Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/22—Absorbing filters
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/22—Absorbing filters
  • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
  • G02F1/133509—Filters, e.g. light shielding masks
• • 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
• • 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
  • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
  • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
• • 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
• • 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
  • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
  • H01J17/00—Gas-filled discharge tubes with solid cathode
  • H01J17/38—Cold-cathode tubes
  • H01J17/48—Cold-cathode tubes with more than one cathode or anode, e.g. sequence-discharge tube, counting tube, dekatron
  • H01J17/49—Display panels, e.g. with crossed electrodes, e.g. making use of direct current

Definitions

• the present invention relates to a photosensitive resin composition, a color filter, and an image display device, and more particularly, to a photosensitive resin composition which maintains high quantum efficiency without deterioration of luminescent properties during a hard bake process and has excellent luminescent properties, a color filter and an image using the same. It relates to a display device.
• a color filter is a thin film type optical component that extracts three colors of red, green, and blue from white light and functions as a fine pixel unit.
• the size of one pixel is about tens to hundreds of micrometers.
• Such a color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate for shielding the boundary between each pixel, and a plurality of colors (typically, red (R) and green (G) to form each pixel. And a pixel portion in which three primary colors of blue (B) are arranged in a predetermined order.
• color filters can be produced by coating three or more colors on a transparent substrate by a dyeing method, electrodeposition method, printing method, pigment dispersion method, etc. Recently, the pigment dispersion method using a pigment dispersion type photosensitive resin is mainly used in the mainstream. Achieve.
• the pigment dispersion method which is one of the methods for implementing the color filter, is intended to coat and form a photosensitive resin composition including a colorant and an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, and an additive on a transparent substrate provided with a black matrix.
• a method of forming a colored thin film by repeating a series of processes of removing a non-exposed part with a solvent and thermally curing it is actively applied to manufacturing LCDs of mobile phones, laptops, monitors, TVs, etc. have.
• the photosensitive resin composition for color filters using pigment dispersion method having various advantages, not only excellent pattern characteristics but also high color reproducibility and improved performance such as high brightness and high contrast ratio are required.
• a method for producing a color filter using a photosensitive resin composition containing a quantum dot (Korean Patent Publication No. 10-2016-0086739).
• the quantum dots can be used to narrow the emission waveform, have a high color realization capability not realized by the pigment, and exhibit excellent luminance characteristics.
• the quantum dot is oxidized during the hard bake process performed at a high temperature for the manufacture of a color filter, so that the light efficiency is lowered. Therefore, it is necessary to develop a method capable of suppressing this.
• One object of the present invention is to provide a photosensitive resin composition that maintains high quantum efficiency and has excellent luminescent properties during a hard bake process without degrading luminescent properties.
• Another object of the present invention is to provide a color filter formed using the photosensitive resin composition.
• the present invention is a photosensitive resin composition
• a photosensitive resin composition comprising a photoluminescent quantum dot particles, a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, a light stabilizer and a solvent, wherein the light stabilizer is a photosensitive resin composition comprising a sterically hindered amine compound To provide.
• the hindered amine compound may be a compound represented by the following formula (1).
• R a and R b are each independently hydrogen or methyl
• R c and R d are each independently hydrogen, C 1-4 alkyl, or C 6-10 aryl,
• R ' is C 1-10 alkyl, C 3-12 cycloalkyl, C 6-15 aryl or ego,
• R ′′ is C 1-10 alkyl, C 3-12 cycloalkyl or C 6-15 aryl.
• the hindered amine compound may be a compound represented by the following formula (2).
• R is Is
• R a and R b are each independently hydrogen or methyl
• R c and R d are each independently hydrogen, C 1-4 alkyl, or C 6-10 aryl,
• the light stabilizer may further comprise at least one light stabilizer selected from the group consisting of a benzotriazole light stabilizer, a triazine light stabilizer and a benzophenone light stabilizer.
• this invention provides the color filter formed using the said photosensitive resin composition.
• the present invention provides an image display device characterized in that the color filter is provided.
