CN109997080B - Photoinitiator and light-shielding photosensitive resin composition containing same - Google Patents

Photoinitiator and light-shielding photosensitive resin composition containing same Download PDF

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CN109997080B
CN109997080B CN201780073323.5A CN201780073323A CN109997080B CN 109997080 B CN109997080 B CN 109997080B CN 201780073323 A CN201780073323 A CN 201780073323A CN 109997080 B CN109997080 B CN 109997080B
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chemical formula
group
resin composition
photosensitive resin
light
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CN109997080A (en
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崔正植
金兑洙
金泰运
施允基
安廷珉
杨英恩
吴泉林
柳权壹
李德熙
李元重
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Samyang Corp
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Samyang Corp
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • 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
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • 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
    • G03F7/16—Coating processes; Apparatus therefor

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  • Spectroscopy & Molecular Physics (AREA)
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  • Materials For Photolithography (AREA)
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  • Polymerisation Methods In General (AREA)

Abstract

The present invention relates to a photoinitiator and a photosensitive resin composition for light shielding comprising the same, and more particularly, to a photoinitiator and a photosensitive resin composition, wherein the photoinitiator comprises two or more compounds selected from the group consisting of a compound of chemical formula 1, a compound of chemical formula 2, and a compound of chemical formula 3, and the photosensitive resin composition comprises the photoinitiator, exhibits improved light shielding properties, exhibits excellent deep curability, and is advantageous for pattern formation and development processes using photolithography, and thus can be suitably used as a photosensitive resin composition for light shielding of an organic light emitting material display panel.

Description

Photoinitiator and light-shielding photosensitive resin composition containing same
Technical Field
The present invention relates to a photoinitiator and a photosensitive resin composition for light shielding including the same, and more particularly, to a photoinitiator and a photosensitive resin composition, wherein the photoinitiator includes two or more compounds selected from the group consisting of a compound of chemical formula 1, a compound of chemical formula 2, and a compound of chemical formula 3, and the photosensitive resin composition includes the photoinitiator, exhibits improved light shielding properties, exhibits excellent deep curability, and is advantageous for pattern formation and development processes using photolithography, and thus can be suitably used as a photosensitive resin composition for light shielding for an organic light-emitting material display panel.
Background
In recent years, low Temperature Polysilicon (LTPS) and oxide thin film transistors have been actively studied as elements for high resolution of Ultra-high Definition (UD) or more and high-speed driving of 240Hz or more in display devices.
In general, since the oxide thin film transistor changes the properties of a semiconductor due to light, the above-described problem is minimized by introducing a light-shielding layer. After the light-shielding layer is formed, a subsequent process such as PE-CVD is performed at a high temperature, and thus a metal light-shielding layer is mainly used as the light-shielding layer. However, since the metal light shielding layer has a high reflectance, light is reflected and enters between the source electrode, the drain electrode, and the light shielding layer, and a parasitic voltage is generated between the source electrode and the drain electrode, which causes an increase in the operating resistance of the device, resulting in a problem that the load on the data line increases.
In particular, a light-shielding layer is introduced into an organic light-emitting material display and a transparent display to eliminate a characteristic of a significant decrease in contrast due to reflection of upper and lower metal wirings.
As conventional examples of the photoinitiator used for the photosensitive composition, acetophenone derivatives, benzophenone derivatives, triazine derivatives, bisimidazole derivatives, acylphosphine oxide derivatives, and oxime ester derivatives are known, among which the oxime ester derivatives have the following advantages: absorbs ultraviolet rays to show almost no color, has high radical generation efficiency, and is excellent in compatibility with photosensitive composition materials and stability. However, oxime derivative compounds developed in the early stage have low photoinitiation efficiency, and particularly in a pattern exposure process, sensitivity is low, and thus it is necessary to increase the exposure amount, thereby having a problem that the yield becomes low. In order to improve such disadvantages, various oxime ester derivative compounds have been proposed as photoinitiators (for example, korean laid-open patent publication Nos. 10-2001-0082580 and 10-2007-0044753).
