TW201927752A - Carbazole oxime ester derivative compounds and photopolymerization initiator and photosensitive composition containing the same - Google Patents

Abstract

The present disclosure relates to a carbazole oxime ester derivative compound represented by Chemical Formula 1 or Chemical Formula 2 and a photopolymerization initiator and a photosensitive composition containing the same. In Chemical Formulas 1 and 2, A and R1-R4 are the same as defined in the detailed description.

Description

Oxazolium ester-derived compound, photopolymerization initiator containing the same, and photosensitive composition

The present disclosure relates to an oxazolidine derivative-derived compound, and a photopolymerization initiator and photosensitive composition therewith, and more particularly to an oxazolidin ester-derived compound and a photopolymerization initiator containing the same The photosensitive composition, the oxazolidine derivative-derived compound has excellent sensitivity, heat resistance, light resistance, chemical resistance, and hardenability.

In general, acetophenone derivatives, benzophenone derivatives, triazine derivatives, biimidazole derivatives, mercaptophosphine oxide derivatives, oxime ester derivatives, etc. have been used as photopolymerization initiators. In the photosensitive composition. Among these, the oxime ester derivative is advantageous in that the oxime ester derivative is almost colorless by absorbing ultraviolet light; exhibits high radical generation efficiency; and compatibility with other components of the photosensitive composition. Excellent sex; and excellent stability. However, the oxime ester-derived compound which has been previously developed has a problem in that the oxime ester-derived compound has a low light-initiating efficiency, and the sensitivity is low during the pattern exposure treatment so that the exposure or the amount of use should be increased, with the result that the yield is decreased.

Therefore, development of a photopolymerization initiator having excellent photosensitivity can save cost because even a small amount of photopolymerization initiator can achieve sufficient sensitivity and productivity can be improved because the sensitivity is excellent. Can reduce exposure.

However, when a conventional photopolymerization initiator is used to form a pattern, the sensitivity is so low in the exposure treatment for pattern formation that it is necessary to increase the amount or exposure dose of the photopolymerization initiator, resulting in the following disadvantages: Contamination during exposure treatment and by-products produced by decomposition of the photopolymerization initiator during high temperature crosslinking reduce the yield, and the exposure treatment time increases with increasing exposure dose so that there is a problem of reduced production, therefore, Try to solve the problem.
[Previous Technical Literature]
(Patent Literature)

Patent Document 1: International Patent Publication No. WO 02/100903 (2002. 12. 19).
Patent Document 2: Japanese Patent Laid-Open Publication No. 2005-025169 (2005. 01. 27).
Patent Document 3: International Patent Publication No. WO07/071497 (2007. 06.28).
Patent Document 4: Korean Patent Publication No. 2013-0124215 (2013. 11. 13).
Patent Document 5: Korean Patent Publication No. 2013-0115272 (2013. 10. 21)

[The problem that the invention wants to solve]
The present disclosure relates to an oxime oxime ester-derived compound having a sensitivity, heat resistance, chemical resistance, and sclerosing property, and a photopolymerization initiator containing the same, and a photosensitive composition containing the same. .

The present disclosure also relates to providing a molded article containing a hardened product of the photosensitive composition.

The present disclosure also relates to providing a display device comprising the molded article.
[Technical means to solve the problem]

In one aspect, the present disclosure provides an oxazolidinate derivative compound exemplified by the embodiments described below.

An example of the first embodiment relates to an oxazolidine derivative-derived compound which is represented by Chemical Formula 1 or Chemical Formula 2:
<Chemical Formula 1><Chemical 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 (C ₁ - C ₂₀ ) alkyl, (C ₆ - C ₂₀ ) aryl, (C ₁ - C ₂₀ ) alkoxy, (C ₆ - C ₂₀ ) aryl (C ₁ - C ₂₀ ) An alkyl group, a hydroxyl group (C ₁ - C ₂₀ ) alkyl group, a hydroxyl group (C ₁ - C ₂₀ ) alkoxy group (C ₁ - C ₂₀ ) alkyl group or a (C ₃ - C ₂₀ ) cycloalkyl group;
R ₃ is (C ₁ - C ₂₀ ) alkyl, (C ₆ - C ₂₀ ) aryl, (C ₆ - C ₂₀ ) aryl (C ₁ - C ₂₀ ) alkyl, (C ₃ - C ₂₀ ) ring An alkyl group or a (C ₃ - C ₂₀ ) cycloalkyl (C ₁ - C ₂₀ ) alkyl group.

An example of the second embodiment relates to an oxazolyl ester derivative compound as described in the example of the first embodiment, wherein
R ₁ and R ₄ are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl or isohexyl;
R ₂ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, n-decene Base, isodecyl, n-dodecyl, cyclopentyl, cyclohexyl, phenyl, benzyl, naphthyl, biphenyl, terphenyl, anthracenyl, fluorenyl, phenanthryl, methoxy, B Oxyl, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxy-isobutyl Base, hydroxy-n-pentyl, hydroxyisopentyl, hydroxy-n-hexyl, hydroxyisohexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethyl Oxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl;
R ₃ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, cyclopentyl, cyclohexyl Or phenyl.

An example of the third embodiment is an example of the first embodiment or an example of the second embodiment, wherein the oxazolyl ester derivative compound is selected from the compounds represented by Chemical Formulas 3-1 to 3-18. Azole ester derived compound:
<Chemical Formula 3-1 to 3-18>





.

In another aspect, the present disclosure provides a photopolymerization initiator as exemplified in the embodiments described below.

An example of the fourth embodiment relates to a photopolymerization initiator comprising the carbazolyl ester derivative compound according to any one of the examples of the first embodiment to the third embodiment.

In another aspect, the present disclosure provides a photosensitive composition of an example of the embodiment described below.

An example of the fifth embodiment relates to a photosensitive composition comprising:
(a) an alkali soluble resin;
(b) a polymerizable compound having an ethylenically unsaturated bond;
(c) A photopolymerization initiator comprising the oxazolidinate derivative compound according to any one of the examples of the first embodiment to the third embodiment.

An example of the sixth embodiment is the photosensitive composition according to the example of the fifth embodiment, wherein the content of the oxazolidine derivative-derived compound is 0.01 to 10 based on 100% by weight of the photosensitive composition. Wt%.

An example of the seventh embodiment is the photosensitive composition according to the example of the fifth embodiment or the example of the sixth embodiment, wherein the photopolymerization initiator further comprises a base of thioxanthone a compound, a monophosphonium oxide based compound, a acetophenone based compound, a biimidazole based compound, a triazine based compound, an O-mercapto oxime based compound or a monothiol base One or more of the groups consisting of the compounds are selected.

