TW202039432A - Carbazole multi β-oxime ester derivative compounds and, photopolymerization initiator and photoresist composition containing the same - Google Patents

Abstract

The present disclosure relates to a carbazole multi [beta]-oxime ester derivative compound represented by the following Chemical Formula 1 and a photopolymerization initiator and a photoresist composition containing the same. In the above Chemical Formula 1, each of A and R1 to R3 is the same as defined in the detailed description.

Description

Carbazole poly β-oxime ester derivative compound and photopolymerization initiator and photoresist composition containing the same

The present disclosure relates to carbazole poly β-oxime ester derivative compounds and photopolymerization initiators and photoresist compositions containing them, and more specifically, relates to excellent sensitivity, heat resistance, chemical resistance and durability Sexual carbazole poly β-oxime ester derivative compound, and photopolymerization initiator and photoresist composition containing it.

Many types are known as typical examples of photopolymerization initiators used in photoresist compositions, such as acetophenone derivatives, benzophenone derivatives, triazine derivatives, biimidazole derivatives, and Phosphine oxide derivatives and oxime ester derivatives, and among them, the advantages of the oxime ester derivatives are that they absorb ultraviolet light almost colorlessly, and have high free radical generation efficiency, good compatibility with the photoresist composition material, and Excellent stability. However, the early developed oxime derivative compounds have low photoinitiation efficiency, and in particular, due to the low sensitivity in the pattern exposure process, they need to increase the exposure dose or amount, resulting in a decrease in yield. In addition, due to the low thermal stability, outgassing may occur during the hard baking process.

Therefore, the development of a photopolymerization initiator with high photosensitivity and heat resistance allows sufficient sensitivity to be obtained with a small amount of photopolymerization initiator, resulting in cost-saving effects, and due to the high sensitivity, the exposure dose is reduced, thereby increasing yield and reducing Pollution caused by outgassing.

However, when a conventional photopolymerization initiator is used to form a pattern, it is necessary to increase the amount of the photopolymerization initiator or the exposure dose due to the low sensitivity in the exposure process used for pattern formation. The disadvantages are that the photomask is contaminated during the exposure process, and the by-products generated after the decomposition of the photopolymerization initiator during the crosslinking process at high temperature reduce the yield. As the exposure process time increases with the increase in exposure dose and the pollution caused by outgassing, the problem of reduced production has occurred. Therefore, efforts are still needed to solve these problems. [Prior Technical Literature] (Patent Document)

Patent Document 1: International Publication WO02/100903 (2002.12.19). Patent Document 2: Japanese Patent Laid-Open No. 2005-025169 (2005.01.27). Patent Document 3: International Publication WO07/071497 (2007.06.28). Patent Document 4: Korean Publication No. 2013-0124215 (2013.11.13). Patent Document 5: Korean Publication No. 2013-0115272 (2013.10.21).

[The problem to be solved by the invention]

The present disclosure aims to provide a carbazole poly β-oxime ester derivative compound with excellent sensitivity, heat resistance, chemical resistance and durability, and a photopolymerization initiator and photoresist composition containing the same.

The present disclosure further aims to provide a molded product containing a cured product of the photoresist composition.

The present disclosure further aims to provide a display device including a molded product. [Technical means to solve the problem]

In order to achieve the above object, according to one aspect of the present disclosure, a carbazole poly β-oxime ester derivative compound according to the following exemplary embodiment is provided.

在以上化學式1中， A為氧或硫； R₁ 為(C1-C12)烷基； R₂ 及R'₂ 各自獨立地為(C1-C12)烷基、(C6-C20)芳基、(C1-C12)烷氧基、(C6-C12)芳基(C1-C12)烷基、羥基(C1-C12)烷基、羥基(C1-C12)烷氧基(C1-C12)烷基或(C3-C8)環烷基；及 R₃ 為(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C3-C20)環烷基或(C3-C20)環烷基(C1-C20)烷基。The first exemplary embodiment relates to a carbazole poly β-oxime ester derivative compound represented by the following chemical formula 1: >Chemical formula 1>

In the above Chemical Formula 1, A is oxygen or sulfur; R ₁ is a (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; and R ₃ is (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) aryl (C1-C20) alkyl, (C3-C20) cycloalkane Group or (C3-C20)cycloalkyl(C1-C20)alkyl.

The second exemplary embodiment relates to the carbazole poly β-oxime ester derivative compound according to the first exemplary embodiment, wherein R ₁ is methyl, ethyl, n-propyl, isopropyl, n-butyl, iso butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl or isohexyl group; R ₂ and R _'2 are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, tertiary butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, n-decyl, isodecyl, n-dodecyl, cyclopentyl, cyclohexyl, phenyl , Benzyl, naphthyl, biphenyl, terphenyl, anthracenyl, indenyl, phenanthryl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy Group, tertiary butoxy, hydroxymethyl, hydroxyethyl, hydroxyn-propyl, hydroxyn-butyl, hydroxyisobutyl, hydroxyn-pentyl, hydroxyisopentyl, hydroxyn-hexyl, hydroxyisohexyl, hydroxy Methoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethyl Oxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl; and R ₃ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n Pentyl, isopentyl, n-hexyl, isohexyl, cyclopentyl, cyclohexyl, or phenyl.

The third exemplary embodiment relates to the carbazole poly β-oxime ester derivative compound according to the first exemplary embodiment or the second exemplary embodiment, wherein the carbazole poly β-oxime ester derivative compound is selected from the following chemical formula 2 Compounds represented by -1 to 2-14. >Chemical formulas 2-1 to 2-14>

According to another aspect of the present disclosure, a photopolymerization initiator according to the following exemplary embodiment is provided.

The fourth exemplary embodiment relates to a photopolymerization initiator including the carbazole poly β-oxime ester derivative compound according to any one of the first exemplary embodiment to the third exemplary embodiment.

According to another aspect of the present disclosure, a photoresist composition according to the following exemplary embodiments is provided.

The fifth exemplary embodiment relates to a photoresist composition, including: (a) Alkali-soluble resin; (b) Polymerizable compounds with ethylenically unsaturated bonds; and (c) A photopolymerization initiator comprising the carbazole poly β-oxime ester derivative compound according to any one of the first exemplary embodiment to the third exemplary embodiment.

The sixth exemplary embodiment relates to the photoresist composition according to the fifth exemplary embodiment, wherein based on 100% by weight of the photoresist composition, the carbazole poly β-oxime ester derivative compound is 0.01 to 10% by weight The amount exists.