• the photosensitive resin composition according to the present invention includes a sterically hindered amine compound as a light stabilizer, thereby inhibiting photoluminescence quantum dot particles from being oxidized during a hard bake process to maintain high quantum efficiency without deterioration of luminescence properties and to improve luminescence properties. great.
• An embodiment of the present invention includes photoluminescent quantum dot particles (A), a photopolymerizable compound (B), a photopolymerization initiator (C), an alkali-soluble resin (D), a light stabilizer (E), and a solvent (F).
• the said light stabilizer relates to the photosensitive resin composition containing a hindered amine compound.
• the photosensitive resin composition of this invention contains photoluminescence quantum dot particle.
• Quantum dots are nanoscale semiconductor materials. Atoms form molecules, and molecules form clusters of small molecules called clusters to form nanoparticles, which are called quantum dots, especially when they are semiconducting.
• the quantum dot When a quantum dot reaches an excited state from the outside, the quantum dot emits energy according to a corresponding energy band gap.
• the photosensitive resin composition of this invention contains such photoluminescence quantum dot particle, and the color filter manufactured from this can emit light (photoluminescence) by light irradiation.
• a color filter In a typical image display apparatus including a color filter, white light is transmitted through the color filter to implement color. In this process, a part of the light is absorbed by the color filter, thereby degrading light efficiency.
• the color filter made of the photosensitive resin composition of the present invention since the color filter emits light by the light of the light source, more excellent light efficiency can be realized.
• the quantum dot particle according to the present invention is not particularly limited as long as it is a quantum dot particle capable of emitting light by stimulation by light, for example, a group II-VI semiconductor compound; Group III-V semiconductor compounds; Group IV-VI semiconductor compounds; A Group IV element or a compound containing the same; And combinations thereof may be selected from the group. These can be used individually or in mixture of 2 or more types.
• the II-VI semiconductor compound may be selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe And CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixture
• the group IV-VI semiconductor compound may be a binary element selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; A three-element compound selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; And SnPbSSe, SnPbSeTe, SnPbSTe, and an elemental compound selected from the group consisting of a mixture thereof, and the group IV element or the compound comprising the same is Si, Ge, and a mixture thereof. An element selected from; And a binary element compound selected from the group consisting of SiC, SiGe, and mixtures thereof.
• Quantum dot particles are homogeneous single structures; Dual structures such as core-shell, gradient structures, and the like; Or a mixed structure thereof.
• the material constituting each core and shell may be made of the above-mentioned different semiconductor compounds.
• the core may include one or more materials selected from the group consisting of CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS, and ZnO, but is not limited thereto.
• the shell may include one or more materials selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe, but is not limited thereto.
• photoluminescence quantum dot particles may be classified into red quantum dot particles, green quantum dot particles, and blue quantum dot particles.
• the quantum dot particles according to the present invention may be red quantum dot particles, green quantum dot particles or blue quantum dot particles.
• Quantum dot particles can be synthesized by a wet chemical process, an organometallic chemical vapor deposition process, or a molecular beam epitaxy process.
• the wet chemical process is a method of growing particles by adding a precursor material to an organic solvent. As the crystal grows, the organic solvent naturally coordinates the surface of the quantum dot crystal and acts as a dispersant, thereby controlling the growth of the crystal. Therefore, organic metal chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE) It is easier and cheaper to control nanoparticle growth than vapor deposition such as epitaxy.
• MOCVD organic metal chemical vapor deposition
• MBE molecular beam epitaxy
• the content of the photoluminescent quantum dot particles is not particularly limited, and may be, for example, 3 to 80% by weight, for example, 5 to 70% by weight based on 100% by weight of the total solids of the photosensitive resin composition.
• the content of the photoluminescence quantum dot particles is less than 3% by weight, the luminous efficiency may be insignificant, and when the content of the photoluminescence quantum dot particles is less than 80% by weight, it may be difficult to form a pixel pattern due to insufficient content of a relatively different composition.
• the photopolymerizable compound (B) contained in the quantum dot photosensitive resin composition of this invention is a compound which can superpose
• monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrroli Money, etc.