The photosensitive composition according to any one of the examples of the fifth embodiment to the seventh embodiment, wherein the photosensitive composition further comprises a coloring material.

In another aspect, the present disclosure provides a molded article of an embodiment of the embodiment described below, and a display device including the same.

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

An example of the tenth embodiment is the molded article according to the example of the ninth embodiment, wherein the molded article is an array of planarizing film, an insulating film, a color filter, a column spacer, and a black Column spacers or a black matrix.

An example of the eleventh embodiment relates to a display device comprising the molded article according to the example of the ninth embodiment or the example of the tenth embodiment.
[efficacy]

The oxazolidine derivative derivative which is an example of the embodiment of the present disclosure exhibits excellent sensitivity when used as a photopolymerization initiator of a photosensitive composition, and also exhibits excellent physical properties such as film residual ratio. , pattern stability, heat resistance, chemical resistance, softness, etc. Therefore, it is possible to reduce the contamination by minimizing the outgassing from the photopolymerization initiator during the exposure and post-baking treatment in the manufacturing process of the thin film transistor liquid crystal display (TFT-LCD), and to enable the generation thereof The defects are minimized.

Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. Before the narrative, it should be understood that the terms used in the specification and the accompanying claims should not be construed as being limited to the meaning of the general and dictionary, but should be construed as allowing the inventor to define the terms appropriately for the best explanation. The principle is based on the meaning and concept of the technical aspects of the present disclosure.

Therefore, the descriptions of the present invention are intended to be illustrative only, and are not intended to limit the scope of the disclosure, and thus it is understood that other equivalents can be made without departing from the scope of the disclosure. And modify it.

The oxazolidinate-derived compound which is one aspect of the present disclosure is as shown in Chemical Formula 1 or 2.
<Chemical Formula 1><Chemical 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 (C ₁ - C ₂₀ ) alkyl, (C ₆ - C ₂₀ ) aryl, (C ₁ - C ₂₀ ) alkoxy, (C ₆ - C ₂₀ ) aryl (C ₁ - C ₂₀ ) An alkyl group, a hydroxyl group (C ₁ - C ₂₀ ) alkyl group, a hydroxyl group (C ₁ - C ₂₀ ) alkoxy group (C ₁ - C ₂₀ ) alkyl group or a (C ₃ - C ₂₀ ) cycloalkyl group;
R ₃ is (C ₁ - C ₂₀ ) alkyl, (C ₆ - C ₂₀ ) aryl, (C ₆ - C ₂₀ ) aryl (C ₁ - C ₂₀ ) alkyl, (C ₃ - C ₂₀ ) ring An alkyl group or a (C ₃ - C ₂₀ ) cycloalkyl (C ₁ - C ₂₀ ) alkyl group.

In the present disclosure, 'alkyl', 'alkoxy' and other substituents containing 'alkyl' moieties include straight-chain or branched forms, and 'cycloalkyl' includes not only monocyclic but also polycyclic Hydrocarbyl group.

Also, in the present disclosure, 'aryl' refers to an organic radical derived from the removal of a hydrogen by an aromatic hydrocarbon and includes a monocyclic or fused ring system and a plurality of aryl groups thereof via a single bond. Connected form.

Also, in the present disclosure, 'hydroxyalkyl group' means an OH-alkyl group in which a hydroxyl group is bonded to the above alkyl group, and 'hydroxyalkoxyalkyl group' means a hydroxyalkyl-O-alkyl group, wherein The alkoxy group is bonded to a hydroxyalkyl group, and the alkenyl group means a structure containing a ketone bonded to an alkyl group or an aryl group.

Further, in the present disclosure, 'arylalkyl' may be exemplified by benzyl or the like, and 'cycloalkyl' may, for example, be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or the like, and 'cycloalkane' The alkyl group 'is exemplified by cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclopropylethyl and the like.

Further, in the present disclosure, '(C ₁ - C ₂₀ ) alkyl group' means an alkyl group having 1 to 20 carbons. The alkyl group may specifically be a (C ₁ - C ₁₀ ) alkyl group, more specifically a (C ₁ - C ₆ ) alkyl group.

'(C ₆ - C ₂₀ ) aryl' means an aryl group having 6 to 20 carbons. The aryl group may specifically be a (C ₆ - C ₁₈ ) aryl group, more specifically a (C ₆ - C ₁₂ ) aryl group.

'(C ₁ - C ₂₀ ) alkoxy' means an alkoxy group having 1 to 20 carbons. The alkoxy group may specifically be a (C ₁ - C ₁₀ ) alkoxy group, more specifically a (C ₁ - C ₄ ) alkyl group.

'(C ₆ - C ₂₀ ) aryl (C ₁ - C ₂₀ ) alkyl ' refers to an alkyl group having 1 to 20 carbons substituted with an aryl group having 6 to 20 carbons. It may specifically be (C ₆ - C ₁₈ ) aryl (C ₁ - C ₁₀ ) alkyl, more specifically (C ₆ - C ₁₈ ) aryl (C ₁ - C ₆ ) alkyl, and more particularly It is (C ₆ - C ₁₂ ) aryl (C ₁ - C ₆ ) alkyl.

'Hydroxy (C ₁ - C ₂₀ ) alkyl' means an alkyl group having 1 to 20 carbons in which a hydrogen is substituted by a hydroxyl group. It may specifically be a hydroxy (C ₁ - C ₁₀ ) alkyl group, more specifically a hydroxy (C ₁ - C ₆ ) alkyl group.

'Hydroxy(C ₁ -C ₂₀ )alkoxy(C ₁ -C ₂₀ )alkyl' means that a hydrogen is substituted by an alkoxy group having from 1 to 20 carbons and one hydrogen of the alkoxy group is via a hydroxyl group Substituting an alkyl group having 1 to 20 carbons. It may specifically be a hydroxyl (C ₁ - C ₁₀ ) alkoxy (C ₁ - C ₁₀ ) alkyl group, more specifically a hydroxyl (C ₁ - C ₄ ) alkoxy (C ₁ - C ₆ ) alkyl group.

'(C ₃ - C ₂₀ )cycloalkyl' means a cycloalkyl group having 3 to 20 carbons, and specifically may be a (C ₃ - C ₁₀ ) cycloalkyl group.