The seventh exemplary embodiment relates to the photoresist composition according to the fifth exemplary embodiment or the sixth exemplary embodiment, wherein the photopolymerization initiator further includes at least one selected from the group consisting of: Thioxanthone-based compounds, thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, O-acetoxime ester-based compounds, and thiol-based compounds .

The eighth exemplary embodiment relates to the photoresist composition according to any one of the fifth exemplary embodiment to the seventh exemplary embodiment, wherein the photoresist composition further includes a colorant.

According to another aspect of the present disclosure, a molded product and a display device including the same according to the following exemplary embodiments are provided.

The ninth exemplary embodiment relates to a molded product including a cured product of the photoresist composition according to any one of the fifth exemplary embodiment to the eighth exemplary embodiment.

The tenth exemplary embodiment relates to a molded product according to the ninth exemplary embodiment, wherein the molded product is an array planarization film, an insulating film, a color filter, a columnar spacer, a black columnar spacer, or a black matrix .

The eleventh exemplary embodiment relates to a display device including a molded product according to the ninth exemplary embodiment or the tenth exemplary embodiment. [Effect of Invention]

When the carbazole poly β-oxime ester derivative compound according to the embodiment of the present disclosure is used as the photopolymerization initiator of the photoresist composition, it has very good sensitivity and has excellent properties, such as the ratio of remaining film thickness), pattern stability, heat resistance, chemical resistance, and ductility. Therefore, they are used in the exposure and post-baking process of manufacturing thin film transistor liquid crystal display (TFT-LCD). Minimize the outgassing produced by the photopolymerization initiator, thereby reducing pollution and minimizing possible defects.

Hereinafter, the present disclosure will be described in detail. Before the description, it should be understood that the terms or words used in the specification and the appended patent scope should not be interpreted as limited to the general meaning and dictionary meaning, but should be interpreted to allow the inventor to properly define the terms to achieve the best The principle of interpretation is based on the meaning and concepts corresponding to the technical aspects of this disclosure.

Therefore, the context disclosed in the embodiments described herein is only the best embodiment, and does not fully describe all the technical aspects of this disclosure. Therefore, it should be understood that many other equivalent forms can be made when submitting this application. And deformation.

According to one aspect of the present disclosure, the carbazole poly β-oxime ester derivative compound is represented by the following chemical formula 1. >Chemical formula 1>

In the above Chemical Formula 1, A is oxygen or sulfur; R ₁ is a (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; and R ₃ is (C1-C12) alkyl, (C6-C12) aryl, (C6-C12) aryl (C1-C12) alkyl, (C3-C20) cycloalkane Group or (C3-C20)cycloalkyl(C1-C20)alkyl.

In the present disclosure, "alkyl", "alkoxy" and other substituents containing "alkyl" moieties include linear and branched forms, and "cycloalkyl" includes not only monocyclic hydrocarbons but also polycyclic hydrocarbons .

In addition, "aryl" as used herein refers to a radical derived from an aromatic hydrocarbon by removing one hydrogen, and includes a single ring or fused ring system, and even multiple aryl groups connected by a single bond.

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

In addition, "arylalkyl" used herein may include, for example, benzyl, "cycloalkyl" may include, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, and "cycloalkylalkyl" may include For example, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl and cyclopropylethyl.

In addition, "(C1-C12)alkyl" as used herein refers to an alkyl group having 1 to 12 carbon atoms, and the alkyl group may preferably be a (C1-C10) alkyl group, more preferably (C1-C6) alkyl.

The "(C6-C20) aryl group" refers to an aryl group having 6 to 20 carbon atoms, and the aryl group may preferably be a (C6-C18) aryl group, more preferably a (C6-C12) aryl group.

"(C1-C12)alkoxy" refers to an alkoxy group having 1 to 12 carbon atoms, and the alkoxy group may preferably be (C1-C10)alkoxy, more preferably (C1-C4)alkyl Oxy.

"(C6-C12)aryl(C1-C12)alkyl" refers to an alkyl group having 1 to 12 carbon atoms and one hydrogen substituted by an aryl group having 6 to 12 carbon atoms, and may preferably be ( C6-C10) aryl(C1-C10)alkyl, more preferably (C6-C8)aryl(C1-C6)alkyl.

"Hydroxy (C1-C12) alkyl" refers to an alkyl group having 1 to 12 carbon atoms and one hydrogen is substituted by a hydroxy group, and may preferably be a hydroxy (C1-C10) alkyl group, more preferably a hydroxy (C1-C10) alkyl group. C6) Alkyl.

"Hydroxy (C1-C12) alkoxy (C1-C12) alkyl" means having 1 to 12 carbon atoms, one hydrogen is substituted by an alkoxy group having 1 to 12 carbon atoms, and one hydrogen of the alkoxy group The alkyl group substituted by a hydroxy group may preferably be a hydroxy(C1-C10)alkoxy(C1-C10)alkyl group, more preferably a hydroxy(C1-C4)alkoxy(C1-C6)alkyl group.

"(C3-C20)cycloalkyl" refers to a cycloalkyl group having 3 to 20 carbon atoms, and may preferably be (C3-C10)cycloalkyl, more preferably (C3-C8)cycloalkyl, Even more preferred is (C3-C6)cycloalkyl.

According to an exemplary embodiment of the present disclosure, in the above chemical formula 1, A may be oxygen or sulfur; R ₁ may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, third butyl, n-pentyl, isopentyl, n-hexyl or isohexyl group; R ₂ and R _'2 are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Tertiary butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, n-decyl, isodecyl, n-dodecyl, cyclopentyl, cyclohexyl, phenyl, benzyl, Naphthyl, biphenyl, terphenyl, anthracenyl, indenyl, phenanthryl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, third Butoxy, hydroxymethyl, hydroxyethyl, hydroxyn-propyl, hydroxyn-butyl, hydroxyisobutyl, hydroxyn-pentyl, hydroxyisopentyl, hydroxyn-hexyl, hydroxyisohexyl, hydroxymethoxymethyl Group, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl , Hydroxyethoxypentyl or hydroxyethoxyhexyl; and R ₃ can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, Isopentyl, n-hexyl, isohexyl, cyclopentyl, cyclohexyl, or phenyl.

More specifically, in the above Chemical Formula 1, A may be an oxygen or sulfur; R ₁ may be methyl, ethyl or n-propyl; R ₂ and R _'2 are each independently methyl, ethyl, n Propyl, isopropyl, n-butyl, n-pentyl, cyclohexyl, phenyl or benzyl; and R ₃ can be methyl, ethyl, n-propyl or phenyl.

