WO2020139042A2 - Carbazole multi beta oxime ester derivative compound and photopolymerization initiator and photoresist composition comprising same - Google Patents

Abstract

The present invention relates to a carbazole multi beta oxime ester derivative compound represented by chemical formula 1 and a photopolymerization initiator and a photoresist composition, each comprising same. [Chemical formula 1] In chemical formula 1, A and R ₁ to R ₃ are each defined in the detailed description of the invention.

Description

Carbazole multi beta oxime ester derivative compound and photopolymerization initiator and photoresist composition comprising the same

The present invention relates to a carbazole multi beta oxime ester derivative compound, and a photopolymerization initiator and photoresist composition comprising the same, more specifically, a carbazole multi beta oxime ester derivative compound excellent in sensitivity, heat resistance, chemical resistance and curability, and It relates to a photopolymerization initiator and a photoresist composition comprising the same.

This application claims priority based on Korean Patent Application No. 10-2018-0171703 filed on December 28, 2018, and all contents disclosed in the specification of the application are incorporated in this application.

General examples of the photopolymerization initiator used in the photoresist composition include acetophenone derivatives, benzophenone derivatives, triazine derivatives, biimidazole derivatives, acylphosphine oxide derivatives, and oxime ester derivatives. It has the advantage of absorbing ultraviolet rays, showing little color, high radical generation efficiency, and excellent compatibility and stability with photoresist composition materials. However, the initially developed oxime derivative compound has a low photo-initiation efficiency, and in particular, it has a low sensitivity in the pattern exposure process, so that the exposure amount or the amount of use must be increased, thereby reducing production. In addition, there is a problem in that outgassing occurs during hard baking due to low stability to heat.

Therefore, the development of a photopolymerization initiator with excellent light sensitivity and heat resistance can realize sufficient sensitivity even with a small amount of photopolymerization initiator, thereby reducing the cost, and due to the excellent sensitivity, the exposure amount can be lowered, thereby increasing the production amount and outgassing. The resulting contamination can be reduced.

However, in the case of forming a pattern using a conventional photopolymerization initiator, the sensitivity during the exposure process for pattern formation was low, so the amount of the photopolymerization initiator had to be increased or the exposure amount had to be increased. Due to this, the mask is contaminated in the exposure process, and the yield is lowered as a by-product generated after decomposition of the photopolymerization initiator during high temperature crosslinking. As the exposure amount increased, the exposure process time increased, resulting in a decrease in production and contamination problems due to outgassing. Therefore, efforts to solve this are still required.

[Advanced technical literature]

[Patent Document]

(Patent Document 1) International Publication Patent WO02/100903 (2002.12.19)

(Patent Document 2) Japanese Patent Publication 2005-025169 (2005.01.27)

(Patent Document 3) International Publication Patent WO07/071497 (2007.06.28)

(Patent Document 4) Korean Patent Publication 2013-0124215 (2013.11.13)

(Patent Document 5) Korean Patent Publication 2013-0115272 (2013.10.21)

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

In addition, another problem to be solved of the present invention is to provide a molded article comprising a cured product of the photoresist composition.

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

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

The first embodiment relates to a carbazole multi beta oxime ester derivative compound represented by Formula 1 below:

<Formula 1>

In Chemical Formula 1,

A is oxygen or sulfur;

R ₁ is (C1-C12)alkyl;

R ₂ and R _'2 are each independently (C1-C12) alkyl, (C6-C20) aryl, (C1-C12) alkoxy, (C6-C12) aryl (C1-C12) alkyl, hydroxy (C1-C12 )Alkyl, hydroxy(C1-C12)alkoxy(C1-C12)alkyl or (C3-C8)cycloalkyl;

R ₃ is (C1-C20)alkyl, (C6-C20)aryl, (C6-C20)aryl(C1-C20)alkyl, (C3-C20)cycloalkyl or (C3-C20)cycloalkyl(C1-C20) Alkyl.

The second embodiment, in the first embodiment,

R ₁ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, or i-hexyl;

R ₂ and R _'2 is methyl, ethyl, each independently, n- propyl, i- propyl, n- butyl, i- butyl, t- butyl, n- pentyl, i- pentyl, n- hexyl, i- hexyl, n- octyl , n-decyl, i-decyl, n-dodecyl, cyclopentyl, cyclohexyl, phenyl, benzyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl, methoxy, ethoxy, n- Propyloxy, i-propyloxy, n-butoxy, i-butoxy, t-butoxy, hydroxymethyl, hydroxyethyl, hydroxyn-propyl, hydroxyn-butyl, hydroxyi-butyl, hydroxy Hydroxyn-pentyl, hydroxyi-pentyl, hydroxyn-hexyl, hydroxyi-hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxye Methoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl;

R ₃ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl, cyclopentyl, cyclohexyl, or It relates to a phenylin carbazole multi beta oxime ester derivative compound.

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

The carbazole multi beta oxime ester derivative compound relates to a carbazole multi beta oxime ester derivative compound selected from compounds represented by the following Chemical Formulas 2-1 to 2-14.

<Formula 2-1 to 2-14>

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

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

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

The fifth embodiment,

(a) alkali-soluble resins;

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

(c) A photoresist composition containing a photopolymerization initiator comprising a carbazole multi beta oxime ester derivative compound of any one of the above-described first to third embodiments.

The sixth embodiment, in the fifth embodiment,

The photoresist composition relates to a photoresist composition containing 0.01 to 10% by weight of the carbazole multi beta oxime ester derivative compound, based on 100% by weight.

In the seventh embodiment, in the fifth or sixth embodiment,

The photopolymerization initiator, thioxanthone-based compound, acylphosphine oxide-based compound acetophenone-based compound, biimidazole-based compound, triazine-based compound, O-acyl oxime ester-based compound or thiol-based compound Or it relates to a photoresist composition further comprising two or more compounds.

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

The photoresist composition relates to a photoresist composition further comprising a color material.

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

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

The tenth embodiment is the ninth embodiment,

The molded article relates to a molded article that is an array planarization 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 comprising the molded article of the ninth or tenth embodiment.