'(C ₃ -C ₂₀ )cycloalkyl(C ₁ -C ₂₀ )alkyl' means an alkyl group having 1 to 20 carbons substituted by a cycloalkyl group having 3 to 20 carbons, and It may specifically be (C ₃ - C ₁₀ ) cycloalkyl (C ₁ - C ₁₀ ) alkyl, more specifically (C ₃ - C ₆ ) cycloalkyl (C ₁ - C ₆ ) alkyl.

In the examples of the embodiments of the present disclosure, in Chemical Formulas 1 and 2,
A can be oxygen or sulfur;
R ₁ and R ₄ may each independently be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl or isohexyl. ;
R ₂ may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, positive Sulfhydryl, isodecyl, n-dodecyl, cyclopentyl, cyclohexyl, phenyl, benzyl, naphthyl, biphenyl, terphenyl, anthracenyl, fluorenyl, phenanthryl, methoxy, Ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxy Butyl, hydroxy-n-pentyl, hydroxyisopentyl, hydroxy-n-hexyl, hydroxyisohexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxy Ethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl;
R ₃ may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, cyclopentyl, ring Hexyl or phenyl.

More specifically, in Chemical Formulas 1 and 2,
A can be oxygen or sulfur;
R ₁ and R ₄ may each independently be a methyl group, an ethyl group or a n-propyl group;
R ₂ may be methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, cyclohexyl, phenyl or benzyl;
R ₃ may be methyl, ethyl, n-propyl or phenyl.

In the examples of the embodiments of the present disclosure, the oxazolyl ester derivative compound may be a compound selected from the compounds of Chemical Formulas 3-1 to 3-18, but the present disclosure is not limited to the compounds.
<Chemical Formula 3-1 to 3-18>





.

The oxazolidinate derivative compound represented by Chemical Formula 1 or Chemical Formula 2 of the present disclosure can be produced according to Reaction Formula 1 or 2, but is not limited thereto.
[Reaction formula 1]

[Reaction formula 2]

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

The photopolymerization initiator of another aspect of the present disclosure contains one or more of the oxazolidinate derivative compounds represented by Chemical Formula 1 or Chemical Formula 2.

Another aspect of the photosensitive composition of the present disclosure contains:
(a) an alkali soluble resin;
(b) a polymerizable compound having an ethylenically unsaturated bond;
(c) a photopolymerization initiator containing one or more selected from the group consisting of the oxazolidinate-derived compounds of Chemical Formula 1 or 2.

The oxazolyl ester-derived compound can be contained as a photopolymerization initiator.

The photosensitive composition of another aspect of the present disclosure has excellent ability to control pattern characteristics and excellent thin-film properties such as heat resistance and chemical resistance. Hereinafter, the components which can be contained in the photosensitive composition of this publication are mentioned in detail.

In the present disclosure, (meth)acryl fluorenyl means propylene fluorenyl and/or methacryl fluorenyl, (meth) acrylate means acrylate and/or methacrylate, and (methyl Acrylic acid means acrylic acid and/or methacrylic acid.

[(a) alkali soluble resin]
As the alkali-soluble resin, an acrylic polymer or an acrylic polymer having an unsaturated acryl bond in its side chain can be used.

The acrylic polymer refers to a polymer (including a homopolymer or a copolymer) of an acrylic monomer. Examples of the monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Hexyl ester, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, decyl (meth)acrylate, laurel (meth)acrylate Ester, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, Dicyclopentanyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-(meth)acrylate Ethoxyethyl ester, (meth)acrylic acid, itaconic acid, maleic acid, maleic anhydride, monoalkyl maleate, monostannic acid, monoalkyl fumarate, (meth)acrylic acid Glycidyl ester, 3,4-epoxybutyl (meth)acrylate, 2,3-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate Ester, 3-methyloxetane (meth)acrylate 3-methyl ester, 3-ethyloxetane-3-methyl (meth)acrylate, styrene, α-methylstyrene, ethoxylated styrene, N-methyl maleate Imine, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, (meth)acrylamide N-methyl(meth)acrylamide or the like, and these may be used singly or in combination.

Further, as an example of the acrylic polymer having an unsaturated acrylic bond in its side chain, a copolymer obtained by adding an epoxy resin to an acrylic copolymer containing a carboxylic acid; by 40 to 180 °C is an epoxy resin obtained by adding an epoxy resin to a carboxylic acid-containing acrylic copolymer obtained by copolymerization of a carboxylic acid-containing acrylic monomer and two or more monomers and a monomer. The epoxy resin is, for example, glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 2,3-epoxycyclohexyl (meth)acrylate, (methyl) 3,4-epoxycyclohexylmethyl acrylate or the like, the carboxylic acid-containing acrylic monomer is, for example, (meth)acrylic acid, itaconic acid, maleic acid, maleic acid monoalkyl ester, etc. More monomer is, for example, an alkyl (meth)acrylate such as methyl (meth)acrylate or hexyl (meth)acrylate, and the like is, for example, cyclohexyl (meth)acrylate, (A) Isobornyl acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentadiene (meth) acrylate Ester, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, styrene, α-methylstyrene, ethoxylated Styrene, N-methylmaleimide, N-ethylmaleimide, N-propyl maleimide, N-butyl maleimide, N-cyclohexylmalay Yttrium imine, (meth) acrylamide, N-methyl (meth) acrylamide, and the like.

Another example of the acrylic polymer having an unsaturated acrylic bond in its side chain can be used as follows: a copolymer obtained by adding a carboxylic acid to an acrylic copolymer containing an epoxy group; by 40 to 180 °C is obtained by adding an acrylic monomer containing a carboxylic acid to an epoxy group-containing acrylic copolymer obtained by using an epoxy group-containing acrylic monomer and two or more monomers and a monomer. The binder resin, the carboxylic acid-containing acrylic monomer is, for example, (meth)acrylic acid, itaconic acid, maleic acid, maleic acid monoalkyl ester or the like, and the epoxy group-containing acrylic monomer is, for example. Glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 2,3-epoxycyclohexyl (meth)acrylate, 3,4-cyclo(meth)acrylate Oxycyclohexyl methyl ester or the like, and the two or more monomers are, for example, alkyl (meth)acrylate such as methyl (meth)acrylate or hexyl (meth)acrylate, and the like is, for example, Cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentane (meth)acrylate , (di) butyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, styrene, Α-methylstyrene, ethoxylated styrene, N-methylmaleimide, N-ethyl maleimide, N-propyl maleimide, N-butyl Malay Yttrium imine, N-cyclohexylmaleimide, (meth) acrylamide, N-methyl (meth) acrylamide, and the like.