According to an exemplary embodiment of the present disclosure, the carbazole poly β-oxime ester derivative compound may be selected from the group consisting of the following chemical formulas 2-1 to 2-14, but the following compounds do not limit the present disclosure. >Chemical formulas 2-1 to 2-14>

[反應式2]

The carbazole poly β-oxime ester derivative compound represented by the above Chemical Formula 1 according to the present disclosure can be prepared as shown in the following Reaction Formula 1 or 2, but is not limited thereto. [Reaction formula 1]

[Reaction formula 2]

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

In addition, the photopolymerization initiator according to another aspect of the present disclosure includes at least one selected from the carbazole poly β-oxime ester derivative compounds represented by Chemical Formula 1 above.

In addition, the photoresist composition according to another aspect of the present disclosure includes: (a) Alkali-soluble resin; (b) Polymerizable compounds with ethylenically unsaturated bonds; and (c) The photopolymerization initiator includes at least one selected from the carbazole poly β-oxime ester derivative compounds of the above chemical formula 1.

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

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

As used herein, "(meth)acryloyl" refers to acryloyl and/or methacryloyl, "(meth)acrylate" refers to acrylate and/or methacrylate, and (former Base) acrylic refers to acrylic and/or methacrylic. (a) Alkali-soluble resin

The alkali-soluble resin may include an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond on the side chain.

Acrylic polymers refer to polymers of acrylic monomers (including homopolymers or copolymers), and examples of monomers may include methyl (meth)acrylate, ethyl (meth)acrylate, acrylic (meth)acrylate Ester, 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, (meth) ) Cetyl acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, (meth) Base) benzyl acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, (meth)acrylic acid, itaconic acid, maleic acid, maleic anhydride, Monoalkyl maleate, monoalkyl fumarate, monoalkyl fumarate, glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (methyl) ) 2,3-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, 3-methyloxo-3-methyl (meth)acrylate, (meth)acrylic acid 3-ethyloxo-3-methyl ester, styrene, α-methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N -Propyl maleimide, N-butyl maleimide, N-cyclohexyl maleimide, (meth)acrylamide and N-methyl (meth)acrylamide, this Such monomers can be used alone or in combination.

In addition, the acrylic polymer with acrylic unsaturated bond on the side chain is a copolymer formed by the addition reaction of an epoxy resin and an acrylic copolymer containing a carboxylic acid, and it can be used at a temperature of 40 to 180ºC. Adhesive resin obtained by addition reaction of epoxy resin and acrylic copolymer containing carboxylic acid, such as glycidyl (meth)acrylate and 3,4-epoxybutyl (meth)acrylate , 2,3-epoxycyclohexyl (meth)acrylate or 3,4-epoxycyclohexyl (meth)acrylate, the carboxylic acid-containing acrylic copolymer is based on at least two of the following monomers Obtained by copolymerization of carboxylic acid monomers, such as (meth)acrylic acid, itaconic acid, maleic acid or maleic acid monoalkyl esters, and monomers, such as (meth)acrylic acid alkyl esters, Such as methyl (meth)acrylate or hexyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, (meth)acrylic acid Dicyclopentyl ester, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, Styrene, α-methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butyl N-methylmaleimide, N-cyclohexylmaleimide, (meth)acrylamide, or N-methyl(meth)acrylamide.

Another example of an acrylic polymer having an acrylic unsaturated bond on the side chain is a copolymer formed by the addition reaction of a carboxylic acid and an epoxy-containing acrylic copolymer, and can be included at a temperature of 40 to 180ºC The following is a binder resin obtained by the addition reaction of an acrylic monomer containing a carboxylic acid and an acrylic copolymer containing an epoxy group. The acrylic monomer containing carboxylic acid such as (meth)acrylic acid, itaconic acid, horse Acrylic acid or maleic acid monoalkyl ester, the epoxy-containing acrylic copolymer is obtained by copolymerization of at least two of the following monomers: epoxy-containing acrylic monomers, such as (methyl) Glycidyl acrylate, 3,4-epoxybutyl (meth)acrylate, 2,3-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, And monomers, such as alkyl (meth)acrylate, such as methyl (meth)acrylate or hexyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, ( Adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate , 2-ethoxyethyl (meth)acrylate, styrene, α-methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide , N-propyl maleimide, N-butyl maleimide, N-cyclohexyl maleimide, (meth)acrylamide or N-methyl(meth)acrylamide .

According to the exemplary embodiment of the present disclosure, based on 100% by weight of the photoresist composition, the alkali-soluble resin may be present in an amount of 3 to 50% by weight, specifically 5 to 45% by weight, more specifically 8 to 40% by weight, Adjust the pattern characteristics and give the film characteristics such as heat resistance and chemical resistance.

The weight average molecular weight of the alkali-soluble resin (the molecular weight of polystyrene calculated by gel permeation chromatography (GPC)) can be 2,000 to 300,000, preferably 4,000 to 100,000, and the dispersion is 1.0 to 10.0 . (b) Polymerizable compounds with ethylenically unsaturated bonds

The polymerizable compound having an ethylenically unsaturated bond is cross-linked by photoreaction when forming a pattern and helps to form a pattern, and is cross-linked when heated at a high temperature to impart chemical resistance and heat resistance.

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

When the polymerizable compound having an ethylenically unsaturated bond is present in excess, the disadvantage is that the degree of crosslinking is excessively increased and the ductility of the pattern decreases.

Specifically, the polymerizable compound having an ethylenically unsaturated bond may include alkyl methacrylate, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethyl methacrylate Base hexyl ester or lauryl methacrylate, glycidyl methacrylate, polyethylene glycol monomethacrylate with 2 to 14 ethylene oxide groups, ethylene glycol dimethacrylate, with 2 Polyethylene glycol dimethacrylate with up to 14 ethylene oxide groups, propylene glycol dimethacrylate with 2 to 14 propylene oxide groups, trimethylolpropane dimethacrylate, double Phenol A diglycidyl ether acrylic acid adduct, phthalic acid diester of β-hydroxyethyl methacrylate, toluene diisocyanate adduct of β-hydroxyethyl methacrylate, by polyol and α, β- Compounds obtained by the esterification reaction of unsaturated carboxylic acids such as trimethylolpropane trimethacrylate, neopentaerythritol trimethacrylate, neopentaerythritol tetramethacrylate, dineopentylerythritol five Methacrylate, dineopentaerythritol hexamethacrylate and dineopentaerythritol trimethacrylate, and acrylic acid adducts of polyglycidyl compounds, such as trimethylolpropane triglycidyl ether acrylic acid Adducts and these polymerizable compounds can be used alone or in combination. (c) Photopolymerization initiator

The photoresist composition of the present disclosure can use at least one selected from the carbazole poly β-oxime ester derivative compounds of the above Chemical Formula 1 as a photopolymerization initiator. Based on 100% by weight of the photoresist composition, it is more effective for the photopolymerization initiator to be present in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, to increase transparency and minimize exposure. (d) Adhesive additives

In addition, if necessary, the photoresist composition of the present disclosure may further include a silicone-based compound having an epoxy group or an amine group as an adhesion assistant.