When the carbazole multi beta oxime ester derivative compound according to an embodiment of the present invention is used as a photopolymerization initiator of a photoresist composition, it exhibits very good sensitivity, and has excellent physical properties such as residual film rate, 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 process during the LCD manufacturing process, thereby reducing contamination and thereby minimizing defects that may occur.

Hereinafter, the present invention will be described in detail. Prior to this, the terms or words used in the present specification and claims should not be construed as being limited to ordinary or lexical meanings, and the inventor appropriately explains the concept of terms to explain his or her invention in the best way. Based on the principle that it can be defined, it should be interpreted as meanings and concepts consistent with the technical spirit of the present invention.

Therefore, the configuration shown in the embodiments described herein is only one of the most preferred embodiments of the present invention and does not represent all of the technical spirit of the present invention, and various equivalents that can replace them at the time of this application It should be understood that there may be and variations.

The carbazole multi beta oxime ester derivative compound according to an aspect of the present invention is represented by the following Chemical Formula 1.

In Chemical Formula 1,

A is oxygen or sulfur;

R ₁ is (C1-C12)alkyl;

R ₂ and R _'2 are each independently (C1-C12) alkyl, (C6-C20) aryl, (C1-C12) alkoxy, (C6-C12) aryl (C1-C12) alkyl, hydroxy (C1-C12 )Alkyl, hydroxy(C1-C12)alkoxy(C1-C12)alkyl or (C3-C8)cycloalkyl;

R ₃ is (C1-C12)alkyl, (C6-C12)aryl, (C6-C12)aryl(C1-C12)alkyl, (C3-C20)cycloalkyl or (C3-C20)cycloalkyl(C1-C20) Alkyl.

Substituents containing "alkyl", "alkoxy" and other "alkyl" portions described herein include both straight-chain or pulverized forms, and "cycloalkyl" includes not only a single ring system but also a plurality of ring-based hydrocarbons. .

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

In addition, "hydroxyalkyl" described herein means OH-alkyl in which a hydroxy group is bonded to an alkyl group as defined above, and "hydroxyalkoxyalkyl" is hydroxyalkyl-O in which an alkoxy group is bonded to the hydroxyalkyl group. -Means alkyl, and alkenyl means a structure including a ketone to which an alkyl or aryl group is bonded.

Further, "arylalkyl" described herein may be exemplified by benzyl, etc., "cycloalkyl" may be exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., and "cycloalkylalkyl" may be cyclopropylmethyl. , Cyclobutyl methyl, cyclopentyl methyl, cyclopropyl ethyl, and the like,

In addition,'(C1-C12)alkyl' described herein means alkyl having 1 to 12 carbon atoms, and such alkyl may preferably be (C1-C10)alkyl, and more preferably (C1-C6). )Alkyl.

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

'(C1-C12)alkoxy' means alkoxy having 1 to 12 carbon atoms, and such alkoxy may preferably be (C1-C10)alkoxy, and more preferably (C1-C4)alkoxy.

'(C6-C12)aryl(C1-C12)alkyl' means alkyl in which one of the alkyls having 1 to 12 carbons is substituted with an aryl group having 6 to 12 carbons, preferably (C6-C10)aryl( C1-C10)alkyl, and more preferably (C6-C8)aryl(C1-C6)alkyl.

'Hydroxy(C1-C12)alkyl' means alkyl in which one hydrogen is substituted with hydroxy in alkyl having 1 to 12 carbon atoms, preferably hydroxy(C1-C10)alkyl, and more preferably Can be hydroxy(C1-C6)alkyl.

In'hydroxy(C1-C12)alkoxy(C1-C12)alkyl', one hydrogen in 1 to 12 carbon atoms is substituted with alkoxy having 1 to 12 carbon atoms, and one hydrogen in alkoxy is substituted with hydroxy. Means a structure, and may preferably be hydroxy (C1-C10) alkoxy (C1-C10) alkyl, more preferably hydroxy (C1-C4) alkoxy (C1-C6) alkyl.

'(C3-C20)cycloalkyl' means a cycloalkyl having 3 to 20 carbon atoms, preferably (C3-C10)cycloalkyl, more preferably (C3-C8)cycloalkyl, even more preferably (C3) -C6) cycloalkyl.

According to an embodiment of the present invention, in Chemical Formula 1,

A is oxygen or sulfur;

R ₁ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, or i-hexyl;

R ₂ and R _'2 are each independently methyl, ethyl, n- propyl, i- propyl, n- butyl, i- butyl, t- butyl, n- pentyl, i- pentyl, n- hexyl, i- hexyl, n-octyl, n-decyl, i-decyl, n-dodecyl, cyclopentyl, cyclohexyl, phenyl, benzyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl, methoxy, ethoxy , n-propyloxy, i-propyloxy, n-butoxy, i-butoxy, t-butoxy, hydroxymethyl, hydroxyethyl, hydroxyn-propyl, hydroxyn-butyl, hydroxyi- Butyl, hydroxyn-pentyl, hydroxyi-pentyl, hydroxyn-hexyl, hydroxyi-hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, Hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl;

R ₃ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl, cyclopentyl, cyclohexyl, or Phenyl.

More specifically, in Chemical Formula 1,

A is oxygen or sulfur;

R ₁ is methyl, ethyl, or n-propyl;

R ₂ and R _'2 are each independently methyl, ethyl, n- propyl, i- propyl, n- butyl, n- pentyl, cyclohexyl, phenyl, or benzyl;

R ₃ may be methyl, ethyl, n-propyl, or phenyl.

According to one embodiment of the present invention, the carbazole multi beta oxime ester derivative compound may include a compound selected from the group consisting of the following Chemical Formulas 2-1 to 2-14, but the following compounds limit the present invention no.

<Formula 2-1 to 2-14>

The carbazole multi beta oxime ester derivative compound represented by Formula 1 according to the present invention may be prepared as shown in Scheme 1 or Scheme 2 below, but is not limited thereto.

[Scheme 1]

[Scheme 2]

In Reaction Scheme 1 or 2, A and R ₁ to R ₃ are as defined in Chemical Formula 1, and X is halogen.

