CN109153658B - Oxime ester derivative compound, photopolymerization initiator containing same, and photosensitive composition - Google Patents
Oxime ester derivative compound, photopolymerization initiator containing same, and photosensitive composition Download PDFInfo
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
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Abstract
The invention discloses an oxime ester derivative compound, and a photopolymerization initiator and a photosensitive composition containing the oxime ester derivative compound.
Description
Technical Field
The present invention relates to an oxime ester derivative compound, and a photopolymerization initiator and a photosensitive composition containing the same. More particularly, the present invention relates to an oxime ester derivative compound having excellent sensitivity, heat resistance, light resistance, chemical resistance, and curing properties, and a photopolymerization initiator and a photosensitive composition comprising the same.
Background
As typical examples of the photopolymerization initiator used in the photosensitive composition, there have been known many types, for example, acetophenone derivatives, benzophenone derivatives, triazine derivatives, bisimidazole derivatives, acylphosphine oxide derivatives, and oxime ester derivative compounds, wherein the oxime ester derivative compounds have advantages that they absorb ultraviolet rays but are almost colorless and have high radical generation efficiency, excellent compatibility with photosensitive composition materials, and excellent stability. However, the oxime ester derivative compounds developed earlier have low photoinitiation efficiency, and in particular, the exposure dose needs to be increased due to low sensitivity during pattern exposure, resulting in a decrease in yield.
Therefore, the development of a photopolymerization initiator having high photosensitivity leads to the realization of sufficient sensitivity in a small amount, the cost-saving effect, and the reduction of exposure dose due to high sensitivity, the increase of throughput.
However, when a pattern is formed using a conventional photopolymerization initiator, it is necessary to increase the amount of the photopolymerization initiator or increase the exposure dose due to low sensitivity in the exposure process for pattern formation, and there are disadvantages in that a mask is contaminated during exposure, and by-products generated after the photopolymerization initiator is decomposed during crosslinking at high temperature decrease yield, and there is a problem in that the yield decreases since the exposure processing time increases with the increase of the exposure dose, and thus, efforts are being made to solve this problem.
Relevant documents
Patent literature
(patent document 1) WO02/100903 (2002, 12 and 19 days)
(patent document 2) japanese patent laid-open No.: 2005-025169 (2005, 27 th month)
(patent document 3) WO07/071497 (2007, 6 and 28 days)
(patent document 4) Korean patent publication No. 2013-0124215 (11/13/2013)
(patent document 5) korean patent laid-open No.: 2013-0115272 (10 months and 21 days 2013).
Disclosure of Invention
Technical problem
The present invention relates to provide an oxime ester derivative compound having excellent sensitivity, heat resistance, chemical resistance and curing properties, and a photopolymerization initiator and a photosensitive composition comprising the same.
The present invention further provides a molded article comprising a cured product of the photosensitive composition.
The present invention further provides a display device comprising the molded article.
Technical scheme
In order to achieve the above object, according to one aspect of the present invention, an oxime ester derivative compound of the following embodiment is provided.
The first embodiment relates to an oxime ester derivative compound represented by formula 1:
< formula 1>
Wherein R is 1 And R 2 Each independently is hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C1-C20) alkoxy, (C6-C20) aryl (C1-C20) alkyl, hydroxy (C1-C20) alkoxy (C1-C20) alkyl, or (C3-C20) cycloalkyl; and
R 3 is (C1-C20) alkyl, (C6-C20) aryl (C1-C20) alkyl or (C3-C20) cycloalkyl.
A second embodiment is directed to the oxime ester derivative compound of the first embodiment wherein R is 1 And R 2 Each independently hydrogen, methyl, ethyl, n-propyl, iso-propylPropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, n-decyl, isodecyl, n-dodecyl, cyclopentyl, cyclohexyl, phenyl, benzyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxyisobutyl, hydroxy-n-pentyl, hydroxyisopentyl, hydroxy-n-hexyl, hydroxyisohexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, 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.
A third embodiment is directed to the oxime ester derivative compound of the first or second embodiment wherein the oxime ester derivative compound is selected from the group consisting of compounds of the following formulae 2-1 to 2-19:
< formulas 2-1 to 2-19>
According to an aspect of the present disclosure, there is provided a photopolymerization initiator of the following embodiments.
A fourth embodiment relates to a photopolymerization initiator including the oxime ester derivative compound of one of the first to third embodiments.
According to one aspect of the present invention, there is provided a photosensitive composition of the following embodiments.