Silicone-based compounds with epoxy or amine groups can improve the adhesion between the ITO electrode and the photoresist composition, and can improve the heat resistance after curing. Silicone-based compounds with epoxy or amino groups may include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3 -Glycidyloxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethyl Methoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane , 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane or aminopropyltrimethoxysilane, etc. The compounds can be used alone or in combination.

Based on 100% by weight of the photoresist composition, the silicone-based compound having an epoxy group or an amine group may be present in an amount of 0.0001 to 3% by weight. When the content is less than this range, no effect of addition is found, and when the content exceeds this range, the exposure characteristics of the unexposed area will be reduced, leaving scum and residue on the lower substrate, ITO or glass substrate. (e) Other additives

If necessary, the photoresist composition of the present disclosure may further include at least one compatible additive selected from a photosensitizer, a thermal polymerization inhibitor, a defoamer, or a leveling agent.

Based on 100% by weight of the photoresist composition, other additives can be present in an amount of 0.1 to 10% by weight, and when the content is less than this range, no effect of addition is found, and when the content exceeds this range, excessive scum may be formed . (f) Solvent

The photoresist composition of the present disclosure is used to form a pattern by the following methods: adding a solvent, coating on a substrate, irradiating ultraviolet rays with a photomask, and developing with an alkaline developer.

Therefore, the content of the solvent can be adjusted so that the sum of the content of the solvent and the content of other components of the photoresist composition is 100% by weight, and therefore, the content of the solvent can be different based on the content of other components of the photoresist composition To change. For example, preferably, the solvent content is adjusted by adding a solvent in an amount of 10 to 95% by weight based on 100% by weight of the photoresist composition, so that the viscosity is in the range of 1 to 50 cps.

In consideration of compatibility with alkali-soluble resins, photopolymerization initiators or other compounds, the solvent may be at least one selected from the group consisting of ethyl acetate, butyl acetate, diglyme, and diethylene glycol Dimethyl ethyl ether, methyl methoxypropionate, ethyl ethoxypropionate (EEP), ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol methyl Propylene glycol methyl ether propionate (PGMEP), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, diethylene glycol Alcohol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N,N-dimethylacetamide (DMAc) ), N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (tetrahydrofuran) , THF), methanol, ethanol, propanol, isopropanol, methoxaloxol, oxaloxol, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexyl Alkane, heptane or octane. (g) Other photopolymerization initiators

The photoresist composition of the present disclosure may include the above-mentioned carbazole poly β-oxime ester derivative compound as the sole photopolymerization initiator, and may further include at least one selected from the group consisting of: thio-based Anthrone compounds, compounds based on phosphine oxides, compounds based on acetophenone, compounds based on biimidazole, compounds based on triazine, compounds based on O-oxime ester, and compounds based on thiol.

Based on 100% by weight of the photoresist composition, the additional photopolymerization initiator may be present in an amount of 0.01 to 5% by weight.

The thioxanthone-based compound may include, for example, at least one selected from the group consisting of thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone , 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone or 2,4- Diisopropyl thioxanthone, but not limited to this.

Compounds based on phosphine oxides may include, for example, diphenyl(2,4,6-trimethylbenzyl) phosphine oxide, phenyl bis(2,4,6-trimethylbenzyl) oxide Phosphine or a combination thereof, but not limited thereto.

The acetophenone-based compound may include, for example, at least one selected from the group consisting of 2-methyl-1-[4-(methylthio)phenyl]-2-(N-morpholinyl)propane-1- Ketone, 2-benzyl-2-dimethylamino-1-(4-(N-morpholinyl)phenyl)butan-1-one or 2-(4-methylbenzyl)-2-( Dimethylamino)-1-(4-(N-morpholinyl)phenyl)butan-1-one, but not limited thereto.

The biimidazole-based compound may include, for example, at least one 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 not limited thereto.

The triazine-based compound may include, for example, at least one selected from the group consisting of 2,4,6-ginseng(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl) Yl)-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-methylphenyl)ethylene Yl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl) Yl)-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)-4,6-bis(trichloromethyl)-s-triazine, but not limited to this.

The O-acetoxime ester-based compound may include, for example, at least one selected from the group consisting of: 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzyl Oxime), ethyl ketone-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetoxime), ethyl ketone -1-[9-Ethyl-6-(2-Methyl-4-tetrahydrofurylmethoxybenzyl)-9H-carbazol-3-yl]-1-(O-acetoxime), Ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzyl}-9H -Carbazol-3-yl)-1-(O-acetoxime) or 2-(acetoxyimino)-1-(9,9'-diethyl-9H-fluoro-2-yl ) Propan-1-one, but not limited to this.

The thiol-based compound may include neopentylerythritol 4 (3-mercaptopropionate) and the like, but is not limited thereto. (h) Coloring agent

The photoresist composition according to the exemplary embodiment of the present disclosure may further include a coloring agent for photoresist applications, and the coloring agent is used to form a color filter or a black matrix.

The colorant may include various pigments, such as red, green, blue, cyan, magenta, yellow and black pigments, more specifically, CI Pigment Yellow 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148, 153, 154, 166 and 168, CI Pigment Orange 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, and Titanium Black.

Based on 100% by weight of the photoresist composition, the colorant may be present in an amount of 5 to 50% by weight. When the content is less than this range, the light-shielding effect is reduced, and when the content exceeds this range, exposure or curing may be unsatisfactory.

The photoresist composition according to the exemplary embodiment of the present disclosure can be applied to soda lime glass, quartz by spin coater, roll coater, bar coater, die coater, curtain coater, and various known printing and deposition methods. Support substrate for glass, semiconductor substrate, metal, paper and plastic. In addition, a film may be formed on a supporting substrate and then transferred to another supporting substrate, and there is no limitation on the method of applying it.