In addition, the photopolymerization initiator according to another aspect of the present invention includes at least one selected from carbazole multi beta oxime ester derivative compounds represented by Chemical Formula 1.

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

(a) alkali-soluble resins;

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

(c) a photopolymerization initiator comprising at least one selected from carbazole multi beta oxime ester derivatives of Formula 1 above.

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

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

As used herein, "(meth)acrylic" means acrylic and/or methacryl, "(meth)acrylate" means acrylate and/or methacrylate, and (meth)acrylic acid is acrylic acid and/or Means methacrylic acid.

(a) alkali-soluble resin

As the alkali-soluble resin, an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in the side chain can be used.

The acrylic polymer means a polymer of an acrylic monomer (including a homopolymer or a copolymer), and examples of such monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth) )Acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth) )Acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth) Acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate , (Meth)acrylic acid, itaconic acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester, monoalkyl itaconate, monoalkyl fumarate, glycidyl (meth)acrylate, 3,4-epoxybutyl( Meth)acrylate, 2,3-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-methyloxetane-3-methyl (meth)acrylate, 3-ethyl Oxetane-3-methyl (meth)acrylate, styrene, α-methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclo Hexyl maleimide, (meth)acrylamide, N-methyl (meth)acrylamide, etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.

In addition, the acrylic polymer having an acrylic unsaturated bond in the side chain is a copolymer in which an epoxy resin is added to an acrylic copolymer containing a carboxylic acid, (meth)acrylic acid, itaconic acid, maleic acid or maleic acid monoalkyl ester, etc. An acrylic monomer containing a carboxylic acid; Alkyl (meth)acrylates such as methyl (meth)acrylate or hexyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (Meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, styrene, α-methyl Styrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, (meth)acrylamide or N-methyl(meth)acrylic Glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 2,3-epoxycyclohexyl in an acrylic copolymer containing a carboxylic acid obtained by copolymerizing two or more monomers such as amide ( A binder resin obtained by addition reaction of an epoxy resin such as meth)acrylate or 3,4-epoxycyclohexylmethyl (meth)acrylate at a temperature of 40 to 180°C can be used.

Another example of an acrylic polymer having an acrylic 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, glycidyl (meth)acrylate, 3,4-epoxybutyl (meth) ) Acrylic monomers containing an epoxy group such as acrylate, 2,3-epoxycyclohexyl (meth)acrylate or 3,4-epoxycyclohexylmethyl (meth)acrylate; Alkyl (meth)acrylates such as methyl (meth)acrylate or hexyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (Meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, styrene, α-methyl Styrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, (meth)acrylamide or N-methyl(meth)acrylic 40 to 180° C. of acrylic monomers containing carboxylic acids such as (meth)acrylic itaconic acid, maleic acid or maleic acid monoalkyl ester in an acrylic copolymer containing an epoxy group obtained by copolymerizing two or more monomers such as amides. The binder resin obtained by addition reaction at the temperature of can be used.

According to an embodiment of the present invention, the alkali-soluble resin is 3 to 50% by weight, specifically 5 to 5% with respect to 100% by weight of the total photoresist composition in order to impart thin film properties such as control of pattern characteristics and heat resistance and chemical resistance 45% by weight, more specifically 8 to 40% by weight can be used.

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

(b) polymerizable compounds having ethylenically unsaturated bonds

The polymerizable compound having an ethylenically unsaturated bond serves to form a pattern by crosslinking by photoreaction when forming a pattern, and crosslinks upon high temperature heating to impart chemical resistance and heat resistance.

The polymerizable compound having an ethylenically unsaturated bond may be included in an amount of 0.001 to 40% by weight, preferably 0.1 to 30% by weight, and more preferably 1 to 20% by weight based on 100% by weight of the photoresist composition.

When the polymerizable compound having an ethylenically unsaturated bond is added in excess, a crosslinking degree may be excessively high, resulting in a deterioration in ductility of the pattern.

The polymerizable compound having an ethylenically unsaturated bond is specifically methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate or lauryl (meth)acrylic. Alkyl ester of (meth)acrylic acid such as rate, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate having 2 to 14 ethylene oxide groups, ethylene glycol di(meth)acrylate, ethylene oxide group Polyethylene glycol di(meth)acrylate having a number of 2 to 14, propylene glycol di(meth)acrylate having a number of propylene oxide groups of 2 to 14, trimethylolpropanedi(meth)acrylate, bisphenol A diglycidyl ether Acrylic acid adduct, phthalic acid diester of β-hydroxyethyl (meth)acrylate, toluene diisocyanate adduct of β-hydroxyethyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tree ( Meta)acrylates, polyhydric alcohols and α, such as pentaerythritol tetra(meth)acrylate, dipentaerythritolpenta(meth)acrylate, dipentaerythritolhexa(meth)acrylate, dipentaerythritol tri(meth)acrylate, and compounds obtained by esterifying β-unsaturated carboxylic acids, acrylic acid adducts of polyvalent glycidyl compounds such as trimethylolpropane triglycidyl ether acrylic acid adducts, and these can be used alone or in combination of two or more. .

(c) photopolymerization initiator

In the photoresist composition of the present invention, one or more selected from carbazole multi beta oxime ester derivatives of Formula 1 may be used as a photopolymerization initiator. In order to increase transparency and minimize exposure, the photopolymerization initiator is more effective to use 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on 100% by weight of the total photoresist composition.

(d) Adhesion aid

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

The silicone-based compound having an epoxy group or an amine group may improve adhesion between the ITO electrode and the photoresist composition, and may increase heat resistance after curing. Examples of the silicone-based compound having an epoxy group or an amine group include (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, and (3-glycidoxypropyl)methyldimethoxysilane Phosphorus, (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, 3,4-epoxybutyl Trimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrie And oxysilane or aminopropyl trimethoxysilane. These may be used alone or in combination of two or more.

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

(e) Other additives

The photoresist composition of the present invention may further include one or more compatible additives selected from a photosensitizer, a thermal polymerization inhibitor, an antifoaming agent or a leveling agent, if necessary.