A fifth embodiment relates to a photosensitive composition, including:
(a) An alkali-soluble resin;
(b) A polymerizable compound having an ethylenically unsaturated bond; and
(c) A photopolymerization initiator comprising the oxime ester derivative compound of one of the first to third embodiments.
A sixth embodiment relates to the photosensitive composition of the fifth embodiment, wherein the amount of the oxime ester derivative compound is 0.01 to 10wt% based on 100wt% of the total amount of the photosensitive composition.
A 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-based compound, an acetophenone-based compound, a biimidazole-based compound, a triazine-based compound, an O-acyloxime ester (O-acyloxime ester) -based compound, and a thiol-based compound.
An eighth embodiment relates to the photosensitive composition of one of the fifth to seventh embodiments, wherein the photosensitive composition further comprises a colorant.
According to an aspect of the present invention, there are provided the molded article of the following embodiments, and a display device including the same.
The ninth embodiment relates to a molded article comprising a cured product of the photosensitive composition of one of the fifth to eighth embodiments.
A tenth embodiment relates to the molded article of the ninth embodiment, wherein the molded article is an array planarization film (array planarization film), an insulating film, a color filter, a columnar spacer, a black columnar spacer, or a black matrix.
An eleventh embodiment is directed to a display device including the film article of the ninth or tenth embodiment.
Advantageous effects
The oxime ester derivative compound according to an embodiment of the present invention is advantageous in that it has excellent sensitivity when used as a photopolymerization initiator for a photosensitive composition, and has outstanding properties such as residual film thickness, pattern stability, heat resistance, chemical resistance, and ductility; and the oxime ester derivative compound minimizes the amount of outgas generated from a photopolymerization initiator during an exposure and post-baking (post-baking) process in the manufacture of a thin film transistor-liquid crystal display (TFT-LCD), thereby reducing contamination and minimizing defects generated therefrom.
Detailed Description
Here, the present invention will be described in further detail. Before the description, it should be understood that the terms and words used in the specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation.
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 the present disclosure, and it should be understood that these embodiments and examples may be substituted with various other equivalents and modifications at the time of filing this application.
An oxime ester derivative compound according to one aspect of the present disclosure is represented by the following formula 1:
< formula 1>
In formula 1, R 1 And R 2 Each independently is hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C1-C20) alkoxy, (C6-C20) aryl (C1-C20) alkyl, hydroxy (C1-C20) alkoxy (C1-C20) alkyl, or (C3-C20) cycloalkyl; and
R 3 is (C1-C20) alkyl, (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 a radical induced by an aromatic hydrocarbon by the removal of one hydrogen, and includes monocyclic or fused ring systems, even aryl groups connected by single bonds.
Further, the term "hydroxyalkyl" as used herein refers to an OH-alkyl group in which a hydroxyl group is bonded to an alkyl group as defined above, the term "hydroxyalkoxyalkyl" as used herein refers to a hydroxyalkyl-O-alkyl group in which an alkoxy group is bonded to a hydroxyalkyl group, and an alkenyl group refers to a ketone-containing structure comprising an alkyl or aryl group bonded thereto.
Further, the term "C1-C20 alkyl" as used herein refers to an alkyl group having 1 to 20 carbon atoms, and the alkyl group may preferably be a (C1-C12) alkyl group.
"C6-C20 aryl" refers to an aryl group having 6 to 20 carbon atoms, and the aryl group may preferably be a (C6-C18) aryl group. "C1-C20 alkoxy" refers to an alkoxy group having 1 to 20 carbon atoms, and the alkoxy group may preferably be a (C1-C10) alkoxy group, and more preferably a (C1-C4) alkoxy group.
"C6-C20 aryl (C1-C20) alkyl" refers to an alkyl group having 1 to 20 carbon atoms with one hydrogen substituted with an aryl group having 6 to 20 carbon atoms, and may preferably be a (C6-C18) aryl (C1-C10) alkyl group, and more preferably a (C6-C18) aryl (C1-C6) alkyl group.
"hydroxy (C1-C20) alkyl" refers to an alkyl group having 1 to 20 carbon atoms in which one hydrogen is replaced by a hydroxy group, and may preferably be hydroxy (C1-C10) alkyl, and more preferably hydroxy (C1-C6) alkyl.