According to another aspect of the present disclosure, a molded product containing the cured product of the above-mentioned photoresist composition is provided.

The molded product may include an array planarization film, an insulating film, a color filter, a columnar spacer, a protective film, a black columnar spacer, or a black matrix, but is not limited thereto.

In addition, according to another aspect of the present disclosure, various types of displays including molded products, such as liquid crystal display devices and OLEDs, are provided.

步驟1：9-(4-甲氧基苯基)咔唑之合成Hereinafter, in order to fully understand the purpose of the present disclosure, the representative compounds of the present disclosure will be described in detail with examples and comparative examples, and the embodiments according to the present disclosure can be modified in many other forms, and the scope of the present disclosure should not be interpreted as Limited to the examples mentioned below. The embodiments of the disclosure are provided to fully and completely explain the disclosure to those skilled in the art. >Preparation of carbazole poly β-oxime ester derivatives> Example 1

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

Place triglyme (40 mL) in the reactor, and add carbazole (30 g, 170.5 mmol), 4-iodoanisole (49.8 g, 204.3 mmol), and powdered copper (11.34) to it. g, 180 mmol) and potassium carbonate (58.8 g, 423.2 mmol), and then stirred at 200ºC for 20 hours. After the completion of the reaction, the mixture was cooled to room temperature and stirred for 30 minutes with the addition of ethyl acetate (300 mL) for crystallization. The solid obtained by filtering the solution was stirred in acetone (300 mL) and dichloromethane (300 mL) for 30 minutes, filtered and washed with water.

Remove the obtained solids or impurities to obtain the filtrate, and distill off the organic solvent in the filtrate under reduced pressure at 40ºC. The resultant product was refrigerated for one day to precipitate the product. Subsequently, petroleum ether (about 200 mL) was added, filtered, and the obtained solid was recrystallized using acetone to obtain the target compound 9-(4-methoxyphenyl)-9H-carbazole (40.7 g, 87.4%). ¹ H NMR (δ ppm, CDCl ₃ , 500 MHz): 3.93 (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)

Add aluminum chloride (13.17 g, 98.01 mmol) to dichloromethane (100 mL), cool to -10 ºC or lower, stir for 10 minutes, and then add the 9-(4-methoxy group) obtained in step 1 Phenyl)-9H-carbazole (10.0 g, 36.3 mmol) was added and stirred for 30 minutes. A solution of propyl chloride (8.7 mL, 98.01 mmol) in dichloromethane (25 mL) was added dropwise for 50 minutes and stirred for 30 minutes. The reaction solution was added to ice water containing ice (300 g) and water (300 mL) and stirred for 30 minutes, and after allowing to stand still, the water layer was removed and the organic layer was thoroughly washed with sodium bicarbonate aqueous solution. Subsequently, the organic layer was dried with anhydrous magnesium sulfate, filtered and 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: 1,1'-(9-(4-methoxyphenyl)-carbazole Synthesis of -3,6-diyl)bis(propan-1-one)-2,2'-bisoxime

The 1,1'-(9-(4-methoxyphenyl)-9H-carbazole-3,6-yl)bis(propan-1-one) obtained in step 2 (6.0 g, 18.2 mmol) , Tetrahydrofuran (120 mL) and 35% hydrochloric acid (1.4 mL) were placed in the reactor and stirred for 30 minutes. A solution of isoamyl nitrite (7.37 mL, 72.8 mmol) in tetrahydrofuran (40 mL) was added dropwise for 30 minutes and stirred for 50 minutes. Subsequently, the product was extracted with ethyl acetate, and washed thoroughly with an aqueous sodium hydrogen carbonate solution. The extracted organic layer was dried with anhydrous magnesium sulfate, filtered and distilled under reduced pressure to obtain a crude product. The obtained crude product was washed 3 times with dichloromethane, and the product was subjected to column separation (MC:acetone=100:1) to obtain the target compound 1,1'-(9-(4-methoxyphenyl)- 9H-carbazole-3,6-diyl)bis(propan-1-one)-2,2'-bisoxime (1.81 g, 26.3%). 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: 1,1'-(9-(4-methoxyphenyl)-carbazole-3,6-diyl ) Synthesis of bis(propan-1-one) 2,2'-bisoxime (O-acetate)

步驟1：9-(4-甲硫基苯基)咔唑之合成The 1,1'-(9-(4-methoxyphenyl)-9H-carbazole-3,6-diyl) bis(propan-1-one)-2,2'- obtained in step 3 Dioxime (0.5 g, 1.4 mmol) was added to ethyl acetate, cooled to -10 ºC or lower, then 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) in ethyl acetate (1 mL) was added dropwise for 10 minutes and stirred for 30 minutes. The reaction solution was extracted with dichloromethane, and washed thoroughly with an aqueous sodium hydrogen carbonate solution. The extracted organic layer was dried with anhydrous magnesium sulfate, filtered and distilled under reduced pressure, and the product was subjected to column separation (MC:acetone 200:1) to obtain the target compound 1,1'-(9-(4-methoxybenzene) Base)-9H-carbazole-3,6-diyl)bis(propan-1-one)-2,2'-bisoxime (O-acetate) (0.16 g, 28.1%). 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: 261.4ºC Example 2

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

Place triglyme (40 ml) under a nitrogen atmosphere, and add carbazole (30 g, 170.5 mmol), 4-iodothioanisole (53.8 g, 204.3 mmol), and powdered copper (11.34 g). , 180 mmol) and potassium carbonate (58.8 g, 423.2 mmol) were added to the reactor, and refluxed at 90ºC for 4 days. After the reaction was completed, the mixture was cooled to room temperature. Subsequently, the reaction solution was transferred to a beaker, and water (300 mL) and dichloromethane (300 mL) were placed in the beaker and stirred for 1 hour. Filter the solution in the beaker through a 2 to 3 cm size silicone (40 to 400 mesh) filter to remove insoluble impurities. Subsequently, the filtrate was extracted 3 times with dichloromethane (300 mL), and the organic layer was dried with anhydrous magnesium sulfate, filtered, distilled under reduced pressure and recrystallized (dichloromethane:hexane=1:1) to obtain the target compound 9- (4-Methylthiophenyl)-carbazole (10.3 g, 66.4%). 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 Steps 2 to 3: 1-(9-(4-(methylthio)phenyl)-6- Synthesis of propyl-carbazol-3-yl)pentan-1-one