The other additives may be included in an amount of 0.1 to 10% by weight based on 100% by weight of the total photoresist composition, and if it is less than the above range, the effect of the addition cannot be confirmed, and if it exceeds the above range, bubbles may be excessively generated.

(f) solvent

The photoresist composition of the present invention is coated on a substrate by adding a solvent, and then a pattern is formed through a method of irradiating ultraviolet rays using a mask to develop with an alkali developer.

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

Examples of the solvent include ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, and ethyl ethoxy pro considering compatibility with alkali-soluble resins, photopolymerization initiators, and other compounds. Cypionate (EEP), ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol methyl ether propionate (PGMEP), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cello Solve acetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2- Pyrrolidone (NMP), γ-butylolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methylcellosolve , Ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane, or a solvent selected from octane may be used alone or in combination of two or more.

(g) Other photopolymerization initiators

The photoresist composition of the present invention may also use the above-mentioned carbazole multi beta oxime ester derivative compound alone as a photopolymerization initiator, and also a thioxanthone-based compound, an acylphosphine oxide-based compound, an acetophenone-based compound, a biimidazole-based compound, Triazine-based compounds, O-acyl oxime ester-based compounds and thiol-based compounds may be used further comprising one or two or more selected from the group consisting of.

The added photopolymerization initiator may be used in an amount of 0.01 to 5% by weight based on 100% by weight of the total photoresist composition.

Examples of the thioxanthone-based compound include, for example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- Dichloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone or one or more selected from 2,4-diisopropyl thioxanthone may be used, but is not limited thereto.

Examples of the acylphosphine oxide-based compound include diphenyl (2,4,6-trimethyl benzoyl) phosphine oxide, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, or combinations thereof. It can be used, but is not limited thereto.

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

As the above-mentioned biimidazole-based compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2, 2'-bis(2,4-dichlororophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis(2,4,6-triclo Rophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole may be used, but is not limited thereto.

As the triazine-based compound, for example, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2 -[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]- 4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-tri Azine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6- Bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine or 2-(4-n-butoxyphenyl) One or more selected from -4,6-bis(trichloromethyl)-s-triazine may be used, but is not limited thereto.

Examples of the O-acyl oxime ester-based compound include 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) and ethanone-1-[9 -Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4- Tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2) -Dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime) or 2-(acetoxyimino)-1-(9,9' One or more selected from -diethyl-9H-fluor-2-yl)propan-1-one may be used, but is not limited thereto.

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

(h) Color material

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

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

The color material may be included in 5 to 50% by weight based on 100% by weight of the total photoresist composition. If it is less than the above range, the light-shielding property decreases, and if it is above the above range, exposure failure or curing failure may occur.

The photoresist composition according to an embodiment of the present invention is a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, a variety of printing, dipping, or other known means, soda glass, quartz glass, semiconductor substrate, metal, It can be applied to supporting gas phases such as paper and plastic. In addition, once carried out on a supporting base such as a film, it can be transferred onto another supporting base, and the application method is not limited.

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

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

In addition, according to another aspect of the present invention, various displays, such as a liquid crystal display device and the OLED, including the molding are provided.

Hereinafter, for a detailed understanding of the present invention, representative compounds of the present invention will be described in detail by way of Examples and Comparative Examples. The embodiments according to the present invention may be modified in various other forms, and the scope of the present invention Should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

<Production of carbazole multi beta oxime ester derivative compound>

Example 1

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

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

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

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

MS ( m/e ): 273

Step 2: Synthesis of 1,1'-(9-(4-methoxyphenyl)-carbazole-3,6-diyl)bis(propan-1-one)

Aluminum chloride (13.17 g, 98.01 mmol) was added to methylene chloride (100 ml), cooled to -10°C or lower, stirred for 10 minutes, and then 9-(4-methoxyphenyl)-9H- obtained in step 1 above. Carbazole (10.0 g, 36.3 mmol) was added and stirred for 30 minutes. A solution of propionyl chloride (8.7 ml, 98.01 mmol) dissolved in methylene chloride (25 ml) was added dropwise over 50 minutes, followed by stirring for 30 minutes. The reaction solution was placed in ice water consisting of ice (300 g) and water (300 ml), stirred for 30 minutes and then left to remove the water layer, and the organic layer was sufficiently washed with a sodium bicarbonate aqueous solution. Then, the organic layer was dried over anhydrous magnesium sulfate, filtered, and then distilled under reduced pressure to obtain the target compound, 1,1'-(9-(4-methoxyphenyl)-9H-carbazole-3,6-yl)bis(propane). -1-one) (9.7 g, 94.3%).

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 1.31 (6H, t), 3.17 (4H, q), 3.93 (3H, s), 7.15 (2H, d), 7.33 (2H, d), 7.43 (2H, d), 8.11 (2H, d), 8.85 (2H, d)

MS ( m/e ): 385

Step 3: Synthesis of 1,1'-(9-(4-methoxyphenyl)-carbazole-3,6-diyl)bis(propan-1-one)-2,2'-bisoxime

1,1'-(9-(4-methoxyphenyl)-9H-carbazole-3,6-yl)bis(propan-1-one) (6.0g, 18.2 mmol), tetra, obtained in step 2 above Hydrofuran (120 ml) and 35% concentrated hydrochloric acid (1.4 ml) were added to the reactor and stirred for 30 minutes. A solution of isopentyl nitrite (7.37 ml, 72.8 mmol) dissolved in tetrahydrofuran (40 ml) was added dropwise over 30 minutes, followed by stirring for 50 minutes. Subsequently, the reaction was extracted with ethyl acetate and washed sufficiently with an aqueous sodium bicarbonate solution. The extracted organic layer was dried using anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to obtain an impure product. The resulting impure product was washed 3 times using methylene chloride, and the product was separated by column (MC:Acetone=100:1) to obtain 1,1'-(9-(4-methoxyphenyl)-9H-carbazole as the target compound. -3,6-Diyl)bis(propan-1-one)-2,2'-bisoxime (1.81g, 26.3%) was obtained.