Disclosure of Invention
Technical problem to be solved
The present invention provides a photosensitive resin composition which exhibits improved light-shielding properties, exhibits excellent deep curability, facilitates pattern formation by photolithography and development processes, and can be suitably used as a light-shielding photosensitive resin composition for an organic light-emitting material display panel, and a photoinitiator particularly suitable for the photosensitive resin composition.
Technical scheme
In order to achieve the above object, the present invention provides a photoinitiator containing two or more compounds selected from the group consisting of a compound of the following chemical formula 1, a compound of the chemical formula 2, and a compound of the chemical formula 3.
[ chemical formula 1]
Figure GDA0002074051520000021
[ chemical formula 2]
Figure GDA0002074051520000022
[ chemical formula 3]
Figure GDA0002074051520000031
In the chemical formulas 1 and 2, R 1 To R 3 Each independently hydrogen, halogen, alkyl, aryl, alkoxy, aralkyl, hydroxyalkyl, hydroxyalkoxyalkyl or cycloalkyl, and A is hydrogen, alkyl, aryl, alkoxy, aralkyl, hydroxyalkyl, hydroxyalkoxyalkyl, cycloalkyl, amino, nitro, cyano or hydroxyl.
In the chemical formula 3, R 4 To R 6 Each independently hydrogen, halogen, alkyl, aryl, alkoxy, aralkyl, hydroxyalkyl, hydroxyalkoxyalkyl or cycloalkyl.
Further, according to another aspect of the present invention, there is provided a photosensitive resin composition for light-shielding comprising [ a ] an alkali-soluble resin, [ B ] a polymerizable compound having an unsaturated bond, [ C ] a colorant, and [ D ] the photoinitiator.
According to another aspect of the present invention, there is provided a cured film formed from the light-shielding photosensitive resin composition.
According to another aspect of the present invention, there is provided a display element (e.g., an organic light emitting material display (OLED) element) including the cured film.
Advantageous effects
The light-shielding photosensitive resin composition containing the photoinitiator of the present invention exhibits improved light-shielding properties and excellent deep curability, and is advantageous for pattern formation and development processes using photolithography, and thus can be suitably used as a light-shielding photosensitive resin composition for an organic light-emitting material display panel.
Detailed Description
The present invention will be described in more detail below.
The photoinitiator of the present invention contains two or more compounds selected from the group consisting of a compound of the following chemical formula 1, a compound of the chemical formula 2, and a compound of the chemical formula 3.
[ chemical formula 1]
Figure GDA0002074051520000041
[ chemical formula 2]
Figure GDA0002074051520000042
[ chemical formula 3]
Figure GDA0002074051520000043
In the chemical formulas 1 and 2, R 1 To R 3 Each independently hydrogen, halogen, alkyl, aryl, alkoxy, aralkyl, hydroxyalkyl, hydroxyalkoxyalkyl or cycloalkyl, and A is hydrogen, alkyl, aryl, alkoxy, aralkyl, hydroxyalkyl, hydroxyalkoxyalkyl, cycloalkyl, amino, nitro, cyano or hydroxyl.
In the chemical formula 3, R 4 To R 6 Each independently hydrogen, halogen, alkyl, aryl, alkoxy, aralkyl, hydroxyalkyl, hydroxyalkoxyalkyl or cycloalkyl.
In the above, specifically, the number of carbon atoms of the alkyl group and the alkoxy group may be 1 to 10, the number of carbon atoms of the cycloalkyl group may be 3 to 8, and the number of carbon atoms of the aryl group may be 6 to 30. More specifically, the number of carbon atoms of the alkyl group and the alkoxy group may be 1 to 8, the number of carbon atoms of the cycloalkyl group may be 3 to 6, and the number of carbon atoms of the aryl group may be 6 to 20.
More specifically, the R 1 To R 6 Can each independently be hydrogen, bromine, chlorine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl,isohexyl, phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, indenyl, phenanthryl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-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; a may be hydrogen or nitro.
The compound of chemical formula 1 of the present invention may representatively include one or more selected from the following group, but the following compound does not limit the present invention.
Figure GDA0002074051520000051
The compound of chemical formula 2 of the present invention may representatively include one or more selected from the following group, but the following compound does not limit the present invention.