• bifunctional monomer examples include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.
• polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol pentaacrylate succinic acid monoester, etc. are mentioned.
• bifunctional or higher polyfunctional monomers are preferably used.
• the content of the photopolymerizable compound may be in the range of usually 5 to 50% by weight, for example 7 to 45% by weight, based on 100% by weight of the total solids in the photosensitive resin composition. If the content of the photopolymerizable compound is within the above range, the intensity and smoothness of the pixel portion tends to be good, so it is preferable.
• the photoinitiator (C) contained in the photosensitive resin composition of this invention is not specifically limited, It may be 1 or more types of compounds chosen from the group which consists of a triazine type compound, an acetophenone type compound, a biimidazole type compound, and an oxime compound. .
• the photosensitive resin composition containing said photoinitiator (C) is highly sensitive, and the pixel pixel formed using this composition becomes favorable the intensity
• photopolymerization start adjuvant (C-1) when photopolymerization start adjuvant (C-1) is used together with a photoinitiator (C), since the photosensitive resin composition containing these becomes more sensitive and productivity at the time of forming a color filter using this composition is preferable, it is preferable.
• triazine type compound it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl) -6, for example. -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (furan
• acetophenone type compound for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2- Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane- 1-one oligomer etc. are mentioned. Moreover, the compound represented by following formula (3) is mentioned.
• R 1 to R 4 are each independently hydrogen, halogen, hydroxyl, C 1 -C 12 alkyl group substituted with or unsubstituted phenyl group, C 1 -C 12 alkyl group substituted with or unsubstituted benzyl group, or a C 1 -C 12 unsubstituted A naphthyl group which is unsubstituted or substituted with an alkyl group.
• Specific examples of the compound represented by Formula 3 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one and 2-ethyl-2-amino (4-morpholinophenyl) ethane- 1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl- 2-amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholin Nophenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane-1- On, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-die
• biimidazole type compound 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2, 3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, a phenyl group at the 4,4', 5,5 'position And imidazole compounds substituted with carboalkoxy groups.
• 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.
• the other photoinitiator etc. which are normally used in this field can also be used together.
• a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound etc. are mentioned, for example. These can be used individually or in combination of 2 or more types, respectively.
• benzoin type compound benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.
• benzophenone type compound for example, benzophenone, methyl 0- benzoyl benzoate, 4-phenyl benzophenone, 4- benzoyl-4'- methyl diphenyl sulfide, 3, 3 ', 4, 4'- tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-di (N, N'-dimethylamino)-benzophenone, etc. are mentioned.
• thioxanthone type compound 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, for example Etc. can be mentioned.
• anthracene type compound 9,10- dimethoxy anthracene, 2-ethyl-9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2-ethyl-9, 10- diethoxy anthracene etc. Can be mentioned.
• At least one compound selected from the group consisting of an amine compound and a carboxylic acid compound may be preferably used as the photopolymerization initiation assistant (C-1) that can be used in combination with the photopolymerization initiator (C).
• amine compound in the photopolymerization start adjuvant examples include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4'- Aromatic amine compounds, such as bis (diethylamino) benzophenone, are mentioned.
• an aromatic amine compound is used preferably.
• carboxylic acid compound examples include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenyl And aromatic heteroacetic acids such as thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.
• the content of the photopolymerization initiator (C) is 0.1 to 20% by weight, for example 1 to 10% by weight, based on 100% by weight of the total solids of the photosensitive resin composition, and the content of the photopolymerization initiator (C-1) is the photosensitive resin composition. It may be 0.1 to 20% by weight, for example 1 to 10% by weight relative to the total 100% by weight of solids of.
• the photosensitive resin composition When the content of the photopolymerization initiator (C) is in the above range, the photosensitive resin composition is highly sensitive, and thus the strength of the pixel portion and smoothness on the surface of the pixel portion tend to be good. In addition, when the content of the photopolymerization initiation assistant (C-1) is in the above range, the sensitivity efficiency of the photosensitive resin composition is further increased, and thus the productivity of the color filter formed using the composition tends to be improved.
