TW201808925A - Oxime ester derivative compounds, photopolymerization initiator, and photosensitive composition containing the same - Google Patents

Abstract

Disclosed is an oxime ester derivative compound of Formula 1, and a photopolymerization initiator and a photosensitive composition comprising the same: wherein each of R1 to R3 is the same as defined in the detailed description.

Description

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

This disclosure relates to an oxime ester-derived compound, and a photopolymerization initiator and a photosensitive composition containing the same. More specifically, it relates to an oxime ester-derived compound having superior sensitivity, heat resistance, light resistance, chemical resistance, and curing properties, and a photopolymerization initiator and a photosensitive composition containing the same.

Many types are known as typical examples of photopolymerization initiators used in photosensitive compositions, such as acetophenone derivatives, benzophenone derivatives, triazine derivatives, Biimidazole derivatives, acylphosphine oxide derivatives, and oxime ester-derived compounds, among which oxime ester-derived compounds have the advantage that they are almost colorless but absorb ultraviolet rays and have high Free radical generation efficiency, excellent compatibility with photosensitive composition materials, and outstanding stability. However, early-developed oxime ester-derived compounds have low light initiation efficiency, especially due to the need to increase the exposure dose due to low sensitivity during pattern exposure, resulting in reduced yield.

Therefore, the development of a photopolymerization initiator having a high light sensitivity results in that sufficient sensitivity can be achieved in a small amount, resulting in a cost-saving effect, and an increase in yield due to a reduction in the exposure dose due to the high sensitivity.

However, when a conventional photopolymerization initiator is used to form a pattern, it is necessary to increase the amount of the photopolymerization initiator or increase the exposure dose due to the low sensitivity in the exposure process of the pattern formation, and the disadvantages are Mold contamination during exposure, and by-product formation after photopolymerization initiator decomposition during cross-linking at high temperatures reduces yield, and because exposure time decreases with increasing exposure dose, yields are being addressed.

The present disclosure is directed to provide an oxime ester-derived compound having superior sensitivity, heat resistance, chemical resistance, and curing properties, and a photopolymerization initiator and a photosensitive composition containing the same.

The present disclosure further provides a molded article comprising the cured product of the photosensitive composition.

The disclosure further provides a display device including the molded article.

In order to achieve the above object, according to one aspect of the present disclosure, oxime ester-derived compounds of the following examples are provided.

The first embodiment relates to an oxime ester-derived compound of Formula 1:

Among them, R ₁ and R ₂ are each independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C1-C20) alkoxy, (C6-C20) aryl (C1-C20) alkane Hydroxy (C1-C20) alkyl, hydroxy (C1-C20) alkoxy (C1-C20) alkyl, or (C3-C20) cycloalkyl; and R ₃ is (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) aryl (C1-C20) alkyl, or (C3-C20) cycloalkyl.

The second embodiment relates to the oxime ester-derived compound in the first embodiment, wherein R ₁ and R ₂ are each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, n-decyl, isodecyl, n-dodecyl, cyclopentyl, cyclohexyl, phenyl, benzyl, naphthalene Group, biphenyl, bitriphenyl, anthryl, indenyl, phenanthryl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, iso Butoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxy-isobutyl, hydroxy-n-pentyl, hydroxy-isoamyl, hydroxy-n-hexyl, hydroxy-isohexyl, Hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxy Ethoxybutyl, 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 third embodiment relates to the oxime ester-derived compound in the first or second embodiment, wherein the oxime ester-derived compound is selected from the compounds of the following formulae 2-1 to 2-19: <Formulas 2-1 to 2-19>

According to one aspect of the present disclosure, the photopolymerization initiators of the following examples are provided.

The fourth embodiment relates to a photopolymerization initiator including the oxime ester-derived compound of one of the first to third embodiments.

According to one aspect of the present disclosure, the photosensitive compositions of the following examples are provided.

The fifth embodiment relates to a photosensitive composition including: (a) an alkaline soluble resin; (b) a polymerizable compound having an ethylenically unsaturated bond; and (c) a photopolymerization process The initiator includes the oxime ester-derived compound of one of the first to third embodiments.

The sixth embodiment relates to the photosensitive composition in the fifth embodiment, wherein the oxime ester-derived compound is present in an amount of 0.01 to 10% by weight relative to the total amount of the photosensitive composition.

The seventh embodiment relates to the photosensitive composition of the fifth or sixth embodiment, wherein the photopolymerization initiator further comprises at least one selected from the group consisting of a thioxanthone compound and an acetophenone compound A group of biimidazole compounds, triazine compounds, O-fluorenyl oxime ester compounds, and thiol compounds.

The eighth embodiment relates to the photosensitive composition of one of the fifth to seventh embodiments, wherein the photosensitive composition further includes a colorant.