Figure GDA0002074051520000052
The compound of chemical formula 3 of the present invention may representatively exemplify one or more selected from the following group, but the following compound does not limit the present invention.
Figure GDA0002074051520000061
The content ratio between the compounds of chemical formulae 1 to 3 contained in the photoinitiator of the present invention is not particularly limited.
In one embodiment, when two compounds (the first compound and the second compound) of the compounds of chemical formulae 1 to 3 are used, the first compound to the second compound may be used, for example, in a weight ratio of 1. The first compound and the second compound represent two compounds selected from three compounds of chemical formulas 1 to 3, and may be chemical formulas 1 and 2, chemical formulas 1 and 3, or chemical formulas 2 and 3, respectively.
In another embodiment, when three compounds (first compound to third compound) of all the compounds of chemical formula 1 to chemical formula 3 are used, the first compound to the second compound to the third compound may be used, for example, in a weight ratio of 1. Wherein, the first compound, the second compound and the third compound respectively represent any one of three compounds of chemical formulas 1 to 3, and they can be chemical formula 1, chemical formula 2, chemical formula 3, chemical formula 1, chemical formula 3, chemical formula 2, chemical formula 1, chemical formula 3, chemical formula 2, chemical formula 3, chemical formula 1, chemical formula 2, or chemical formula 3, chemical formula 2, chemical formula 1.
The photosensitive resin composition for light-shielding of the present invention comprises [ A ] an alkali-soluble resin, [ B ] a polymerizable compound having an unsaturated bond, [ C ] a colorant, and [ D ] the photoinitiator of the present invention.
The film of the light-shielding photosensitive resin composition of the present invention is excellent in physical properties, suppresses the occurrence of a phenomenon of inhibiting color difference, and is advantageous in deep curing, thereby facilitating pattern formation.
As the [ a ] alkali-soluble resin contained in the photosensitive resin composition for light-shielding of the present invention as the binder resin, an acrylic binder resin (an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in a side chain), a silicone (silicone) binder resin, a cardo (cardo) binder resin, and an imide binder resin can be used.
Although not limited thereto, the content of the alkali-soluble resin contained in 100 wt% of the photosensitive resin composition of the present invention is preferably 3 to 50 wt%, more preferably 5 to 40 wt%, from the viewpoint of physical properties of the film (e.g., control of pattern characteristics, heat resistance, chemical resistance, etc.). In addition, the weight average molecular weight of the alkali-soluble resin is preferably 2,000 to 300,000, more preferably 4,000 to 100,000. In addition, the dispersion degree of the alkali-soluble resin is preferably 1.0 to 10.0.
In one embodiment, the acrylic polymer may be a (co) polymer of monomers including acrylic monomers. <xnotran> () , () , () , () , () , () , () , () , () , () , () , () , () , () , () , () , () , () , () , () ,2- () ,2- () , () , , , , , , , () ,3,4- () ,2,3- () ,3,4- () ,3- -3- () , </xnotran> 3-ethyloxetane-3-methyl (meth) acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, and the like, and they may be used each alone or in combination of two or more. In the present invention, a copolymer obtained by copolymerizing such an acrylic monomer with a monomer such as styrene, α -methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, or N-cyclohexylmaleimide, can also be used.
In one specific example, the acrylic polymer having an acrylic unsaturated bond in a side chain may be a copolymer obtained by an addition reaction of an acrylic copolymer containing a carboxylic acid and an epoxy resin. For example, a copolymer obtained by addition reaction of an acrylic copolymer containing a carboxylic acid with an epoxy monomer (e.g., glycidyl acrylate, glycidyl methacrylate, 3, 4-epoxybutyl (meth) acrylate, 2, 3-epoxycyclohexyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, etc.) at a temperature of 40 to 180 ℃ can be used as the binder resin, wherein the carboxylic acid-containing acrylic copolymer is obtained by copolymerizing a carboxylic acid-containing acrylic monomer such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl maleate and the like with an alkyl (meth) acrylate such as methyl (meth) acrylate, hexyl (meth) acrylate and the like, 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-butylmaleimide, N-cyclohexylmaleimide, (meth) acrylamide, N-methyl (meth) acrylamide and the like.
