolymerization initiator used must be increased or the amount of exposure must be increased, thereby contaminating the mask in the exposure process, There is a disadvantage in that yield is lowered as a byproduct which is generated after decomposition of the photopolymerization initiator in the photopolymerization initiator, and there is a problem that the production time is increased due to an increase of the exposure amount and the production amount is decreased.

International Patent Publication WO02 / 100903 (Dec. 19, 2002) Japanese Patent Laid-Open No. 2005-025169 (2005.01.27) WO07 / 071497 (Jun. 28, 2007) Korean Published Patent Application No. 2013-0124215 (November 13, 2013) Korean Published Patent Application No. 2013-0115272 (Oct. 21, 2013)

A 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 containing the same, and a photosensitive composition.

Another object of the present invention is to provide a molded article comprising a cured product of the photosensitive composition.

Another object of the present invention is to provide a display device including the molded article.

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

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

    &Lt; Formula 1 > < EMI ID =

■

In the above 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 selected from the group consisting of (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl (C1-C20) alkoxy (C1-C20) alkyl or (C3-C20) cycloalkyl;

R ₃ is selected from the group consisting of (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 6 -C 20) aryl (C 6 -C 20) alkyl, (C 3 -C 20) cycloalkyl, Alkyl.

The second embodiment, in the first embodiment,

Wherein R ₁ and R ₄ are each independently selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t- butyl, n-pentyl, ego;

R ₂ is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, iodecyl, 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-pentyl, hydroxy n-hexyl, hydroxy i-hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, Hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl;

R ₃ is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, Phenyl-carbazole oxime ester derivative compound.

The third embodiment is, in the first embodiment or the second embodiment,

The carbazole oxime ester derivative compound is a carbazole oxime ester derivative compound selected from the 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.

A fourth embodiment relates to a photopolymerization initiator comprising a 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 embodiments.

A fifth embodiment is directed to a resin composition comprising: (a) an alkali soluble resin;

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

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

The sixth embodiment is, in the fifth embodiment,

Wherein the carbazole oxime ester derivative compound is contained in an amount of 0.01 to 10% by weight based on 100% by weight of the total amount of the photosensitive composition.

The seventh embodiment is, in the fifth or sixth embodiment,

Wherein the photopolymerization initiator is at least one compound selected from the group consisting of a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, an O-acyloxime ester compound or a thiol compound The present invention further relates to a photosensitive composition comprising the same.

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

Wherein the photosensitive composition further comprises a coloring material.

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

The ninth embodiment relates to a molded article comprising a cured product of the photosensitive composition according to any one of the fifth to eighth embodiments.

The tenth embodiment is, in the ninth embodiment,

Wherein the molding is an array planarizing film, an insulating film, a color filter, a column spacer, a black column spacer, or a black matrix.

The eleventh embodiment relates to a display device including a molded article of the ninth or tenth embodiment.

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, it exhibits excellent sensitivity and is excellent in physical properties such as residual film ratio, pattern stability, heat resistance, chemical resistance and ductility, It is possible to minimize the outgassing generated from the photopolymerization initiator in the exposure and post-baking steps in the process, thereby reducing contamination and minimizing defects that may occur.

Hereinafter, the present invention will be described in detail. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It should be interpreted in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined.

Therefore, the configurations shown in the embodiments described herein are merely the most preferred embodiments of the present invention, and are not intended to represent all of the technical ideas of the present invention, so that various equivalents And variations are possible.

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

[Chemical Formula 1] &lt; EMI ID =

In the above 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 selected from the group consisting of (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl (C1-C20) alkoxy (C1-C20) alkyl or (C3-C20) cycloalkyl;

R ₃ is selected from the group consisting of (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 6 -C 20) aryl (C 6 -C 20) alkyl, (C 3 -C 20) cycloalkyl, Alkyl.

The substituents comprising "alkyl", "alkoxy" and other "alkyl" moieties described herein include both linear and branched forms, and "cycloalkyl" includes not only a single ring system but also several cyclic hydrocarbons.

The term "aryl" as used herein also includes an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination, including a single or fused ring system, and a plurality of aryls connected by a single bond.

The term "hydroxyalkyl" as used herein means OH-alkyl in which a hydroxy group is bonded to the alkyl group defined above, and "hydroxyalkoxyalkyl" means a hydroxyalkyl-O -Alkyl &lt; / RTI &gt; and alkenyl means a structure comprising a ketone to which an alkyl or aryl group is attached.

