KR102509606B1 - Novel quinolinyl beta oxime ester derivative compound, photopolymerization initiator, and photoresist composition containing the same - Google Patents

Abstract

A novel quinolinyl beta oxime ester derivative compound, a photopolymerization initiator and a photoresist composition containing the same are provided.

Description

Novel quinolinyl beta oxime ester derivative compound, photopolymerization initiator containing the same, and photoresist composition

The present invention relates to a novel quinolinyl beta oxime ester compound, a photopolymerization initiator containing the same, and a photoresist composition, and more specifically, a novel β-oxime ester fluorene compound with excellent sensitivity even when used in a small amount, which It relates to a photoresist composition with excellent physical properties such as a photopolymerization initiator containing a film remaining rate, pattern stability, chemical resistance and ductility.

Common examples of photopolymerization initiators used in photoresist compositions include acetophenone derivatives, benzophenone derivatives, triazine derivatives, biimidazole derivatives, acylphosphine oxide derivatives, and oxime ester derivatives. Among them, oxime ester derivatives are known. It has the advantages of almost no color by absorbing ultraviolet rays, high radical generation efficiency, and excellent compatibility and stability with photoresist composition materials. However, the initially developed oxime derivative compound has a low photoinitiation efficiency and, in particular, a low sensitivity during a pattern exposure process, so an exposure amount must be increased, thereby reducing production volume.

Therefore, the development of a photopolymerization initiator with excellent light sensitivity can implement sufficient sensitivity with a small amount, thereby reducing the amount of light exposure due to cost reduction effect and excellent sensitivity, thereby increasing production.

Various oxime ester compound derivatives represented by the following formula A that can be used as photopolymerization initiators in photoresist compositions are already known.

[Formula A]

In the case of a photopolymerization initiator having an oxime ester group, it is easy to synthesize various photopolymerization initiators capable of adjusting the absorption area of the photopolymerization initiator by introducing appropriate substituents to R, R', and R" of the compound.

The oxime ester compound can polymerize and cure a polymerizable compound having an unsaturated bond by irradiating the photoresist composition with light of 365-435 nm, and is used in black matrices, color filters, column spacers, flexible insulating films, and photoresist compositions for overcoats. there is.

Therefore, photoinitiators have high sensitivity to long-wavelength light sources such as 365-435nm, have good photopolymerization reactivity, are easy to manufacture, have high thermal stability and storage stability, are easy to handle, and have good resistance to solvents (PGMEA; propylene glycol monomethyl ether acetate). There is a continuous demand for new photoinitiators suitable for various uses that can meet industrial requirements such as satisfactory solubility.

Recently, with respect to photoresist compositions used in thin-film displays such as liquid crystal displays and OLEDs, in more detail, they are developed with an alkaline developer to form organic insulating films of liquid crystal displays such as TFT-LCDs, column spacers, UV overcoats, and R.G.B. A lot of research on photoresist compositions containing highly sensitive photopolymerization initiators capable of forming patterns with color resists and black matrices has been conducted.

In general, as a resist composition used to form a pattern, a photoresist composition containing a binder resin, a polyfunctional monomer having an ethylenically unsaturated bond, and a photopolymerization initiator is preferred.

However, when forming a pattern using a conventional photopolymerization initiator, the sensitivity is low during the exposure process for pattern formation, so the amount of photopolymerization initiator used or the amount of exposure must be increased. There is a disadvantage that the yield is lowered as a by-product generated after decomposition, and there is a problem that the exposure process time increases due to the increase in the amount of exposure and the production volume decreases. Efforts are being made to solve this.

[Patent Document 1] PCT WO02/100903 (2002.12.19) [Patent Document 2] Japanese Unexamined Patent Publication 2005-025169 (2005.01.27) [Patent Document 3] PCT WO07/071497 (2007.06.28) [Patent Document 4] PCT WO08/138733 (2008.11.20) [Patent Document 5] KR 2013-0049811 (2013.05.03) [Patent Document 6] KR 1020130115272 A (2013. 10.21)

Therefore, the problem to be solved by the present invention is a novel quinolinyl beta oxime ester derivative compound, a photopolymerization initiator containing the same, and a sensitivity higher than that even when the amount of these is reduced, heat resistance, light resistance, chemical resistance and developing resistance It is to provide this excellent photoresist composition.

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

In addition, another object to be solved of the present invention is to provide a liquid crystal display device including the molded article.

According to one aspect of the present invention in order to solve the above problems, a quinolinyl beta oxime ester derivative compound represented by Formula 1 is provided.

[Formula 1]

In Formula 1,

R ₁ and R ₈ are each independently hydrogen, (C ₁ -C ₂₀ )alkyl, (C ₆ -C ₂₀ )aryl, (C ₁ -C ₂₀ )alkoxy, (C ₆ -C ₂₀ )aryl(C ₁ - C ₂₀ )alkyl, hydroxy(C ₁ -C ₂₀ )alkyl, hydroxy(C ₁ -C ₂₀ )alkoxy(C ₁ -C ₂₀ )alkyl or (C ₃ -C ₂₀ )cycloalkyl;

R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are each independently (C ₁ -C ₂₀ )alkyl, (C ₆ -C ₂₀ )aryl, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl, or (C ₃ -C ₂₀ )cycloalkyl;

A is O or S.

R ₁ and R ₈ are each independently hydrogen, methyl, ethyl, n -propyl, i-propyl, n - butyl, i -butyl, t -butyl, n -pentyl, i -pentyl, n -hexyl, i- hexyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl, methoxy, ethoxy, n -propyloxy, i -propyloxy, n -butoxy, i -butoxy, t -butoxy, hydroxymethyl, hydroxyethyl, hydroxy n -propyl, hydroxy n -butyl, hydroxy i -butyl, hydroxy n -pentyl, hydroxy i -pentyl, hydroxy n -hexyl, hydroxyi -hexyl , hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl , hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl;

R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are each independently hydrogen, methyl, ethyl, n -propyl, i -propyl, n -butyl, i -butyl, t -butyl, n- pentyl, i -pentyl, n -hexyl, i -hexyl, cyclopentyl, cyclohexyl, phenyl, benzyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl;

A can be O or S.