• Alkali-soluble resin (D) may be polymerized including an ethylenically unsaturated monomer having a carboxyl group. It is a component which provides solubility to the alkaline developing solution used at the developing process process at the time of forming a pattern.
• the ethylenically unsaturated monomer which has a carboxyl group is not specifically limited, For example, Monocarboxylic acids, such as acrylic acid, methacrylic acid, a crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid and anhydrides thereof; and mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as? -carboxypolycaprolactone mono (meth) acrylate, and preferably acrylic acid and methacrylic acid. These can be used individually or in mixture of 2 or more types.
• Monocarboxylic acids such as acrylic acid, methacrylic acid, a crotonic acid
• Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid and anhydrides thereof
• Alkali-soluble resin according to the present invention may be polymerized further comprising at least one other monomer copolymerizable with the monomer.
• styrene vinyltoluene, methyl styrene, p-chlorostyrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p Aromatic vinyl compounds such as -vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenyl
• (meth) acrylate means acrylate or methacrylate.
• the content of the alkali-soluble resin is not particularly limited, for example, may be included in 5 to 80% by weight, for example 10 to 70% by weight based on 100% by weight total solids of the photosensitive resin composition.
• the solubility in the developing solution is sufficient, so that pattern formation is easy, and the film reduction of the pixel portion of the exposed portion at the time of development is prevented, so that the missing property of the non-pixel portion can be improved.
• the light stabilizer includes a hindered amine compound.
• the photosensitive resin composition of the present invention includes a hindered amine compound, thereby suppressing oxidation of photoluminescent quantum dot particles during a hard bake process, thereby maintaining high quantum efficiency without deteriorating luminescent properties and excellent luminescent properties. Do.
• the hindered amine compound may be a compound represented by the following formula (1).
• R a and R b are each independently hydrogen or methyl
• R c and R d are each independently hydrogen, C 1-4 alkyl, or C 6-10 aryl,
• R ' is C 1-10 alkyl, C 3-12 cycloalkyl, C 6-15 aryl or ego,
• R ′′ is C 1-10 alkyl, C 3-12 cycloalkyl or C 6-15 aryl.
• the hindered amine compound may be a compound represented by the following formula (2).
• R is Is
• R a and R b are each independently hydrogen or methyl
• R c and R d are each independently hydrogen, C 1-4 alkyl, or C 6-10 aryl,
• Alkyl referred to in the present invention includes straight or branched, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, n- Octyl, n-decyl and the like.
• Alkenyl is also alkyl having at least one carbon-carbon double bond
• alkynyl is alkyl having at least one carbon-carbon triple bond
• Aryl mentioned in the present invention includes phenyl, biphenyl, terphenyl, stilbene, naphthyl, anthracenyl, phenanthryl, pyrenyl and the like.
• Cycloalkyl referred to in the present invention includes cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclohexyl, adamantyl, and substituted and unsubstituted bornyl, norbornyl and norbornenyl and the like.
• Alkoxy mentioned in the present invention includes methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, pentoxy and the like.
• the acyl may be, for example, formyl, acetyl, trifluoroacetyl, pivaloyl, acryloyl, methacryloyl, Oleoyl, cinnamoyl, benzoyl, benzoyl, 2,6-xylyl, xyloyl, tert-butoxycarbonyl, ethylcarbamoyl, phenylcarba Phenylcarbamoyl and the like.
• the acyloxy is acetoxy, trifluoroacetoxy, pivaloyloxy, acryloyloxy, methacryloyloxy, benzoyloxy, and the like. Can be.
• R a , R b , R c and R d are hydrogen, R e is hydrogen or C 1 -C 18 alkoxy, Y is —OC ( ⁇ O) —R′-C ( ⁇ O) -O-, and R 'may be C 1 -C 10 alkyl.
• R a , R b , R c and R d may be hydrogen, and R e may be hydrogen or C 1 -C 18 alkyl.
• TINUVIN 123 Commercially available products of the compound represented by Formula 1 include TINUVIN 123, TINUVIN 770DF, and TINUVIN 292 (above, BASF Corporation).