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 2.26 (6H, s), 3.93 (3H, s), 7.14 (2H, d), 7.32 (2H, d), 7.41 (2H, d), 8.1 (2H, d), 8.85 (2H, d)

MS ( m/e ): 443

Step 4: Synthesis of 1,1'-(9-(4-methoxyphenyl)-carbazole-3,6-diyl)bis(propan-1-one)2,2'-bisoxime (O-acetate)

1,1'-(9-(4-methoxyphenyl)-9H-carbazole-3,6-diyl)bis(propan-1-one)-2,2'-bisoxime obtained in step 3 above ( 0.5 g, 1.4 mmol) was added to ethyl acetate, cooled to -10°C or lower, and triethylamine (0.31 ml, 2.8 mmol) was added dropwise and stirred for 10 minutes. Subsequently, a solution of acetyl chloride (0.16 ml, 2.8 mmol) dissolved in ethyl acetate (1 ml) was added dropwise for 10 minutes, followed by stirring for 30 minutes. The reaction solution was extracted with methylene chloride and washed sufficiently with aqueous sodium bicarbonate solution. The extracted organic layer was dried using anhydrous magnesium sulfate, filtered, and then distilled under reduced pressure to separate the product by column (MC:Acetone 200:1) and target compound 1,1'-(9-(4-methoxyphenyl)-9H. -Carbazole-3,6-diyl)bis(propan-1-one)-2,2'-bisoxime (O-acetate) (0.16g, 28.1%) was obtained.

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 2.31 (6H, s), 2.38 (6H, s), 3.94 (3H, s), 7.15 (2H, d), 7.35 (2H, d), 7.42 (2H, d), 8.24 (2H, d), 9.00 (2H, d)

MS ( m/e ): 527

Decomposition point: 261.4℃

Example 2

Step 1: Synthesis of 9-(4-methylthiophenyl)-carbazole

Triethylene glycol dimethyl ether (40 ml) was added under a nitrogen atmosphere, and carbazole (30 g, 170.5 mmol), 4-iodothioanisole (53.8 g, 204.3 mmol), and copper in powder form (11.34 g, 180 mmol) ) And potassium carbonate (58.8 g, 423.2 mmol) were put in a reactor and reacted at reflux at 90° C. for 4 days. After the reaction was completed, it was cooled to room temperature. Subsequently, the reaction solution was transferred to a beaker and water (300 ml) and methylene chloride (300 ml) were added to the beaker, followed by stirring for 1 hour. The insoluble impurities were removed by filtering the beaker solution in a filter with a silica gel (40 to 400 mesh) having a size of 2 to 3 cm. Subsequently, the filtrate was extracted three times with methylene chloride (300 ml), and the organic layer was dried using anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to recrystallize (methylene chloride:hexane = 1:1) to obtain the target compound. 9-(4-methylthiophenyl)-carbazole (10.3 g, 66.4%) was obtained.

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 1.31 (6H, t), 3.12 (6H, q), 3.89 (3H, s), 7.13 (2H, d), 7.34 (2H, d), 7.46 (2H, d), 8.12 (2H, d) 8.88 (2H, d)

MS ( m/e ): 289

Step 2 to Step 3: Synthesis of 1-(9-(4-(methylthio)phenyl)-6-propionyl-carbazol-3-yl)pentan-1-one

Aluminum chloride (6.85 g, 49.00 mmol) was added to methylene chloride (100 ml), cooled to -10°C or lower, stirred for 10 minutes, and then 9-(4-methylthiophenyl)-carba obtained in step 1 above. Sol (10.0 g, 36.3 mmol) was added and stirred for 30 minutes. A solution in which propionyl chloride (4.47 ml, 49.00 mmol) is dissolved in methylene chloride (25 ml) is added dropwise for 50 minutes, stirred for 30 minutes, aluminum chloride (6.85 g, 49.00 mmol) is added again, stirred for 10 minutes, and then pentane. A solution in which noyl chloride (6.07 ml, 49.00 mmol) was dissolved in methylene chloride (25 ml) was added dropwise for 50 minutes and stirred for 30 minutes. The reaction solution was placed in ice water consisting of ice (300 g) and water (300 ml). After stirring for 30 minutes, the water layer was removed by standing, and the organic layer was sufficiently washed with an aqueous sodium bicarbonate solution. Then, the organic layer was dried using anhydrous magnesium sulfate, filtered, and then distilled under reduced pressure to obtain the target compound, 1-(9-(4-(methylthio)phenyl)-6-propionyl-carbazol-3-yl)pentane-1. -On (7.9 g, 72.6%) was obtained.

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 2.62 (6H, s), 3.97 (3H, s), 7.13 (2H, d), 7.35 (2H, d), 7.43 (2H, d), 7.43 (2H, d), 8.01 (2H, d), 8.8 (2H, d)

MS ( m/e ): 429

Step 4: 2-(hydroxyimino)-1-(6-(2-(hydroxyimino)propanoyl)-9-(4-(methylthio)phenyl)-carbazol-3-yl)pentane- Synthesis of 1-on

1-(9-(4-(methylthio)phenyl)-6-propionyl-carbazol-3-yl)pentan-1-one (6.0g, 18.2 mmol), tetrahydro obtained in steps 2 to 3 above Furan (120 ml) and 35% concentrated hydrochloric acid (1.4 ml) were added to the reactor and stirred for 30 minutes. A solution of isopentyl nitrite (7.37 ml, 72.8 mmol) dissolved in tetrahydrofuran (40 ml) was added dropwise over 30 minutes, followed by stirring for 50 minutes. Subsequently, the reaction was extracted with ethyl acetate and washed sufficiently with an aqueous sodium bicarbonate solution. The extracted organic layer was dried using anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to obtain an impure product. The resulting impure product was washed 3 times using methylene chloride, and the product was separated by column (MC:Acetone=100:1) to obtain 2-(hydroxyimino)-1-(6-(2-(hydroxyimino) as a target compound. )Propanoyl)-9-(4-(methylthio)phenyl)-carbazol-3-yl)pentan-1-one (1.68g, 24.8%).