According to another aspect of the present invention, a photopolymerization initiator comprising the above-described quinolinyl beta oxime ester derivative compound is provided.

According to another aspect of the present invention, a photoresist composition including the above-described quinolinyl beta oxime ester derivative compound, a binder resin, a polymerizable compound having an ethylenically unsaturated bond, and a solvent is provided.

Based on 100 parts by weight of the photoresist composition, 0.01 to 10 parts by weight of the quinolinyl beta oxime ester derivative, 3 to 50 parts by weight of a binder resin, 0.001 to 40 parts by weight of a polymeric compound having an ethylenically unsaturated bond, and 10 to 10 parts by weight of a solvent 95 parts by weight.

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

When the novel quinolinyl beta oxime ester derivative compound of the present invention is used as a photoinitiator of a photoresist composition, it has excellent sensitivity even when used in a small amount, and has excellent physical properties such as remaining film rate, pattern stability, chemical resistance and ductility, There is an advantage in that outgassing generated from the photopolymerization initiator in the exposure and post-bake process during the LCD manufacturing process can be minimized, thereby reducing contamination and minimizing defects that may occur due to this.

Hereinafter, the present invention will be described in detail. Prior to this, the terms or words used in this specification and claims should not be construed as being limited to the usual or dictionary meaning, and the inventor appropriately uses the concept of the term in order to explain his/her invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined.

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

Another quinolinyl beta oxime ester derivative compound according to one aspect of the present invention is represented by Formula 1 below:

[Formula 1]

In Formula 1,

R ₁ and R ₈ are each independently hydrogen, (C ₁ -C ₂₀ )alkyl, (C ₆ -C ₂₀ )aryl, (C ₁ -C ₂₀ )alkoxy, (C ₆ -C ₂₀ )aryl(C ₁ - C ₂₀ )alkyl, hydroxy(C ₁ -C ₂₀ )alkyl, hydroxy(C ₁ -C ₂₀ )alkoxy(C ₁ -C ₂₀ )alkyl or (C ₃ -C ₂₀ )cycloalkyl;

R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are each independently (C ₁ -C ₂₀ )alkyl, (C ₆ -C ₂₀ )aryl, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl, or (C ₃ -C ₂₀ )cycloalkyl;

A is O or S.

Substituents including "alkyl", "alkoxy", and other "alkyl" moieties described herein include both straight-chain and branched-chain hydrocarbons, and "cycloalkyl" includes not only single-ring hydrocarbons but also multi-cyclic hydrocarbons. In addition, "aryl" as described herein is an organic radical derived from an aromatic hydrocarbon by removing one hydrogen, and each ring has preferably 4 to 7, preferably 5 or 6, single or 6 ring atoms. It includes a fused ring system, and even includes a form in which a plurality of aryls are connected by single bonds. "Hydroxyalkyl" refers to OH-alkyl in which a hydroxy group is bonded to the above-defined alkyl group, and "hydroxyalkoxyalkyl" refers to hydroxyalkyl- O -alkyl in which an alkoxy group is bonded to the hydroxyalkyl group.

In addition, the '(C ₁ -C ₂₀ )alkyl' group described in the present invention means an alkyl group having 1 to 20 carbon atoms, preferably (C ₁ -C ₁₀ )alkyl, and more preferably ( C ₁ -C ₆ )alkyl.

A '(C ₆ -C ₂₀ )aryl' group means an aryl group having 6 to 20 carbon atoms, preferably (C ₆ -C ₁₈ )aryl.

A '(C ₁ -C ₂₀ )alkoxy' group means an alkoxy group having 1 to 20 carbon atoms, preferably (C ₁ -C ₁₀ )alkoxy, more preferably (C ₁ -C ₄ )alkoxy. .

The '(C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl' group means an arylalkyl group in which an alkyl group having 1 to 20 carbon atoms is bonded to an aryl group having 6 to 20 carbon atoms, and preferably (C ₆ -C ₁₈ )aryl(C ₁ -C ₁₀ )alkyl, more preferably (C ₆ -C ₁₈ )aryl(C ₁ -C ₆ )alkyl.

The 'hydroxy(C ₁ -C ₂₀ )alkyl' group refers to a hydroxyalkyl group in which an alkyl group having 1 to 20 carbon atoms is bonded to a hydroxyl group, preferably hydroxy(C ₁ -C ₁₀ )alkyl, and further It is preferably hydroxy(C ₁ -C ₆ )alkyl.

A 'hydroxy(C ₁ -C ₂₀ )alkoxy(C ₁ -C ₂₀ )alkyl' group is a hydroxy group in which an alkoxy having 1 to 20 carbon atoms is bonded to hydroxy, followed by an alkyl group having 1 to 20 carbon atoms. It means a hydroxyalkoxyalkyl group, preferably hydroxy (C ₁ -C ₁₀ ) alkoxy (C ₁ -C ₁₀ ) alkyl, more preferably hydroxy (C ₁ -C ₄ ) alkoxy (C ₁ -C ₆ ) is an alkyl.

A '(C ₃ -C ₂₀ )cycloalkyl' group means a cycloalkyl group having 3 to 20 carbon atoms, and is preferably (C ₃ -C ₁₀ )cycloalkyl.

Specifically, R ₁ and R ₈ are each independently hydrogen, methyl, ethyl, n -propyl, i -propyl, n -butyl, i -butyl, t -butyl, n -pentyl, i -pentyl, n -hexyl, i -hexyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl, methoxy, ethoxy, n -propyloxy, i -propyloxy, n -butoxy , i -butoxy, t -butoxy, hydroxymethyl, hydroxyethyl, hydroxy n-propyl, hydroxy n -butyl, hydroxy i - butyl, hydroxy n -pentyl, hydroxy i -pentyl, hydroxy hydroxy n -hexyl, hydroxy i -hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyae hydroxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl.

In addition, specifically, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are hydrogen, methyl, ethyl, n -propyl, i -propyl, n -butyl, i -butyl, t -butyl, n -pentyl, i -pentyl, n -hexyl, i -hexyl, cyclopentyl, cyclohexyl, phenyl, benzyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl.