The term "arylalkyl" as used herein may be exemplified by benzyl and the like, and "cycloalkyl" may be exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like, and "cycloalkylalkyl" , Cyclobutylmethyl, cyclopentylmethyl, cyclopropylethyl, and the like,

The term "(C 1 -C 20) alkyl" as used herein refers to an alkyl having 1 to 20 carbon atoms, which may be preferably (C 1 -C 10) alkyl, more preferably (C 1 -C 6) ) &Lt; / RTI &gt;

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

The term "(C1-C20) alkoxy" means alkoxy having 1 to 20 carbon atoms, which alkoxy may preferably be (C1-C10) alkoxy and more preferably (C1-C4) alkoxy.

The term "(C6-C20) aryl (C1-C20) alkyl" means an alkyl in which one hydrogen of the alkyl of 1 to 20 carbon atoms is substituted with an aryl group having 6 to 20 carbon atoms, preferably (C6-C18) aryl (C1-C6) alkyl, more preferably (C6-C18) aryl (C1-C6) alkyl and more preferably (C6-C12) aryl

'Hydroxy (C1-C20) alkyl' means alkyl in which one hydrogen in the alkyl having 1 to 20 carbons is substituted with hydroxy, preferably hydroxy (C1-C10) alkyl, more preferably 0.0 &gt; (Cl-C6) &lt; / RTI &gt; alkyl.

The term "hydroxy (C1-C20) alkoxy (C1-C20) alkyl" refers to an alkyl group having 1 to 20 carbon atoms in which one hydrogen is substituted with 1 to 20 carbon atoms and one hydrogen in the alkoxy is substituted with hydroxy (C1-C10) alkoxy (C1-C10) alkyl, and more preferably hydroxy (C1-C4) alkoxy (C1-C6) alkyl.

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

The term "(C3-C20) cycloalkyl (C1-C20) alkyl" means an alkyl in which one hydrogen in the alkyl of 1 to 20 carbon atoms is substituted by cycloalkyl of 3 to 20 carbon atoms, preferably (C3-C10) Cycloalkyl (C1-C10) alkyl, and more preferably (C3-C6) cycloalkyl (C1-C6) alkyl.

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

A is oxygen or sulfur;

R ₁ and R ₄ are each independently selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t- butyl, n-pentyl, ;

R ₂ is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, iodecyl, 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-pentyl, hydroxy n-hexyl, hydroxy i-hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, Hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl;

R ₃ is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, Phenyl.

More specifically, in the above general 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 can be methyl, ethyl, n-propyl, or phenyl.

According to one embodiment of the present invention, the carbazole oxime ester derivative compound may be a compound selected from the group consisting of the following 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 represented by the above formula (1) or (2) according to the present invention can be prepared as shown in the following reaction formula (1) or (2), but is not limited thereto.

[Reaction Scheme 1]

[Reaction Scheme 2]

In the above Reaction 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.

The photopolymerization initiator according to another aspect of the present invention includes at least one selected from carbazole oxime ester derivative compounds represented by the above general formula (1) or (2).

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

(a) an alkali-soluble resin;

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

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

The carbazole oxime ester derivative compound may be included as a photopolymerization initiator.

The photosensitive composition according to another aspect of the present invention is excellent in physical properties such as heat resistance and chemical resistance. Hereinafter, each component that can be included in the photosensitive composition of the present invention will be described in detail.

"(Meth) acrylate" means acrylate and / or methacrylate, "(meth) acrylate" means acrylic acid and / or methacrylate, Methacrylic acid.

(a) an 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.

(Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and the like. Examples of the acrylic polymer include polymers of acrylic monomers (including homopolymers or copolymers) (Meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl Acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, isobonyl (meth) acrylate, adamantyl (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (Meth) acrylic acid, maleic acid, maleic acid anhydride, maleic acid monoalkyl ester, monoalkyl itaconate, monoalkyl fumarate, glycidyl (meth) acrylate, 3,4-epoxy (Meth) acrylate, 3-methylcyclohexylmethyl (meth) acrylate, 3-methylcyclohexylmethyl (meth) acrylate, (Meth) acrylate, styrene,? -Methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N -Cyclohexylmaleimide, (meth) acrylamide or N-methyl (meth) acrylamide. These may be used alone or in combination of two or more.

The acrylic polymer having an acrylic unsaturated bond in the side chain is a copolymer obtained by addition reaction of an epoxy resin to an acrylic copolymer containing a carboxylic acid, such as (meth) acrylic acid, itaconic acid, maleic acid or maleic acid monoalkyl ester An acrylic monomer containing a carboxylic acid; (Meth) acrylate such as methyl (meth) acrylate or hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (Meth) acrylamide or N-methyl (meth) acrylamide, N-methylmaleimide, N-methylmaleimide, N-butylmaleimide, (Meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate and the like are added to an acrylic copolymer containing a carboxylic acid obtained by copolymerizing two or more kinds of monomers Methacrylate or 3,4- (Meth) acrylate, or the like, at a temperature of 40 to 180 占 폚 may be used as the binder resin.