In an example of the embodiment of the present disclosure, in order to control the pattern characteristics and provide film properties such as heat resistance and chemical resistance, the alkali-soluble resin may be used in an amount of 3 to 50% by weight based on 100% by weight of the photosensitive composition. More specifically, it is an amount of 5 to 45 wt%, and more specifically 8 to 40 wt%.

The weight average molecular weight of the alkali-soluble resin (the average molecular weight measured by gel permeation chromatography (GPC) in terms of polystyrene) may be 2,000 to 300,000, more specifically 4,000 to 100,000, and the density may be It is 1.0 to 10.0.

[(b) Polymerizable compound having an ethylenically unsaturated bond]
The polymerizable compound having an ethylenically unsaturated bond contributes to pattern formation by cross-linking by photoreaction during pattern formation, and provides chemical resistance and heat resistance by crosslinking during heating.

The polymerizable compound having an ethylenically unsaturated bond may contain 0.001 to 40% by weight, more specifically 0.1 to 30% by weight, still more specifically 1 to 20%, based on 100% by weight of the photosensitive composition. The amount of %.

If an excessive amount of a polymerizable compound having an ethylenically unsaturated bond is added, the crosslinking density may be excessively increased to reduce the softness of the pattern.

Specifically, the polymerizable compound having an ethylenically unsaturated bond may be an alkyl (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate or butyl (meth)acrylate. , 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, etc.; glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate having 2 to 14 oxyethylene groups Ester, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups, propylene glycol di(meth)acrylic acid having 2 to 14 ethylene oxide groups Ester, trimethylolpropane di(meth)acrylate, bisphenol A diglycidyl ether acrylic acid adduct, (meth)acrylic acid β-hydroxyethyl phthalate diester, (methyl) a toluene diisocyanate adduct of β-hydroxyethyl acrylate; a compound obtained by esterification of a polyhydric alcohol with an α,β-unsaturated carboxylic acid, such as trimethylolpropane tri(meth)acrylate or pentaerythritol III ( Methyl) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol (meth) acrylate or dipentaerythritol tri (meth) acrylate; etc.; an acrylic acid adduct of a polyglycidyl compound, such as a trimethylolpropane triglycidyl ether acrylic acid adduct, etc., and the like Used alone or in combination.

[(c) Photopolymerization initiator]
The photosensitive composition of the present disclosure may use one or more of the oxazolidinate-derived compounds of Chemical Formula 1 or 2 as a photopolymerization initiator. In order to increase the transparency and minimize the exposure, the photopolymerization initiator may be used in an amount of 0.01 to 10% by weight, more specifically 0.1 to 5% by weight based on 100% by weight of the photosensitive composition.

[(d) Adhesive Additives]
If necessary, the photosensitive composition of the present disclosure may contain a compound having an epoxy group or an amine group as an adhesion aid.

The compound having an epoxy group or an amine group can improve the adhesion between the indium tin oxide (ITO) electrode and the photosensitive composition, and can enhance the heat resistance characteristics after hardening. The compound having an epoxy group or an amine group can be: (3-glycidoxypropyl)trimethoxynonane, (3-glycidoxypropyl)triethoxydecane, (3-shrinkage) Glyceroxypropyl)methyldimethoxydecane, (3-glycidoxypropyl)methyldiethoxydecane, (3-glycidoxypropyl)dimethylmethoxydecane, (3-glycidoxypropyl) dimethyl ethoxy decane, 3,4-epoxy butyl trimethoxy decane, 3,4-epoxy butyl triethoxy decane, 2-( 3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, aminepropyltrimethoxydecane, etc., and the like They can be used alone or in combination.

The compound having a ruthenium group based on 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 photosensitive composition. If the amount is less than the above range, the effect of the addition may not be achieved. Further, if it exceeds the above range, the development characteristics of the unexposed portion are reduced so that scum, residue, and the like may remain on the lower substrate, ITO, or glass substrate.

[(e) Other Additives]
If necessary, the photosensitive composition of the present disclosure may further comprise one or more compatible additives selected from the group consisting of a sensitizer, a thermal polymerization initiator, an antifoaming agent or a leveling agent. .

Other additives may be contained in an amount of 0.1 to 10% by weight based on 100% by weight of the photosensitive composition. If the amount is less than the above range, the effect of addition may not be achieved. Also, if it exceeds the above range, excessive foam may be generated.

[(f) solvent]
The photosensitive composition of the present disclosure is added to a solvent and coated on a substrate, and patterned by irradiating ultraviolet rays (UV) with a mask to develop with an alkali developing solution.

Since the content of the solvent can be controlled so that the total amount of the components of the photosensitive composition becomes 100% by weight, the content of the other components of the photosensitive composition can be variously changed. For example, the solvent may be added in an amount of 10 to 95% by weight so as to have a viscosity of 1 to 50 cps based on 100% by weight of the photosensitive composition.

As the solvent, compatibility with an alkali-soluble resin, a photopolymerization initiator or other compound may be considered, and a solvent selected from the following may be used alone or in combination: ethyl acetate, butyl acetate, and Ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, methyl methoxypropionate, ethyl ethoxy propionate (EEP), ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA) ), propylene glycol methyl ether propionate (PGMEP), propylene glycol methyl ether, propylene glycol propyl ether, methyl cyproterone acetate, ethyl cyproterone 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-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether (diglyme), tetrahydrofuran (THF), methanol, ethanol, Propanol, isopropanol, methyl cyproterone, ethyl cyproterone, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, g Alkane or octane.

[(g) Other photopolymerization initiators]
The photosensitive composition of the present disclosure may contain the above-mentioned carbazolyl ester derivative compound as a single photopolymerization initiator, and may further contain a compound based on a compound based on a thioxanthone, a monophosphonium oxide, One or more selected from the group consisting of a monoacetophenone-based compound, a biimidazole-based compound, a triazine-based compound, an O-mercapto-decyl ester-based compound, or a monothiol-based compound A variety.

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

The thioxanthone-based compound may be, for example, one or more selected from the group consisting of thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone , 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Thioxanthone, but is not limited thereto.

The mercaptophosphine oxide-based compound may be, for example, one or more selected from the group consisting of diphenyl (2,4,6-trimethylbenzylidene)phosphine oxide or phenyl double (2,4,6-trimethylbenzylidene)phosphine oxide, but is not limited thereto.