According to one aspect of the present disclosure, a molded article of the following embodiments and a display device including the same are provided.

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

The tenth embodiment relates to the molded article in the ninth embodiment, wherein the molded article is an array planarization film, an insulating film, a color filter, and a column spacer ( column spacers), black column spacers, or black matrices.

An eleventh embodiment relates to a display device including the film product in the tenth or ninth embodiment.

The advantage of the oxime ester-derived compound according to one embodiment of the present disclosure is that it has excellent sensitivity when used as a photopolymerization initiator of a photosensitive composition, and has outstanding characteristics such as residual film thickness, pattern stability, Heat resistance, chemical resistance, and ductility, and minimizing the amount of outgassed from photopolymerization initiators during exposure and post-baking processes in the manufacture of thin film transistor liquid crystal displays (TFT-LCD), Thereby reducing contamination and minimizing the resulting defects.

Here, the present disclosure will be described in further detail. Before describing, it should be understood that the terms and words used in this specification and the scope of the attached patent application should not be interpreted as being limited to general and dictionary meanings, but rather to correspond to the technical meanings and concepts of this disclosure, based on permission The inventors appropriately define terms to explain the principles of best interpretation.

Therefore, the embodiments described herein and the examples shown in the drawings are only the most preferred examples, and do not represent all the technical aspects of this disclosure. Therefore, it should be understood that various other equivalents and modifications can be used when submitting an application. To replace.

An oxime ester-derived compound according to one aspect of the present disclosure is represented by the following Formula 1:

In Formula 1, R ₁ and R ₂ are each independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C1-C20) alkoxy, (C6-C20) aryl (C1- C20) alkyl, hydroxy (C1-C20) alkyl, hydroxy (C1-C20) alkoxy (C1-C20) alkyl, or (C3-C20) cycloalkyl; and R ₃ is (C1-C20) Alkyl, (C6-C20) aryl, (C6-C20) aryl (C1-C20) alkyl, or (C3-C20) cycloalkyl.

As used herein, "alkyl", "alkoxy" and other substituents containing an "alkyl" moiety include straight or branched chain types, and "cycloalkyl" includes monocyclic and polycyclic hydrocarbons.

Furthermore, the term "aryl" as used herein refers to free radicals induced by the removal of one hydrogen from an aromatic hydrocarbon, and includes a single or thick and cyclic system, and even multiple aryl groups connected by a single bond.

In addition, the term "hydroxyalkyl" herein refers to an OH-alkyl group in which a hydroxyl group is bonded to an alkyl group as defined above, and the term "hydroxyalkoxyalkyl" refers to a hydroxyalkyl group in which an alkoxy group is bonded to a hydroxyalkyl group The group -O-alkyl, and alkenyl refers to a structure containing a ketone of an alkyl group or an aryl group bonded thereto.

In addition, the term “(C1-C20) alkyl” refers to an alkyl group having 1 to 20 carbon atoms, and the alkyl group may preferably be a (C1-C12) alkyl group.

The "(C6-C20) aryl group" means an aryl group having 6 to 20 carbon atoms, and the aryl group may be preferably a (C6-C18) aryl group. "(C1-C20) alkoxy" means an alkoxy group having 1 to 20 carbon atoms, and the alkoxy group may be preferably (C1-C10) alkoxy, and more preferably (C1-C4) Alkoxy.

"(C6-C20) aryl (C1-C20) alkyl" means an alkyl group having 1 to 20 carbon atoms in which one hydrogen is replaced with an aryl group having 6 to 20 carbon atoms, and may be preferably (C6 -C18) aryl (C1-C10) alkyl, and more preferably (C6-C18) aryl (C1-C6) alkyl.

"Hydroxy (C1-C20) alkyl" means an alkyl group having 1 to 20 carbon atoms in which one hydrogen is replaced by a hydroxyl group, and may be preferably a hydroxy (C1-C10) alkyl group, and more preferably a hydroxy (C1- C6) alkyl.

"Hydroxy (C1-C20) alkoxy (C1-C20) alkyl" means that one hydrogen is substituted with an alkoxy group having 1 to 20 carbon atoms, and the other hydrogen is substituted with a hydroxy group having 1 to 20 carbons An atomic alkyl group, and may be preferably a hydroxy (C1-C10) alkoxy (C1-C10) alkyl group, and more preferably a hydroxy (C1-C4) alkoxy (C1-C6) alkyl group.

"(C3-C20) cycloalkyl" means a cycloalkyl group having 3 to 20 carbon atoms, and may be preferably a (C3-C10) cycloalkyl group.