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 2.26 (6H, s), 3.90 (6H, s), 7.18 (2H, d), 7.22 (2H, d), 7.46 (2H, d), 8.01 (2H, d), 8.85 (2H, d)

MS ( m/e ): 487

Step 5 2-(acetoxyimino)-1-(6-(2-(acetoxyimino)propanoyl)-9-(4-(methylthio)phenyl)-carbazol-3-yl)pentane-1 -On synthesis

2-(hydroxyimino)-1-(6-(2-(hydroxyimino)propanoyl)-9-(4-(methylthio)phenyl)-carbazol-3-yl obtained in step 4 above )Pentan-1-one (0.5 g, 1.4 mmol) was added to ethyl acetate, cooled to -10°C or lower, and triethylamine (0.31 ml, 2.8 mmol) was added dropwise and stirred for 10 minutes. Subsequently, a solution of acetyl chloride (0.16 ml, 2.8 mmol) dissolved in ethyl acetate (1 ml) was added dropwise for 10 minutes, followed by stirring for 30 minutes. The reaction solution was extracted with methylene chloride and washed sufficiently with aqueous sodium bicarbonate solution. The extracted organic layer was dried using anhydrous magnesium sulfate, filtered, and then distilled under reduced pressure to separate the product from the column (MC:Acetone 200:1) to separate the target compound, 2-(acetoxyimino)-1-(6-(2-( Acetoxyimino)propanoyl)-9-(4-(methylthio)phenyl)-carbazol-3-yl)pentan-1-one (0.15g, 26.1%) was obtained.

¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 2.31 (6H, s), 2.38 (6H, s), 3.94 (3H, s), 7.04 (2H, d), 7.33 (2H, d), 7.42 (2H, d), 9.0062H, d)

MS ( m/e ): 571

Decomposition point: 268.3℃

Examples 3 to 14

Carbazole multi beta oxime ester derivative compounds were synthesized under the same conditions as in Example 1 or 2, respectively, in the compositions shown in Tables 1 and 2 below.

Example	Chemical formula	A	R 1	R 2, R '2	R 3	1 H NMR (δ ppm; CDCl 3 )	Decomposition point
3	2-2	O	C 2 H 5	CH 3	CH 3	2.32 (6H, s), 2.38 (6H, s), 3.12 (6H, t), 3.90 (4H, q), 7.15 (2H, d), 7.35 (2H, d), 7.42 (2H, d), 8.23 (2H, d), 9.00 (2H, d)	261.1℃
4	2-3	O	CH 3	CH 3		2.42 (6H, s), 2.59 (6H, s), 3.93 (3H, s), 7.40-7.72 (16H, d), 8.19 (2H, d), 8.98 (2H, s)	267.3℃
5	2-4	O	CH 3	C 2 H 5	CH 3	2.10 (6H, t), 2.34 (6H, s), 2.37 (4H, q), 3.95 (3H, s), 7.11 (2H, d), 7.43 (2H, d), 7.52 (2H, d), 8.20 (2H, d), 8.91 (2H, d)	261.6℃
6	2-5	O	CH 3	CH 3	C 2 H 5	1.72 (6H, s), 2.38 (4H, q), 2.37 (6H, s), 3.95 (3H, s), 7.11 (2H, d), 7.42 (2H, d), 7.50 (2H, d), 8.20 (2H, d), 8.98 (2H, d)	260.7℃
7	2-6	O	CH 3		CH 3	2.31 (6H, s), 3.91 (3H, s), 7.23-7.65 (16H, m), 8.19 (2H, t), 8.99 (2H, s)	266.3℃
8	2-7	S	CH 3		CH 3	1.68-2.12 (10H, m), 2.47 (6H, s), 3.81 (6H, s), 7.46 (2H, d), 7.4 (5H, d), 8.02 (2H, d), 8.99 (2H, s)	264.3℃
9	2-8	S	C 2 H 5	CH 3	CH 3	2.30 (6H, s), 2.38 (6H, s), 3.13 (6H, t), 3.92 (4H, q), 7.15 (2H, d), 7.35 (2H, d), 7.43 (2H, d), 8.20 (2H, d), 9.02 (2H, d)	262.5℃
10	2-9	S	CH 3	CH 3		2.40 (6H, s), 2.61 (6H, s), 3.94 (3H, s), 7.38-7.72 (16H, d), 8.18 (2H, d), 8.99 (2H, s)	266.6℃
11	2-10	S	CH 3	C 2 H 5	CH 3	2.09 (6H, s), 2.33 (6H, s), 2.37 (4H, q), 3.95 (3H, s), 7.13 (2H, d), 7.34 (2H, d), 7.46 (3H, d), 8.19 (2H, d), 9.01 (1H, s)	264.6℃
12	2-11	S	CH 3	CH 3	C 2 H 5	1.74 (6H, s), 2.37 (4H, q), 2.37 (6H, s), 3.96 (3H, s), 7.11 (2H, d), 7.43 (2H, d), 7.51 (2H, d), 8.20 (2H, d), 9.00 (2H, d)	263.1℃
13	2-12	S	CH 3	C 3 H 7	CH 3	1.62 (6H, s), 2.01-2.26 (4H, m), 2.38 (6H, s), 2.72 (4H, d), 3.95 (3H, s), 7.16 (2H, d), 7.35 (2H, d) , 7.42(2H, d), 8.21(2H, d), 9.02(2H, d)	263.5℃

Example	Chemical formula	A	R 1	R 2	R '2	R 3	1 H NMR (δ ppm; CDCl 3 )	Decomposition point
14	2-13	O	CH 3	CH 3	C 3 H 7	CH 3	1.62(6H, s), 2.01-2.26(4H, m), 2.38(6H, s), 2.72(4H, d), 3.95(3H, s), 7.08(1H, dd), 7.12(2H, dd) , 7.24(1H, d), 7.31(1H, d), 7.42(2H, dd), 7.67(1H, d), 8.16(1H, dd), 8.93(1H, d)	267.3℃

<Production of alkali-soluble resin> Production Example 1: Preparation of acrylic polymer (a-1)

After adding 200 mL of propylene glycol methyl ether acetate (PGMEA) and 1.5 g of azobisisobutyronitrile (AIBN) to a 500 mL polymerization vessel, methacrylic acid, glycidyl methacrylic acid, methyl methacrylic acid and The dicyclopentanyl acrylic acid was added at a molar ratio of 20:20:40:20, respectively, and the solid content of the acrylic monomer was added at 40% by weight, and then polymerized with stirring under nitrogen atmosphere at 70°C for 5 hours to obtain the acrylic polymer (a-1). It was prepared. The prepared polymer (a-1) had a weight average molecular weight of 25,000 and a dispersion degree of 1.8.