The acetophenone-based compound may be, for example, one or more selected from the group consisting of 2-methyl-1-[4-(methylthio)phenyl]-2-(N-morpholinyl) Propan-1-one, 2-benzyl-2-ylamino-1-(4-(N-morpholinyl)phenyl)butan-1-one or 2-(4-methylbenzyl 2-(dimethylamino)-1-(4-(N-morpholinyl)phenyl)butan-1-one, but is not limited thereto.

The biimidazole-based compound may be, for example, one or more selected from the group consisting of 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl- 1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole or 2,2 '-Bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, but is not limited thereto.

The triazine-based compound may be, for example, one or more selected from the group consisting of 2,4,6-gin(trichloromethyl)-s-triazine, 2-methyl-4,6- Bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methyl) Phenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-double (trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxybenzene Vinyl)-4,6-bis(trichloromethyl)-s-triazine or 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine , but not limited to this.

The O-mercaptoester based compound may be, for example, one or more selected from the group consisting of: 1,2-octanedione-1-[4-(phenylthio)phenyl]-2- (O-benzylidene hydrazine), ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-B Ethyl ketone), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-1-( O-acetinyl), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxy Benzobenzyl}-9H-carbazol-3-yl]-1-(O-ethylindenyl) (ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2) -dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime)) or 2-(ethyloxyimino)-1-(9,9'- Diethyl-9H-indol-2-yl)propan-1-one, but is not limited thereto.

The thiol-based compound may be, but is not limited to, pentaerythritol lanthanum (3-mercaptopropionate).

[(h) coloring material]
In an example of an embodiment of the present disclosure, the photosensitive composition may further comprise a coloring material which is included for application to a resist which is used to form a color filter or a black matrix.

As the coloring material, various pigments can be used. Examples include: red, green, blue, cyan, magenta, yellow, and black pigments. More specifically, for example, the following pigments: CI Pigment Yellow 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148 can be used. , 153, 154, 166 and 168; CI Pigment Oranges 36, 43, 51, 55, 59 and 61; CI Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217 , 220, 223, 224, 226, 227, 228 and 240; CI Pigment Violet 19, 23, 29, 30, 37, 40 and 50; CI Pigment Blue 15, 15:1, 15:4, 15:6, 22 60 and 64; CI Pigment Green 7 and 36; CI Pigment Brown 23, 25 and 26; CI Pigment Black 7; Titanium Black.

The coloring material may contain 5 to 50% by weight based on 100% by weight of the photosensitive composition. If the amount is less than the above range, the light shielding property may be unsatisfactory. Also, if it exceeds the above range, exposure or hardening may not be satisfactory.

In an example of an embodiment of the present disclosure, the photosensitive composition can be supplied to the substrate using known printing or impregnation means, such as a spin coater, a roll coater, a bar coater, a die coat. A cloth or curtain coater which is manufactured by the following: soda lime glass, quartz glass, semiconductor, metal, paper, plastic, and the like. Further, it can be supplied to a support such as a film and then transferred to the substrate.

In another aspect, the present disclosure provides a molded article comprising the hardened product of the above photosensitive composition.

The molded article may be an array of planarizing film, an insulating film, a color filter, a column spacer, an overcoat layer, a black column spacer or a black matrix, etc., but is not limited thereto.

In another aspect, the present disclosure provides various display devices including the molded article including a liquid crystal display, an organic light emitting diode (OLED), and the like.

Hereinafter, representative compounds of the present disclosure will be described in detail by way of examples and comparative examples to help further understanding the present disclosure. However, the examples of the embodiments of the present disclosure can be changed to various other forms and should not be construed as limiting the scope of the disclosure by the following examples. The embodiments of the present disclosure are provided to more fully explain the present disclosure to those of ordinary skill in the art.

<Preparation of oxazolidine derivative compounds>
[Production Example 1: 1-(9-(4-methoxyphenyl)-9H-indazol-3-yl]-1-propanone oxime) (O-acetate) [Chemical Formula 3-1]]

[Step 1: Synthesis of 9-(4-methoxyphenyl)-9H-carbazole]
Add triethylene glycol dimethyl ether (40 mL) to the reactor and then add carbazole (30 g, 170.5 mmol), 4-iodoanisole (49.8 g, 204.3 mmol), copper After the powder (11.34 g, 180 mmol) and potassium carbonate (58.8 g, 423.2 mmol), the mixture was stirred at 200 ° C for 20 hours. After the reaction was completed, the mixture was cooled to room temperature and crystallized by adding ethyl acetate (300 mL) and stirring for 30 minutes. After solids were obtained by filtering the solution, the solid was stirred in acetone (300 mL) and dichloromethane (300 mL), and then washed with water.

The solid obtained was discarded as an impurity, and the filtrate was distilled at 40 ° C under reduced pressure. The resulting product was precipitated by storage in a refrigerator for 1 day. Then, after adding petroleum ether (about 200 mL) and then filtering, the resulting solid was recrystallized from acetone to obtain the target compound 9-(4-methoxyphenyl)-9H-carbazole (40.7 g, 87.4%).

[Step 2: Synthesis of 1-(9-(4-methoxyphenyl)-9H-indazol-3-yl)propan-1-one]
After adding aluminum chloride (5.91 g, 43.9 mmol) to dichloromethane (200 mL), cooling to -10 ° C or lower and stirring for 10 minutes, the 9-(4-methoxy group) obtained in the step 1 was added. Phenyl)-9H-carbazole (10.0 g, 36.3 mmol), and the mixture was stirred for 30 min. After adding propionyl chloride (3.89 mL, 43.9 mmol) in dichloromethane (25 mL) dropwise dropwise for 50 min, the mixture was stirred for 30 min. After the reaction solution was added to ice water consisting of ice (490 g) and water (500 mL) and stirred for 30 minutes, the aqueous layer was removed, and the organic layer was thoroughly washed with an aqueous sodium hydrogen carbonate solution. Then, the organic layer was dried over anhydrous magnesium sulfate, filtered, and then distilled under reduced pressure to give the title compound 1-(9-(4-methoxyphenyl)-9H-indazol-3-yl)propyl- 1-ketone (11.8 g, 98.9%).