• LA-52 As a commercial item of the compound represented by the said Formula (2), LA-52, LA-57 (above, Adeka Corporation) etc. are mentioned.
• the light stabilizer may further include a known light stabilizer in addition to the sterically hindered amine compound.
• the light stabilizer may further include at least one light stabilizer selected from the group consisting of a benzotriazole light stabilizer, a triazine light stabilizer, and a benzophenone light stabilizer.
• benzotriazole-based light stabilizer known benzotriazole-based derivatives can be used and can be obtained from commercially available products. Specifically 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy- 3 ', 5-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole or 2- (2'-hydroxy-3', 5 '-Di-tert-octylphenyl) benzotriazole or commercially available TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUBIN 571, TINUVIN 900, TINUVIN 928 or TINUVIN 1130 (above BASF) This can be illustrated.
• a hydroxyphenyl triazine type ultraviolet absorber is preferable. It may be commercially available and includes, for example, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 or TINUVIN 1577 (above BASF Corporation).
• a benzophenone derivative known as a light stabilizer can be used and can be obtained from a commercial item. Specifically 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy benzophenone, 2-hydroxy-4-methoxy benzophenone-5-sulfonic acid, 2-hydroxy-4-n-octyl Oxy benzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxy benzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'- dihydroxy-4-methoxy benzophenone or 2,2'- dihydroxy-4,4'- dimethoxy benzophenone, CHIMASSORB81 (above BASF Corporation) etc. as a commercial thing are mentioned. Can be.
• the additional light stabilizer may be used in an amount of 0.2 to 2 parts by weight per 1 part by weight of the hindered amine compound.
• the content of the light stabilizer may be 0.025 to 10% by weight, for example 0.01 to 7% by weight, based on 100% by weight of the total solids of the photosensitive resin composition.
• the fall of the light efficiency of the photosensitive resin composition can be prevented, and it can make it possible to form a pattern well, without disturbing the action of a photoinitiator.
• the solvent is not particularly limited and may be an organic solvent commonly used in the art.
• ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether
• Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether
• Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate
• Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether
• Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate, and methoxy pen
• the content of the solvent is not particularly limited, for example, may be included in 60 to 90% by weight of the total weight of the photosensitive resin composition, for example may be included in 70 to 85% by weight. When the content of the solvent is within the above range, the applicability may be good.
• the photosensitive resin composition of this invention can use together additives (G), such as a filler, another high molecular compound, an adhesion promoter, and an aggregation inhibitor, as needed.
• G additives
• the filler examples include glass, silica, alumina and the like.
• curable resin such as an epoxy resin and a maleimide resin
• thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.
• adhesion promoter for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane etc. are mentioned.
• aggregation inhibitor examples include sodium polyacrylate and the like.
• One embodiment of the present invention relates to a color filter formed by using the photosensitive resin composition described above.
• the color filter of the present invention When the color filter of the present invention is applied to an image display device, since the light is emitted by the light of the display device light source, it is possible to implement more excellent light efficiency. In addition, since light having color is emitted, color reproducibility is more excellent, and light is emitted in all directions by photoluminescence, and thus viewing angle may be improved.
• the color filter includes a substrate and a pattern layer formed on the substrate.
• the substrate may be a substrate of the color filter itself, or may be a portion where the color filter is positioned in a display device or the like, and is not particularly limited.
• the substrate may be glass, silicon (Si), silicon oxide (SiO x ), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).
• the pattern layer is a layer including the photosensitive resin composition of the present invention, and may be a layer formed by applying the photosensitive resin composition and exposing, developing and thermosetting in a predetermined pattern.
• the pattern layer formed of the photosensitive resin composition may include a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles.
• the red pattern layer emits red light
• the green pattern layer emits green light
• the blue pattern layer emits blue light.
• the emission light of the light source is not particularly limited when applied to the image display device, but a light source that emits blue light may be used in view of better color reproducibility.
• the pattern layer may include only a pattern layer of two colors of a red pattern layer, a green pattern layer, and a blue pattern layer.
