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WO2018093090A1 - Photosensitive resin composition, color filter, and image display device - Google Patents

Photosensitive resin composition, color filter, and image display device Download PDF

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Publication number
WO2018093090A1
WO2018093090A1 PCT/KR2017/012621 KR2017012621W WO2018093090A1 WO 2018093090 A1 WO2018093090 A1 WO 2018093090A1 KR 2017012621 W KR2017012621 W KR 2017012621W WO 2018093090 A1 WO2018093090 A1 WO 2018093090A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
aryl
resin composition
photosensitive resin
alkoxy
Prior art date
Application number
PCT/KR2017/012621
Other languages
French (fr)
Korean (ko)
Inventor
신규철
왕현정
홍성훈
Original Assignee
동우 화인켐 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 동우 화인켐 주식회사 filed Critical 동우 화인켐 주식회사
Priority to CN201780070514.6A priority Critical patent/CN109964175B/en
Priority to JP2019520531A priority patent/JP6793253B2/en
Publication of WO2018093090A1 publication Critical patent/WO2018093090A1/en

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Classifications

    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/22Absorbing filters
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/22Absorbing filters
    • G02B5/223Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509Filters, e.g. light shielding masks
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007Filters, e.g. additive colour filters; Components for display devices
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0048Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J17/00Gas-filled discharge tubes with solid cathode
    • H01J17/38Cold-cathode tubes
    • H01J17/48Cold-cathode tubes with more than one cathode or anode, e.g. sequence-discharge tube, counting tube, dekatron
    • H01J17/49Display 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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Abstract

The present invention provides a photosensitive resin composition, a color filter produced using same, and an image display device, the photosensitive resin composition comprising photoluminescence quantum dot particles, a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, a light stabilizer, and a solvent, wherein the light stabilizer comprises a sterically hindered amine compound. The photosensitive resin composition according to the present invention maintains a high quantum efficiency without diminishing luminous properties during a hard-bake process and has excellent luminous properties.

Description

감광성 수지 조성물, 컬러필터 및 화상표시장치Photosensitive resin composition, color filter and image display device
본 발명은 감광성 수지 조성물, 컬러필터 및 화상표시장치에 관한 것으로, 보다 상세하게는 하드베이크 공정 중에 발광 특성의 저하 없이 높은 양자효율을 유지하고 발광 특성이 우수한 감광성 수지 조성물, 이를 이용한 컬러필터 및 화상표시장치에 관한 것이다.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.
컬러필터는 백색광에서 적색, 녹색, 청색의 3가지 색을 추출하여 미세한 화소단위로 기능하게 하는 박막 필름형 광학부품으로서, 한 화소의 크기가 수십에서 수백 마이크로미터 정도이다. 이러한 컬러필터는 각각의 화소 사이의 경계부분을 차광하기 위해서 투명 기판 상에 정해진 패턴으로 형성된 블랙 매트릭스 층 및 각각의 화소를 형성하기 위해 복수의 색(통상적으로, 적색(R), 녹색(G) 및 청색(B))의 3원색을 정해진 순서로 배열한 화소부가 차례로 적층된 구조를 취하고 있다. 일반적으로 컬러필터는 염색법, 전착법, 인쇄법, 안료분산법 등에 의하여 3종 이상의 색상을 투명 기판상에 코팅하여 제조할 수 있으며, 최근에는 안료 분산형의 감광성 수지를 이용한 안료 분산법이 주류를 이룬다.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. In general, 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.
컬러필터를 구현하는 방법 중의 하나인 안료분산법은 흑색 매트릭스가 제공된 투명한 기질 위에 착색제를 비롯하여 알칼리 가용성 수지, 광중합성 화합물, 광중합 개시제, 용제, 및 첨가제를 포함하는 감광성 수지 조성물을 코팅하고, 형성하고자 하는 형태의 패턴을 노광한 후, 비노광 부위를 용제로 제거하여 열경화시키는 일련의 과정을 반복함으로써 착색 박막을 형성하는 방법으로, 휴대폰, 노트북, 모니터, TV 등의 LCD를 제조하는데 활발하게 응용되고 있다. 근래에는 여러 가지 장점을 가지는 안료분산법을 이용한 컬러필터용 감광성 수지 조성물에 있어서도 우수한 패턴 특성뿐만 아니라 높은 색재현율과 함께 고휘도 및 고명암비 등 더욱 향상된 성능이 요구되고 있는 실정이다. 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. After exposing the pattern in the form of a pattern, 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. In recent years, in 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.