According to an embodiment of the present disclosure, R ₁ and R ₂ may be each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, iso Amyl, n-hexyl, isohexyl, n-octyl, n-decyl, isodecyl, n-dodecyl, cyclopentyl, cyclohexyl, phenyl, benzyl, naphthyl, biphenyl, bitriphenyl Group, anthryl, indenyl, phenanthryl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, Hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxy-isobutyl, hydroxy-n-pentyl, hydroxy-isopentyl, hydroxy-n-hexyl, hydroxy-isohexyl, hydroxymethoxymethyl, hydroxymethyl Oxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxy Pentyl, or hydroxyethoxyhexyl.

In addition, R ₃ may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, cyclopentyl, Cyclohexyl, or phenyl.

More specifically, R ₁ and R ₂ may each independently be methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-octyl, n-decyl, isodecyl, n-dodecyl Alkyl, cyclohexyl, phenyl, or benzyl; and R ₃ may be methyl, ethyl, n-propyl; or phenyl.

According to one embodiment of the present disclosure, the oxime ester-derived compound includes, but is not limited to, compounds of the following formulae 2-1 to 2-19.

The oxime ester-derived compound according to Formula 1 according to the present disclosure can be prepared from the following Reaction Formula 1.

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

In addition, a photopolymerization initiator according to one aspect of the present disclosure includes at least one type 1 oxime ester-derived compound.

In addition, a photosensitive composition according to one aspect of the present disclosure includes: (a) an alkaline soluble resin; (b) a polymerizable compound having an ethylenically unsaturated bond; and (c) a photopolymerization initiator , Comprising an oxime ester-derived compound of formula 1.

Here, the oxime ester-derived compound can be used as a photopolymerization initiator.

According to one aspect of the present disclosure, the patterning characteristics of the photosensitive composition are excellent in adjustability, and have outstanding film characteristics such as heat resistance and chemical resistance. A detailed description is provided below.

(a) Alkali soluble resin

The alkaline soluble resin contains an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond on a side chain.

An acrylic polymer refers to a polymer of acrylic monomers (including homopolymers and copolymers). Examples of acrylic monomers include methyl methacrylate, ethyl methacrylate, Propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, formic acid Decyl acrylate, dodecylmethacrylate (laurylmethacrylate), tetradecylmethacrylate, hexatradecylmethacrylate, hexadecylmethacrylate, isobornylmethacrylate, Adamantylmethacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, benzyl methacrylate, 2-methoxyethyl methacrylate, 2-methacrylic acid 2- Ethoxyethyl, acrylic, methacrylic, itaconic acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester, Monoalkyl itaconate, monoalkyl fumarate, glycidyl acrylate, glycidyl methacrylate thacrylate), 3,4-epoxybutyl methacrylate, 2,3-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethylmethacrylate, 3-methyloxetane-3-methylmethacrylate, 3-ethyloxetane-3-methylmethacrylate, styrene, α-methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide Amine, N-butylmaleimide, N-cyclohexylmaleimide, methacrylamide, and N-methylmethacrylamide are used alone or in combination.

In addition, an acrylic polymer having an acrylic unsaturated bond in a side chain is a copolymer formed by an addition reaction of an epoxy resin and an acrylic copolymer containing a carboxylic acid, and includes an addition reaction of 40 to 50% by an addition reaction of an epoxy resin. Adhesive resins obtained at 180 ° C, such as glycidylacrylate, glycidylmethacrylate, 3,4-methacrylic acid The addition of butyl oxide, 2,3-epoxycyclohexyl methacrylate, and 3,4-epoxycyclohexylmethylmethacrylate to methacrylic acid Carboxylic acid-containing acrylic copolymer obtained by bulk copolymerization, the aforementioned carboxylic acid acrylic acid, methacrylic acid, itaconic acid, maleic acid, and maleic acid monoalkyl ester monoalkyl ester), and at least two alkyl methacrylate monomers, such as the aforementioned alkyl methacrylates such as methyl methacrylate, and hexyl methacrylate, cyclohexyl methacrylate, isotyl methacrylate ( isobornylmethacrylate), adamantylmethacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, benzyl methacrylate, 2-methoxyethyl methacrylate, methyl 2-ethoxyethyl acrylate, styrene, α-methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide Arsenimine, N-propylmaleimide, N-butylmaleimide , N- cyclohexylmaleimide (PEI) methyl acrylamide (methacrylamide), and N- methyl acrylamide.