Another example of the acrylic polymer having an acrylic unsaturated bond in a side chain thereof is a copolymer obtained by addition reaction of an epoxy group-containing acrylic copolymer with a carboxylic acid. For example, a copolymer obtained by addition reaction of an epoxy group-containing acrylic copolymer with a carboxylic acid-containing acrylic monomer (e.g., acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl maleate, etc.) at a temperature of 40 to 180 ℃ can be used as the binder resin, wherein the epoxy group-containing acrylic copolymer is obtained by copolymerizing an epoxy group-containing acrylic monomer such as glycidyl acrylate, glycidyl methacrylate, 3, 4-epoxybutyl (meth) acrylate, 2, 3-epoxycyclohexyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate and the like with a monomer such as methyl (meth) acrylate, alkyl (meth) acrylate 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, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, (meth) acrylamide, N-methyl (meth) acrylamide and the like.
In one embodiment, the silicone binder resin contains a polymerized unit represented by the following chemical formula 4.
[ chemical formula 4]
X-R 7 SiO (4-n)/2
In the chemical formula 4, R 7 Is a linear or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an aryl-alkylene group having 7 to 20 carbon atoms in total, an alkyl-arylene group having 7 to 20 carbon atoms in total, or an alkylene-arylene group having 7 to 20 carbon atoms in total; x is a hydroxyl group, a carboxylic acid group, a carboxylic anhydride derivative group, an imide derivative group, an amide derivative group, an amine group or a mercapto group; n is an integer of 0 to 3; the polymerized unit with n =3 may be used together with other polymerized units with n being other than 3.
Further, for example, one or more monomers selected from the group consisting of tetraalkoxysilane, trialkoxysilane, methyltrialkoxysilane, ethyltrialkoxysilane, n-propyltrialkoxysilane, isopropyltrialkoxysilane, n-butyltrialkoxysilane, tert-butyltrialkoxysilane, phenyltrialkoxysilane, naphthyltrialkoxysilane, vinyltrialkoxysilane, methacryloxymethyltrialkoxysilane, 2-methacryloxyethyltrialkoxysilane, 3-methacryloxypropyltrialkoxysilane, 3-methacryloxypropylmethyldialkoxysilane, 3-methacryloxypropylethyldialkoxysilane, acryloxymethyltrialkoxysilane, 2-acryloxyethyltrialkoxysilane, 3-acryloxypropyltrialkoxysilane, 3-acryloxypropylmethyldialkoxysilane, 3-acryloxypropylethyldialkoxysilane, 3-glycidyloxypropyltrialkoxysilane, 2-epoxycyclohexylethyltrialkoxysilane, 3-cyclohexylpropyltrialkoxysilane, dimethylalkoxysilane, diethyldialkoxysilane, dipropyldialkoxysilane, diphenyldialkoxysilane, diphenylsilandiol and phenylmethylalkoxysilane may be used. The alkoxy group may be a linear, branched or cyclic aliphatic or aromatic alkoxy group having 1 to 7 carbon atoms. In addition, hydrolyzable halogenated organosilicon compounds may also be used as monomers.
In one embodiment, the cardoid type binder resin contains a polymerization unit derived from a compound represented by the following chemical formula 5.
[ chemical formula 5]
Figure GDA0002074051520000101
In the chemical formula 5, R 9 Each independently of the others is hydrogen or
Figure GDA0002074051520000102
R 10 And R 11 The substituents are the same or different and each independently hydrogen, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms; r 12 Is hydrogen, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 10 carbon atoms or-C (= O) -R 12’ Wherein R is 12’ Is hydrogen, hydroxy, linear, branched or cyclic alkyl having 1 to 20 carbon atoms or aryl having 6 to 10 carbon atoms; y is
Figure GDA0002074051520000103
Wherein R is 13 、R 14 And R 15 The substituents, which may be the same or different from each other, are each independently hydrogen, a linear, halogen-substituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 10 carbon atoms.
In one embodiment, the imide-based binder resin contains a polymerized unit derived from a compound represented by the following chemical formula 6.