More specifically, R ₁ and R ₈ are each independently methyl, ethyl, n -pentyl, cyclohexyl, or phenyl; R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ may each independently be methyl, ethyl, n -propyl, n -butyl, n -heptyl or benzyl.

Examples of the quinolinyl beta oxime ester derivative compounds according to the present invention include compounds represented by the following Chemical Formulas 2-1 to 2-16, but the following compounds are not intended to limit the present invention.

<Formula 2-1 to 2-16>

The quinolinyl beta oxime ester derivative compound represented by Chemical Formula 1 according to the present invention can be prepared as shown in Scheme 1 below.

[Scheme 1]

In Reaction Scheme 1, A and R ₁ to R ₈ are the same as defined in Formula 1, and X ₁ to X ₃ are each independently halogen.

In addition, according to one aspect of the present invention, a photopolymerization initiator including the quinolinyl beta oxime ester derivative compound represented by Formula 1 is provided.

In addition, according to one aspect of the present invention, a photoresist composition including the quinolinyl beta oxime ester derivative compound represented by Chemical Formula 1 is provided.

In the present invention, the quinolinyl beta oxime ester derivative compound represented by Chemical Formula 1 may be included in the photoresist composition as a photopolymerization initiator.

According to one embodiment of the present invention, the photoresist composition includes a photoinitiator including the biphenyl oxime ester derivative compound represented by Chemical Formula 1, an alkali-soluble resin, and a polymerizable compound having an ethylenically unsaturated bond.

In addition, the photoinitiator is selected from the group consisting of thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, thiol-based compounds, and O-acyloxime-based compounds other than the compound represented by Formula 1 One or two or more of them may be further included.

Examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 2,4-dichloro. Thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like can be used.

Examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc. can be used.

Examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-biimidazole. '-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichloro phenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole and the like.

Examples of the triazine compound include 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, and 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-triazine , 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, 2-(4-n-butoxyphenyl)- 4,6-bis(trichloromethyl)-s-triazine and the like can be used.

Examples of the O-acyloxime 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-tetrahydrofura Nylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6- X2-methyl-4-(2,2-dimethyl-1 ,3-dioxolanyl)methoxybenzoyl r-9H-carbazol-3-yl]-1-(O-acetyloxime) and the like can be used.

In the photoresist composition of the present invention, the addition amount of the biphenyl oxime ester derivative compound of Formula 1 used as a photopolymerization initiator is 0.01 to 10% by weight, preferably 0.01 to 10% by weight, based on 100% by weight of the photoresist composition, as an amount to increase transparency and minimize exposure amount. Preferably, it is more effective to use 0.1 to 5% by weight.

According to one embodiment of the present invention, the photoresist composition includes a quinolinyl beta oxime ester derivative compound represented by Formula 1, a binder resin, a polymerizable compound having an ethylenically unsaturated bond and a solvent, and the pattern characteristics Excellent thin film properties such as control, heat resistance and chemical resistance.

According to one embodiment of the present invention, an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in a side chain may be used as the binder resin.

The binder resin is used in an amount of 3 to 50 parts by weight, preferably 5 to 20 parts by weight, more preferably 8 to 13 parts by weight, based on 100 parts by weight of the photoresist composition, in order to adjust pattern characteristics and provide thin film properties such as heat resistance and chemical resistance. Parts by weight may be used.

The binder resin preferably has a weight average molecular weight of 2,000 to 300,000 and a degree of dispersion of 1.0 to 10.0, more preferably a weight average molecular weight of 4,000 to 100,000.

The acrylic polymer refers to a polymer of an acrylic monomer, and examples of such an acrylic monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 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, and hexadecyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclo Fentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, acrylic acid, methacrylic acid , itaconic acid, maleic acid, maleic acid anhydride, maleic acid monoalkyl ester, monoalkyl itaconate, monoalkyl fumarate, glycidylacrylic acid, glycidylmethacrylic acid, dicyclopentanylacrylic acid, cyclohexylacrylic acid, cyclo Hexylmethacrylic acid, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth)acrylate, 2,3-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-methyl oxetane-3-methyl (meth)acrylate, 3-ethyloxetane-3-methyl (meth)acrylate, styrene, α-methylstyrene, acetoxystyrene, N -methyl polymers such as maleimide, N -ethylmaleimide, N -propylmaleimide, N -butylmaleimide, N -cyclohexylmaleimide, (meth)acrylamide, and N -methyl(meth)acrylamide.

The acrylic polymer may be a homopolymer formed from one of the aforementioned acrylic monomers, or a copolymer formed from two or more types of acrylic monomers.

The acrylic polymer having an acrylic unsaturated bond in the side chain may be a polymer obtained by addition reaction of an epoxy resin to an acrylic copolymer containing a carboxylic acid. For example, the acrylic polymer having an acrylic unsaturated bond in the side chain is an acrylic monomer containing a carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic acid monoalkyl ester, and methyl (meth)acrylate. Alkyl (meth)acrylates such as 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-methylstyrene, acetoxystyrene, Two monomers such as N -methylmaleimide, N -ethylmaleimide, N -propylmaleimide, N -butylmaleimide, N -cyclohexylmaleimide, (meth)acrylamide, and N -methyl(meth)acrylamide Glycidyl acrylic acid, glycidyl methacrylic acid, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth)acrylate in an acrylic copolymer containing carboxylic acid obtained by copolymerization of the above , 2,3-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate and the like can be obtained by an addition reaction at a temperature of 40 to 180 ℃.

Another example of the acrylic polymer having an acrylic unsaturated bond in the side chain may be a copolymer obtained by adding carboxylic acid to an acrylic copolymer containing an epoxy group.

For example, the acrylic polymer having an acrylic unsaturated bond in the side chain is glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth)acrylate, 2,3-epoxycyclohexyl (meth) Acrylic monomers containing an epoxy group such as acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, and alkyl (meth) acrylates such as methyl (meth) acrylate and 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-methylstyrene, acetoxystyrene, N -methylmaleimide, N -ethylmaleimide, N -propylmaleimide, N -Butyl maleimide, N -cyclohexyl maleimide, (meth)acrylamide, N -methyl (meth)acrylamide, etc. monomers 2 or 2 or more obtained by copolymerization of acrylic copolymer containing an epoxy group, acrylic acid, meta It can be obtained by addition reaction at a temperature of 40 to 180 ℃ with an acrylic monomer containing a carboxylic acid such as acrylic acid, itaconic acid, maleic acid, maleic acid monoalkyl ester.