Another example of an acrylic polymer having an acrylic unsaturated bond in a side chain is a copolymer formed by addition reaction of a carboxylic acid and an acrylic copolymer containing an epoxy group, and Binder resin obtained at an addition reaction at 40 to 180 ° C, the aforementioned carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and maleic acid monoalkyl ester ( maleic acid monoalkyl ester), added to an acrylic copolymer containing epoxy groups obtained by copolymerization of acrylic monomers containing epoxy groups, the aforementioned acrylic monomers such as glycidyl acrylate, methacrylic acid shrink Glycidylmethacrylate, 3,4-epoxybutyl methacrylate, 2,3-epoxycyclohexyl methacrylate, and 3,4-epoxycyclohexyl methyl methacrylate (3,4- epoxycyclohexylmethylmethacrylate), and at least two alkyl methacrylate monomers, such as methyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, isocyanate methacrylate Ester (isobornylmethacrylate), adamantylmethacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, benzyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, styrene, α-methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethyl Maleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, methacrylamide, and N-methyl Methacrylamide.

According to an embodiment of the present disclosure, in order to adjust pattern characteristics and impart properties such as heat resistance and chemical resistance, the alkaline soluble resin may be present in an amount of 3 to 50% by weight relative to the total amount of the photosensitive composition. , Specifically 5 to 45 weight percent, and more specifically 8 to 40 weight percent.

The alkaline soluble resin may have a weight average molecular weight of 2,000 to 300,000, specifically 4,000 to 100,000, and a degree of dispersion of 1 to 10.0.

(b) Polymerizable compounds having ethylenically unsaturated bonds

The polyalkaline compound having an ethylenically unsaturated bond is cross-linked by a photoreaction when forming a pattern, and contributes to the formation of the pattern. When cross-heated at a high temperature, the cross-linking imparts chemical resistance and heat resistance.

The polymerizable compound having an ethylenically unsaturated bond may be present in an amount of 0.001 to 40 weight percent, specifically 0.1 to 30 weight percent, and more specifically 1 to 20 weight percent with respect to the total amount of the photosensitive composition.

When there is an excessive amount of a polymerizable compound having an ethylenically unsaturated bond, the disadvantage is that the degree of crosslinking is excessively increased, and the ductility of the pattern is decreased.

The polymerizable compound having an ethylenically unsaturated bond specifically includes an alkyl ester of methacrylic acid, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, a Dodecyl acrylate, glycidyl methacrylate, polyethylene glycol monomethacrylate with 2 to 14 ethylene oxide groups, ethylene glycol dimethacrylate ), Polyethylene glycol dimethacrylate with 2 to 14 ethylene oxide groups, propylene glycol dimethacrylate with 2 to 14 propylene oxide groups , Trimethylolpropanedimethacrylate, adduct of bisphenol A diglycidyletheracrylic acid, phthalate diester of β-hydroxyethylmethacrylate (phthalic acid diester of β-hydroxyethylmethacrylate), toluene diisocyanate adduct of β-hydroxyethyl methacrylate (toluene diis ocyannate adduct of β-hydroxyethylmethacrylate), compounds obtained by esterification of polyhydric alcohols and β-unsaturated carboxylic acids, such as trimethylolpropanetrimethacrylate, pentaerythritoltrimethacrylate, Pentaerythritoltetramethacrylate, dipentaerythritolpentamethacrylate, dipentaerythritolhexamethacrylate, and dipentaerythritol trimethacrylate, and polyglycidyl compound Acrylic acid adducts of poly glycidyl compounds, such as trimethylolpropanetriglycidyletheracrylic acid, are used alone or in combination.

(c) Photopolymerization initiator

In the photosensitive composition of the present disclosure, as a photopolymerization initiator, an oxime ester-derived compound of Formula 1 can be used. Relative to the total amount of the photosensitive composition being 100% by weight, it is more effective that the photopolymerization initiator is present at 0.01 to 10% by weight, and preferably 0.1 to 5% by weight, so as to improve transparency while minimizing the exposure dose.

(d) Auxiliary adhesive

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

A siloxane-based compound having an epoxy group or an amine group can improve adhesion between an ITO electrode and a photosensitive composition, and improve heat resistance characteristics after curing. Siloxyalkyl compounds having epoxy or amine groups include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, and (3-glycidoxypropyl) trimethoxysilane. (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane ) (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-epoxypropyl) ((3-glycidoxypropyl) dimethylethoxysilane), 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyl Triethoxysilane (3,4-epoxybutyltriethoxysilane), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4- (epoxycyclohexyl) ethyltriethoxysilane and 3-aminopropyltrimethoxysilane Alone or in combination.

The siloxane-based compound having an epoxy group or an amine group may be present in an amount of 0.0001 to 3% by weight based on the total weight of the photosensitive composition. When the content is less than the range, no additional effects are found, and when the content exceeds the range, the characteristics of the unexposed area deteriorate, scum, and residues remain on the lower substrate, ITO, or glass substrate.

(e) Other additives

If necessary, the photosensitive composition of the present disclosure may further include compatible additives, such as a photosensitizer; a thermal polymerization inhibitor; a defoaming agent; and a leveling agent.