[ chemical formula 6]
Figure GDA0002074051520000111
In the chemical formula 6, R 16 Each independently is hydrogen, hydroxy, linear, branched or cyclic alkyl having 1 to 20 carbon atoms, or aryl having 6 to 10 carbon atoms; r 17 Is hydrogen, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 10 carbon atoms or
Figure GDA0002074051520000112
Wherein R is 18 Is hydrogen, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 10 carbon atoms.
The polymerizable compound having an unsaturated bond [ B ] contained in the photosensitive resin composition for light-shielding of the present invention functions to form a pattern by crosslinking through photoreaction at the time of forming the pattern, and imparts chemical resistance and heat resistance by crosslinking at the time of heating at high temperature.
Although not limited thereto, the content of the polymerizable compound having an unsaturated bond contained in 100% by weight of the photosensitive resin composition of the present invention may be, for example, 0.001 to 40% by weight, more specifically, 0.01 to 30% by weight. If the polymerizable compound having an unsaturated bond is added to the photosensitive resin composition in an excessive amount, the degree of crosslinking becomes too high, which disadvantageously reduces the pattern extensibility.
In one specific example, the polymerizable compound having an unsaturated bond may be a polymerizable unsaturated compound having a hydroxyl group or a carboxyl group.
In one specific example, the polymerizable compound having an unsaturated bond includes alkyl esters of (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and the like; glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate in which the number of ethylene oxide groups is 2 to 14, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate in which the number of ethylene oxide groups is 2 to 14, polypropylene glycol di (meth) acrylate in which the number of propylene oxide groups is 2 to 14, trimethylolpropane di (meth) acrylate, bisphenol a diglycidyl ether acrylic acid adduct, phthalic acid diester of dihydroxyethyl (meth) acrylate, toluene diisocyanate adduct of dihydroxyethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol tri (meth) acrylate, compounds obtained by esterification of polyhydric alcohols such as α, β -unsaturated carboxylic acids, acrylic acid adducts of glycidyl compounds such as trimethylolpropane triglycidyl ether acrylic acid adduct, and the like may be used each alone or in combination of two or more.
The [ C ] colorant contained in the photosensitive resin composition for light-shielding of the present invention plays a role of imparting light-shielding properties to a film formed from the composition.
Although not limited thereto, the content of the colorant contained in 100% by weight of the photosensitive resin composition of the present invention may be, for example, 3 to 40% by weight, and more specifically, 5 to 30% by weight. If the content of the colorant in the photosensitive resin composition is too small, the light-shielding property is deteriorated, while if the content of the colorant in the photosensitive resin composition is too large, the manufacturability of forming a pattern of a light-shielding film is deteriorated.
In one specific example, the colorant includes carbon black, titanium black, aniline black, perylene black (perylene black), lactam black (lactam black), c.i. pigment black 7, and the like, and these may be used alone or in combination of two or more.
The light-shielding photosensitive resin composition of the present invention contains the photoinitiator of the present invention described in [ D ].
Although not limited thereto, from the viewpoint of minimizing the reflectance of the photoresist for light shielding, suppressing the generation of color difference, and smoothly achieving deep curing, it is effective that the content of the photoinitiator contained in 100 wt% of the photosensitive resin composition of the present invention is 0.01 to 10 wt% of each of the compounds of chemical formula 1 to 3, and more effective that 0.1 to 5 wt% is independently.
The photosensitive resin composition for light-shielding of the present invention may further contain, in addition to the components [ a ] to [ D ], a silicone compound having an epoxy group or an amine group as an adhesion aid, if necessary.
The silicone compound may be used to improve the adhesive force between the ITO electrode and the photosensitive resin composition and to increase the heat resistance after curing, and may be used in an amount of 0.0001 to 3 wt% with respect to 100 wt% of the composition, but is not limited thereto.
Specific examples of the silicone compound having an epoxy group or an amine group include (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, aminopropyltrimethoxysilane and the like, and these compounds may be used alone or in combination of two or more.
In addition, the photosensitive resin composition for light-shielding of the present invention may further include one or more additives having compatibility such as a photosensitizer, a thermal polymerization inhibitor, an antifoaming agent, a leveling agent, a dispersing agent, and the like, as necessary.