[Step 3: Synthesis of 1-(9-(4-methoxyphenyl)-9H-indazol-3-yl)-1-propanone-2-indole]
1-(9-(4-Methoxyphenyl)-9H-indazol-3-yl)propan-1-one (6.0 g, 18.2 mmol) obtained in Step 2, tetrahydrofuran (132 mL) After 35% hydrochloric acid (8.7 mL) was added to the reactor, the mixture was stirred for 30 minutes. After 30 minutes of dropwise addition of a solution of isoamyl nitrite (5.1 mL, 36.4 mmol) in tetrahydrofuran (10 mL), the mixture was stirred for 50 min. The product was then extracted with ethyl acetate and washed thoroughly with aqueous sodium bicarbonate. The organic layer after extraction was dried using anhydrous magnesium sulfate, filtered, and then distilled under reduced pressure to give a crude product. The obtained crude product was washed 3 times with dichloromethane to obtain the title compound 1-(9-(4-methoxyphenyl)-9H-indazol-3-yl)-1-propanone-2-肟 (2.03 g, 31.1%).

[Step 4: Synthesis of 1-(9-(4-methoxyphenyl)-9H-indazol-3-yl)-1-propanone oxime (O-acetate)]
1-(9-(4-Methoxyphenyl)-9H-indazol-3-yl)-1-propanone-2-indole (0.5 g, 1.4 mmol) obtained in Step 3 was added to ethyl acetate After cooling to -10 ° C or lower, triethylamine (0.39 mL, 2.8 mmol) was added dropwise, and the mixture was stirred for 10 min. Then, after adding a solution of ethyl hydrazine chloride (0.22 mL, 3.08 mmol) in ethyl acetate (1 mL) for 10 minutes, the mixture was stirred for 30 minutes. The reaction solution was extracted with dichloromethane and thoroughly washed with an aqueous sodium hydrogencarbonate solution. The organic layer after extraction was dried using anhydrous magnesium sulfate, filtered, and then distilled under reduced pressure to give the title compound 1-(9-(4-methoxyphenyl)-9H-indazol-3-yl)- 1-Acetone oxime (O-acetate) (0.53 g, 94.3%).

Decomposition point: 241.8 ° C

[Examples 2 to 12]
The oxazolidinate derivative compound described in Table 1 was synthesized under the same conditions as in Example 1.

[Table 1]

[Example 13: 2-(hydroxyimino)-1-(6-methoxy-9-(4-methoxyphenyl)-9H-indazol-3-yl)propan-1-one ( Preparation of O-acetate) [Chemical Formula 3-13]]

[Step 1: Synthesis of 3-methoxy-9H-carbazole]
Add 3-bromo-9H-carbazole (19.8 g, 78.8 mmol), copper iodide (8.0 g, 41.76 mmol), 25% sodium methoxide in methanol (750 mL), ethyl acetate (15 mL). After toluene (15 mL) was added to the reactor, the mixture was refluxed at 90 ° C for 4 days. After the reaction was completed, the reaction mixture was cooled to room temperature. Then, the reaction solution was transferred to a beaker, and after adding water (300 mL) and dichloromethane (300 mL) to a beaker, the mixture was stirred for 1 hour. The mixture solution was filtered through a 2 to 3 cm size silicone (40 to 400 sieve) filter to remove undissolved impurities. The filtrate was extracted three times with dichloromethane (300 mL), and the organic layer was dried over anhydrous magnesium sulfate, filtered, distilled under reduced pressure and then recrystallized (dichloromethane:hexane = 1:1) The title compound 3-methoxy-9H-carbazole (10.3 g, 66.4%) was obtained.

[Step 2: Synthesis of 3-methoxy-9-(4-methoxyphenyl)-9H-carbazole]
3-methoxy-9H-carbazole (3.0 g, 15.2 mmol), 4-iodoanisole (4.34 g, 17.8 mmol), copper powder (1.01 g, 15.8 mmol), carbonic acid obtained in the addition of Step 1. Potassium (5.28 g, 38 mmol) and triethylene glycol dimethyl ether (5.3 mL, 29.3 mmol) were placed in the reactor and the mixture was stirred at 200 ° C for 24 hours. After the reaction was completed, the mixture was cooled to room temperature and then stirred for 1 hour (60 mL) after the addition of dichloromethane. The reaction solution was filtered through a 2 to 3 cm size silicone (40 to 400 sieve) filter. Then, the dichloromethane and triethylene glycol dimethyl ether remaining in the filtrate were removed by distillation under reduced pressure, and then separated by a column (dichloromethane:hexane = 1:5). The title compound 3-methoxy-9-(4-methoxyphenyl)-9H-carbazole (4.05 g, 88.2%) was obtained.

[Step 3: Synthesis of 1-(6-methoxy-9-(4-methoxyphenyl)-9H-indazol-3-yl)propan-1-one]
After adding aluminum chloride (2.32 g, 17.2 mmol) to dichloromethane (40 mL), the mixture was cooled to -10 ° C or lower. After the 3-methoxy-9-(4-methoxyphenyl)-9H-carbazole (4.0 g, 13.2 mmol) obtained in Step 2 was added dropwise to dichloromethane (5 mL), The mixture was stirred for 20 minutes. After adding propional chloride (1.52 mL, 17.2 mmol) dropwise for 30 minutes, 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 the organic layer was extracted by adding dichloromethane (100 mL). The extracted organic layer was thoroughly washed with an aqueous solution of sodium hydrogencarbonate. The organic layer after extraction was dried using anhydrous magnesium sulfate, filtered, and then distilled under reduced pressure to give the title compound 1-(6-methoxy-9-(4-methoxyphenyl)-9H-carbazole. 3-yl)propan-1-one (4.5 g, 94.7%).

[Step 4: Synthesis of 2-(hydroxyimino)-1-(6-methoxy-9-(4-methoxyphenyl)-9H-indazol-3-yl)propan-1-one ]
Add 1-(6-methoxy-9-(4-methoxyphenyl)-9H-indazol-3-yl)propan-1-one (4.91 g, 13.7 mmol) obtained in Step 3 and 35 Hydrochloric acid (2.4 mL, 27.4 mmol) was added to tetrahydrofuran (40 mL) and stirred for 30 min. Then, after a solution of isoamyl nitrite (3.83 mL, 27.4 mmol) dissolved in tetrahydrofuran (8 mL) was added dropwise for 20 minutes, the mixture was stirred for 5 hours. After the reaction was completed, the organic layer was extracted by adding ethyl acetate (100 mL). The extracted organic layer was thoroughly washed with an aqueous solution of sodium hydrogencarbonate. The extracted organic layer was dried using anhydrous magnesium sulfate and then filtered. Then, after distilling under reduced pressure, the title compound (2-(hydroxyimino)-1-(6-methoxy-9) was obtained by the column (ethyl acetate:hexane = 1:1). -(4-Methoxyphenyl)-9H-indazol-3-yl)propan-1-one (1.63 g, 30.7%).