Aluminum chloride (6.85 g, 49.00 mmol) was added to dichloromethane (100 ml), cooled to -10°C or lower and stirred for 10 minutes, and then the 9-(4-methylthio) obtained in step 1 Phenyl)-carbazole (10.0 g, 36.3 mmol) was added and stirred for 30 minutes. Add dropwise a solution of propyl chloride (4.47 ml, 49.00 mmol) in dichloromethane (25 ml) for 50 minutes and stir for 30 minutes, then add aluminum chloride (6.85 g, 49.00 mmol) and stir for 10 minutes, add dropwise pentyl chloride (6.07 ml, 49.00 mmol) in dichloromethane (25 ml) for 50 minutes and stirred for 30 minutes. The reaction solution was added to ice water containing ice (300 g) and water (300 ml) and stirred for 30 minutes, and after allowing to stand still, the water layer was removed and the organic layer was thoroughly washed with sodium bicarbonate aqueous solution. Subsequently, the organic layer was dried with anhydrous magnesium sulfate, filtered and distilled under reduced pressure to obtain the target compound 1-(9-(4-(methylthio)phenyl)-6-propanyl-carbazol-3-yl)pentan -1-one (7.9 g, 72.6%). 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-(hydroxyl Synthesis of (amino)propionyl)-9-(4-(methylthio)phenyl)-carbazol-3-yl)pentan-1-one

The 1-(9-(4-(methylthio)phenyl)-6-propanyl-carbazol-3-yl)pentan-1-one (6.0 g, 18.2 mmol) obtained in steps 2 to 3 , Tetrahydrofuran (120 ml) and 35% hydrochloric acid (1.4 ml) were added to the reactor and stirred for 30 minutes. A solution of isoamyl nitrite (7.37 ml, 72.8 mmol) in tetrahydrofuran (40 ml) was added dropwise for 30 minutes and stirred for 50 minutes. Subsequently, the product was extracted with ethyl acetate, and washed thoroughly with an aqueous sodium hydrogen carbonate solution. The extracted organic layer was dried with anhydrous magnesium sulfate, filtered and distilled under reduced pressure to obtain a crude product. The obtained crude product was washed 3 times with dichloromethane, and the product was subjected to column separation (MC:acetone=100:1) to obtain the target compound 2-(hydroxyimino)-1-(6-(2-( Hydroxyimino)propionyl)-9-(4-(methylthio)phenyl)carbazol-3-yl)pentan-1-one (1.68 g, 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-(Acetoxyimine) Synthesis of propyl)propionyl)-9-(4-(methylthio)phenyl)-carbazol-3-yl)pentan-1-one

The 2-(hydroxyimino)-1-(6-(2-(hydroxyimino)propionyl)-9-(4-(methylthio)phenyl)-carbazole obtained in step 4 -3-yl)pentan-1-one (0.5 g, 1.4 mmol) was added to ethyl acetate, cooled to -10°C or lower, then trimethylamine (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) in ethyl acetate (1 ml) was added dropwise over 10 minutes and stirred for 30 minutes. The reaction solution was extracted with dichloromethane, and washed thoroughly with an aqueous sodium hydrogen carbonate solution. The extracted organic layer was dried with anhydrous magnesium sulfate, filtered and distilled under reduced pressure, and the product was subjected to column separation (MC:acetone 200:1) to obtain the target compound 2-(acetoxyimino)-1-( 6-(2-(Acetoxyimino)propionyl)-9-(4-(methylthio)phenyl)-carbazol-3-yl)pentan-1-one (0.15 g, 26.1 %). 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), 9.00(2H, d) MS( m/e ): 571 Decomposition point: 268.3℃ Examples 3 to 14

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 CH₃ C₂ H₅ CH₃ 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 CH₃ CH₃ C₂ H₅ 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 CH₃

CH₃ 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 CH₃

CH₃ 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 C₂ H₅ CH₃ CH₃ 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) 262.5℃ 10 2-9 S CH₃ CH₃

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) 266.6℃ 11 2-10 S CH₃ C₂ H₅ CH₃ 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 CH₃ CH₃ C₂ H₅ 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) 263.1℃ 13 2-12 S CH₃ C₃ H₇ CH₃ 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℃ [表2] 實例 化學式 A R₁ R₂ R'₂ R₃ ¹ H NMR(δppm；CDCl₃ ) 分解點 14 2-13 O CH₃ CH₃ C₃ H₇ CH₃ 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℃ >鹼溶性樹脂之製備> 製備實例1：丙烯酸聚合物(a-1)之製備Under the same conditions as in Example 1 or 2, the carbazole poly β-oxime ester derivative compound was synthesized with the composition described in Tables 1 and 2. [Table 1] Instance Chemical formula A R ₁ R _2, R _'2 R ₃ ¹ H NMR(δppm; 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°C 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°C 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°C 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°C 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°C 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°C 9 2-8 S 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) 262.5°C 10 2-9 S 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) 266.6°C 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°C 12 2-11 S 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) 263.1°C 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°C [Table 2] Instance Chemical formula A R ₁ R ₂ R _'2 R ₃ ¹ H NMR(δppm; 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°C >Preparation of alkali-soluble resin> Preparation example 1: Preparation of acrylic polymer (a-1)

Place 200 mL of propylene glycol methyl ether acetate (PGMEA) and 1.5 g of azobisisobutyronitrile (AIBN) in a 500 mL polymerization vessel, and add methacrylate and methacrylic acid Glycidyl ester, methyl methacrylate and dicyclopentyl acrylate were added at a molar ratio of 20:20:40:20 under the condition of 40% by weight of solid acrylic monomer, and then stirred at 70ºC under a nitrogen atmosphere. Polymerization was carried out for 5 hours to prepare acrylic polymer (a-1). It was found that the weight average molecular weight of the prepared polymer (a-1) was 25,000 and the degree of dispersion was 1.8. Preparation example 2: Preparation of acrylic polymer (a-2)

Put 200 mL propylene glycol methyl ether acetate and 1.0 g AIBN in a 500 mL polymerization vessel, and mix methacrylate, styrene, methyl methacrylate, and cyclohexyl methacrylate in a ratio of 40:20:20: The molar ratio of 20 was added under the condition of 40% by weight of solid acrylic monomer, and then polymerized for 5 hours while stirring at 70ºC under nitrogen atmosphere to synthesize the copolymer. Subsequently, based on 100 moles of total monomers, 0.3 g of N,N-dimethylaniline and 20 moles of glycidyl methacrylate were added to the reactor, and stirred at 100ºC for 10 hours to prepare An acrylic polymer (a-2) having an acrylic unsaturated bond on the side chain. It was found that the weight average molecular weight of the acrylic polymer (a-2) prepared was 20,000 and the degree of dispersion was 2.0. Preparation Example 3: Preparation of acrylic polymer (a-3)