Another example of an acrylic polymer having an acryl-unsaturated bond in the side chain is a copolymer obtained by addition reaction of a carboxylic acid to an acrylic copolymer containing an epoxy group, and includes glycidyl (meth) acrylate, 3,4-epoxybutyl ) Acrylate, 2,3-epoxycyclohexyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate; (Meth) acrylate such as methyl (meth) acrylate or hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (Meth) acrylamide or N-methyl (meth) acrylamide, N-methylmaleimide, N-methylmaleimide, N-butylmaleimide, N- (Meth) acrylate, maleic acid or maleic acid monoalkyl ester) is added to an acrylic copolymer containing an epoxy group obtained by copolymerizing two or more kinds of monomers such as acrylic acid, A binder resin obtained by an addition reaction at a temperature of 180 ° C can be used.

According to one embodiment of the present invention, the alkali-soluble resin is used in an amount of 3 to 50% by weight, more preferably 5 to 45% by weight based on 100% by weight of the total amount of the photosensitive composition for imparting physical properties such as heat resistance, chemical resistance, By weight, more specifically 8 to 40% by weight.

The weight average molecular weight (measured by gel permeation chromatography (GPC) in terms of polystyrene conversion) 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 is crosslinked by a photoreaction at the time of pattern formation to form a pattern, and is crosslinked upon heating at a high temperature to impart chemical resistance and heat resistance.

The polymerizable compound having an ethylenically unsaturated bond may be contained in an amount of 0.001 to 40% by weight, preferably 0.1 to 30% by weight, 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 becomes excessively high and the ductility of the pattern may be deteriorated.

The polymerizable compound having an ethylenically unsaturated bond is specifically exemplified by methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) (Meth) acrylate, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate having a number of ethylene oxide groups of 2 to 14, ethylene glycol di (meth) acrylate, ethylene oxide Propylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, trimethylolpropane di (meth) acrylate, bisphenol A diglycidyl ether (meth) acrylate having 2 to 14 carbon atoms, Acrylic acid adduct, a phthalic acid diester of? -Hydroxyethyl (meth) acrylate, a toluene diisocyanate of? -Hydroxyethyl (meth) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra A compound obtained by esterifying a polyhydric alcohol and an alpha, beta -unsaturated carboxylic acid such as dipentaerythritol tri (meth) acrylate, an acrylic acid adduct of a polyglycidyl compound such as trimethylolpropane triglycidyl ether acrylic acid adduct These may be used alone or in combination of two or more.

(c) a photopolymerization initiator

In the photosensitive composition of the present invention, at least one selected from the oxime ester derivative compounds of the above general formula (1) or (2) can be used as a photopolymerization initiator. It is more effective to use the photopolymerization initiator in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight based on 100% by weight of the total amount of the photosensitive composition, in order to increase the transparency and minimize the exposure dose.

(d) Adhesion preparation

Further, the photosensitive composition of the present invention may further contain a silicone compound having an epoxy group or an amine group as an adhesive aid, if necessary.

The silicone compound having an epoxy group or an amine group improves the adhesion between the ITO electrode and the photosensitive composition and can increase the heat resistance after curing. Examples of the silicone compound having an epoxy group or an amine group include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyl (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- Methoxysilane, and aminopropyltrimethoxysilane. These may be used alone or in combination of two or more.

The silicone compound having an epoxy group or an amine group may be contained in an amount of 0.0001 to 3% by weight based on 100% by weight of the total amount of the photosensitive composition. If the amount is less than the above range, the effect of the addition can not be confirmed. If it exceeds the above range, the developing property of the non-exposed portion is lowered, and scum and residue may remain on the lower substrate, ITO or glass substrate.

(e) Other additives

The photosensitive composition of the present invention may further comprise at least one compatible additive selected from a photosensitizer, a thermal polymerization inhibitor, a defoaming agent or a leveling agent, if necessary.

The other additives may be contained in an amount of 0.1 to 10% by weight based on 100% by weight of the total amount of the photosensitive composition. If the amount is less than the above range, the effect of addition can not be confirmed.

(f) Solvent

The photosensitive composition of the present invention is coated on a substrate by adding a solvent, and then patterned by a method of irradiating ultraviolet rays using a mask and developing with an alkaline developer.

Therefore, the content of the solvent can be controlled so that the total amount is 100% by weight in addition to the contents of the other components of the above-mentioned photosensitive composition, and thus can be variously changed depending on the contents of the other components of the photosensitive compositions. For example, it is preferable to add a solvent in an amount of 10 to 95% by weight based on 100% by weight of the photosensitive composition to adjust the viscosity to 1 to 50 cps.

As the solvent, in view of compatibility with an alkali-soluble resin, a photopolymerization initiator and other compounds, ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propyl (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, (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (DMF), acetonitrile, Pyrrolidone (NMP),? -Butyrolactone, diethyl ether, ethylene glycol dimethyl ether, Diglym (e), e), tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, Xylene, hexane, heptane or octane may be used alone or in admixture of two or more.