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

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

Production Example 3: Preparation of acrylic polymer (a-3)

After adding 200 mL of propylene glycol methyl ether acetate and 1.0 g of AIBN to a 500 mL polymerization vessel, glycidylmethacrylic acid, styrene, methylmethacrylic acid, and cyclohexylmethacrylic acid were added at 40:20:20:20, respectively. After adding the solid content of the acrylic monomer in a molar ratio to 40% by weight, the polymer was synthesized by stirring under nitrogen atmosphere at 70° C. for 5 hours to polymerize. Subsequently, on the basis of 0.3 g of N,N-dimethylaniline and 100 mol of solids of the total monomers, 20 mol of acrylic acid was added, followed by stirring at 100° C. for 10 hours to obtain an acrylic polymer having an acrylic unsaturated bond in the side chain (a-3). Was prepared. The prepared acrylic polymer (a-2) had a weight average molecular weight of 18,000 and a dispersion degree of 1.9.

<Production of photoresist composition>

Examples 15 to 30: Preparation of photoresist composition

Alkali-soluble resin according to the components and contents shown in Table 3 below in the reaction mixing tank in which the sunscreen and the stirrer are installed; Polymerizable compounds having ethylenically unsaturated bonds; The photopolymerization initiator of the present invention; And FC-430 (leveling agent of 3M company) was sequentially added, stirred at room temperature (23° C.), and then PGMEA was added as a solvent so that the composition was 100% by weight, to obtain the photoresist compositions of Examples 15 to 30 . It was prepared.

<Production of colored photoresist composition>

Examples 31-32: Preparation of colored photoresist composition

As shown in Table 3, a colored photoresist composition of Example 31 was prepared in the same manner as in Example 15 , except that 50% by weight of the carbon black dispersion dispersed in PGMEA of 25% by weight of solid content was added. The colored photoresist composition of Example 32 was prepared in the same manner as in Example 15, except that 50% by weight of a dispersion of Pigment Red 177 (PR 177) dispersed in PGMEA of 25% by weight of solid content was added.

Example 33

As shown in Table 3 below, a photoresist composition was prepared in the same manner as in Example 15, except that the following Formula 3 was mixed with the compound of Example 1 as a photopolymerization initiator.

<Formula 3>

<ingredient>

(a) Alkali-soluble resin: acrylic polymers (a-1 to a-3) of Preparation 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: trimethylolpropane triglycidyl ether acrylic acid adduct

(c) Photopolymerization initiator: Carbazole multi beta oxime ester derivative compounds prepared in Examples 1 to 14

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

(h) Color material

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

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

Example	(a) Ingredient (% by weight)	(b) Ingredient (% by weight)	(c) Ingredient (% by weight)	(e) Ingredient (% by weight)	(h) Ingredient (% by weight)
15	a-1 (40)	b-1 (20)	Example 1 (0.5)	FC-430 (0.1)	-
16	a-1 (40)	b-3 (20)	Example 3 (0.5)	FC-430 (0.1)	-
17	a-1 (40)	b-5 (10) b-6 (10)	Example 4 (0.5)	FC-430 (0.1)	-
18	a-1 (40)	b-2 (20)	Example 6 (0.5)	FC-430 (0.1)	-
19	a-1 (40)	b-1 (20)	Example 8 (0.5)	FC-430 (0.1)	-
20	a-1 (40)	b-3 (20)	Example 9 (0.5)	FC-430 (0.1)	-
21	a-1 (40)	b-5 (10) b-6 (10)	Example 11 (0.5)	FC-430 (0.1)	-
22	a-1 (40)	b-1 (20)	Example 12 (0.5)	FC-430 (0.1)	-
23	a-1 (40)	b-3 (20)	Example 13 (0.5)	FC-430 (0.1)	-
24	a-1 (40)	b-5 (10) b-6 (10)	Example 14 (0.5)	FC-430 (0.1)	-
25	a-2 (40)	b-7 (20)	Example 1 (0.5)	FC-430 (0.1)	-
26	a-2 (40)	b-8 (20)	Example 6 (0.5)	FC-430 (0.1)	-
27	a-3 (40)	b-3 (20)	Example 1 (0.5)	FC-430 (0.1)	-
28	a-3 (40)	b-4 (20)	Example 5 (0.5)	FC-430 (0.1)	-
29	a-1 (20)a-2 (20)	b-1 (20)	Example 1 (0.5)	FC-430 (0.1)	-
30	a-1 (20)a-3 (20)	b-1 (20)	Example 1 (0.5)	FC-430 (0.1)	-
31	a-1 (20)	b-1 (10)	Example 1 (0.5)	FC-430 (0.1)	h-1 (50)
32	a-1 (20)	b-1 (10)	Example 1 (0.5)	FC-430 (0.1)	h-2 (50)
33	a-1 (40)	b-1 (20)	Example 1 (0.4) Formula 4 (0.1)	FC-430 (0.1)	-

Comparative Example 1

A photoresist composition was prepared in the same manner as in Example 15, except that the compound of Formula 4 below was used instead of the compound of Formula 2-1 of Example 1 as a photopolymerization initiator.

<Formula 4>

Comparative Example 2

A photoresist composition was prepared in the same manner as in Example 15, except that the compound of Formula 5 below was used instead of the compound of Formula 2-1 of Example 1 as the photopolymerization initiator.