그러나, 색 재현은 광원에서 조사된 광이 컬러필터를 투과하여 구현되는 것인데, 이 과정에서 광의 일부가 컬러필터에 흡수되므로 광 효율이 저하되고, 또한 색 필터로서의 안료특성으로 인해 완벽한 색 재현에는 못 미치는 근본적인 한계가 있다.However, color reproduction is realized by the light emitted from the light source passing through the color filter. In this process, some of the light is absorbed by the color filter, and thus the light efficiency is lowered. There are fundamental limitations.
이러한 문제를 해결할 수 있는 방안으로, 양자점을 함유하는 감광성 수지 조성물을 이용한 컬러필터 제조방법이 있다[대한민국 공개특허 제10-2016-0086739호]. 양자점을 사용하여 발광 파형을 좁힐 수 있고 안료에서는 구현하지 못하는 높은 색 구현 능력을 가지게 되며, 우수한 휘도 특성을 발휘할 수 있다. 하지만, 양자점은 컬러필터의 제조를 위해 고온에서 수행되는 하드베이크 공정 중에 산화되어 광효율이 떨어지는 문제가 있어 이를 억제할 수 있는 방안의 개발이 필요하다.As a solution to this problem, there is 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. However, 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.
본 발명의 한 목적은 하드베이크 공정 중에 발광 특성의 저하 없이 높은 양자효율을 유지하고 발광 특성이 우수한 감광성 수지 조성물을 제공하는 것이다.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.
본 발명의 다른 목적은 상기 감광성 수지 조성물을 이용하여 형성되는 컬러필터를 제공하는 것이다.Another object of the present invention is to provide a color filter formed using the photosensitive resin composition.
본 발명의 또 다른 목적은 상기 컬러필터를 구비한 화상표시장치를 제공하는 것이다.It is still another object of the present invention to provide an image display device having the color filter.
한편으로, 본 발명은 광루미네선스 양자점 입자, 광중합성 화합물, 광중합 개시제, 알칼리 가용성 수지, 광안정제 및 용제를 포함하는 감광성 수지 조성물로서, 상기 광안정제는 입체장애아민 화합물을 포함하는 감광성 수지 조성물을 제공한다.On the other hand, the present invention is 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.
본 발명의 일 실시형태에서, 상기 입체장애아민 화합물은 하기 화학식 1로 표시되는 화합물일 수 있다.In one embodiment of the present invention, the hindered amine compound may be a compound represented by the following formula (1).