"hydroxy (C1-C20) alkoxy (C1-C20) alkyl" refers to an alkyl group having 1 to 20 carbon atoms with one hydrogen substituted by an alkoxy group having 1 to 20 carbon atoms and the other hydrogen substituted by a hydroxy group, and may preferably be a hydroxy (C1-C10) alkoxy (C1-C10) alkyl group, and more preferably a hydroxy (C1-C4) alkoxy (C1-C6) alkyl group.
"C3-C20 cycloalkyl" refers to a cycloalkyl group having 3 to 20 carbon atoms, and may preferably be a (C3-C10) cycloalkyl group.
According to an embodiment of the present disclosure, R 1 And R 2 Can each independently be 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, terphenyl, anthracenyl, indenyl, phenanthryl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxyisobutyl, hydroxy-n-pentyl, hydroxyisopentyl, hydroxy-n-hexyl, hydroxyisohexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl.
Furthermore, R 3 Can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, cyclopentyl, cyclohexyl or phenyl.
More specifically, R 1 And R 2 Can each independently be methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-octyl, n-decyl, isodecyl, n-dodecyl, cyclohexyl, phenyl or benzyl; and R 3 It may be methyl, ethyl, n-propyl or phenyl.
According to embodiments of the present disclosure, oxime ester derivative compounds include, but are not limited to, the following compounds of formulas 2-1 to 2-19:
< formulas 2-1 to 2-19>
Oxime ester derivative compounds of formula 1 according to the present disclosure can be prepared by reaction formula 1 as follows:
< reaction formula 1>
In reaction formula 1, R 1 To R 3 The same as defined in formula 1, and X is halogen.
Further, the photopolymerization initiator according to an aspect of the present disclosure includes at least one type of oxime ester derivative compound represented by formula 1.
Further, a photosensitive composition according to an aspect of the present disclosure includes:
(a) An alkali-soluble resin;
(b) A polymerizable compound having an ethylenically unsaturated bond; and
(c) A photopolymerization initiator comprising an oxime ester derivative compound of formula 1.
Here, the oxime ester derivative compound may serve as a photopolymerization initiator.
The photosensitive composition according to an aspect of the present disclosure is excellent in pattern characteristic controllability, and has outstanding film characteristics such as heat resistance and chemical resistance. A detailed description is provided below.
(a) Alkali soluble resin
The alkali-soluble resin contains an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in a side chain.
The acrylic polymer refers to a polymer (including a homopolymer and a copolymer) of an acrylic monomer, examples of the acrylic monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, isobornyl methacrylate, adamantyl methacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, benzyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, monoalkyl maleate, monoalkyl itaconate, monoalkyl fumarate, glycidyl acrylate, glycidyl methacrylate, 3, 4-epoxybutyl methacrylate, 2, 3-epoxycyclohexyl methacrylate, 3, 4-epoxycyclohexylmethyl methacrylate, 3-methyloxetane-3-methacrylate, 3-ethyloxetane-3-methacrylate, styrene- α -styrene, N-octylstyrene-maleimide, N-cyclohexylmaleimide, N-maleimide, N-cyclohexylmaleimide and N-methyl maleimide, they may be used alone or in combination.
Further, the acrylic polymer having an acrylic unsaturated bond in a side chain is a copolymer formed by an addition reaction of an epoxy resin, such as glycidyl acrylate, glycidyl methacrylate, 3, 4-epoxybutyl methacrylate, 2, 3-epoxycyclohexyl methacrylate and 3, 4-epoxycyclohexylmethyl methacrylate, with an acrylic copolymer containing a carboxylic acid, obtained by copolymerization of an acrylic monomer containing a carboxylic acid (such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and monoalkyl maleate) with at least two alkylmethacrylate monomers, and includes a binder resin obtained by an addition reaction of an epoxy resin, such as glycidyl acrylate, glycidyl methacrylate, 3, 4-epoxybutyl methacrylate, 2, 3-epoxycyclohexyl methacrylate and 3, 4-epoxycyclohexylmethyl methacrylate, with an acrylic copolymer containing a carboxylic acid, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and monoalkyl maleate, the at least two alkylmethacrylate-based monomers are, for example, methyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, adamantyl methacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, benzyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, styrene, alpha-methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, methacrylamide and N-methylmethacrylamide.