(g) Other photopolymerization initiator

The photosensitive composition of the present invention may contain the above-described carbazole oxime ester derivative compound as a photopolymerization initiator alone, or may be a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, an O-acyloxime ester compound A compound and a thiol-based compound may be further contained.

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

Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- Dichlorotioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, or 2,4-diisopropylthioxanthone may be used, but the present invention is not limited thereto.

Examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- (4-morpholinophenyl) butan-1-one or 2- (4-methylbenzyl) -2- But is not limited thereto.

Examples of the non-imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis (2,4,6- Phenylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole may be used, but the present invention is not limited thereto.

Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6- 4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) ethenyl] -4,6-bis Bis (trichloromethyl) -s-triazine or 2- (4-n-butoxyphenyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, but the present invention is not limited thereto.

Examples of the O-acyloxime ester compound include 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O- benzoyloxime) -Ethyl] -6- (2-methyl-4- (2-methylbenzoyl) -9H-carbazol- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl- Yl) -1- (O-acetyloxime) or 2- (acetoxyimino) -1- (9,9 ' -Diethyl-9H-fluoro-2-yl) propan-1-one can be used, but is not limited thereto.

As the thiol compound, pentaerythritol tetrakis (3-mercaptopropionate) and the like can be used, but it is not limited thereto.

(h) Coloring material

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

As the coloring material, various pigments can be used. For example, cyan, magenta, yellow and black pigments of red, green, blue and a mixture of navy blue are available. More specifically, CI Pigment Yellow 12 , 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148, 153, 154, 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 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 coloring material may be contained in an amount of 5 to 50% by weight based on 100% by weight of the total amount of the photosensitive composition. If the amount is less than the above range, the light shielding property is deteriorated, and if the above range is exceeded, exposure failure or curing failure may result.

The photosensitive composition according to an embodiment of the present invention may be applied to a substrate such as a soda glass, a quartz glass, a semiconductor substrate, a metal, a paper sheet, a paper substrate, or the like by a known means such as a spin coater, a roll coater, a bar coater, a die coater, , Plastics, and the like. Further, it can be once transferred onto a supporting substrate such as a film, and then transferred onto another supporting substrate.

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

The molding may be, but not limited to, an array planarizing film, an insulating film, a color filter, a column spacer, an overcoat, a black column spacer, or a black matrix.

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

For a better understanding of the present invention, representative compounds of the present invention will be described in detail with reference to Examples and Comparative Examples. However, the embodiments according to the present invention can be modified into various other forms, Should not be construed as being limited to the embodiments described below. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art.

&Lt; Preparation of carbazole oxime ester derivative compound >

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

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

To the reactor was added triethylene glycol dimethyl ether (40 ml), carbazole (30 g, 170.5 mmol), 4-iodoanisole (49.8 g, 204.3 mmol), powdered copper (11.34 g, Potassium carbonate (58.8 g, 423.2 mmol) was added thereto, followed by stirring at 200 占 폚 for 20 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, ethyl acetate (300 ml) was added, and the mixture was stirred for 30 minutes to crystallize. This solution was filtered, and the resulting solid was further stirred in acetone (300 ml) and methylene chloride (300 ml) for 30 minutes, and then filtered and washed with water.

The solid obtained was discarded as impurities and the filtrate was taken. The organic solvent in the filtrate was distilled under reduced pressure at 40 占 폚, and the product was stored in a refrigerator for one day to precipitate the product. The resulting solid was recrystallized from acetone to obtain the objective compound, 9- (4-methoxyphenyl) -9H-carbazole (40.7 g, 87.4%) as a colorless oil. .

^{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, &lt; / RTI &gt; d), 8.15 (2H, d)

MS ( m / e ): 273

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

(5.91 g, 43.9 mmol) was added to methylene chloride (200 ml), cooled to -10 ° C or lower and stirred for 10 minutes, and then 9- (4-methoxyphenyl) -9H- Carbazole (10.0 g, 36.3 mmol) was added thereto, followed by stirring for 30 minutes. A solution of propionyl chloride (3.89 ml, 43.9 mmol) in methylene chloride (25 ml) was added dropwise over 50 minutes, and the mixture was stirred for 30 minutes. The reaction solution was poured into ice water (490 g) and water (500 ml), stirred for 30 minutes, allowed to stand to remove the water layer, and the organic layer was sufficiently washed with sodium bicarbonate aqueous solution. Thereafter, the organic layer was dried over anhydrous magnesium sulfate, filtered and distilled under reduced pressure to obtain 11.8 g of 1- (9- (4-methoxyphenyl) -9H-carbazol-3-yl) propan- , 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