[화학식 1][Formula 1]
Figure PCTKR2017012621-appb-I000001
Figure PCTKR2017012621-appb-I000001
상기 식에서,Where
Ra 및 Rb는 각각 독립적으로 수소 또는 메틸이고,R a and R b are each independently hydrogen or methyl,
Rc 및 Rd는 각각 독립적으로 수소, C1-4 알킬 또는 C6-10 아릴이며,R c and R d are each independently hydrogen, C 1-4 alkyl, or C 6-10 aryl,
Re는 수소; C1-18 알킬; C1-18 알콕시; 히드록시로 치환된 C2-7 알킬 또는 C2-7 알콕시; C2-18 알케닐; C2-18 알케닐옥시; C3-18 알키닐; C3-18 알키닐옥시; C3-12 시클로알킬; C3-12 시클로알콕시; C6-10 바이시클로알킬; C6-10 바이시클로알콕시; C3-8 시클로알케닐; C3-8 시클로알케닐옥시; C1-4 알킬, C1-4 알콕시 또는 할로겐으로 치환 또는 비치환된 C6-20 아릴; C1-4 알킬, C1-4 알콕시 또는 할로겐으로 치환 또는 비치환된 C6-20 아릴옥시; -C(=O)-H, -C(=O)-C1-19 알킬, -C(=O)-C2-19 알케닐, -C(=O)-C2-4 알케닐-C6-10 아릴, -C(=O)-C6-10 아릴, -C(=O)-O-C1-6 알킬, -C(=O)-O-C6-10 아릴, -C(=O)-NH-C1-6 알킬, -C(=O)-NH-C6-10 아릴 및 -C(=O)-N(C1-6 알킬)2로부터 선택되는 아실; 또는 -O-C(=O)-C1-19 알킬, -O-C(=O)-C2-19 알케닐 및 -OC(=O)-C6-10 아릴로부터 선택되는 아실옥시이고,R e is hydrogen; C 1-18 alkyl; C 1-18 alkoxy; C 2-7 alkyl or C 2-7 alkoxy substituted with hydroxy; C 2-18 alkenyl; C 2-18 alkenyloxy; C 3-18 alkynyl; C 3-18 alkynyloxy; C 3-12 cycloalkyl; C 3-12 cycloalkoxy; C 6-10 bicycloalkyl; C 6-10 bicycloalkoxy; C 3-8 cycloalkenyl; C 3-8 cycloalkenyloxy; C 6-20 aryl unsubstituted or substituted with C 1-4 alkyl, C 1-4 alkoxy or halogen; C 6-20 aryloxy unsubstituted or substituted with C 1-4 alkyl, C 1-4 alkoxy or halogen; -C (= 0) -H, -C (= 0) -C 1-19 alkyl, -C (= 0) -C 2-19 alkenyl, -C (= 0) -C 2-4 alkenyl- C 6-10 aryl, -C (= 0) -C 6-10 aryl, -C (= 0) -OC 1-6 alkyl, -C (= 0) -OC 6-10 aryl, -C (= 0) Acyl selected from) -NH-C 1-6 alkyl, -C (= 0) -NH-C 6-10 aryl and -C (= 0) -N (C 1-6 alkyl) 2 ; Or an acyloxy selected from -OC (= 0) -C 1-19 alkyl, -OC (= 0) -C 2-19 alkenyl and -OC (= 0) -C 6-10 aryl,
Y는 -O-C(=O)-R'-C(=O)-O-이며, Y is -O-C (= O) -R'-C (= O) -O-,
R'는 C1-10 알킬, C3-12 시클로알킬, C6-15 아릴 또는
Figure PCTKR2017012621-appb-I000002
이고,
R 'is C 1-10 alkyl, C 3-12 cycloalkyl, C 6-15 aryl or
Figure PCTKR2017012621-appb-I000002
ego,
R"는 C1-10 알킬, C3-12 시클로알킬 또는 C6-15 아릴이다.R ″ is C 1-10 alkyl, C 3-12 cycloalkyl or C 6-15 aryl.
본 발명의 일 실시형태에서, 상기 입체장애아민 화합물은 하기 화학식 2로 표시되는 화합물일 수 있다.In one embodiment of the present invention, the hindered amine compound may be a compound represented by the following formula (2).