[Step 5: 2-(hydroxyimino)-1-(6-methoxy-9-(4-methoxyphenyl)-9H-indazol-3-yl)propan-1-one (O -acetate synthesis]
Addition of 2-(hydroxyimino)-1-(6-methoxy-9-(4-methoxyphenyl)-9H-indazol-3-yl)propan-1-one obtained in Step 4. (0.76 g, 1.96 mmol) to ethyl acetate (15 mL) and cooled to -10 ° C or lower. After the addition of triethylamine (0.55 mL, 3.92 mmol), the mixture was stirred for 10 min. Then, after a solution of ethyl hydrazine chloride (0.29 mL, 3.92 mmol) dissolved in ethyl acetate (2 mL) was added dropwise for 5 minutes, the mixture was stirred for 20 minutes. After completion of the reaction, the organic layer was extracted by adding dichloromethane (50 mL), and the extracted organic layer was thoroughly washed with aqueous sodium hydrogen carbonate. The organic layer after extraction was dried using anhydrous magnesium sulfate and distilled under reduced pressure to give the title compound 2-(hydroxyimino)-1-(6-methoxy-9-(4-methoxybenzene). Base 9-9-oxazol-3-yl)propan-1-one (O-acetate) (0.77 g, 91.3%).

Decomposition point: 248.3 ° C

[Examples 14 to 18]
The oxazolidinate derivative compound described in Table 2 was synthesized under the same conditions as in Example 13.

[Table 2]

<Preparation of alkali soluble resin>
[Preparation Example 1: Preparation of Acrylic Polymer (a-1)]
After adding propylene glycol methyl ether acetate (PGMEA) 200 mL and azobisisobutyronitrile (AIBN) 1.5 g to 500 mL polymerization reactor, molar ratio was added based on the solid content of the acrylic monomer. 20:20:40:20 methacrylic acid, glycidyl methacrylic acid, methyl methacrylic acid, and dicyclopentylactyl acid 40 wt%. The acrylic polymer (a-1) was prepared by carrying out polymerization by stirring the mixture at 70 ° C for 5 hours in a nitrogen atmosphere. The prepared polymer (a-1) had a weight average molecular weight of 25,000 and a density of 1.9.

[Preparation Example 2: Preparation of Acrylic Polymer (a-2)]
After adding propylene glycol methyl ether acetate 200 mL and AIBN 1.0 g to 500 mL polymerization reactor, methacrylic acid with a molar ratio of 40:20:20:20 was added based on the solid content of the acrylic monomer. , styrene, methyl methacrylic acid and cyclohexyl methacrylic acid 40 wt%. Then, the copolymer was synthesized by carrying out polymerization by stirring the mixture at 70 ° C for 5 hours in a nitrogen atmosphere. Then, after adding N,N-dimethylaniline 0.3 g and glycidyl methacrylic acid 20 mol to the reactor on the basis of 100 mol of all monomers, the mixture was prepared by stirring at 100 ° C for 10 hours. The chain has an acrylic polymer (a-2) having an unsaturated acrylic bond. The prepared acrylic polymer (a-2) had a weight average molecular weight of 20,000 and a density of 2.0.

[Preparation Example 3: Preparation of Acrylic Polymer (a-3)]
After adding propylene glycol methyl ether acetate 200 mL and AIBN 1.0 g to 500 mL polymerization reactor, a glycidyl group with a molar ratio of 40:20:20:20 was added based on the solid content of the acrylic monomer. Methacrylic acid, styrene, methyl methacrylic acid and cyclohexyl methacrylic acid 40 wt%. Then, the copolymer was synthesized by carrying out polymerization by stirring the mixture at 70 ° C for 5 hours in a nitrogen atmosphere. Then, after adding N,N-dimethylaniline 0.3 g and 20 mol of acrylic acid to the reactor on the basis of 100 mol of all monomers, the side chain was made to have unsaturated acrylic acid by stirring at 100 ° C for 10 hours. Key acrylic polymer (a-3). The prepared acrylic polymer (a-3) had a weight average molecular weight of 18,000 and a density of 1.8.

<Preparation of photosensitive composition>
[Examples 19 to 34: Preparation of photosensitive composition]
An alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator of the present disclosure, and FC-430 (a coating agent of 3M) are continuously added to the composition according to the composition described in Table 3. In a reactor having an anti-UV film and a stirrer and stirring at room temperature (23 ° C), the photosensitivity of Examples 19 to 34 was prepared by adding PGMEA as a solvent so that all components of the composition were 100 wt%. Sexual composition.

<Preparation of coloring photosensitive composition>
[Examples 35 to 36: Preparation of coloring photosensitive composition]

The coloring photosensitive composition of Example 35 was prepared in the same manner as in Example 19 except that 50 wt% of the carbon black dispersion dispersed in PGMEA as a solid component of 25 wt% was added as described in Table 3. Things. Further, the coloring sensitivity of Example 36 was prepared in the same manner as in Example 19, except that 50 wt% of the dispersion of Pigment Red 177 (PR 177) dispersed in PGMEA as a solid component of 25 wt% was added. Composition.

[Example 37]
A photosensitive composition was prepared in the same manner as in Example 19 except that the compound of Chemical Formula 4 was used together with the compound of Example 1 as a photopolymerization initiator as described in Table 3.
<Chemical Formula 4>

<component>
(a) Alkali-soluble resin: Acrylic polymers (a-1 to a-3) of Preparation Examples 1 to 3
(b) Polymerizable compound having an ethylenically unsaturated bond-b-1: dipentaerythritol hexaacrylate-b-2: dipentaerythritol pentaacrylate-b-3: pentaerythritol triacrylate-b-4: pentaerythritol trimethyl Acrylate-b-5: trimethylolpropane triacrylate-b-6: ethylene glycol diacrylate-b-7: bisphenol-A diglycidyl ether acrylic acid adduct-b-8: Trimethylolpropane triglycidyl ether acrylic acid adduct
(c) Photopolymerization initiator: the carbazole oxime derivative compound prepared in Examples 1 to 18
(e) Coating agent: FC-430 (3M company's coating agent)
(h) coloring material
H-1: carbon black (solid content 25 wt%)
H-2: Pigment Red 177 (PR 177) (solid content 25 wt%)

[table 3]

[Comparative Example 1]
A photosensitive composition was prepared in the same manner as in Example 19 except that the compound of Chemical Formula 5 was used instead of the compound of Chemical Formula 3-1 of Example 1 as a photopolymerization initiator.
<Chemical Formula 5>

[Comparative Example 2]
A photosensitive composition was prepared in the same manner as in Example 19 except that the compound of Chemical Formula 6 was used instead of the compound of Chemical Formula 3-1 of Example 1 as a photopolymerization initiator.
<Chemical Formula 6>

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

1) Sensitivity After the photoresist was spin-coated on a glass substrate and dried on a hot plate at 100 ° C for 1 minute and exposed using a step mask, development was carried out in a 0.04% KOH aqueous solution. The amount of exposure that maintains 80% of the initial thickness of the stage mask pattern is evaluated as sensitivity.