MS ( m / e ): 329

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

1-one (6.0 g, 18.2 mmol), tetrahydrofuran (132 ml) and 35 (5-benzyloxy- % Concentrated hydrochloric acid (8.7 ml) was added to the reactor and stirred for 30 minutes. A solution of isopentyl nitrite (5.1 ml, 36.4 mmol) in tetrahydrofuran (10 ml) was added dropwise for 30 minutes, and the mixture was stirred for 50 minutes. The reaction was then extracted with ethyl acetate and washed well 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 the target compound, 1- (9- (4-methoxyphenyl) -9H-carbazol-3-yl) , 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

MS ( m / e ): 358

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

2-oxime (0.5 g, 1.4 mmol) obtained in the above Step 3 was added to ethyl acetate and the mixture was stirred at room temperature for 3 hours. After cooling to below 10 &lt; 0 &gt; C, triethylamine (0.39 ml, 2.8 mmol) was added dropwise and stirred for 10 min. Then, a solution of acetyl chloride (0.22 ml, 3.08 mmol) in ethyl acetate (1 ml) was added dropwise over 10 minutes, and the mixture was stirred for 30 minutes. The reaction solution was extracted with methylene chloride and sufficiently washed with an 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) -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 to 12

Carbazole oxime ester derivative compounds were synthesized under the same conditions as in Example 1 with the compositions shown in Table 1 below.

Example The 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 Q), 7.41 (3H, q), 8.19 (3H, s), 2.31 (3H, s) (2H, t), 8.99 (1 H, s) 242.1 DEG C 3 3-3 O CH ₃ CH ₃

T), 7.65 (1H, t), 8.17 (3H, s), 7.33 (2H, (2H, d), 8.27 (2H, d, d), 9.1 (1H, s) 247.3 DEG C 4 3-4 O CH ₃ C ₂ H ₅ CH ₃ Q), 7.41 (3H, q), 8.19 (3H, q), 2.10 (3H, t), 2.31 (2H, t), 8.99 (1 H, s) 241.6 DEG C 5 3-5 O CH ₃ CH ₃ C ₂ H ₅ (3H, q), 2.37 (3H, s), 3.93 (3H, s), 7.13 (2H, t), 8.99 (1 H, s) 240.7 DEG C 6 3-6 O CH ₃

CH ₃ M), 8.19 (2H, t), 8.99 (1H, s), 3.93 (3H, s) 246.3 DEG C 7 3-7 S CH ₃ CH ₃ CH ₃ (1H, s), 2.31 (3H, s), 2.37 (3H, s), 2.59 (3H, s), 7.36 242.3 DEG C 8 3-8 S C ₂ H ₅ CH ₃ CH ₃ Q), 7.41 (3H, q), 8.19 (3H, s), 2.31 (3H, s) (2H, t), 8.99 (1 H, s) 242.5 DEG C 9 3-9 S CH ₃ CH ₃

(2H, t), 8.17 (2H, d), 8.24 (2H, t), 2.5 (3H, s), 2.6 (1 H, d), 8.29 (1 H, d), 9.09 (1 H, s) 246.6 DEG C 10 3-10 S CH ₃ C ₂ H ₅ CH ₃ Q), 8.19 (3H, q), 7.39 (3H, q), 2.09 (3H, t), 2.33 (2H, t), 9.01 (1 H, s) 244.6 DEG C 11 3-11 S CH ₃ CH ₃ C ₂ H ₅ (3H, q), 2.38 (3H, s), 3.93 (3H, s), 7.12 (2H, d), 7.34 (2H, t), 8.99 (1 H, s) 243.1 DEG C 12 3-12 S CH ₃ C ₃ H ₇ CH ₃ (2H, d), 7.34 (3H, q), 1.62 (3H, t), 2.01-2.25 (7H, m), 2.33 , 7.46 (3H, q), 8.19 (2H, t), 9.01 (1H, s) 243.5 DEG C

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

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

(19.8 g, 78.8 mmol), copper iodide (8.0 g, 41.76 mmol), sodium methoxide 25% methanol solution (750 ml), ethyl acetate (15 ml) and toluene (15 ml) were charged into a reactor and subjected to a reflux reaction at 90 ° C for 4 days. After completion of the reaction, the reaction mixture was cooled to room temperature. Then, the reaction solution was transferred to a beaker, and water (300 ml) and methylene chloride (300 ml) were put in a beaker, followed by stirring for 1 hour. The beaker solution was filtered through a filter equipped with a silica gel (40-400 mesh) having a size of 2-3 cm to remove undissolved impurities. Subsequently, the filtrate was extracted three times with methylene chloride (300 ml), and the organic layer was dried over anhydrous magnesium sulfate and filtered. The residue was purified by recrystallization (methylene chloride: hexane = 1: 1) 3-methoxy-9H-carbazole (10.3 g, 66.4%).