<Formula 5>

<Evaluation of photoresist composition>

The evaluation of the photoresist compositions prepared in Examples 15 to 33 and Comparative Examples 1 to 2 was performed on a glass substrate, and the performance of the photoresist composition, such as sensitivity, residual film rate, pattern stability, chemical resistance, and ductility, was measured. The results are shown in Table 4 below.

1) Sensitivity

The 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 then developed in a 0.04% KOH aqueous solution. The exposure amount at which the step mask pattern maintains 80% thickness compared to the initial thickness was evaluated by sensitivity.

2) Residual rate

After coating the photoresist composition on a substrate with a spin coater, it is pre-baked at 100°C for 1 minute, exposed at 365 nm, and then post-baked at 230°C for 20 minutes to post-bake the resist film. The thickness ratio (%) before and after was measured.

3) Pattern stability

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

4) Chemical resistance

After applying the photoresist composition on a substrate using a spin coater, a resist film formed through processes such as prebake and postbake is soaked in a stripper solution at 40°C for 10 minutes, and then the resist film We examined whether there is a change in transmittance and thickness. If the change in transmittance and thickness was 2% or less, it was determined as'good', and if the change in transmittance and thickness was more than 2%, it was determined as'bad'.

5) Ductility

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

division		Sensitivity (mJ/cm 2 )	Residual rate (%)	Pattern stability	Chemical resistance	ductility
Example	15	85	91	Good	Good	Good
	16	85	90	Good	Good	Good
	17	100	90	Good	Good	Good
	18	85	89	Good	Good	Good
	19	92	88	Good	Good	Good
	20	90	91	Good	Good	Good
	21	85	90	Good	Good	Good
	22	85	90	Good	Good	Good
	23	100	92	Good	Good	Good
	24	85	92	Good	Good	Good
	25	95	90	Good	Good	Good
	26	80	91	Good	Good	Good
	27	80	92	Good	Good	Good
	28	90	91	Good	Good	Good
	29	80	91	Good	Good	Good
	30	80	89	Good	Good	Good
	31	95	88	Good	Good	Good
	32	90	91	Good	Good	Good
	33	95	90	Good	Good	Good
Comparative example	One	200	82	Close	Bad	Bad
	2	120	85	Close	Bad	Good

From Tables 3 and 4, the carbazole multi beta oxime ester derivative compound according to the present invention has a high thermal stability with a decomposition point of at most 240°C or higher, and is excellent in sensitivity even when used in a small amount when used as a photopolymerization initiator of a photoresist composition. It was confirmed that the physical properties such as residual film rate, pattern stability, chemical resistance and ductility are excellent. Accordingly, it was confirmed that the outgassing generated from the photopolymerization initiator in the exposure and post-baking process during the TFT-LCD manufacturing process can be minimized, thereby reducing contamination and minimizing defects that may occur.

Claims (12)

1. Carbazole multi beta oxime ester derivative compound represented by the following formula (1):

   <Formula 1>

   

   In Chemical Formula 1,

   A is oxygen or sulfur;

   R ₁ is (C1-C12)alkyl;

   R ₂ and R _'2 are each independently (C1-C12) alkyl, (C6-C20) aryl, (C1-C12) alkoxy, (C6-C12) aryl (C1-C12) alkyl, hydroxy (C1-C12 )Alkyl, hydroxy(C1-C12)alkoxy(C1-C12)alkyl or (C3-C8)cycloalkyl;

   R ₃ is (C1-C12)alkyl, (C6-C12)aryl, (C6-C12)aryl(C1-C12)alkyl, (C3-C20)cycloalkyl or (C3-C20)cycloalkyl(C1-C20) Alkyl.
2. According to claim 1,

   A is oxygen or sulfur;

   R ₁ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, or i-hexyl;

   R ₂ and R _'2 are each independently methyl, ethyl, n- propyl, i- propyl, n- butyl, i- butyl, t- butyl, n- pentyl, i- pentyl, n- hexyl, i- hexyl, n-octyl, n-decyl, i-decyl, n-dodecyl, cyclopentyl, cyclohexyl, phenyl, benzyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl, methoxy, ethoxy , n-propyloxy, i-propyloxy, n-butoxy, i-butoxy, t-butoxy, hydroxymethyl, hydroxyethyl, hydroxyn-propyl, hydroxyn-butyl, hydroxyi- Butyl, hydroxyn-pentyl, hydroxyi-pentyl, hydroxyn-hexyl, hydroxyi-hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, Hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl;

   R ₃ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl, cyclopentyl, cyclohexyl, or Phenyl phosphorus, carbazole multi beta oxime ester derivative compound.
3. According to claim 1,

   The carbazole multi beta oxime ester derivative compound is at least one selected from compounds represented by the following formulas 2-1 to 2-14, carbazole multi beta oxime ester derivative compounds.

   <Formula 2-1 to 2-14>

   

   
4. A photopolymerization initiator comprising the carbazole multi beta oxime ester derivative compound of any one of claims 1 to 3.
5. (a) alkali-soluble resins;

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

   (c) A photoresist composition comprising a photopolymerization initiator comprising the carbazole multi beta oxime ester derivative compound according to any one of claims 1 to 3.
6. The method of claim 5,

   The content of the carbazole multi beta oxime ester derivative compound is 0.01 to 10% by weight, based on 100% by weight of the total photoresist composition, photoresist composition.
7. The method of claim 5,

   The photopolymerization initiator is one type selected from the group consisting of thioxanthone compounds, acylphosphine oxide compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime ester compounds and thiol compounds Or further comprising two or more, photoresist composition.
8. The method of claim 5,

   The photoresist composition further comprises a colorant, a photoresist composition.
9. The method of claim 7,

   The photoresist composition further comprises a colorant, a photoresist composition.
10. A molded article comprising a cured product of the photoresist composition of claim 5.
11. The method of claim 10,

    The molded article is an array planarization film, an insulating film, a color filter, a column spacer, an overcoat, a black column spacer or a black matrix.
12. A display device comprising the molding of claim 10.