[화학식 2][Formula 2]
Figure PCTKR2017012621-appb-I000003
Figure PCTKR2017012621-appb-I000003
상기 식에서, Where
R은
Figure PCTKR2017012621-appb-I000004
이며,
R is
Figure PCTKR2017012621-appb-I000004
Is,
Ra 및 Rb는 각각 독립적으로 수소 또는 메틸이고,R a and R b are each independently hydrogen or methyl,
Rc 및 Rd는 각각 독립적으로 수소, C1-4 알킬 또는 C6-10 아릴이며,R c and R d are each independently hydrogen, C 1-4 alkyl, or C 6-10 aryl,
Re는 수소; C1-18 알킬; C1-18 알콕시; 히드록시로 치환된 C2-7 알킬 또는 C2-7 알콕시; C2-18 알케닐; C2-18 알케닐옥시; C3-18 알키닐; C3-18 알키닐옥시; C3-12 시클로알킬; C3-12 시클로알콕시; C6-10 바이시클로알킬; C6-10 바이시클로알콕시; C3-8 시클로알케닐; C3-8 시클로알케닐옥시; C1-4 알킬, C1-4 알콕시 또는 할로겐으로 치환 또는 비치환된 C6-20 아릴; C1-4 알킬, C1-4 알콕시 또는 할로겐으로 치환 또는 비치환된 C6-20 아릴옥시; -C(=O)-H, -C(=O)-C1-19 알킬, -C(=O)-C2-19 알케닐, -C(=O)-C2-4 알케닐-C6-10 아릴, -C(=O)-C6-10 아릴, -C(=O)-O-C1-6 알킬, -C(=O)-O-C6-10 아릴, -C(=O)-NH-C1-6 알킬, -C(=O)-NH-C6-10 아릴 및 -C(=O)-N(C1-6 알킬)2로부터 선택되는 아실; 또는 -O-C(=O)-C1-19 알킬, -O-C(=O)-C2-19 알케닐 및 -OC(=O)-C6-10 아릴로부터 선택되는 아실옥시이다.R e is hydrogen; C 1-18 alkyl; C 1-18 alkoxy; C 2-7 alkyl or C 2-7 alkoxy substituted with hydroxy; C 2-18 alkenyl; C 2-18 alkenyloxy; C 3-18 alkynyl; C 3-18 alkynyloxy; C 3-12 cycloalkyl; C 3-12 cycloalkoxy; C 6-10 bicycloalkyl; C 6-10 bicycloalkoxy; C 3-8 cycloalkenyl; C 3-8 cycloalkenyloxy; C 6-20 aryl unsubstituted or substituted with C 1-4 alkyl, C 1-4 alkoxy or halogen; C 6-20 aryloxy unsubstituted or substituted with C 1-4 alkyl, C 1-4 alkoxy or halogen; -C (= 0) -H, -C (= 0) -C 1-19 alkyl, -C (= 0) -C 2-19 alkenyl, -C (= 0) -C 2-4 alkenyl- C 6-10 aryl, -C (= 0) -C 6-10 aryl, -C (= 0) -OC 1-6 alkyl, -C (= 0) -OC 6-10 aryl, -C (= 0) Acyl selected from) -NH-C 1-6 alkyl, -C (= 0) -NH-C 6-10 aryl and -C (= 0) -N (C 1-6 alkyl) 2 ; Or an acyloxy selected from -OC (= 0) -C 1-19 alkyl, -OC (= 0) -C 2-19 alkenyl and -OC (= 0) -C 6-10 aryl.
본 발명의 일 실시형태에서, 상기 광안정제는 벤조트리아졸계 광안정제, 트리아진계 광안정제 및 벤조페논계 광안정제로 구성된 군으로부터 선택되는 1종 이상의 광안정제를 더 포함할 수 있다.In one embodiment of the present invention, 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.
다른 한편으로, 본 발명은 상기 감광성 수지 조성물을 이용하여 형성되는 컬러필터를 제공한다.On the other hand, this invention provides the color filter formed using the said photosensitive resin composition.
또 다른 한편으로, 본 발명은 상기 컬러필터가 구비된 것을 특징으로 하는 화상표시장치를 제공한다.On the other hand, the present invention provides an image display device characterized in that the color filter is provided.
본 발명에 따른 감광성 수지 조성물은 입체장애아민 화합물을 광안정제로서 포함함으로써, 하드베이크 공정 중에 광루미네선스 양자점 입자가 산화되는 것을 억제하여 발광 특성의 저하가 없이 높은 양자효율을 유지하고 발광 특성이 우수하다.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.
이하, 본 발명을 보다 상세히 설명한다. Hereinafter, the present invention will be described in more detail.