The light-shielding photosensitive resin composition of the present invention may further contain one or more compounds selected from thioxanthone compounds, ketone compounds, bisimidazoles, triazine compounds, O-acyloxime (O-acyloxime) compounds, and thiol compounds, as necessary.
The photosensitive resin composition for light-shielding of the present invention is patterned by the following method: the substrate is spin-coated with a solvent, and then is developed with an alkaline developer by irradiating ultraviolet rays through a mask, and preferably, the viscosity is adjusted to a range of 1 to 50cps by adding 10 to 95 wt% of the solvent to 100 wt% of the composition.
As the solvent, in consideration of compatibility with the binder resin, the photoinitiator, and other compounds, ethyl acetate, butyl acetate, diethylene glycol dimethyl 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 acetate cellosolve (methyl cellosolve acetate), ethyl acetate cellosolve, 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 (Diglyme), 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, octane, and the like solvents may be used alone or in a mixture of two or more thereof.
In one embodiment, the solvent as described above may be contained in the photosensitive resin composition for light-shielding of the present invention. In this case, the content of the solvent in the composition is the balance excluding the content of the remaining components in the total weight of the composition.
Hereinafter, representative compounds of the present invention will be described in detail by way of examples and comparative examples, in order to understand the present invention in detail. However, the examples of the present invention may be modified into various other embodiments, and the scope of the present invention should not be construed as being limited to the examples described in detail below. Embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.
[ examples ]
Synthesis example: preparation of alkali soluble resins
a) Preparation of A-1 resin
After 1.5g of Azobisisobutyronitrile (AIBN) was added to 200mL of Propylene Glycol Methyl Ether Acetate (PGMEA), methacrylic acid, glycidyl methacrylate, methyl methacrylate, and dicyclopentyl acrylate were added at a molar ratio of 20. It was confirmed that the weight average molecular weight of the copolymer prepared as described above was 25,000.
b) Preparation of A-2 resin
62.5g (0.05 mole) of methyl3- (triethoxysilyl) propionate (methyl 3- (triethoxysilyl) propionate), 51.6g (0.04 mole) of bicycloheptanyltriethoxysilane (bicycloheptanyltriethoxysilane), 6.8g (0.01 mole) of methyltrimethoxysilane, and 200g of propylene glycol monomethyl ether acetate were quantitatively mixed, and the obtained solution was stirred while a mixture of 10.4g (0.02 mole) of a 35% aqueous hydrochloric acid solution, 47.2g of water, and 50g of tetrahydrofuran was added dropwise. After completion of the dropwise addition, the reaction temperature was raised to 85 ℃ and the reaction was carried out at the raised temperature for 6 hours. After the reaction, appropriate amount of tetrahydrofuran and methanol was evaporated off, ether (ether) and water were added for extraction, and the organic phase was recovered, and residual alcohol and solvent were evaporated off to obtain 54g of silicone resin. The obtained silicone resin was dissolved in 125.5g of propylene glycol monomethyl ether acetate. The weight average molecular weight of the silicone polymer A-2 resin prepared as described above was 6,000.
c) Preparation of A-3 resin
231g of 9,9-bis (4-epoxypropyloxyphenyl) fluorene, 150mg of tetrabutylammonium chloride and 74g of propionic acid were heated and reacted at 120 ℃ for 12 hours. The reaction was terminated by analyzing propionic acid by GC, and an intermediate in a solid phase was obtained (yield: 92%). 280g of the obtained solid phase intermediate was dissolved in 400mL of Propylene Glycol Methyl Ether Acetate (PGMEA), and then 101.4g of 3,3', 4' -biphenyltetracarboxylic dianhydride and 500mg of tetrabutylammonium chloride were added and reacted at 120 ℃. Finally, 35g of phthalic anhydride was mixed, reacted at 90 ℃ and then terminated to obtain carbopol type polymer A-3 resin. The weight average molecular weight was 3,800.