According to one embodiment of the present invention, the polymerizable compound having an ethylenically unsaturated bond serves to form a pattern by being crosslinked by photoreaction when forming a pattern, and is crosslinked when heated to a high temperature to impart chemical resistance and heat resistance.

The polymerizable compound having an ethylenically unsaturated bond may be included in an amount of 0.001 to 40 parts by weight, preferably 1 to 20 parts by weight, and more preferably 5 to 15 parts by weight, based on 100 parts by weight of the photoresist composition.

When the polymerizable compound having an ethylenically unsaturated bond satisfies this range, the demerit of deterioration in ductility of the pattern due to an excessively high degree of crosslinking can be prevented, and the demerit of deterioration in ductility can be prevented.

Specifically, the polymerizable compound having an ethylenically unsaturated bond is dipentaerythritol hexaacrylic acid, pentaerythritol triacrylic acid, pentaerythritol trimethacrylic acid, trimethylolpropane triacrylic acid, ethylene glycol diacrylic acid; alkyl esters of (meth)acrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate; glycidyl (meth)acrylate; Polyethylene glycol mono(meth)acrylate having 2 to 14 ethylene oxide groups, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups, and propylene oxide groups having 2 to 14 ethylene oxide groups. 2 to 14 propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, bisphenol A diglycidyl ether acrylic acid adduct, phthalic acid diester of β-hydroxyethyl (meth)acrylate, β -Toluene diisocyanate adduct of hydroxyethyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate ) Compounds obtained by esterifying a polyhydric alcohol and α,β-unsaturated carboxylic acid, such as acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol tri(meth)acrylate; acrylic acid adducts of polyhydric glycidyl compounds, such as trimethylolpropane triglycidyl ether acrylic acid adducts; These etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.

In addition, according to one embodiment of the present invention, the addition amount of the quinolinyl beta oxime ester compound of Chemical Formula 1 used as the photopolymerization initiator is 0.01 part by weight based on 100 parts by weight of the photoresist composition as an amount to increase transparency and minimize exposure amount. It is more effective to use 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 0.2 to 3 parts by weight.

In addition, according to one embodiment of the present invention, the photoresist composition may further include a silicon-based compound having an epoxy group or an amine group as an adhesion adjuvant, if necessary.

The silicon-based compound may improve adhesion between the ITO electrode and the photoresist composition, and 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)ethyltriene There are toxysilane and aminopropyl trimethoxy silane, and these may be used individually or in combination of two or more. The silicon-based compound having an epoxy group or an amine group may be included in an amount of 0.0001 to 3 parts by weight, preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the photoresist composition.

In addition, according to one embodiment of the present invention, the photoresist composition may further include compatible additives such as a photosensitizer, a thermal polymerization inhibitor, an antifoaming agent, and a leveling agent, if necessary.

The photoresist composition of the present invention is spin-coated on a substrate by adding a solvent, and then irradiated with ultraviolet rays using a mask to form a pattern through a method of developing with an alkaline developer. 10 to 95 parts by weight based on 100 parts by weight of the photoresist composition It is preferable to adjust the viscosity to be in the range of 1 to 50 cps by adding a portion of solvent.

The solvent includes ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, and ethyl ethoxy propionate in consideration of compatibility with binder resins, photoinitiators and other compounds. (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 cellosolve acetate , diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N , N -dimethylacetamide (DMAc), N -methyl-2-pyrroly Money (NMP), γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methylcellosolve, ethyl Solvents such as cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane, and octane may be used alone or in combination of two or more.

The photoresist composition according to an embodiment of the present invention may further include carbon black to be used for a black matrix, and may further include a colorant to be used for a color matrix.

Color materials included to be applied as photoresists for color filters or black matrices include cyan, magenta, yellow, and black pigments of red, green, and blue and subtractive color mixtures. C.I. Pigment Yellow 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148, 153, 154, 166, 168 , C.I. Pigment Orange 36, 43, 51, 55, 59, 61, C.I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226 , 227, 228, 240, C.I. Pigment Violet 19, 23, 29, 30, 37, 40, 50, C.I. Pigment Blue 15, 15:1, 15:4, 15:6, 22, 60, 64, C.I. Pigment Green 7, 36, C.I. Pigment Brown 23, 25, 26, C.I. Pigment Black 7, and Titanium Black.

According to one aspect of the present invention, a molding comprising a cured product of the photoresist composition described above is provided.

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

In addition, according to one aspect of the present invention, various displays such as liquid crystal display devices and OLEDs including the molded article are provided. Specifically, it is as follows.

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, various types of printing, dipping, and the like, and soda glass, quartz glass, semiconductor substrates, metals, It can be applied on a support substrate such as paper or plastic. In addition, once applied on a supporting substrate such as a film, it can be transferred to another supporting substrate, and there is no limitation on the application method.

The photoresist composition according to an embodiment of the present invention is a photocurable paint or varnish, a photocurable adhesive, a printed circuit board, or a color matrix in a color liquid crystal display device such as a color television, PC monitor, portable information terminal, or digital camera. , electrode materials for plasma display panels, powder coatings, printing inks, printing plates, adhesives, dental compositions, gel coatings, photoresists for electronic engineering, electroplating resists, etching resists, both liquid and dry films, solder resists, various displays Resist for manufacturing a color matrix for use or for forming a structure in the manufacturing process of a plasma display panel, electroluminescent display device, and LCD, a composition for encapsulating electric and electronic parts, magnetic recording materials, and micromechanical parts , waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, materials for producing three-dimensional objects by stereolithography, holographic recording materials, image recording materials, microelectronic circuits, Decolorization materials, decolorization materials for image recording materials, decolorization materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, sequential lamination of printed circuit boards It can be used for various applications such as a photoresist material used for forming a dielectric layer in or a protective film, and the application is not particularly limited.