Another example of the acrylic polymer having an acrylic unsaturated bond in a side chain is a copolymer formed by an addition reaction of a carboxylic acid with an epoxy group-containing acrylic copolymer obtained by copolymerization of an epoxy group-containing acrylic monomer, such as glycidyl acrylate, glycidyl methacrylate, 3, 4-epoxybutyl methacrylate, 2, 3-epoxycyclohexyl methacrylate, and 3, 4-epoxycyclohexylmethyl methacrylate, and an addition reaction of an acrylic monomer containing a carboxylic acid (e.g., acrylic acid, methacrylic acid, itaconic acid, maleic acid, and monoalkyl maleate) with an acrylic copolymer containing an epoxy group, such as methyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, adamantyl methacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, benzyl methacrylate, 2-methoxyethyl methacrylate, N-methoxyethyl styrene, N-ethoxystyrene, N-methacryloyl styrene, N-maleimide, N-ethoxystyrene, N-maleimide, N-methacryloyl maleimide, and N-ethoxystyrene maleimide, and the adhesive resin at 40 to 180 ℃.
According to an embodiment of the present disclosure, the alkali soluble resin may be present in an amount of 3 to 50wt%, particularly 5 to 45wt%, and more particularly 8 to 40wt%, based on 100wt% of the total amount of the photosensitive composition, in order to adjust pattern characteristics and impart film properties such as heat resistance and chemical resistance.
The alkali-soluble resin may have a weight average molecular weight of 2,000 to 300,000, particularly 4,000 to 100,000, and a dispersity of 1 to 10.0.
(b) Polymerizable compound having ethylenically unsaturated bond
The polymerizable compound having an ethylenically unsaturated bond is crosslinked by photoreaction at the time of forming a pattern and contributes to pattern formation, and when heat is applied at high temperature, the polymerizable compound having an ethylenically unsaturated bond is crosslinked to impart chemical resistance and heat resistance.
The amount of the polymerizable compound having an ethylenically unsaturated bond may be 0.001 to 40wt%, particularly 0.1 to 30wt%, more particularly 1 to 20wt%, based on 100wt% of the total amount of the photosensitive composition.
When the polymerizable compound having an ethylenically unsaturated bond is present in excess, there are disadvantages in that the degree of crosslinking excessively increases and the pattern ductility decreases.
The polymerizable compound having an ethylenically unsaturated bond specifically includes alkyl esters of methacrylic acid, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, glycidyl methacrylate, polyethylene glycol monomethacrylate having 2 to 14 ethylene oxide groups, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate having 2 to 14 ethylene oxide groups, propylene glycol dimethacrylate having 2 to 14 propylene oxide groups, trimethylolpropane dimethacrylate, bisphenol a diglycidyl ether acrylic acid adduct, phthalic diester of β -hydroxyethyl methacrylate, toluene diisocyanate adduct of β -hydroxyethyl methacrylate, compounds obtained by esterification of polyhydric alcohol and α, β -unsaturated carboxylic acid (for example, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethylacrylate, dipentaerythritol hexamethacrylate, and dipentaerythritol trimethacrylate), and acrylic acid adducts of polyglycidyl compounds (for example, trimethylolpropane triglycidyl ether acrylic acid adducts, which may be used alone or in combination.
(c) Photopolymerization initiator
In the photosensitive composition of the present disclosure, as a photopolymerization initiator, an oxime ester derivative compound of formula 1 can be used. The amount of the photopolymerization initiator is more effectively 0.01 to 10wt%, preferably 0.1 to 5wt%, based on 100wt% of the total amount of the photosensitive composition, thereby improving transparency while minimizing the exposure dose.
(d) Auxiliary adhesive
In addition, the photosensitive composition of the present disclosure may further include a siloxane-based compound having an epoxy group or an amine group as an auxiliary binder, if necessary.
The siloxane-based compound having an epoxy group or an amine group can improve the adhesion between the ITO electrode and the photosensitive composition and improve heat resistance after curing. The siloxane-based compound having an epoxy group or an amine group includes (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3, 4-epoxybutyltrimethoxysilane, 3, 4-epoxybutyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, and aminopropyltrimethoxysilane, which may be used alone or in combination.
The amount of the siloxane-based compound having an epoxy group or an amine group may be 0.0001 to 3wt% based on 100wt% of the total amount of the photosensitive composition. When the content is less than the range, no additional effect is found, and when the content exceeds the range, the characteristics of the unexposed area are deteriorated, and scum (scum) and residue may remain on the lower substrate, ITO or glass substrate.
(e) Other additives
The photosensitive composition of the present invention may further contain additives having compatibility, for example, a photosensitizer, a thermal polymerization inhibitor, an antifoaming agent and a leveling agent, if necessary.
The amount of other additives may be 0.1 to 10wt% based on 100wt% of the total amount of the photosensitive composition, and when the content is less than this range, no additional effect is found, and when the content exceeds this range, excessive scum may be formed.