Relative to the total amount of the photosensitive composition is 100% by weight, other additives may be present at 0.1 to 10% by weight, and when the content is less than the range, no additional effect is found, and when the content exceeds the range, an excessive amount may be formed. scum.

(f) Solvent

The photosensitive composition of the present disclosure is used to form a pattern by adding a solvent, coating on a substrate, radiating ultraviolet rays using a photomask, and developing using an alkaline developer solution.

Accordingly, the content of the solvent can be adjusted so that the sum of the content of the solvent and the content of the other components of the photosensitive composition is 100% by weight. Therefore, the content of the solvent can be changed according to the content of the other components of the photosensitive composition. For example, it is preferable to adjust the content of the solvent to 100% by weight based on the total amount of the photosensitive composition, and the amount of the solvent to be added is 10 to 95% by weight, so that the viscosity ranges from 1 to 50 centipoise (cps).

Considering compatibility with basic soluble resins, photoinitiators, and other compounds, the solvents include ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, and diethylene glycol dimethyl ethyl ether ( diethyleneglycol dimethylethylether), methylmethoxy propionate, ethylethoxy propionate (EEP), ethyl lactate, propylene glycol Monomethyl ether acetate (PGMEA), propylene glycol methyl ether propionate (PGMEP), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethylcellulose Threoacetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, Tetrahydrofuran (THF), methanol, ethanol, propanol, isopropanol, methyl cyperidine, ethyl cyperidine, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, Toluene, xylene, hexane, heptane, and octane, which are used alone or in combination.

(g) Other photopolymerization initiators

As for the photopolymerization initiator, the photosensitive composition of the present disclosure may use an oxime ester-derived compound alone, and the oxime ester-derived compound and at least one selected from the group consisting of a thioxanthone-based compound and an acetophenone-based compound may be used. Compounds of the group consisting of compound, biimidazole-based compound, triazine-based compound, O-fluorenyl oxime ester-based compound, and thiol-based compound are used in combination.

The photopolymerization initiator may be added in an amount of 0.01 to 5 weight percent with respect to the total amount of the photosensitive composition.

The thioxanthone-based compound includes, for example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichloro Thiothanone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone.

Acetophenone-based compounds include, for example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinylphenyl) butan-1-one, and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinylphenyl) Butan-1-one.

The biimidazole-based compound includes, for example, 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, and 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole.

Triazine-based compounds include, for example, 2,4,6-ginseno (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [ 2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) vinyl]- 4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) vinyl] -4,6-bis (trichloro (Methyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -s-triazine, 2- ( 4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, and 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.

The O-fluorenyl oxime ester compound includes, for example, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzylidene oxime), and ethyl ketone-1- [ 9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -1- (O-ethylamidoxime), ethyl ketone-1- [9-ethyl- 6- (2-methyl-4-tetrahydrofurylmethoxybenzylidene) -9H-carbazol-3-yl] -1- (O-acetamidooxime), and ethyl ketone-1- [9 -Ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanylmethoxymethoxybenzyl)}-9H-carbazole- 3-yl] -1- (O-acetamidooxime).

The thiol-based compound includes pentaerythritol tetrakis (3-mercaptopropionate).

(h) Colorants

The photosensitive composition according to an embodiment of the present disclosure may further include a colorant for anti-corrosion applications forming a color filter or a black matrix.

The colorant contains various pigments, such as a mixed system of red, green, blue, and brown, and cyan, magenta, yellow, and black pigments, and more specifically, the pigments include CI Pigment yellow 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148, 153, 154, 166, 168, CI pigment orange 36, 43, 51, 55, 59, 61, CI pigment red 9, 97, 122, 123, 149 , 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, CI pigment violet 19, 23, 29, 30, 37, 40, 50, CI pigment blue Colors 15, 15: 1, 15: 4, 15: 6, 22, 60, 64, CI Pigment Green 7, 36, CI Pigment Brown 23, 25, 26, CI Pigment Black 7, and Titan Black.

The colorant may be present in an amount of 5 to 50% by weight based on the total amount of the photosensitive composition. When the content is less than the range, the light-shielding performance is reduced, and when the content exceeds the range, faulty exposure or curing may occur.

According to an aspect of the present disclosure, a molded article including a cured product of the photosensitive composition is provided.

Molded products include, but are not limited to, array planarization film, insulating film, color filter, column spacer, black column spacer, Or black matrix.

In addition, according to one aspect of the present disclosure, various forms of displays including the molded article, such as a liquid crystal display and an OLED, are provided.

The photosensitive composition according to an embodiment of the present disclosure can be passed through a spin coater, a roll coater, a bar coater, and a slit coater. , Curtain coater, and various known printing and deposition methods for soda-lime glass, quartz glass, semiconductor substrate, metal, paper, and plastic support Substrate. In addition, a film can be formed on a support substrate and then transferred to another support substrate, and there are no restrictions on its application method.