Put 200 mL of propylene glycol methyl ether acetate and 1.0 g of AIBN in a 500 mL polymerization vessel, and mix glycidyl methacrylate, styrene, methyl methacrylate and cyclohexyl methacrylate in a ratio of 40:20: The molar ratio of 20:20 was added under the condition of 40% by weight solid acrylic monomer, and then polymerized for 5 hours while stirring at 70ºC under nitrogen atmosphere to synthesize the copolymer. Subsequently, based on 100 moles of total monomers, 0.3 g of N,N-dimethylaniline and 20 moles of acrylic acid were added to the reactor, and stirred at 100ºC for 10 hours to prepare acrylic acid on the side chain Unsaturated acrylic polymer (a-3). It was found that the prepared acrylic polymer (a-3) had a weight average molecular weight of 18,000 and a dispersion degree of 1.8. >Preparation of photoresist composition> Examples 15 to 30: Preparation of photoresist composition

The alkali-soluble resin, the polymerizable compound with ethylenically unsaturated bonds, the photopolymerization initiator of the present disclosure, and FC-430 (3M leveling agent) are based on the components and their contents described in Table 3 below. Sequentially add to the reaction mixing tank with UV shield and stirrer, stir at room temperature (23ºC), and add solvent PGMEA to make the composition 100% by weight to prepare the photoresist composition of Examples 15 to 30 . >Preparation of colored photoresist composition> Examples 31 to 32: Preparation of colored photoresist composition

As described in Table 3 below, the colored photoresist composition of Example 31 was prepared by the same method as Example 15, except that 50% by weight of carbon black dispersion in PGMEA was added at 25% by weight of solids. The colored photoresist composition of Example 32 was prepared by the same method as Example 15, except that 50% by weight of pigment red 177 (PR177) dispersion in PGMEA was added at 25% by weight of solids. Example 33

>組分> (a) 鹼溶性樹脂：製備實例1至3(a-1至a-3)之丙烯酸聚合物 (b) 具有烯鍵式不飽和鍵之可聚合化合物 - b-1：二新戊四醇六丙烯酸酯 - b-2：二新戊四醇五丙烯酸酯 - b-3：新戊四醇三丙烯酸酯 - b-4：新戊四醇三甲基丙烯酸酯 - b-5：三羥甲基丙烷三丙烯酸酯 - b-6：乙二醇二丙烯酸酯 - b-7：雙酚A二縮水甘油醚丙烯酸加合物 - b-8：三羥甲基丙烷三縮水甘油醚丙烯酸加合物 (c) 光聚合起始劑：實例1至14中製備之咔唑多β-肟酯衍生物化合物 (e) 調平劑：FC-430(3M調平劑) (h) 著色劑 h-1：炭黑(25重量%固體) h-2：顏料紅177(P.R.177)(25重量%固體) [表3] 實例 (a) 組分(重量%) (b) 組分(重量%) (c) 組分(重量%) (e) 組分(重量%) (h) 組分(重量%) 15 a-1 (40) b-1 (20) 實例1(0.5) FC-430(0.1) - 16 a-1 (40) b-3 (20) 實例3(0.5) FC-430(0.1) - 17 a-1 (40) b-5 (10) b-6 (10) 實例4(0.5) FC-430(0.1) - 18 a-1 (40) b-2 (20) 實例6(0.5) FC-430(0.1) - 19 a-1 (40) b-1 (20) 實例8(0.5) FC-430(0.1) - 20 a-1 (40) b-3 (20) 實例9(0.5) FC-430(0.1) - 21 a-1 (40) b-5 (10) b-6 (10) 實例11(0.5) FC-430(0.1) - 22 a-1 (40) b-1 (20) 實例12(0.5) FC-430(0.1) - 23 a-1 (40) b-3 (20) 實例13(0.5) FC-430(0.1) - 24 a-1 (40) b-5 (10) b-6 (10) 實例14(0.5) FC-430(0.1) - 25 a-2 (40) b-7 (20) 實例1(0.5) FC-430(0.1) - 26 a-2 (40) b-8 (20) 實例6(0.5) FC-430(0.1) - 27 a-3 (40) b-3 (20) 實例1(0.5) FC-430(0.1) - 28 a-3 (40) b-4 (20) 實例5(0.5) FC-430(0.1) - 29 a-1 (20) a-2 (20) b-1 (20) 實例1(0.5) FC-430(0.1) - 30 a-1 (20) a-3 (20) b-1 (20) 實例1(0.5) FC-430(0.1) - 31 a-1 (20) b-1 (10) 實例1(0.5) FC-430(0.1) h-1 (50) 32 a-1 (20) b-1 (10) 實例1(0.5) FC-430(0.1) h-2 (50) 33 a-1 (40) b-1 (20) 實例1(0.4) 化學式4(0.1) FC-430(0.1) - 比較例1As described in Table 3 below, the photoresist composition was prepared by the same method as in Example 15, except that the compound of Example 1 and the mixture of the following Chemical Formula 3 were used as the photopolymerization initiator. >Chemical formula 3>

>Components> (a) Alkali-soluble resin: Preparation examples 1 to 3 (a-1 to a-3) of acrylic polymers (b) Polymerizable compounds with ethylenically unsaturated bonds-b-1: Erxin Pentaerythritol hexaacrylate-b-2: Dineopentaerythritol pentaacrylate-b-3: Neopentaerythritol triacrylate-b-4: Neopentaerythritol 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 poly β-oxime ester derivative compound prepared in Examples 1 to 14 (e) Leveling agent: FC-430 (3M leveling agent) (h) Coloring agent h-1: Carbon black (25% by weight solids) h-2: Pigment Red 177 (PR177) (25% by weight solids) [Table 3] Instance (a) Components (wt%) (b) Components (wt%) (c) Components (wt%) (e) Components (wt%) (h) Components (wt%) 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) - twenty one a-1 (40) b-5 (10) b-6 (10) Example 11 (0.5) FC-430(0.1) - twenty two a-1 (40) b-1 (20) Example 12 (0.5) FC-430(0.1) - twenty three a-1 (40) b-3 (20) Example 13 (0.5) FC-430(0.1) - twenty four 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) Chemical formula 4 (0.1) FC-430(0.1) - Comparative example 1