^{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, &lt; / RTI &gt; d), 8.15 (2H, d)

MS ( m / e ): 197

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

(3.0 g, 15.2 mmol), 4-iodoanisole (4.34 g, 17.8 mmol), copper (1.01 g, 15.8 mmol) in powder form, potassium carbonate (5.28 g, 38 mmol) and triethyleneglycol dimethyl ether (5.3 ml, 29.3 mmol) were charged into the reactor, respectively, and stirred at 200 ° C for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and methylene chloride (60 ml) was added thereto, followed by stirring for 1 hour. The reaction solution was filtered through a filter equipped with silica gel (40 to 400 mesh) having a size of 2 to 3 cm. Then, methylene chloride and triethylene glycol dimethyl ether present in the filtrate were removed by distillation under reduced pressure, and a column (methylene chloride: hexane = 1: 5) was separated to obtain the objective compound, 3-methoxy-9- ) -9H-carbazole (4.05 g, 88.2%).

^{1 H NMR (δ ppm, CDCl3} , 500 MHz): 3.91 (3H, s), 3.95 (3H, s), 7.04 (1H, dd), 7.10 (2H, dd), 7.24 (2H, m), 7.32 ( D), 7.38 (1H, m), 7.44 (2H, dd), 7.61

MS (m / e): 303

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

Aluminum chloride (2.32 g, 17.2 mmol) was added to methylene chloride (40 ml) and cooled to -10 占 폚 or lower. The 3-methoxy-9- (4-methoxyphenyl) -9H-carbazole (4.0 g, 13.2 mmol) obtained in the above step 2 was added dropwise to methylene chloride (5 ml) and stirred for 20 minutes. Propionyl chloride (1.52 ml, 17.2 mmol) was added dropwise over 30 minutes, and the mixture was stirred for 20 minutes. After completion of the reaction, the reaction solution was poured into water (200 ml), stirred for 1 hour, and then methylene chloride (100 ml) was added thereto to extract an organic layer. The extracted organic layer was sufficiently washed with a sodium bicarbonate aqueous solution. The extracted organic layer was dried using anhydrous magnesium sulfate, filtered and distilled under reduced pressure to obtain 1- (6-methoxy-9- (4-methoxyphenyl) -9H-carbazol- One (4.5 g, 94.7%).

^{1 H NMR (δ ppm, CDCl3} , 500 MHz): 1.30 (3H, t), 3.15 (2H, q), 3.91 (3H, s), 3.95 (3H, s), 7.07 (1H, dd), 7.11 ( D, 2H), 7.24 (1H, d), 7.29 (1H, d), 7.42

MS ( m / e ): 359

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

(4.91 g, 13.7 mmol) obtained in the above Step 3 and 35% concentrated hydrochloric acid (2.4 ml, 27.4 mmol) were added to tetrahydrofuran (40 ml) and stirred for 30 minutes. Then, a solution of isopentyl iodide (3.83 ml, 27.4 mmol) in tetrahydrofuran (8 ml) was added dropwise over 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 a sodium bicarbonate aqueous solution. The extracted organic layer was dried using anhydrous magnesium sulfate and filtered. (Ethyl acetate: hexane = 1: 4) to obtain the target compound, 2- (hydroxyimino) -1- (6-methoxy-9- (4- methoxyphenyl) -9H-carbazole Yl) propan-1-one (1.63 g, 30.7%).

^{1 H NMR (δ ppm, CDCl3} , 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

MS ( m / e ): 388

Step 5 : 2-( Hydroxyimino ) -1- (6- Methoxy -9- (4- Methoxyphenyl ) -9H- Carbazole Yl) propan-1-one (O-acetate)

9- (4-methoxyphenyl) -9H-carbazol-3-yl) propan-1-one obtained in the above step 4 (0.76 g, 1.96 mmol) was added to ethyl acetate (15 ml), cooled to -10 ° C or lower, triethylamine (0.55 ml, 3.92 mmol) was added thereto, and the mixture was stirred for 10 minutes. Then, a solution of acetyl chloride (0.29 ml, 3.92 mmol) in ethyl acetate (2 ml) was added dropwise for 5 minutes, and the mixture was 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 sufficiently washed with an aqueous sodium bicarbonate solution. The extracted organic layer was dried using anhydrous magnesium sulfate and distilled under reduced pressure to obtain the target compound 2- (hydroxyimino) -1- (6-methoxy-9- (4-methoxyphenyl) -9H- Yl) propan-1-one (O-acetate) (0.77 g, 91.3%).