In the following, in order to fully understand the purpose of this disclosure, the representative compounds of this disclosure will be described in detail through examples and comparative examples, and the examples according to this disclosure may be modified in many different forms. The scope of this disclosure should not be interpreted as It is limited to the examples mentioned below. The embodiments of this disclosure are provided to more fully describe the skilled artisan.

<Preparation of oxime ester-derived compound>

Example 1

Step 1: Synthesis of 10-butyl-10H-phenothiazine. Dissolve 10H-phenolthiazine (30g) in the reactor with dimethylsulfine (90ml), and add tetrabutylammonium bromide (2g). ) And 50% sodium hydroxide solution (120 ml), and after stirring for 30 minutes, 1-bromobutane (32.6 ml) was added dropwise and stirred at room temperature for 24 hours. After the reaction was completed, it was extracted three times with ethyl acetate and water. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The column was purified with hexane as a developing solvent to produce the target. Compound (27.0 g, 70.5%).

¹ H NMR (δ ppm; CDCl ₃ ): 0.93 (3H, t), 1.40-1.50 (4H, m), 1.74-1.82 (2H, q), 6.71-7.05 (2H, m), 7.11-7.14 (2H , m)

MS (m / e): 255

Step 2: Synthesis of 1,1 '-(10-butyl-10H-phenolthiazine-3,7-diyl) dibutan-1-one

After dissolving the product of Step 1 (27 g) in the reactor with dichloromethane (135 ml), aluminum chloride (42.0 g) and butanyl chloride (33.6 g) were added at 0 ° C or lower, and at room temperature Stir for 8 hours. After the reaction is completed, the reaction solution is added to ice water, stirred and left to remove the water layer. The organic layer is washed twice with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The alkane (1:10) was purified by column chromatography as a developing solvent to give the target product (17.0 g, 41%).

¹ H NMR (δ ppm; CDCl ₃ ): 0.96 (3H, t), 1.23 (6H, t), 1.35-1.70 (6H, m), 1.82-2.01 (2H, m), 2.45-2.76 (4H, m ), 4.10-4.14 (2H, m), 7.46-7.50 (2H, m), 8.29-8.33 (2H, m), 8.75 (2H, s)

MS (m / e): 395

Step 3: Synthesis of 1,1 '-(10-butyl-10H-phenolthiazine-3,7-diyl) bis (2- (hydroxyimino) butan-1-one)

After the product of step 2 (17.0 g) was added to tetrahydrofuran (85 ml) in the reactor, strong hydrochloric acid (10.8 mL) and isobutyl nitrite (13.3 g) were slowly added dropwise, followed by stirring at room temperature for 1 hour After 30 minutes of extraction with ethyl acetate and water 3 times, the organic layer was dried over anhydrous magnesium sulfate and crystallized from ethyl acetate to give the target compound (10.7 g, 55.0%).

¹ H NMR (δ ppm; CDCl ₃ ): 1.08 (3H, t), 1.24-1.28 (6H, m), 1.51-1.70 (2H, m), 1.82-2.01 (2H, m), 2.70-2.76 (4H , q), 4.10-4.14 (2H, m), 7.48-7.51 (2H, m), 8.30-8.34 (2H, m), 8.76 (2H, s)

MS (m / e): 453

Step 4: Synthesis of 1,1 '-(10-butyl-10H-phenolthiazin-3,7-diyl) bis (2- (ethoxyimino) butan-1-one)

After adding the product of step 3 (10.7 g) to ethyl acetate (107 ml) in the reactor, trimethylamine (7.3 g) and acetamidine chloride (5.65 g) were sequentially added dropwise at room temperature. After stirring at room temperature for 1 hour, distilled water was added, and the organic layer was washed twice with distilled water, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The obtained product was crystallized with ethyl acetate and hexane (1: 1) solvents to give the target Compound (8.7 g, 67.4%).

¹ H NMR (δ ppm; CDCl ₃ ): 1.09 (3H, t), 1.18-1.26 (6H, m), 1.59-1.67 (2H, m), 1.85-2.01 (2H, m), 2.31 (6H, s ), 2.80-2.87 (4H, m), 4.29-4.34 (2H, m), 7.54 (2H, d), 8.48 (2H, d), 8.81 (2H, s)

MS (m / e): 537

Decomposition point: 200.8 ℃

Examples 2 to 19

Under the same conditions as in Example 1, an oxime ester-derived compound was synthesized based on the compositions in Tables 1 and 2 below.