A color filter, which is one of the embodiments using the colored photoresist composition according to an embodiment of the present invention, may be manufactured by the following manufacturing method, but is not limited thereto.

After applying the above-described colored photoresist composition to a thickness of, for example, 0.5 to 10 μm using an appropriate method such as spin coating, roller coating, spray coating, etc. on a glass substrate, a pattern required for a color filter is formed on the substrate illuminate the light to As a light source used for irradiation, UV, electron beams, or X-rays may be used, and for example, UV in a range of 190 to 450 nm, specifically, 200 nm to 400 nm may be irradiated.

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In addition, the irradiation step may be performed using a photoresist mask.

After performing the irradiation process in this way, the colored photoresist composition layer patterned by irradiation of the light source is treated with a developing solution. In this case, the non-exposed portion of the colored photoresist composition layer may be dissolved to form a pattern required for a color filter. By repeating this process according to the number of colors required, a color filter having a desired pattern can be obtained. In addition, when the image pattern obtained by development in the above process is heated again or cured by irradiation with actinic rays, a color filter with improved crack resistance and solvent resistance can be implemented.

Hereinafter, representative compounds of the present invention will be described in detail with Examples and Comparative Examples for a detailed understanding of the present invention. should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

[Example 1] <Synthesis of Chemical Formula 2-1>

Step 1: Synthesis of 1-(8-hydroxyquinolin-5-yl)butan-1-one

8-Hydroxyquinoline (30g, 0.195mol) was dissolved in ethylene chloride in a reactor, and butyryl chloride (24.9g, 0.234mol) was slowly added dropwise while maintaining the temperature at 25-30°C. After completion of the dropwise addition, stirring was continued for 20 minutes, and aluminum chloride (64.9 g, 0.487 mol) was slowly added while maintaining the temperature at 25 to 30 ° C, followed by heating to 70 ° C and stirring. After completion of the reaction, the reaction solution was slowly added to a beaker containing 600 mL of ice water and 30 mL of concentrated hydrochloric acid. The resulting solid was filtered, washed with acetone, and vacuum dried to obtain a hydrochloride salt. 300 mL of purified water and 200 mL of methylene chloride were added to the solid, stirred, and then neutralized with a saturated sodium bicarbonate solution. The organic layer was separated, concentrated under reduced pressure, and recrystallized from isopropyl ether to obtain the target compound (22.1 g, 52.8%).

¹ H NMR (δ ppm; CDCl ₃ ): 1.03 (3H, t), 1.81 (2H, m), 3.03 (2H, t), 7.15 (1H, d), 7.58 (1H, m), 8.14 (1H, d), 8.80 (1H, d), 9.48 (1H, d)

MS( m/e ):215

Step 2: Synthesis of 1-(8-(benzyloxy)quinolin-5-yl)butan-1-one

After dissolving the first stage product (11.5g, 0.0534mol) in acetone in a reactor, potassium carbonate (8.12g, 0.059mol) and benzyl bromide (12.8g, 0.075mol) were added and stirred under reflux. After reacting for 2 hours, the mixture was cooled to room temperature, and insoluble solids were filtered and washed with hot ethyl acetate. The filtrate was concentrated under reduced pressure, a small amount of acetone was added, and the crystallized solid was filtered, washed with a mixed solvent of isopropyl ether and acetone, and vacuum dried to obtain the target compound (11.81 g, 72.4%).

¹ H NMR (δ ppm; CDCl ₃ ): 1.02 (3H, t), 1.78 (2H, m), 2.99 (2H, t), 5.52 (2H, s), 7.00 (1H, d), 7.30-7.57 ( 6H, m), 7.98 (1H, d), 9.05 (1H, d), 9.34 (1H, d)

MS( m/e ):305

Step 3: Synthesis of 1-(8-(benzyloxy)quinolin-5-yl)-2-(hydroxyimino)butan-1-one

After adding the second-stage product (5g, 0.0164mol) to tetrahydrofuran in the reactor, concentrated hydrochloric acid (2.05mL, 0.025mol) and isobutyl nitrous acid (2.03g, 0.020mol) were slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at 50° C. for 20 hours, cooled to room temperature, and ethyl acetate was added. After washing with purified water three times, the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The product was purified by column chromatography using ethyl acetate and hexane as a 1:2 developing solvent to obtain the target compound (2.5 g, 45.7%).

¹ H NMR (δ ppm; CDCl ₃ ): 1.22 (3H, t), 2.81 (2H, q), 5.52 (2H, s), 7.03 (1H, d), 7.35-7.63 (6H, m), 8.03 ( 1H, d), 9.03 (1H, d), 9.32 (1H, d)

MS( m/e ):333

Step 4: Synthesis of 2-(acetoxyimino)-1-(8-(benzyloxy)quinolin-5-yl)butan-1-one

After adding the product of the third step (1.2g, 0.0036mol) to ethyl acetate in the reactor, triethylamine (0.74mL, 0.0054mol) and acetyl chloride (0.38mL, 0.0054mL) were added dropwise in that order at room temperature. After stirring at room temperature, it was cooled and purified water was added. The organic layer was washed twice with purified water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The product was purified by column chromatography using ethyl acetate and hexane as a developing solvent in a ratio of 1:2 to obtain the target compound (0.9 g, 66.4%).