(f) Solvent(s)
The photosensitive composition of the present disclosure is used for forming a pattern by a method of adding a solvent, coating on a substrate, irradiating ultraviolet rays using a mask, and developing using an alkaline developer solution.
Accordingly, the content of the solvent can be adjusted so that the total of the content of the solvent and the content of the other components of the photosensitive composition is 100wt%, and therefore, the content of the solvent can be changed according to the content of the other components of the photosensitive composition. For example, the content of the solvent is preferably adjusted so that the amount of the solvent added is 10 to 95wt% based on 100wt% of the total amount of the photosensitive composition to provide a viscosity in the range of 1 to 50 centipoise (cps).
The solvent includes ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxypropionate, ethyl Ethoxypropionate (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-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ -butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran (THF), methanol, ethanol, propanol, isopropanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol diethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane, and octane, which may be used alone or in combination, in consideration of compatibility with alkali-soluble resins, photoinitiators, and other compounds.
(g) Other photopolymerization initiators
As the photopolymerization initiator, the photosensitive composition of the present invention may use an oxime ester derivative compound alone, or may use an oxime ester derivative compound in combination with at least one compound selected from the group consisting of a thioxanthone-based compound, an acetophenone-based compound, a bisimidazole-based compound, a triazine-based compound, an O-acyloxime ester-based compound, and a thiol (thiol) -based compound.
The photopolymerization initiator may be added in an amount of 0.01 to 5wt% based on 100wt% of the total amount of the photosensitive composition.
The thioxanthone-based compounds include, for example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-dichlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone and 2, 4-diisopropylthioxanthone.
Acetophenone compounds include, for example, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.
The biimidazole-based compound includes, for example, 2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2, 4-dichlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole and 2,2 '-bis (2, 4, 6-trichlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole.
Triazine compounds include, for example, 2,4, 6-tris (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 (trichloromethyl) -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-acyloxime ester-based compounds include, for example, 1, 2-octanedione-1- [4- (phenylthio) phenyl ] -2- (o-benzoyloxime), ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (o-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl ] -1- (o-acetyloxime), and ethanone-1- [ 9-ethyl-6- { 2-methyl-4- (2, 2-dimethyl-1, 3-dioxanone-yl) methoxybenzoyl } -9H-carbazol-3-yl ] -1- (o-acetyloxime.
The thiol-based compound includes pentaerythritol tetrakis (3-mercaptopropionate).
(h) Colouring agent
The photosensitive composition according to an embodiment of the present invention may further include a colorant for anti-corrosion application for forming a color filter or a black matrix.
The colorant includes various pigments, for example, red, green, blue and brown color mixing systems, i.e., cyan, magenta, yellow and black pigments, and more specifically, available pigments include 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, 4, 15; c.i. pigment green 7, 36; c.i. pigment brown 23, 25, 26; c.i. pigment black 7; and titanium black.
The amount of the colorant may be 5 to 50wt% based on 100wt% of the total amount of the photosensitive composition. When the content is less than this range, light-shielding performance is lowered, and when the content exceeds this range, faulty exposure or curing may occur.
According to an aspect of the present invention, there is provided a molded article comprising a cured product of the photosensitive composition.
The molded article includes, but is not limited to, an array planarization film (array planarization film), an insulating film (insulating film), a color filter (color filter), a column spacer (column spacer), a black column spacer (black column spacer), or a black matrix (black matrix).
Further, according to an aspect of the present invention, there are provided various forms of displays, for example, liquid crystal displays and OLEDs, including the molded article.
The photosensitive composition according to an embodiment of the present invention can be applied to a support substrate of soda-lime glass, quartz glass, a semiconductor substrate, metal, paper, and plastic by a spin coater, a roll coater, a bar coater, a slit coater, a curtain coater, and various known printing and deposition methods. Further, a film may be formed on a support substrate and then transferred to another support substrate, and the method of applying it is not limited.
Hereinafter, representative compounds of the present invention will be described in detail by examples and comparative examples for the purpose of sufficiently understanding the present invention, and embodiments according to the present invention may be modified in many different forms, and the scope of the present invention should not be construed as being limited to the examples mentioned below. Embodiments of the present invention will be provided to those skilled in the art to more fully describe the invention.