<Preparation of alkaline soluble resin>

Synthesis of Example 1

Propylene glycol monomethyl ether acetate (PGMEA, 200 mL) and azobisisobutyronitrile (AIBN, 1.5 g) were added to a 500 mL polymerization vessel, and methyl was added at a molar ratio of 20: 20: 40: 20, respectively. Acrylic acid ester, glycidyl methacrylate, methyl methacrylate, and dicyclopentanyl acrylate and 40% by weight of solid acrylic monomers were then polymerized by stirring in a nitrogen atmosphere at 70 ° C. for 5 hours to An acrylic polymer (a-1) was prepared. The weight average molecular weight of the obtained polymer was 25,000, and the degree of dispersion was 1.9.

Synthesis of Example 2

Propylene glycol monomethyl ether acetate (200 mL) and AIBN (1.0 g) were added to a 500 mL polymerization container, and methacrylate, styrene, and methacrylic acid were added at a molar ratio of 40: 20: 20: 20, respectively. Methyl ester, cyclohexyl methacrylate, and a 40% by weight solid acrylic monomer were polymerized by stirring in a nitrogen atmosphere at 70 ° C. for 5 hours to synthesize a copolymer. N, N-xylylamine (0.3 g) and glycidyl methacrylate in a 20 mole ratio per 100 moles of total monomers were put into a reaction flask, and stirred at 100 ° C for 10 hours to prepare An acrylic polymer (a-2) having an acrylic unsaturated bond in a side chain. The weight average molecular weight of the obtained polymer was 20,000, and the degree of dispersion was 2.0.

Synthesis of Example 3

Propylene glycol monomethyl ether acetate (200 mL) and AIBN (1.0 g) were added to a 500 mL polymerization container, and glycidyl methacrylate, styrene, and formazan were added at a molar ratio of 40: 20: 20: 20, respectively. Methyl acrylate, and cyclohexyl methacrylate and 40 weight percent solid acrylic monomer were polymerized by stirring in a nitrogen atmosphere at 70 ° C. for 5 hours to synthesize a polymer. N, N-xylylamine (0.3 g) and acrylic acid in a molar ratio of 20 moles per 100 moles of total monomers were put into a reaction flask, and stirred at 100 ° C for 10 hours to prepare acrylic acid having a side chain Unsaturated acrylic polymer (a-3). The weight average molecular weight of the obtained polymer was 18,000, and the degree of dispersion was 1.8.

Examples 20 to 35: Preparation of photosensitive composition

In Examples 20 to 35, basic soluble resins a-1 to a-3; polymerizable compounds having ethylenically unsaturated bonds; photopolymerization initiators of the present disclosure; and FC-430 (3M leveling agent) According to the ingredients listed in Table 3 below and their contents, they are sequentially placed in a reaction mixing tank with a UV shield and a stirrer, followed by stirring at room temperature, adding PGMEA solvent to equilibrate, so that The total weight percentage of the assembly is 100 to prepare a photosensitive composition.

Examples 36 to 37: Preparation of colored photosensitive composition

A colored photosensitive composition was prepared by the same method as in Example 17, except that in Example 36, 50% by weight of a carbon black dispersion was added to PGMEA having 25% by weight of solids, and in Example 37, To PGMEA with 25 weight percent solids was added 50 weight percent pigment red 177 (PR177) dispersion, as described in Table 3 below.

Example 38

A photosensitive composition was prepared by the same method as in Example 17, except that a mixture of the compound of Example 1 and the following formula 3 was used as a photopolymerization initiator, as described in Table 3 below.

<Ingredients>

(a) Alkali soluble resin

(b) Polymerizable compounds having ethylenically unsaturated bonds

b-1: dipentaerythritol hexaacrylate

b-2: dipentaerythritol pentaacrylate

b-3: pentaerythritoltriacrylate

b-4: pentaerythritoltrimethacrylate

b-5: trimethylolpropantriacrylate

b-6: ethyleneglycoldiacrylate

b-7: bisphenol-A diglycidyletheracrylate adduct

b-8: trimethylolpropantriglycidyletheracrylate adduct

(c) Photopolymerization initiator

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

(h) Colorants

h-1: carbon black (25 weight percent solids)

h-2: Pigment Red 177 (P.R.177) (25 weight percent solids)

Comparative Example 1

A photopolymerizable composition was prepared by the same method as in Example 17, except that the photopolymerization initiator was used, instead of the compound of Example 1, the following formula 4 was used.

Comparative Example 2

A photopolymerizable composition was prepared by the same method as in Example 17, except that a photopolymerization initiator was used, instead of Example 1, Formula 5 was used.

<Evaluation>

The evaluation of the photosensitive compositions prepared in Examples 20 to 38 and Comparative Examples 1 to 2 was performed on a glass substrate, and the properties of the photosensitive composition such as sensitivity, residual film thickness, pattern stability, The evaluation results of chemical resistance and ductility are shown in Table 4 below.