본 발명의 일 실시형태는 광루미네선스 양자점 입자(A), 광중합성 화합물(B), 광중합 개시제(C), 알칼리 가용성 수지(D), 광안정제(E) 및 용제(F)를 포함하는 감광성 수지 조성물로서, 상기 광안정제는 입체장애아민 화합물을 포함하는 감광성 수지 조성물에 관한 것이다.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). As a photosensitive resin composition, the said light stabilizer relates to the photosensitive resin composition containing a hindered amine compound.
광루미네선스 양자점 입자(A)Photoluminescence quantum dot particle (A)
본 발명의 감광성 수지 조성물은 광루미네선스 양자점 입자를 포함한다.The photosensitive resin composition of this invention contains photoluminescence quantum dot particle.
양자점이란 나노 크기의 반도체 물질이다. 원자가 분자를 이루고, 분자는 클러스터라고 하는 작은 분자들의 집합체를 구성하여 나노 입자를 이루는데, 이러한 나노 입자들이 특히 반도체 특성을 띠고 있을 때 이를 양자점이라고 한다.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.
양자점은 외부에서 에너지를 받아 들뜬 상태에 이르면, 자체적으로 해당하는 에너지 밴드갭에 따른 에너지를 방출한다.When a quantum dot reaches an excited state from the outside, the quantum dot emits energy according to a corresponding energy band gap.
본 발명의 감광성 수지 조성물은 이러한 광루미네선스 양자점 입자를 포함하여, 이로부터 제조된 컬러필터는 광 조사에 의해 발광(광루미네선스)할 수 있다.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.
컬러필터를 포함하는 통상의 화상표시장치에서는 백색광이 컬러필터를 투과하여 컬러가 구현되는데, 이 과정에서 광의 일부가 컬러필터에 흡수되므로 광 효율이 저하된다. 그러나, 본 발명의 감광성 수지 조성물로 제조된 컬러필터를 포함하는 경우에는, 컬러필터가 광원의 광에 의해 자체 발광하므로, 보다 뛰어난 광 효율을 구현할 수 있다.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. However, in the case of including 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.
또한, 색상을 가진 광이 방출되는 것이므로 색 재현성이 보다 우수하고, 광루미네선스에 의해 전 방향으로 광이 방출되므로 시야각도 개선될 수 있다.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.
본 발명에 따른 양자점 입자는 광에 의한 자극으로 발광할 수 있는 양자점 입자라면 특별히 한정되지 않으며, 예를 들면 II-VI족 반도체 화합물; III-V족 반도체 화합물; IV-VI족 반도체 화합물; IV족 원소 또는 이를 포함하는 화합물; 및 이들의 조합으로 이루어진 군에서 선택될 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.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.
상기 II-VI족 반도체 화합물은 CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, 및 이들의 혼합물로 이루어진 군에서 선택되는 이원소 화합물; CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe 및 이들의 혼합물로 이루어진 군에서 선택되는 삼원소 화합물; 및 CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, 및 이들의 혼합물로 이루어진 군에서 선택되는 사원소 화합물로 이루어진 군에서 선택될 수 있고, 상기 III-V족 반도체 화합물은 GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, 및 이들의 혼합물로 이루어진 군에서 선택되는 이원소 화합물; GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, 및 이들의 혼합물로 이루어진 군에서 선택되는 삼원소 화합물; 및 GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, 및 이들의 혼합물로 이루어진 군에서 선택되는 사원소 화합물로 이루어진 군에서 선택될 수 있고, 상기 IV-VI족 반도체 화합물은 SnS, SnSe, SnTe, PbS, PbSe, PbTe, 및 이들의 혼합물로 이루어진 군에서 선택되는 이원소 화합물; SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, 및 이들의 혼합물로 이루어진 군에서 선택되는 삼원소 화합물; 및 SnPbSSe, SnPbSeTe, SnPbSTe, 및 이들의 혼합물로 이루어진 군에서 선택되는 사원소 화합물로 이루어진 군에서 선택될 수 있고, 상기 IV족 원소 또는 이를 포함하는 화합물은 Si, Ge, 및 이들의 혼합물로 이루어진 군에서 선택되는 원소; 및 SiC, SiGe, 및 이들의 혼합물로 이루어진 군에서 선택되는 이원소 화합물로 이루어진 군에서 선택될 수 있다.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 mixtures thereof, and the group III-V semiconductor compound , A binary element selected from the group consisting of GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; Three-element compounds selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, and mixtures thereof; And an elemental compound selected from the group consisting of GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. 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.