2) Film Residual Rate After the photosensitive composition was supplied onto the substrate using a spin coater, prebaking was performed at 100 ° C for 1 minute, exposure was performed at 365 nm, post-baking was performed at 230 ° C for 20 minutes, and measurement was performed. The ratio (%) of the thickness of the photoresist film before and after baking.

3) Pattern stability The silicon wafer on which the photoresist pattern is formed is cut in a direction perpendicular to the hole pattern, and is observed in the cross-sectional direction of the pattern. If the angle between the side wall of the pattern and the substrate is 55, the pattern stability is evaluated as 'good', and if the film is reduced, the pattern stability is evaluated as 'reduction'.

4) Chemical resistance The photoresist film was formed at 40 ° C in a scavenger by using a spin coater to supply a photosensitive composition onto a substrate and pre-baking and post-baking to form a photoresist film. The solution was immersed for 10 minutes, and then the difference in transmittance and thickness of the photoresist film was investigated. If the penetration rate and thickness were changed by 2% or less, the chemical resistance was evaluated as 'good', and if the transmittance and thickness were changed by more than 2%, it was evaluated as 'bad'.

5) Softness After the photosensitive composition was spin-coated on a substrate, it was prebaked at 100 ° C for 1 minute, exposed, and developed with a KOH aqueous solution to form a 20 μm × 20 μm pattern. The formed pattern was crosslinked by post-baking at 230 ° C for 20 minutes, and the softness of the pattern was measured using a nanoindenter. If the total variable is 500 nm or more under a load of 5 gf, the softness is evaluated as 'good', and if the variable is less than 500 nm, it is evaluated as 'bad'.

[Table 4]

As is apparent from Table 4, when the carbazole oxime ester-derived compound of the present disclosure is used as a photopolymerization initiator of a photosensitive composition, it exhibits remarkably excellent sensitivity and excellent physical properties such as film residue even when used in a small amount. Rate, pattern stability, chemical resistance, softness, etc. Thus, it has been confirmed that the contamination can be reduced by minimizing the outgas generated from the photopolymerization initiator during the exposure and post-baking treatment in the TFT-LCD manufacturing process, and the defects generated therefrom can be minimized.

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Claims (12)

An oxazolyl ester-derived compound which is represented by Chemical Formula 1 or Chemical Formula 2: <Chemical Formula 1><Chemical 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 (C ₁ - C ₂₀ ) alkyl, (C ₆ - C ₂₀ An aryl group, a (C ₁ - C ₂₀ ) alkoxy group, a (C ₆ - C ₂₀ ) aryl group (C ₁ - C ₂₀ ) alkyl group, a hydroxy group (C ₁ - C ₂₀ ) alkyl group, a hydroxyl group (C ₁ - C ₂₀ ) alkoxy (C ₁ - C ₂₀ ) alkyl or (C ₃ - C ₂₀ ) cycloalkyl; and R ₃ is (C ₁ - C ₂₀ ) alkyl, (C ₆ - C ₂₀ ) aryl (C ₆ - C ₂₀ ) aryl (C ₁ - C ₂₀ ) alkyl, (C ₃ - C ₂₀ ) cycloalkyl or (C ₃ - C ₂₀ ) cycloalkyl (C ₁ - C ₂₀ ) alkyl . The oxazolidine derivative-derived compound according to claim 1, wherein A is oxygen or sulfur; and R ₁ and R ₄ are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl or iso Butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl or isohexyl; R ₂ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl Base, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, n-decyl, isodecyl, n-dodecyl, cyclopentyl, cyclohexyl, phenyl, benzyl, naphthyl ,biphenyl, terphenyl, anthracenyl, fluorenyl, phenanthryl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy , hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxyisobutyl, hydroxy-n-pentyl, hydroxyisopentyl, hydroxy-n-hexyl, hydroxyisohexyl, hydroxymethoxymethyl, hydroxy Methoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethyl Oxypentyl Hydroxyethoxy hexyl group; and R ₃ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert.butyl, n-pentyl, isopentyl, n-hexyl, isohexyl , cyclopentyl, cyclohexyl or phenyl. The oxazolidine derivative-derived compound according to claim 1, wherein the oxazolidinyl ester-derived compound is one or more selected from the group consisting of the compounds represented by Chemical Formulas 3-1 to 3-18. Derivative compound: <Chemical Formula 3-1 to 3-18> . A photopolymerization initiator comprising the oxazolidinate derivative compound according to any one of claims 1 to 3. A photosensitive composition comprising: (a) an alkali soluble resin; (b) a polymerizable compound having an ethylenically unsaturated bond; (c) A photopolymerization initiator comprising the oxazolidinate derivative compound according to any one of claims 1 to 3. The photosensitive composition according to claim 5, wherein the content of the oxazolidine derivative-derived compound is 0.01 to 10% by weight based on 100% by weight of the photosensitive composition. The photosensitive composition according to claim 5, wherein the photopolymerization initiator further comprises a compound based on a thioxanthone, a compound based on a fluorenylphosphine oxide, a compound based on acetophenone, One or more selected from the group consisting of a compound of a diimidazole base, a compound of a triazine base, a compound of an O-mercaptopurinyl ester or a compound of a monothiol group. The photosensitive composition according to claim 5, wherein the photosensitive composition further comprises a coloring material. The photosensitive composition according to claim 7, wherein the photosensitive composition further comprises a coloring material. A molded article comprising the hardened product of the photosensitive composition of claim 5. The molded article of claim 10, wherein the molded article is an array of planarizing film, an insulating film, a color filter, a column spacer, an outer coating, a black column spacer or a Black matrix. A display device comprising the molded article of claim 10.