^{1 H NMR (δ ppm, CDCl3} , 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

MS ( m / e ): 430

Decomposition point: 248.3 ℃

Examples 14 to 18

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

Example The 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 (3H, d), 7.12 (2H, dd), 2.30 (3H, s), 2.35-2.86 (1H, d), 7.24 (1H, d), 7.31 (1H, d), 7.42 248.3 DEG C 15 3-15 O CH ₃ CH ₃

CH ₃ (1H, d), 7.34 (1H, d), 7.44 (1H, dd) (2H, dd), 7.54 (2H, t), 7.66 (1H, t), 7.70 248.7 DEG C 16 3-16 S CH ₃ CH ₃ CH ₃ CH ₃ D), 7.28 (1H, d), 7.35 (1H, d), 7.45 (3H, s) (1H, s), 7.66 (1H, d), 8.47 (1H, 247.3 DEG C 17 3-17 S C ₂ H ₅

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

CH ₃ D), 7.29 (1H, d), 7.39 (1H, d), 7.47 (4H, m), 7.54 (3H, s) (2H, t), 7.66 (1H, t), 7.70 (1H, d), 8.17 247.2 DEG C

&Lt; Preparation of alkali-soluble resin >

Production Example 1: Preparation of acrylic polymer (a-1)

200 mL of propylene glycol methyl ether acetate (PGMEA) and 1.5 g of azobisisobutyronitrile (AIBN) were added to a 500 mL polymerization vessel, and then a solution of methacrylic acid, glycidyl methacrylic acid, methyl methacrylic acid, Dicyclohexylmethacrylate, dicyclohexylmethacrylate, dicyclopentanyl acrylic acid at a molar ratio of 20:20:40:20, and then the mixture was stirred at 70.degree. C. for 5 hours under a nitrogen atmosphere to polymerize the acrylic polymer (a-1) . The polymer (a-1) produced had a weight average molecular weight of 25,000 and a degree of dispersion of 1.9.

Production Example 2: Preparation of acrylic polymer (a-2)

200 mL of propylene glycol methyl ether acetate and 1.0 g of AIBN were added to a 500-mL polymerization vessel, and then methacrylic acid, styrene, methylmethacrylic acid, and cyclohexylmethacrylic acid were mixed in a molar ratio of 40: 20: 20: The solid content of the monomer was added in an amount of 40% by weight, and the resulting mixture was polymerized under stirring in a nitrogen atmosphere at 70 캜 for 5 hours to synthesize a copolymer. Subsequently, 0.3 g of N, N-dimethylaniline and 20 mol of glycidyl methacrylate were added to the reactor based on 100 mol of the solid content of the whole monomers, followed by stirring at 100 DEG C for 10 hours to obtain an acrylic polymer having acryl- (a-2). The weight average molecular weight of the acrylic polymer (a-2) prepared was 20,000 and the degree of dispersion was found to be 2.0.

Manufacturing example  3: Acrylic polymer (a- 3) of  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, methyl methacrylic acid, and cyclohexyl methacrylic acid were mixed in a ratio of 40:20:20:20 The solid content of the acrylic monomer was added in a molar ratio of 40% by weight, and the resultant mixture was polymerized under stirring in a nitrogen atmosphere at 70 캜 for 5 hours to synthesize a copolymer. Subsequently, 0.3 g of N, N-dimethylaniline and 20 mol of acrylic acid were added to the reactor based on 100 mol of the solid content of the whole monomers, followed by stirring at 100 DEG C for 10 hours to obtain an acrylic polymer (a-3) having an acryl- . The weight average molecular weight of the acrylic polymer (a-2) prepared was 18,000 and the degree of dispersion was found to be 1.8.

&Lt; Preparation of photosensitive composition >

Examples 19 to 34: Preparation of photosensitive composition

An alkali-soluble resin was added to the reaction mixture tank equipped with an ultraviolet shielding film and a stirrer according to the contents and contents shown in Table 3 below. A polymerizable compound having an ethylenically unsaturated bond; A photopolymerization initiator of the present invention; , And FC-430 (leveling agent of 3M company) were sequentially added, and the mixture was stirred at room temperature (23 캜). PGMEA was then added to the composition so that the total amount of the composition was 100% by weight to prepare the photosensitive compositions of Examples 19 to 34 Respectively.

&Lt; Preparation of colored photosensitive composition >

Examples 35 to 36: Preparation of colored photosensitive composition

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

Example 37

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

&Lt; Formula 4 >

<Component>

(a) Alkali-soluble resin: The acrylic polymer (a-1 to a-3) of Production Examples 1 to 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: trimethylol propane triglycidyl ether acrylic acid adduct

(c) Photopolymerization initiator: The carbazole oxime ester derivative compound prepared in Examples 1 to 18

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

(h) Coloring material

h-1: Carbon black (solid content: 25% by weight)

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)
(4) FC-430 (0.1) -

Comparative Example  One

A photosensitive composition was prepared in the same manner as in Example 19, except that the compound represented by the following general formula (5) was used instead of the compound represented by the general formula (3-1) in Example 1 as a photopolymerization initiator.