1) Sensitivity

A photoresist was spin-coated on a glass substrate, dried on a hot plate at 100 ° C. for 1 minute, then exposed using a step mask, and developed in a 0.04% potassium hydroxide aqueous solution. Sensitivity was evaluated based on an exposure dose where the thickness of the step mask pattern was maintained at 80% of the initial thickness.

2) Residual film thickness

After applying the photosensitive composition to the substrate using a spin coater, pre-baking was performed at 100 ° C for 1 minute, followed by exposure at 365 nanometers (nm), and then at 230 ° C. Post-baking was performed for 20 minutes, and the thickness ratio (%) of the resist film before and after the post-baking was measured.

3) Pattern stability

A silicon wafer having a photoresist pattern was cut in a direction perpendicular to the hole pattern, and observation results in a cross-sectional direction of the pattern were displayed using a microscope. The sidewall of the pattern stood up to an angle of 55 degrees or more with respect to the substrate, and no film reduction was defined as "excellent", and a decrease in film observed was defined as "film reduction".

4) Chemical resistance

After the photosensitive composition was applied to the substrate using a spin coater, the resist film formed through the pre-baking process and the post-baking process was immersed in a peeling solution at 40 ° C for 10 minutes, and whether a resist film was observed Any change in transmittance and thickness. Changes in transmittance and thickness of 2% or less are defined as "good", and changes in transmittance and thickness of 2% or less are defined as "bad".

5) ductility

The photosensitive composition was spin-coated on the substrate, and then pre-baked at 100 ° C for 1 minute, exposed to a sensitive photoresist, and developed under a potassium hydroxide aqueous solution to form a pattern of 20 microns (μm) x 20μm . The formed pattern was crosslinked by post-baking at 230 ° C for 20 aliquots, and the pattern was measured using a nano indentor to judge ductility. The measurement of the nanoindenter was performed under a load of 5 gravity units (g). A total variation of 500 nm or more was defined as "good", and a total variation of 500 nm or less was defined as "bad".

It can be found from Table 4 that the oxime ester-derived compound of the present disclosure has remarkably excellent sensitivity, and has outstanding properties such as post-residue degree, pattern stability, chemical resistance, and ductility, even when used as photosensitivity The composition has a small amount of a photopolymerization initiator.

Claims (12)

An oxime ester derivative compound of formula 1: Among them, R ₁ and R ₂ are each independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C1-C20) alkoxy, (C6-C20) aryl (C1-C20) alkane Hydroxy (C1-C20) alkyl, hydroxy (C1-C20) alkoxy (C1-C20) alkyl, or (C3-C20) cycloalkyl; and R ₃ is (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) aryl (C1-C20) alkyl, or (C3-C20) cycloalkyl. The oxime ester-derived compound according to item 1 in the scope of the patent application, wherein R ₁ and R ₂ are each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert- Butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, n-decyl, isodecyl, n-dodecyl, cyclopentyl, cyclohexyl, phenyl, benzyl, naphthyl , Biphenyl, bitriphenyl, anthryl, indenyl, phenanthryl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy Group, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxy-isobutyl, hydroxy-n-pentyl, hydroxy-isopentyl, hydroxy-n-hexyl, hydroxy-isohexyl, hydroxymethoxymethyl, Hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxy Ethoxypentyl, or hydroxyethoxyhexyl; and R ₃ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl ,positive Hexyl, isohexyl, cyclopentyl, cyclohexyl, or phenyl. The oxime ester-derived compound according to item 1 of the scope of the patent application, wherein the oxime ester-derived compound is selected from the group consisting of the following formulas 2-1 to 2-19: A photopolymerization initiator includes the oxime ester-derived compound described in any one of claims 1 to 3. A photosensitive composition comprising: (a) an alkali-soluble resin; (b) a polymerizable compound having an ethylenically unsaturated bond; and (c) a photopolymerization initiator, including patent applications ranging from 1 to The oxime ester-derived compound according to any one of 3 items. The photosensitive composition according to item 5 of the scope of patent application, wherein the oxime ester-derived compound is present in an amount of 0.01 to 10% by weight relative to the total amount of the photosensitive composition. The photosensitive composition according to item 5 of the scope of application for a patent, wherein the photopolymerization initiator further comprises a compound selected from the group consisting of thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, O -At least one of the group consisting of a fluorenyl oxime ester compound and a thiol compound. The photosensitive composition according to item 5 of the scope of patent application, wherein the photosensitive composition further comprises a colorant. The photosensitive composition according to item 7 of the scope of the patent application, wherein the photosensitive composition further comprises a colorant. A molded product comprising the cured product of the photosensitive composition described in item 5 of the scope of patent application. The molded article according to item 10 of the patent application scope, wherein the molded article is an array planarization film, an insulating film, a color filter, a column spacer, a black column spacer, or a black matrix. A display device includes the molded product described in item 10 of the scope of patent application.