Examples
< preparation of Oxime ester derivative Compound >
Example 1
Step 1: synthesis of 10-butyl-10H-phenothiazine
10H-phenothiazine (30 g) was dissolved in dimethyl sulfoxide (90 ml) in a reactor, and tetrabutylammonium bromide (2 g) and 50% sodium hydroxide solution (120 ml) were added. After stirring for 30 minutes, 1-bromobutane (32.6 ml) was added dropwise and stirred at room temperature for 24 hours. After completion of the reaction, it was extracted 3 times with ethyl acetate and water, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. Purification by column chromatography using hexane as developing solvent gave the title compound (27.0 g, 70.5%).
1H NMR(δppm；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-phenothiazine-3, 7-diyl) dibutin-1-one
The product of step 1 (27 g) was dissolved in methylene chloride (135 ml) in a reactor, and aluminum chloride (42.0 g) and butyryl chloride (33.6 g) were added at 0 ℃ or lower and stirred at room temperature for 8 hours. After completion of the reaction, the reaction solution was added to ice water, stirred and left to stand to remove an aqueous layer, and an organic layer was washed 2 times with water. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. Purification was performed by column chromatography using ethyl acetate: hexane (1.
1H NMR(δppm；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
And step 3: synthesis of 1,1' - (10-butyl-10H-phenothiazine-3, 7-diyl) bis (2- (hydroxyimino) butan-1-one)
Become into
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 30 minutes, extraction with ethyl acetate and water 3 times, drying of the organic layer with anhydrous magnesium sulfate, and crystallization with ethyl acetate yielded the objective compound (10.7 g, 55.0%).
1H NMR(δppm；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
And 4, step 4:1,1' - (10-butyl-10H-phenothiazine-3, 7-diyl) bis (2- (acetoxyimino) butan-1-one)
Synthesis of (2)
The product of step 3 (10.7 g) was added to ethyl acetate (107 ml) in a reactor, and trimethylamine (7.3 g) and acetyl chloride (5.65 g) were added dropwise in this order at room temperature. After stirring at room temperature for 1 hour, distilled water was added. The organic layer was washed 2 times with distilled water and dried over anhydrous magnesium sulfate, followed by concentration under reduced pressure, and the obtained product was crystallized from a solvent of ethyl acetate and hexane (1).
1H NMR(δppm；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 DEG C
Examples 2 to 19
Oxime ester derivative compounds were synthesized according to the compositions in the following tables 1 and 2 under the same conditions as in example 1.
[ Table 1]
[ Table 2]
< preparation of alkali-soluble resin >
Synthesis example 1
200mL of Propylene Glycol Monomethyl Ether Acetate (PGMEA) and 1.5g of Azobisisobutyronitrile (AIBN) were charged into a 500mL polymerization vessel, and methacrylate, glycidyl methacrylate, methyl methacrylate and dicyclopentanyl acrylate and 40wt% acrylic acid monomer solids were added at a molar ratio of 20. The weight average molecular weight of the resulting polymer was 25,000, and the dispersity was 1.9.
Synthesis example 2
200mL of propylene glycol monomethyl ether acetate and 1.0g of AIBN were charged into a 500mL polymerization vessel, and methacrylate, styrene, methyl methacrylate and cyclohexyl methacrylate were added at a molar ratio of 40. 0.3g of N, N-dimethylaniline and glycidyl methacrylate in a proportion of 20 mol relative to 100 mol of the total monomer solids were placed in a reactor and stirred at 100 ℃ for 10 hours to prepare an acrylic polymer (a-2) having an acrylic unsaturated bond in the side chain. The weight average molecular weight of the resulting polymer was 20,000, and the dispersity was 2.0.
Synthesis example 3
200mL of propylene glycol monomethyl ether acetate and 1.0g of AIBN were charged into a 500mL polymerization vessel, and glycidyl methacrylate, styrene, methyl methacrylate and cyclohexyl methacrylate were added at a molar ratio of 40. 0.3g of N, N-dimethylaniline and acrylic acid in a proportion of 20 mol relative to 100 mol of the total monomer solids were placed in a reactor and stirred at 100 ℃ for 10 hours to prepare an acrylic polymer (a-3) having an acrylic unsaturated bond in a side chain. The weight average molecular weight of the resulting polymer was 18,000, and the dispersity was 1.8.