양자점 입자는 균질한(homogeneous) 단일 구조; 코어-쉘(core-shell), 그래디언트(gradient) 구조 등과 같은 이중 구조; 또는 이들의 혼합 구조일 수 있다.Quantum dot particles are homogeneous single structures; Dual structures such as core-shell, gradient structures, and the like; Or a mixed structure thereof.
코어-쉘(core-shell)의 이중 구조에서, 각각의 코어(core)와 쉘(shell)을 이루는 물질은 상기 언급된 서로 다른 반도체 화합물로 이루어질 수 있다. 예를 들면, 상기 코어는 CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS 및 ZnO로 이루어진 군으로부터 선택된 하나 이상의 물질을 포함할 수 있으나, 이에 한정되는 것은 아니다. 상기 쉘은 CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe 및 HgSe으로 이루어진 군으로부터 선택된 하나 이상의 물질을 포함할 수 있으나, 이에 한정되는 것은 아니다.In the dual structure of the core-shell, the material constituting each core and shell may be made of the above-mentioned different semiconductor compounds. For example, 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.
통상의 컬러필터 제조에 사용되는 착색 감광성 수지 조성물이 색상 구현을 위해 적, 녹, 청의 착색제를 포함하듯이, 광루미네선스 양자점 입자도 적 양자점 입자, 녹 양자점 입자 및 청 양자점 입자로 분류될 수 있으며, 본 발명에 따른 양자점 입자는 적 양자점 입자, 녹 양자점 입자 또는 청 양자점 입자일 수 있다. As the colored photosensitive resin composition used in the manufacture of conventional color filters includes colorants of red, green, and blue for color realization, photoluminescence quantum dot particles may be classified into red quantum dot particles, green quantum dot particles, and blue quantum dot particles. In addition, the quantum dot particles according to the present invention may be red quantum dot particles, green quantum dot particles or blue quantum dot particles.
양자점 입자는 습식화학공정(wet chemical process), 유기금속 화학증착 공정 또는 분자선 에피택시 공정에 의해 합성될 수 있다. Quantum dot particles can be synthesized by a wet chemical process, an organometallic chemical vapor deposition process, or a molecular beam epitaxy process.
습식 화학 공정은 유기용제에 전구체 물질을 넣어 입자들을 성장시키는 방법이다. 결정이 성장될 때 유기용제가 자연스럽게 양자점 결정의 표면에 배위되어 분산제 역할을 하여 결정의 성장을 조절하게 되므로, 유기금속 화학증착(MOCVD, metal organic chemical vapor deposition)이나 분자선 에피택시(MBE, molecular beam epitaxy)와 같은 기상증착법보다 더 쉽고 저렴한 공정을 통하여 나노 입자의 성장을 제어할 수 있다. 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.
상기 광루미네선스 양자점 입자의 함량은 특별히 한정되지 않으며, 예를 들면 감광성 수지 조성물의 고형분 전체 100 중량%에 대하여 3 내지 80 중량%, 예를 들어 5 내지 70 중량%일 수 있다. 광루미네선스 양자점 입자의 함량이 3 중량% 미만이면 발광 효율이 미미할 수 있고, 80 중량% 초과이면 상대적으로 다른 조성의 함량이 부족하여 화소 패턴을 형성하기 어려운 문제가 있을 수 있다.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. When 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.