¹ H NMR (δ ppm; CDCl ₃ ): 1.21 (3H, t), 2.23 (3H, s), 2.84 (2H, q), 5.53 (2H, s), 7.04 (1H, d), 7.36-7.62 ( 6H, m), 8.04 (1H, d), 9.02 (1H, d), 9.33 (1H, d)

MS( m/e ):376

Beta oxime ester quinoline compounds according to the present invention were synthesized as shown in Table 1 below under the same conditions as in Example 1. (R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are hydrogen)

Example
NO. chemical formula R _{1 R2 R8} A ¹ H NMR (δ ppm; CDCl ₃ ) 2 2-2 C ₅ H ₁₁

CH ₃ O 0.87 (3H, t), 1.25-1.35 (4H, m), 1.61 (3H, t), 1.75 (2H, m), 2.23 (3H, s), 2.85 (2H, t), 5.53 (2H, s) , 7.04 (1H, d), 7.36-7.62 (6H, m), 8.04 (1H, d), 9.02 (1H, d), 9.33 (1H, d) 3 2-3 C ₂ H ₅ C ₂ H ₅ CH ₃ O 1.10 (3H, t), 2.30 (3H, s), 2.82 (2H, t), 3.09 (2H, q), 4.40 (2H, q), 7.03 (1H, d), 7.54 (1H, m), 7.65 (1H, d), 8.98 (1H, d), 9.39 (1H, d) 4 2-4 C ₅ H ₁₁ C ₂ H ₅ CH ₃ O 0.87 (3H, t), 1.25-1.35 (4H, m), 1.68 (3H, t), 1.75 (2H, m), 2.24 (3H, s), 2.95 (2H, t), 4.40 (2H, q) , 7.04 (1H, d), 7.53 (1H, m), 8.04 (1H, d), 9.02 (1H, d), 9.33 (1H, d) 5 2-5 C ₂ H ₅

O 1.66 (3H, t), 4.41 (2H, q), 5.55 (2H, s), 7.03 (1H, d), 7.37-7.65 (6H, m), 7.64-8.13 (6H, m), 9.01 (1H, d), 9.30 (1H, d) 6 2-6 C ₅ H ₁₁

O 0.89 (3H, t), 1.24-1.35 (4H, m), 1.60 (3H, s), 1.76 (2H, m) 2.85 (2H, t), 5.55 (2H, s), 7.03 (1H, d), 7.37-7.64 (6H, m), 7.65-8.14 (6H, m), 9.00 (1H, d), 9.32 (1H, d) 7 2-7 C ₂ H ₅ C ₂ H ₅

O 1.10 (3H, t), 2.82 (2H, t), 3.09 (2H, q), 4.40 (2H, q), 7.03 (1H, d), 7.54 (1H, m), 7.64-8.13 (6H, m) , 9.02 (1H, d), 9.36 (1H, d) 8 2-8 C ₅ H ₁₁ C ₂ H ₅

O 0.89 (3H, t), 1.26-1.37 (4H, m), 1.70 (3H, t), 1.76 (2H, m), 2.98 (2H, t), 4.42 (2H, q), 7.05 (1H, d) , 7.52 (1H, m), 7.63-8.12 (6H, m), 9.01 (1H, d), 9.32 (1H, d) 9 2-9 C ₂ H ₅

CH ₃ S 1.10 (3H, t), 2.28 (3H, s), 2.86 (2H, q), 4.12 (2H, s), 7.24-7.43 (6H, m), 7.50 (1H, d), 7.65 (1H, d) , 8.82 (1H, d), 9.13 (1H, d) 10 2-10 C ₅ H ₁₁

CH ₃ S 0.89 (3H, t), 1.25-1.37 (4H, m), 1.62 (3H, s), 1.74 (2H, m), 2.23 (3H, s), 2.84 (2H, t), 5.56 (2H, s) , 7.03 (1H, d), 7.33-7.60 (6H, m), 7.99 (1H, d), 9.01 (1H, d), 9.34 (1H, d) 11 2-11 C ₂ H ₅ C ₂ H ₅ CH ₃ S 1.12 (3H, t), 2.28 (3H, s), 2.80 (2H, t), 3.08 (2H, q), 4.42 (2H, q), 7.04 (1H, d), 7.55 (1H, m), 7.64 (1H, d), 8.95 (1H, d), 9.36 (1H, d) 12+ 2-12 C ₅ H ₁₁ C ₂ H ₅ CH ₃ S 0.88 (3H, t), 1.26-1.37 (4H, m), 1.70 (3H, t), 1.76 (2H, m), 2.25 (3H, s), 2.96 (2H, t), 4.38 (2H, q) , 7.02 (1H, d), 7.52 (1H, m), 8.01 (1H, d), 9.03 (1H, d), 9.32 (1H, d) 13 2-13 C ₂ H ₅

S 1.65 (3H, t), 4.39 (2H, q), 5.54 (2H, s), 7.03 (1H, d), 7.35-7.64 (6H, m), 7.65-8.12 (6H, m), 8.98 (1H, d), 9.28 (1H, d) 14 2-14 C ₅ H ₁₁

S 0.87 (3H, t), 1.22-1.34 (4H, m), 1.58 (3H, s), 1.75 (2H, m) 2.84 (2H, t), 5.54 (2H, s), 7.02 (1H, d), 7.37-7.66 (6H, m), 7.64-8.14 (6H, m), 9.01 (1H, d), 9.31 (1H, d) 15 2-15 C ₂ H ₅ C ₂ H ₅

S 1.11 (3H, t), 2.83 (2H, t), 3.08 (2H, q), 4.42 (2H, q), 7.02 (1H, d), 7.53 (1H, m), 7.63-8.12 (6H, m) , 9.01 (1H, d), 9.34 (1H, d) 16 2-16 C ₅ H ₁₁ C ₂ H ₅

S 0.86 (3H, t), 1.26-1.35 (4H, m), 1.69 (3H, t), 1.75 (2H, m), 2.94 (2H, t), 4.38 (2H, q), 7.03 (1H, d) , 7.51 (1H, m), 7.62-8.10 (6H, m), 9.00 (1H, d), 9.31 (1H, d)

<Manufacture of binder resin>

a) Preparation of Binder Resin 1

After adding 200 mL of propylene glycol methyl ether acetate (PGMEA) and 1.5 g of AIBN (azobisisobutyronitrile) to a 500 mL polymerization vessel, methacrylic acid, glycidyl methacrylic acid, methyl methacrylic acid and dicyclopentanyl acrylic acid were added at a molar ratio of 20:20:40:20 to 40% by weight of the acrylic monomer, and then polymerized while stirring at 70° C. for 5 hours under a nitrogen atmosphere to prepare binder resin 1, which is an acrylic polymer. The weight average molecular weight of the copolymer thus prepared was confirmed to be 25,000 and the degree of dispersion was 1.9.