• the pattern layer further includes a transparent pattern layer containing no quantum dot particles.
• a light source that emits light having a wavelength representing the remaining colors not included can be used.
• the light source which emits blue light can be used.
• the red quantum dot particles emit red light
• the green quantum dot particles emit green light
• the transparent pattern layer exhibits blue light as it is transmitted through as it is.
• the color filter including the substrate and the pattern layer as described above may further include a partition formed between each pattern, and may further include a black matrix.
• a protective film formed on the pattern layer of the color filter may be further included.
• One embodiment of the present invention relates to an image display apparatus equipped with the above-described color filter.
• the color filter of the present invention can be applied to various image display devices such as electroluminescent display devices, plasma display devices, field emission display devices, as well as ordinary liquid crystal display devices.
• a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared. Separately, 45 parts by weight of N-benzyl maleimide, 45 parts by weight of methacrylic acid, 10 parts by weight of tricyclodecyl methacrylate, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, propylene glycol monomethyl ether 40 parts by weight of acetate (hereinafter referred to as PGMEA) was added thereto, followed by stirring and mixing to prepare a monomer dropping lot.
• N-benzyl maleimide 45 parts by weight of methacrylic acid
• 10 parts by weight of tricyclodecyl methacrylate 10 parts by weight of tricyclodecyl methacrylate
• 4 parts by weight of t-butylperoxy-2-ethylhexanoate propylene glycol monomethyl ether 40 parts by weight of
• the components were mixed (unit: wt%), and diluted with propylene glycol monomethyl ether acetate so that the total solid content was 20 wt%, followed by sufficiently stirring to obtain a photosensitive resin composition.
• E-3 LA-52 (manufactured by Adeka) -a hindered amine compound ( a compound of Formula 2 wherein R a , R b , R c and R d are hydrogen and R e is methyl)
• E-4 LA-57 (manufactured by Adeka) -a hindered amine compound ( a compound of Formula 2 wherein R a , R b , R c and R d are hydrogen and R e is hydrogen)
• Each photosensitive resin composition was applied onto a glass substrate by spin coating, then placed on a heating plate and held at a temperature of 100 ° C. for 3 minutes to form a thin film. Subsequently, a test photomask having a transmissive pattern of horizontal ⁇ vertical 20 mm ⁇ 20 mm squares and a line / space pattern of 1 ⁇ m to 100 ⁇ m was placed on the thin film and irradiated with ultraviolet rays at a distance of 100 ⁇ m from the test photomask.
• the ultraviolet light source was irradiated with an exposure amount (365 nm) of 200 mJ / cm 2 under an air atmosphere using an ultrahigh pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd., and no special optical filter was used.
• the thin film irradiated with ultraviolet rays was developed by soaking for 80 seconds in a KOH aqueous solution developing solution of pH 10.5.
• the thin glass-coated glass substrate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150 ° C. for 10 minutes to prepare a color filter.
• the film thickness of the color filter manufactured above was 3.0 ⁇ m.
• the size of the pattern which was obtained through a line / space pattern mask designed to 100 ⁇ m in the color filter manufactured using the photosensitive resin composition, was measured through an OM apparatus (ECLIPSE LV100POL Nikon Corporation).
• the pattern error was calculated by comparing the width of the light transmission pattern formed on the pattern mask with the width (measured pattern width) of the measured color filter pattern. That is, the pattern error is obtained by the following equation.
• Pattern error ( ⁇ ) (width of light transmission pattern)-(measured pattern width)
• the process defect may be caused.
• the hard bake was carried out at 230 ° C. for 60 minutes to measure the luminescence intensity before and after the hard bake and the luminescence intensity retention compared to Comparative Example 1, and is shown in Table 2.
• the photosensitive resin composition of Examples 1 to 7 including the sterically hindered amine compound according to the present invention as a light stabilizer compared to the photosensitive resin composition of Comparative Examples 1 to 2 that do not include the fine pattern It can be confirmed that the luminescence intensity can be maintained higher by suppressing oxidation of the quantum dots even after hard baking.

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