광중합성 화합물(B)Photopolymerizable Compound (B)
본 발명의 양자점 감광성 수지 조성물에 함유되는 광중합성 화합물(B)은 광 및 후술하는 광중합 개시제의 작용으로 중합할 수 있는 화합물로서, 단관능 단량체, 2관능 단량체, 그 밖의 다관능 단량체 등을 들 수 있다.The photopolymerizable compound (B) contained in the quantum dot photosensitive resin composition of this invention is a compound which can superpose | polymerize by the action of light and the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned. have.
단관능 단량체의 구체예로는 노닐페닐카르비톨아크릴레이트, 2-히드록시-3-페녹시프로필아크릴레이트, 2-에틸헥실카르비톨아크릴레이트, 2-히드록시에틸아크릴레이트, N-비닐피롤리돈 등을 들 수 있다.Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrroli Money, etc.
2관능 단량체의 구체예로는 1,6-헥산디올디(메타)아크릴레이트, 에틸렌글리콜디(메타)아크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트, 트리에틸렌글리콜디(메타)아크릴레이트, 비스페놀 A의 비스(아크릴로일옥시에틸)에테르, 3-메틸펜탄디올디(메타)아크릴레이트 등을 들 수 있다. Specific examples of the bifunctional monomer 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.
그 밖의 다관능 단량체의 구체예로서는 트리메틸올프로판트리(메타)아크릴레이트, 펜타에리트리톨트리(메타)아크릴레이트, 펜타에리트리톨테트라(메타)아크릴레이트, 디펜타에리트리톨펜타(메타)아크릴레이트, 디펜타에리트리톨헥사(메타)아크릴레이트, 디펜타에리트리톨펜타아크릴레이트숙신산모노에스테르 등을 들 수 있다.Specific examples of other 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.
이들 중에서 2관능 이상의 다관능 단량체가 바람직하게 사용된다.Of these, bifunctional or higher polyfunctional monomers are preferably used.
상기 광중합성 화합물의 함량은 감광성 수지 조성물 중의 고형분 전체 100 중량%에 대해서 통상 5 내지 50 중량%, 예를 들어 7 내지 45 중량%의 범위일 수 있다. 광중합성 화합물의 함량이 상기 범위이면 화소부의 강도나 평활성이 양호하게 되는 경향이 있기 때문에 바람직하다.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.
광중합 개시제(C)Photoinitiator (C)
본 발명의 감광성 수지 조성물에 함유되는 광중합 개시제(C)는 특별히 제한되지 않으나, 트리아진계 화합물, 아세토페논계 화합물, 비이미다졸계 화합물 및 옥심 화합물로 이루어지는 군으로부터 선택되는 1종 이상의 화합물일 수 있다. 상기한 광중합 개시제(C)를 함유하는 감광성 수지 조성물은 고감도이고, 이 조성물을 사용하여 형성되는 화소 픽셀은 그 화소부의 강도나 패턴성이 양호해진다. Although 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 | strength and pattern property of the pixel part.
또한, 광중합 개시제(C)에 광중합 개시 보조제(C-1)를 병용하면, 이들을 함유하는 감광성 수지 조성물이 더욱 고감도가 되어 이 조성물을 사용하여 컬러필터를 형성할 때의 생산성이 향상되므로 바람직하다.Moreover, 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.
트리아진계 화합물로서는, 예를 들면 2,4-비스(트리클로로메틸)-6-(4-메톡시페닐)-1,3,5-트리아진, 2,4-비스(트리클로로메틸)-6-(4-메톡시나프틸)-1,3,5-트리아진, 2,4-비스(트리클로로메틸)-6-피페로닐-1,3,5-트리아진, 2,4-비스(트리클로로메틸)-6-(4-메톡시스티릴)-1,3,5-트리아진, 2,4-비스(트리클로로메틸)-6-[2-(5-메틸퓨란-2-일)에테닐]-1,3,5-트리아진, 2,4-비스(트리클로로메틸)-6-[2-(퓨란-2-일)에테닐]-1,3,5-트리아진, 2,4-비스(트리클로로메틸)-6-[2-(4-디에틸아미노-2-메틸페닐)에테닐]-1,3,5-트리아진, 2,4-비스(트리클로로메틸)-6-[2-(3,4-디메톡시페닐)에테닐]-1,3,5-트리아진 등을 들 수 있다. As a 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- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.