b) Preparation of Binder Resin 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 mixed at a molar ratio of 40:20:20:20, respectively, to solid content of acrylic monomers. was added at 40% by weight, and then polymerized while stirring at 70° C. for 5 hours under a nitrogen atmosphere to synthesize a copolymer. In this reactor, 0.3 g of N,N -dimethylaniline and 20 moles of glycidylmethacrylic acid based on 100 moles of the solid content of the total monomers were added, followed by stirring at 100 ° C. for 10 hours to obtain a binder, which is an acrylic polymer having acrylic unsaturated bonds in the side chain. Resin 2 was prepared. The average molecular weight of the copolymer prepared in this way was confirmed to be 20,000, and the degree of dispersion was 2.0.

c) Preparation of Binder Resin 3

After adding 200 mL of propylene glycol methyl ether acetate and 1.0 g of AIBN to a 500 mL polymerization vessel, glycidyl methacrylic acid, styrene, methyl methacrylic acid and cyclohexyl methacrylic acid were mixed with acrylic acid at a molar ratio of 40:20:20:20, respectively. A copolymer was synthesized by adding 40% by weight of the solid content of the monomer, followed by polymerization with stirring at 70° C. for 5 hours under a nitrogen atmosphere. In this reactor, 0.3 g of N,N -dimethylaniline and 20 moles of acrylic acid based on 100 moles of the solid content of all monomers were added, followed by stirring at 100 ° C. for 10 hours to prepare binder resin 3, which is an acrylic polymer having acrylic unsaturated bonds in the side chain. did The average molecular weight of the copolymer thus prepared was 18,000, and the degree of dispersion was confirmed to be 1.8.

[Examples 17 to 32] Preparation of photoresist compositions

Binder resins 1 to 3 according to the components and contents shown in Table 2 below in a reaction mixing tank equipped with an ultraviolet blocking film and an agitator; photoreactive compounds; photopolymerization initiator of the present invention; And FC-430 (3M's leveling agent) were sequentially added, stirred at room temperature, and then PGMEA was added as a solvent to prepare a photoresist composition so that the total amount of the composition was 100 parts by weight.

[Example 33] Preparation of photoresist composition for black matrix

As shown in Table 2 below, 20 parts by weight of binder resin 1, 10 parts by weight of dipentaerythritol hexaacrylic acid, 0.5 parts by weight of compound 2-1, and 25 parts by weight of solid content in a reaction mixing tank equipped with a sunscreen and a stirrer were PGMEA. 50 parts by weight of carbon black dispersed in and 0.1 part by weight of FC-430 (a leveling agent from 3M) were sequentially added, stirred at room temperature, and then PGMEA was added as a solvent so that the composition was 100 parts by weight in total to form a black matrix A photoresist composition was prepared.

[Example 34] Preparation of red photoresist composition

As shown in Table 2 below, the red photoresist composition was prepared in the same manner as in Example 33, except that 50 parts by weight of Pigment Red 177 (P.R. 177) dispersion having a solid content of 25 parts by weight was used instead of carbon black. was manufactured.

Example bookbinder
profit
(parts by weight) having ethylenically unsaturated bonds
polymeric compound
(parts by weight) light polymerization
initiator
(parts by weight) additive
(parts by weight) 17 1 (40) Dipentaerythritol Hexaacrylic Acid (20) compound 2-1
(0.5) FC-430
(0.1) 18 1 (40) Pentaerythritoltriacrylic acid (20) compound 2-2
(0.5) FC-430
(0.1) 19 1 (40) Trimethylolpropanetriacrylic acid (10)
Ethylene glycol diacrylic acid (10) compound 2-3
(0.5) FC-430
(0.1) 20 1 (40) dipentaerythritol pentaacrylic acid (20) Compounds 2-5
(0.5) FC-430
(0.1) 21 1 (40) Dipentaerythritol Hexaacrylic Acid (20) compound 2-6
(0.5) FC-430
(0.1) 22 1 (40) Pentaerythritoltriacrylic acid (20) compounds 2-9
(0.5) FC-430
(0.1) 23 1 (40) Trimethylolpropanetriacrylic acid (10)
Ethylene glycol diacrylic acid (10) Compounds 2-10
(0.5) FC-430
(0.1) 24 1 (40) Dipentaerythritol Hexaacrylic Acid (20) compound 2-11
(0.5) FC-430
(0.1) 25 1 (40) Pentaerythritoltriacrylic acid (20) Compounds 2-13
(0.5) FC-430
(0.1) 26 1 (40) Trimethylolpropanetriacrylic acid (10)
Ethylene glycol diacrylic acid (10) Compounds 2-14
(0.5) FC-430
(0.1) 27 2 (40) Bisphenol-A diglycidyl ether acrylic acid adduct (20) compound 2-1
(0.5) FC-430
(0.1) 28 2 (40) Trimethylolpropane triglycidyl ether acrylic acid adducts (20) compounds 2-9
(0.5) FC-430
(0.1) 29 3 (40) Pentaerythritoltriacrylic acid (20) compound 2-1
(0.5) FC-430
(0.1) 32 3 (40) Pentaerythritol Trimethacrylic Acid (20) compounds 2-9
(0.5) FC-430
(0.1) 31 1 (20)
2 (20) Dipentaerythritol Hexaacrylic Acid (20) compound 2-1
(0.5) FC-430
(0.1) 32 1 (20)
3 (20) Dipentaerythritol Hexaacrylic Acid (20) compound 2-1
(0.5) FC-430
(0.1) 33 1 (20) dipentaerythritol hexaacrylic acid (10) compound 2-1
(0.5) FC-430 (0.1)
Carbon Black (50) 34 1 (20) dipentaerythritol hexaacrylic acid (10) compound 2-1
(0.5) FC-430 (0.1)
PR177 (50)

[Comparative Example 1] Preparation of photoresist composition

A photoresist composition was prepared in the same manner as in Example 17, except that the photopolymerization initiator of Chemical Formula B was used instead of Compound 2-1 as the photopolymerization initiator.

[Formula B]

[Comparative Example 2] Preparation of photoresist composition

Except for using "3-(acetoxyimino)-1-(6-nitro-9H-fluoren-3-yl)propan-1-one" as the photopolymerization initiator instead of Compound 2-1, A photoresist composition was prepared in the same manner as in Example 17.