&Lt; Formula 5 >

Comparative Example 2

A photosensitive composition was prepared in the same manner as in Example 19, except that the compound represented by the following general formula (6) was used instead of the compound represented by the general formula (3-1) in Example 1 as a photopolymerization initiator.

(6)

&Lt; Evaluation of photosensitive composition >

The evaluation of the photosensitive compositions prepared in Examples 19 to 37 and Comparative Examples 1 and 2 was carried out on a glass substrate and the performances such as sensitivity, residual film ratio, pattern stability, chemical resistance and ductility of the photosensitive composition were measured, Are shown in Table 4 below.

1) Sensitivity

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 in 0.04% KOH aqueous solution. The exposure amount at which the step mask pattern was maintained at 80% thickness with respect to the initial thickness was evaluated as sensitivity.

2)

The photosensitive composition was applied on a substrate by a spin coater, prebaked at 100 ° C for 1 minute, exposed at 365 nm, and postbaked at 230 ° C for 20 minutes to post-bake (%) Was measured.

3) Pattern stability

The silicon wafer having the photoresist pattern formed thereon was cut from the vertical direction of the hole pattern and observed with an electron microscope in the cross-sectional direction of the pattern. The side wall of the pattern was erected at an angle of 55 degrees or more with respect to the substrate, the film was not reduced and the film was judged to be 'good'.

4) Chemical resistance

The photosensitive composition was applied on a substrate using a spin coater, and then a resist film formed by a process such as prebake and postbake was immersed in a stripper solution at 40 캜 for 10 minutes, and then the transmittance of the resist film And whether there was a change in thickness. 'Good' when the transmittance and thickness were less than 2%, and 'Bad' when the transmittance and thickness were more than 2%.

5) ductility

The photosensitive composition was spin-coated on the substrate, prebaked at 100 占 폚 for 1 minute, exposed with a photoresist sensitivity, and developed with a KOH aqueous solution to form a pattern of 20 占 퐉 x 20 占 퐉. The formed pattern was post-baked at 230 캜 for 20 minutes to crosslink, and the pattern was measured for ductility using a nanoindentor. The measurement of the nanoindentor was judged as "good" when the total amount of shift was 500 nm or more, and "poor" when the total amount was 500 nm or less.

division Sensitivity (mJ / cm ² ) Remaining film ratio (%) 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 Hard feeling Bad Bad 2 120 85 Hard feeling Bad Good

From Table 4, it can be seen that the carbazole oxime ester derivative compound according to the present invention is superior in sensitivity even when a small amount is used when it is used as a photopolymerization initiator of a photosensitive composition and has excellent properties such as residual film ratio, pattern stability, chemical resistance and ductility Respectively. Therefore, it is possible to minimize the outgassing generated from the photopolymerization initiator in the exposure and post-baking process in the TFT-LCD manufacturing process, thereby reducing the contamination and minimizing the defects that may occur.

Claims (12)

A carbazole oxime ester derivative compound represented by the following formula 1 or 2:
&Lt; Formula 1 >< EMI ID =

In the above 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 selected from the group consisting of (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl (C1-C20) alkoxy (C1-C20) alkyl or (C3-C20) cycloalkyl;
R ₃ is selected from the group consisting of (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 6 -C 20) aryl (C 6 -C 20) alkyl, (C 3 -C 20) cycloalkyl, Alkyl. The method according to claim 1,
A is oxygen or sulfur;
R ₁ and R ₄ are each independently selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t- butyl, n-pentyl, ;
R ₂ is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, iodecyl, 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-pentyl, hydroxy n-hexyl, hydroxy i-hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, Hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl;
R ₃ is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, Phenyl-carbazole oxime ester derivative compound. The method according to claim 1,
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>

A photopolymerization initiator comprising the carbazole oxime ester derivative compound of any one of claims 1 to 3. (a) an alkali-soluble resin;
(b) a polymerizable compound having an ethylenically unsaturated bond; And
(c) a photopolymerization initiator comprising the carbazole oxime ester derivative compound of any one of claims 1 to 3. 6. The method of claim 5,
Wherein the content of the carbazole oxime ester derivative compound is 0.01 to 10% by weight based on 100% by weight of the total amount of the photosensitive composition. 6. The method of claim 5,
Wherein the photopolymerization initiator is one or more selected from the group consisting of a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, an O-acyloxime ester compound or a thiol compound, &Lt; / RTI &gt; 6. The method of claim 5,
Wherein the photosensitive composition further comprises a coloring material. 8. The method of claim 7,
Wherein the photosensitive composition further comprises a coloring material. A molded article comprising the cured product of the photosensitive composition of claim 5. 11. The method of claim 10,
Wherein the molding is an array planarizing 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.