d) Preparation of A-4 resin
231g of 9, 9-bis (4-epoxypropyloxyphenyl) fluorene, 150mg of tetrabutylammonium chloride, 100mg of 2, 6-di-t-butyl-4-methylphenol and 72g of acrylic acid were heated and reacted at 120 ℃ for 12 hours. The reaction was terminated by analyzing acrylic acid by GC to obtain an intermediate in a solid phase (yield: 92%). 280g of the obtained solid phase intermediate was dissolved in 400mL of Propylene Glycol Methyl Ether Acetate (PGMEA), and then 101.4g of 3,3', 4' -biphenyltetracarboxylic dianhydride and 500mg of tetrabutylammonium chloride were added and reacted at 120 ℃. Finally, 35g of phthalic anhydride was mixed, reacted at 90 ℃ and then terminated to obtain carbopol type polymer A-4 resin. The weight average molecular weight was 4,800.
e) Preparation of A-5 resin
20.1g of 2, 2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane and 17.6g of 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl were dissolved in 180mL of Propylene Glycol Methyl Ether Acetate (PGMEA), and then 14.5g of 5- (2, 5-dioxotetrahydrofuryl) -3-Methyl-3-cyclohexene-1, 2-dicarboxylic anhydride was slowly added thereto for reaction, and then 24.4g of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride was added thereto for reaction at 25 ℃ for 4 hours and at 50 ℃ for 20 hours to obtain an imide polymer A-5 resin. The weight average molecular weight was 2,800.
f) Preparation of A-6 resin
114g of 4,4' -diaminodiphenyl ether, 12.3g of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane and 81.8g of 3-aminophenol were dissolved in 800g of N-methyl-2-pyrrolidone (NMP). Then, 310g of bis (3, 4-dicarboxyphenyl) ether dianhydride and 200g of NMP were added together, and reacted at 20 ℃ for 1 hour and 50 ℃ for 4 hours. Thereafter, 150g of xylene was added, and the reaction was terminated after stirring at 150 ℃ for 5 hours. The resin after the termination reaction was precipitated in purified water, washed, and dried in a vacuum dryer at 80 ℃ for 20 hours to obtain an imide polymer A-6 resin. The weight average molecular weight was 15,000.
Examples 1 to 28 and comparative examples 1 to 6: preparation of photosensitive resin composition
A photosensitive resin composition was prepared by adding 20% by weight of [ A ] alkali-soluble resin (solid content: 50% by weight, dissolved in solvent (PGMEA)), 5% by weight of [ B ] dipentaerythritol hexaacrylate, [ C ] lactam black (solid content: 25% by weight, dispersed in PGMEA), 20% by weight of [ D ] photoinitiator and other additives FC-430 (leveling agent, 0.1% by weight, available from 3M corporation) to a reaction mixing tank equipped with an ultraviolet shielding film and a stirrer, stirring at normal temperature, and then adding the remaining amount of solvent so that the total amount of the composition became 100% by weight. The types of alkali-soluble resins and the types and contents of photoinitiators used in the examples and comparative examples are shown in table 1 below.
[ Compound 1]
Figure GDA0002074051520000161
[ Compound 2]
Figure GDA0002074051520000162
[ Compound 3]
Figure GDA0002074051520000163
[ chemical formula 4]
Figure GDA0002074051520000171
[ chemical formula 5]
Figure GDA0002074051520000172
[ Table 1]
Figure GDA0002074051520000173
Figure GDA0002074051520000181
Figure GDA0002074051520000191
< evaluation of physical Properties >
The photosensitive resin compositions prepared in examples 1 to 28 and comparative examples 1 to 6 were measured for properties such as sensitivity, pattern characteristics, and the like, and the evaluation results thereof are shown in table 2 below.
1) Exposure for critical dimensions
The resin composition was spin-coated on a glass substrate, and after a preheating treatment at 120 ℃ for 90 seconds, a coating film having a thickness of about 1.3 μm was formed. Exposing with a high pressure mercury lamp using a photomask at a concentration of 20mJ/cm 2 At the beginning, each increase was 10mJ/cm 2 Then, the reaction was carried out in a 2.38% aqueous solution of Tetramethylammonium hydroxide (TMAH)And (6) shadow. Thereafter, the film was washed with pure water, dried, and post-heat treated in a convection oven at 230 ℃ for 30 minutes to form a light-shielding pattern. As for the sensitivity, the exposure amount that saturates the size of the negative pattern of the Critical dimension (c.d.) is expressed as the sensitivity of each sample.