比較例2The photoresist composition was prepared by the same method as in Example 15, except that the compound of Chemical Formula 4 below was used instead of the compound of Chemical Formula 2-1 of Example 1 as the photopolymerization initiator. >Chemical formula 4>

Comparative example 2

>光阻組成物之評估>The photoresist composition was prepared by the same method as in Example 15, except that the compound of the following Chemical Formula 5 was used instead of the compound of Chemical Formula 2-1 of Example 1 as the photopolymerization initiator. >Chemical formula 5>

>Evaluation of photoresist composition>

The photoresist composition prepared in Examples 15 to 33 and Comparative Examples 1 to 2 were evaluated on a glass substrate, and the performance of the photoresist composition was measured, such as sensitivity, residual film rate, pattern stability, chemical resistance and elongation The results are listed in Table 4 below. 1) Sensitivity

The photoresist was spin-coated on the glass substrate and dried on a hot plate at 100ºC for 1 minute, then exposed using a step mask and developed in a 0.04% KOH aqueous solution. The sensitivity is evaluated based on the exposure dose when the thickness of the step mask pattern is maintained at 80% of the initial thickness. 2) Residual film rate

Use a spin coater to coat the photoresist composition on the substrate, and pre-bake at 100ºC for 1 minute, then expose at 365 nm and post-bake at 230ºC for 20 minutes, and before and after the bake after measurement The ratio of the thickness of the photoresist film (%). 3) Pattern stability

The silicon wafer with the photoresist pattern was cut in the direction perpendicular to the hole pattern, and the observation in the cross-sectional direction of the pattern using an electron microscope was demonstrated. The sidewalls of the pattern are at an angle of 55° or more with respect to the substrate, and no film reduction is determined as "good", and the observed film reduction is determined as "decrease". 4) Chemical resistance

Use a spin coater to coat the photoresist composition on the substrate, and then perform pre-baking and post-baking to form a photoresist film. The photoresist film is immersed in a release agent solution at 40ºC for 10 minutes, and the photoresist film is observed Whether the thickness and transmittance have changed. A transmittance and thickness change of 2% or less was determined to be "good", and a transmittance and thickness change of 2% or more were determined to be "bad". 5) ductility

The photoresist composition is spin-coated on the substrate, and then pre-baked at 100ºC for 1 minute, exposed to the sensitivity of the photoresist, and developed in KOH aqueous solution to form a 20 um x 20 um pattern. The formed pattern was cross-linked by baking at 230ºC for 20 minutes, and the ductility of the pattern was measured using a nano indenter. The measurement of the nano indenter was performed under a load of 5 gf. A total change of 500 nm or more was determined to be "good", and a total change of less than 500 nm was determined to be "bad". [Table 4] classification Sensitivity (mJ/cm ² ) Residual film rate (%) Pattern stability Chemical resistance Malleability Instance 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 twenty one 85 90 good good good twenty two 85 90 good good good twenty three 100 92 good good good twenty four 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 1 200 82 reduce Poor Poor 2 120 85 reduce Poor good

As can be seen from Table 3 and Table 4 above, most of the carbazole poly β-oxime ester derivative compounds according to the present disclosure have high thermal stability due to the decomposition point of 240°C or higher, and show excellent characteristics. Such as residual film rate, pattern stability, chemical resistance and ductility, even when the amount of the photopolymerization initiator used as the photoresist composition is small. Therefore, it has been found that during the exposure and post-baking process of the TFT-LCD manufacturing method, the outgassing generated by the photopolymerization initiator can be minimized, thereby reducing pollution and minimizing corresponding defects.

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Claims (12)

A carbazole poly β-oxime ester derivative compound represented by the following chemical formula 1: >Chemical formula 1>

Wherein A is oxygen or sulfur; R ₁ is a (C1-C12) alkyl; R ₂ and R _'2 are each independently (C1-C12) alkyl, (C6-C20) aryl, (C1-C12) alkoxy Oxy, (C6-C12) aryl (C1-C12) alkyl, hydroxy (C1-C12) alkyl, hydroxy (C1-C12) alkoxy (C1-C12) alkyl or (C3-C8) ring Alkyl; and 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. The carbazole poly β-oxime ester derivative compound according to claim 1, wherein A is oxygen or sulfur; R ₁ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl or isohexyl group; R ₂ and R _'2 are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl , Tertiary butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, n-decyl, isodecyl, n-dodecyl, cyclopentyl, cyclohexyl, phenyl, benzyl , Naphthyl, biphenyl, terphenyl, anthracenyl, indenyl, phenanthryl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, the first Tributoxy, hydroxymethyl, hydroxyethyl, hydroxyn-propyl, hydroxyn-butyl, hydroxyisobutyl, hydroxyn-pentyl, hydroxyisopentyl, hydroxyn-hexyl, hydroxyisohexyl, hydroxymethoxy Methyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl Group, hydroxyethoxypentyl or hydroxyethoxyhexyl; 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 carbazole poly β-oxime ester derivative compound according to claim 1, wherein the carbazole poly β-oxime ester derivative compound is at least one selected from the compounds represented by the following chemical formulas 2-1 to 2-14 By: >Chemical formulas 2-1 to 2-14>

A photopolymerization initiator comprising the carbazole poly β-oxime ester derivative compound according to any one of claims 1 to 3. A photoresist composition comprising: (a) An alkali-soluble resin; (b) A polymerizable compound with ethylenically unsaturated bonds; and (c) A photopolymerization initiator comprising the carbazole poly β-oxime ester derivative compound described in any one of claims 1 to 3. The photoresist composition according to claim 5, wherein the carbazole poly β-oxime ester derivative compound is present in an amount of 0.01 to 10% by weight based on 100% by weight of the photoresist composition. The photoresist composition according to claim 5, wherein the photopolymerization initiator further comprises at least one selected from the group consisting of: a thioxanthone-based compound, a compound based on phosphine oxide, Acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, O-acetoxime ester-based compounds, and thiol-based compounds. The photoresist composition according to claim 5, wherein the photoresist composition further comprises a colorant. The photoresist composition according to claim 7, wherein the photoresist composition further comprises a colorant. A molded product comprising a cured product of the photoresist composition described in claim 5. The molded product according to claim 10, wherein the molded product is an array planarization film, an insulating film, a color filter, a columnar spacer, a protective film, a black columnar spacer or a Black matrix. A display device comprising the molded product described in claim 10.