[evaluation]

Evaluation of the photoresist compositions prepared in Examples 17 to 34 and Comparative Examples 1 and 2 prepared by the above method was performed on a glass substrate, and sensitivity, remaining film rate, pattern stability, chemical resistance and ductility of the photoresist composition were evaluated. Performance was measured and the evaluation results are shown in Table 3 below.

1) Sensitivity

The photoresist compositions prepared in Examples 17 to 34 and Comparative Examples 1 and 2 were 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 0.04% KOH aqueous solution. . The exposure amount at which the step mask pattern maintains 80% thickness compared to the initial thickness was evaluated as sensitivity.

2) Remaining film rate

The photoresist compositions prepared in Examples 17 to 34 and Comparative Examples 1 and 2 were applied on a substrate using a spin coater, prebaked at 100° C. for 1 minute, exposed at 365 nm, and then heated at 230° C. Postbake was performed for 20 minutes at , and the thickness ratio (%) of the resist film before and after postbake 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 of observation with an electron microscope in the cross-sectional direction of the pattern were shown. A case in which the pattern side wall was erected at an angle of 55 degrees or more with respect to the substrate and the film was not reduced was evaluated as 'good', and a case in which film reduction was observed was judged as 'film thinning'.

4) Chemical resistance

After applying the photoresist composition prepared in Examples 17 to 34 and Comparative Examples 1 and 2 on a substrate using a spin coater, a resist film formed through processes such as prebake and postbake is stripper ( Stripper) solution at 40°C for 10 minutes, and then changes in transmittance and thickness of the resist film were examined. When the change in transmittance and thickness was 2% or less, it was judged as 'good', and when the change in transmittance and thickness was 2% or more, it was judged as 'poor'.

5) ductility

The photoresist compositions prepared in Examples 17 to 34 and Comparative Examples 1 and 2 were coated on a substrate with a spin coater, prebaked at 100 ° C. for 1 minute, exposed to light at the sensitivity of the photoresist, and KOH It was developed with an aqueous solution to form a pattern of 20 μm×20 μm. The formed pattern was crosslinked by postbake at 230° C. for 20 minutes, and the ductility of the pattern was measured using a nano indentor. The measurement of the nanoindenter was determined to be 'good' if the total displacement was 500 nm or more and 'poor' if the total displacement was 500 nm or less with 5 g.f loading.

Example Sensitivity
(mJ/cm ² ) remaining film rate
(%) pattern stability chemical resistance ductility 17 75 91 Good Good Good 18 85 91 Good Good Good 19 80 90 Good Good Good 20 80 89 Good Good Good 21 85 90 Good Good Good 22 85 90 Good Good Good 23 80 91 Good Good Good 24 85 90 Good Good Good 25 80 92 Good Good Good 26 80 92 Good Good Good 27 85 90 Good Good Good 28 80 91 Good Good Good 29 80 91 Good Good Good 32 85 91 Good Good Good 31 85 90 Good Good Good 32 80 90 Good Good Good 33 80 90 Good Good Good 34 85 91 Good Good Good Comparative Example 1 200 86 closed error Good Comparative Example 2 250 80 closed error error

From Table 3, when the quinolinyl beta oxime ester derivative compound according to an embodiment of the present invention is used as a photopolymerization initiator in a photoresist composition, the sensitivity is excellent even when used in a small amount, and the remaining film rate, pattern stability, chemical resistance and It was confirmed that due to excellent physical properties such as ductility, outgassing generated from the photopolymerization initiator in the exposure and post-bake process during the TFT-LCD manufacturing process can be minimized, contamination can be reduced, and defects that may occur due to this can be minimized.

Claims (12)

A quinolinyl beta oxime ester derivative compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
R ₁ and R ₈ are each independently hydrogen, (C ₁ -C ₂₀ )alkyl or (C ₆ -C ₂₀ )aryl;
R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are each independently hydrogen, (C ₁ -C ₂₀ )alkyl, (C ₆ -C ₂₀ )aryl, or (C ₆ -C ₂₀ )aryl (C ₁ -C ₂₀ )alkyl;
A is O or S. According to claim 1,
R ₁ and R ₈ are each independently hydrogen, methyl, ethyl, n -propyl, i-propyl, n -butyl, i -butyl, t -butyl, n -pentyl, i - pentyl, n -hexyl, i- hexyl, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, or phenanthryl;
R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are each independently hydrogen, methyl, ethyl, n -propyl, i -propyl, n -butyl, i -butyl, t -butyl, n- pentyl, i -pentyl, n -hexyl, i -hexyl, phenyl, benzyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl;
A is a quinolinyl beta oxime ester derivative compound, characterized in that O or S. According to claim 1,
A quinolinyl beta oxime ester derivative compound, characterized in that the quinolinyl beta oxime ester derivative compound is a compound represented by the following Chemical Formulas 2-1 to 2-16.
<Formula 2-1 to 2-16>

A photopolymerization initiator comprising the quinolinyl beta oxime ester derivative compound according to any one of claims 1 to 3. A photoresist composition comprising the photopolymerization initiator of claim 4, a binder resin, a polymerizable compound having an ethylenically unsaturated bond, and a solvent. According to claim 5,
Based on 100 parts by weight of the photoresist composition, 0.01 to 10 parts by weight of the quinolinyl beta oxime ester derivative, 3 to 50 parts by weight of a binder resin, 0.001 to 40 parts by weight of a polymeric compound having an ethylenically unsaturated bond, and 10 to 10 parts by weight of a solvent A photoresist composition comprising 95 parts by weight. According to claim 5,
The photoresist composition, characterized in that the binder resin is an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in the side chain.
According to claim 5,
The photoresist composition is selected from the group consisting of thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, thiol-based compounds, and O-acyloxime-based compounds other than the compound represented by Formula 1 A photoresist composition further comprising one or two or more photopolymerization initiators. According to claim 5,
The photoresist composition, characterized in that the photoresist composition further comprises a colorant. A molding comprising a cured product of the photoresist composition of claim 5. According to claim 10,
The molded article, characterized in that the molded article is an array planarization film, insulating film, color filter, column spacer, black column spacer, black matrix or color matrix. A display comprising the molding of claim 10.