2) The exposure amount for adhesion after the development process is achieved
A resist was spin-coated on a glass substrate, and after a pre-heat treatment at 120 ℃ for 90 seconds, a coating film having a thickness of about 1.3 μm was formed. Exposing with a high pressure mercury lamp using a photomask at a concentration of 20mJ/cm 2 At the beginning, each increase was 10mJ/cm 2 Then, development was performed in 2.38% aqueous tmah solution. After the development, the pattern adhesion was judged from the exposure amount at which the 10 μm fine line pattern was not peeled.
3) Degree of surface curing
After exposure at the exposure amount determined in the sensitivity evaluation and development, the number of pinholes formed on the light-shielding surface was determined to be ∘ when the number was less than 0 to 3 within 10mm × 10mm, Δ when the number was less than 3 to 7, and X when the number was 7 or more.
4) Characteristics of developing process
After exposure at the exposure amount determined in the above sensitivity evaluation, development was performed, and the development process latitude (BP-BT) was determined by setting BT as the development time of the non-exposed portion and BP as the peeling time of the 10 μm fine line pattern of the exposed portion.
5) Linearity of pattern
The composition for light shielding was coated on a substrate using a spin coater, and then the linearity of a pattern for light shielding formed through the processes of pre-bake (pre-bake), exposure, post-bake (post-bake), and development was confirmed. The pattern was judged as o when no wrinkle or tear occurred, as Δ when either wrinkle or tear occurred in the pattern, and as X when both wrinkle and tear occurred.
[ Table 2]
Figure GDA0002074051520000201
Figure GDA0002074051520000211

Claims (10)

1. A photoinitiator comprising
(1) A compound of two groups of the following chemical formula 1 and chemical formula 3, wherein the weight ratio of the group of chemical formula 1 to the group of chemical formula 3 is 1; or
(2) A compound of two groups of the following chemical formula 2 and chemical formula 3, wherein the weight ratio of the group of chemical formula 2 to the group of chemical formula 3 is 0.1 to 10;
[ group of chemical formula 1]
Figure FDA0003739542130000011
[ group of chemical formula 2]
Figure FDA0003739542130000012
[ group of chemical formula 3]
Figure FDA0003739542130000021
2. A photoinitiator comprising compounds in three groups of the following chemical formulas 1 to 3 used together, wherein the weight ratio of the group of chemical formula 1 to the group of chemical formula 2 to the group of chemical formula 3 is 1.1 to 10,
[ group of chemical formula 1]
Figure FDA0003739542130000022
[ group of chemical formula 2]
Figure FDA0003739542130000031
[ group of chemical formula 3]
Figure FDA0003739542130000032
3. A photosensitive resin composition for light-shielding comprising:
[A] an alkali soluble resin;
[B] a polymerizable compound having an unsaturated bond;
[C] a colorant; and
[D] the photoinitiator of claim 1 or 2.
4. The photosensitive resin composition for light-shielding according to claim 3, wherein [ A ] the alkali-soluble resin is one or more selected from an acrylic resin, a silicone resin, a cardlike resin, and an imide resin.
5. The light-shielding photosensitive resin composition according to claim 3, wherein [ B ] the polymerizable compound having an unsaturated bond is a polymerizable unsaturated compound having a hydroxyl group or a carboxyl group.
6. The photosensitive resin composition for light-shielding according to claim 3, wherein the [ C ] colorant is at least one selected from the group consisting of carbon black, titanium black, aniline black, perylene black, lactam black and C.I. pigment black 7.
7. The photosensitive resin composition for light-shielding according to claim 4, wherein the amount of the compound of the group of chemical formula 1 to the compound of the group of chemical formula 3 present in the [ D ] photoinitiator is each independently 0.01 to 10% by weight based on 100% by weight of the photosensitive resin composition.
8. The photosensitive resin composition for light-shielding according to claim 3, further comprising one or more compounds selected from thioxanthone compounds, ketone compounds, bisimidazoles, triazine compounds, O-acyloximes, and thiol compounds.
9. A cured film formed from the photosensitive resin composition for light-shielding described in any one of claims 3 to 8.
10. A display element comprising the cured film of claim 9.
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