Examples 20 to 35: preparation of photosensitive composition
In examples 20 to 35, the alkali-soluble resins a-1 to a-3; a polymerizable compound having an ethylenically unsaturated bond; the photopolymerization initiator of the present invention; and FC-430 (3M leveling agent) were placed in a reaction mixing tank having a UV shield and a stirrer in the order of the components and contents listed in Table 3 below, followed by stirring at room temperature, and the balance of solvent PGMEA was added to make the total weight percentage of the composition 100wt%, 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, 50% by weight of a pigment Red 177 (P.R.177) dispersion was added to PGMEA having 25% by weight of solids, 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 example 1 and a compound of the following formula 3 was used as a photopolymerization initiator, as described in table 3 below.
< formula 3>
< ingredient >
(a) Alkali soluble resin
(b) Polymerizable compound having ethylenically unsaturated bond
b-1: dipentaerythritol hexaacrylate
b-2 dipentaerythritol pentaacrylate
b-3 pentaerythritol triacrylate
b-4 pentaerythritol trimethacrylate
b-5 trimethylolpropane triacrylate
b-6: ethylene glycol diacrylate
b-7 bisphenol-A Diglycidyl Ether propionate adducts
b-8 trimethylolpropane tri-propylene oxide ether acrylate adduct
(c) Photopolymerization initiator
(e) Homogenizing agent: FC-430 (3M homogenizing agent)
(h) Colouring agent
h-1 carbon Black (25 wt% solids)
h-2 pigment Red 177 (P.R.177) (25% by weight solids)
[ Table 3]
Comparative example 1
A photopolymerizable composition was prepared by the same method as example 17, except that a photopolymerization initiator was used, instead of the compound of example 1, the compound of the following formula 4 was used.
< formula 4>
Comparative example 2
A photopolymerizable composition was prepared by the same method as example 17, except that a photopolymerization initiator was used instead of example 1, the compound of formula 5.
< formula 5>
< evaluation >
The photosensitive compositions prepared in examples 20 to 38 and comparative examples 1 to 2 were evaluated on a glass substrate, and the properties of the photosensitive compositions, such as sensitivity, residual film thickness, pattern stability, chemical resistance and elongation, were measured, and the evaluation results are shown in table 4 below.
1) Sensitivity of the device
The photoresist was spin-coated on a glass substrate and prebaked at 100 ℃ for 1 minute, followed by exposure using a step mask and development in a 0.04% aqueous potassium hydroxide solution. Sensitivity was evaluated based on the exposure dose with the thickness of the stepped mask pattern maintained at 80% of the initial thickness.
2) Residual film thickness
After the photosensitive composition was applied to a substrate using a spin coater, pre-baking (pre-baking) was performed at 100 ℃ for 1 minute, followed by exposure to 365nm light, post-baking (post-baking) was performed at 230 ℃ for 20 minutes, and the thickness ratio (%) of the resist film before and after the post-baking was measured.
3) Stability of pattern
The silicon wafer having the photoresist pattern was cut in a direction perpendicular to the hole pattern, and observation results in a cross-sectional direction of the pattern were shown using an electron microscope. The sidewalls of the pattern were erected at an angle of 55 degrees or more with respect to the substrate, and no film reduction was defined as "excellent", and the observed film reduction was defined as "film reduction".
4) Chemical resistance
After the photosensitive composition was applied to a substrate using a spin coater, the resist film formed by the pre-bake treatment and the post-bake treatment was immersed in a stripping solution at 40 ℃ for 10 minutes, and it was observed whether there was any change in the transmittance and thickness of the resist film. The change in the transmittance and the thickness of 2% or less is defined as "excellent", and the change in the transmittance and the thickness of 2% or more is defined as "poor".
5) Ductility of the alloy
The photosensitive composition was spin-coated on a substrate, followed by prebaking at 100 ℃ for 1 minute, exposure to light at the sensitivity of the photoresist, and development under an aqueous solution of potassium hydroxide to form a pattern of 20 μm × 20 μm. The formed pattern was cross-linked by post-baking at 230 ℃ for 20 minutes, and the pattern was measured using a nanoindenter to judge ductility. The nanoindenter measurement was performed under a load of 5g, and a total variation of 500nm or more was defined as "excellent", and a total variation of 500nm or less was defined as "poor".
[ Table 4]
From table 4, it can be found that the oxime ester derivative compounds of the present disclosure have remarkably excellent sensitivity, and have excellent properties such as after-film residue, pattern stability, chemical resistance, and ductility, even in a small amount when used as a photopolymerization initiator for photosensitive compositions.
Claims (12)
1. An oxime ester derivative compound represented by formula 1:
< formula 1>
Wherein R is 1 Is hydrogen, C3-C20 alkyl, C6-C20 aryl, C1-C20 alkoxy, C6-C20 arylC 1-C20 alkyl, hydroxyC 1-C20 alkoxyC 1-C20 alkyl or C3-C20 cycloalkyl;
R 2 is hydrogen, C1-C20 alkyl, C6-C20 aryl, C1-C20 alkoxy, C6-C20 arylC 1-C20 alkyl, hydroxyC 1-C20 alkoxyC 1-C20 alkyl or C3-C20 cycloalkyl; and
R 3 is C1-C20 alkyl, C6-C20 aryl, C6-C20 arylC 1-C20 alkyl or C3-C20 cycloalkyl.
2. The oxime ester derivative compound of claim 1 wherein R is 1 Is hydrogen, 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, terphenyl, anthracenyl, indenyl, phenanthryl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy,Hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxyisobutyl, hydroxy-n-pentyl, hydroxyisopentyl, hydroxy-n-hexyl, hydroxyisohexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl;
R 2 is 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, terphenyl, anthracenyl, indenyl, phenanthryl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxyisobutyl, hydroxy-n-pentyl, hydroxyisopentyl, hydroxy-n-hexyl, hydroxyisohexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, 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.
3. The oxime ester derivative compound of claim 1 wherein said oxime ester derivative compound is selected from the group consisting of compounds represented by the following formulae 2-1 to 2-8, 2-13 to 2-19:
< formulas 2-1 to 2-8, 2-13 to 2-19>
4. A photopolymerization initiator comprising the oxime ester derivative compound as claimed in any one of claims 1 to 3.
5. A photosensitive composition comprising:
(a) An alkali-soluble resin;
(b) A polymerizable compound having an ethylenically unsaturated bond; and
(c) A photopolymerization initiator comprising the oxime ester derivative compound as defined in any one of claims 1 to 3.
6. The photosensitive composition according to claim 5, wherein the amount of the oxime ester derivative compound is 0.01 to 10% by weight based on 100% by weight of the total amount of the photosensitive composition.
7. The photosensitive composition according to claim 5, wherein the photopolymerization initiator further comprises at least one selected from the group consisting of a thioxanthone-based compound, an acetophenone-based compound, a biimidazole-based compound, a triazine-based compound, an o-acyloxime ester-based compound, and a thiol-based compound.
8. The photosensitive composition according to claim 5, wherein the photosensitive composition further comprises a colorant.
9. The photosensitive composition according to claim 7, wherein the photosensitive composition further comprises a colorant.
10. A molded article comprising a cured product of the photosensitive composition of claim 5.
11. The molded article of claim 10, 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.
12. A display device comprising the molded article of claim 10.
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| KR10-2017-0054677 | 2017-04-27 | ||
| PCT/KR2017/005250 WO2017200354A1 (en) | 2016-05-19 | 2017-05-19 | Oxime ester derivative compound, photopolymerization initiator comprising same, and photosensitive composition |
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| JP7217977B2 (en) * | 2020-02-04 | 2023-02-06 | アジア原紙株式会社 | Active energy ray-curable composition |
| KR102547857B1 (en) * | 2020-12-31 | 2023-06-28 | (주)켐이 | Penothiazine compound, photopolymerization initiator containing the same, and composition for electronic materials containing the same |
| JP7219378B1 (en) | 2021-12-09 | 2023-02-08 | 東洋インキＳｃホールディングス株式会社 | Photosensitive coloring composition, optical filter, image display device, and solid-state imaging device |
| CN115109028B (en) * | 2022-08-29 | 2023-06-02 | 安庆师范大学 | Oxime ester compound and preparation method and application thereof |
| JP7448757B1 (en) | 2022-10-27 | 2024-03-13 | ａｒｔｉｅｎｃｅ株式会社 | Photosensitive compositions, films, optical filters, solid-state imaging devices, image display devices, and infrared sensors |
| JP7397269B1 (en) * | 2022-10-28 | 2023-12-13 | 東洋インキＳｃホールディングス株式会社 | Photosensitive compositions, optical filters, solid-state imaging devices, image display devices, and infrared sensors |
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| JP2021011486A (en) | 2021-02-04 |
| JP7002617B2 (en) | 2022-01-20 |
| JP2019519518A (en) | 2019-07-11 |
| KR20170131218A (en) | 2017-11-29 |
| TWI644903B (en) | 2018-12-21 |
| TW201808925A (en) | 2018-03-16 |
| CN109153658A (en) | 2019-01-04 |
| KR101892086B1 (en) | 2018-08-27 |
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