아세토페논계 화합물로서는, 예를 들면, 디에톡시아세토페논, 2-히드록시-2-메틸-1-페닐프로판-1-온, 벤질디메틸케탈, 2-히드록시-1-[4-(2-히드록시에톡시)페닐]-2-메틸프로판-1-온, 1-히드록시시클로헥실페닐케톤, 2-메틸-1-(4-메틸티오페닐)-2-모르폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)부탄-1-온, 2-히드록시-2-메틸-1-[4-(1-메틸비닐)페닐]프로판-1-온의 올리고머 등을 들 수 있다. 또한, 하기 화학식 3으로 표시되는 화합물을 들 수 있다. As an 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.
[화학식 3][Formula 3]
Figure PCTKR2017012621-appb-I000005
Figure PCTKR2017012621-appb-I000005
상기 식에서, Where
R1 내지 R4는 각각 독립적으로 수소, 할로겐, 히드록시기, C1-C12 알킬기로 치환되거나 비치환된 페닐기, C1-C12 알킬기로 치환되거나 비치환된 벤질기, 또는 C1-C12 알킬기로 치환되거나 비치환된 나프틸기를 나타낸다.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.
상기 화학식 3으로 표시되는 화합물의 구체예로는 2-메틸-2-아미노(4-모르폴리노페닐)에탄-1-온, 2-에틸-2-아미노(4-모르폴리노페닐)에탄-1-온, 2-프로필-2-아미노(4-모르폴리노페닐)에탄-1-온, 2-부틸-2-아미노(4-모르폴리노페닐)에탄-1-온, 2-메틸-2-아미노(4-모르폴리노페닐)프로판-1-온, 2-메틸-2-아미노(4-모르폴리노페닐)부탄-1-온, 2-에틸-2-아미노(4-모르폴리노페닐)프로판-1-온, 2-에틸-2-아미노(4-모르폴리노페닐)부탄-1-온, 2-메틸-2-메틸아미노(4-모르폴리노페닐)프로판-1-온, 2-메틸-2-디메틸아미노(4-모르폴리노페닐)프로판-1-온, 2-메틸-2-디에틸아미노(4-모르폴리노페닐)프로판-1-온 등을 들 수 있다. 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-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. have.
상기 비이미다졸계 화합물로는, 예를 들면 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라페닐비이미다졸, 2,2'-비스(2,3-디클로로페닐)-4,4',5,5'-테트라페닐비이미다졸, 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라(알콕시페닐)비이미다졸, 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라(트리알콕시페닐)비이미다졸, 4,4',5,5' 위치의 페닐기가 카르보알콕시기에 의해 치환되어 있는 이미다졸 화합물 등을 들 수 있다. 이들 중에서 2,2'비스(2-클로로페닐)-4,4',5,5'-테트라페닐비이미다졸, 2,2'-비스(2,3-디클로로페닐)-4,4',5,5'-테트라페닐비이미다졸이 바람직하게 사용된다. As said 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. Among them, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.
상기 옥심 화합물로는, 하기의 화학식 4, 화학식 5 또는 화학식 6으로 표시되는 화합물 등을 들 수 있다. As said oxime compound, the compound etc. which are represented by following formula (4), (5) or (6) are mentioned.
[화학식 4][Formula 4]
Figure PCTKR2017012621-appb-I000006
Figure PCTKR2017012621-appb-I000006
[화학식 5][Formula 5]
Figure PCTKR2017012621-appb-I000007
Figure PCTKR2017012621-appb-I000007
[화학식 6][Formula 6]
Figure PCTKR2017012621-appb-I000008
Figure PCTKR2017012621-appb-I000008
또한, 본 발명의 효과를 손상하지 않는 정도이면 이 분야에서 통상 사용되고 있는 그 밖의 광중합 개시제 등을 추가로 병용할 수도 있다. 그 밖의 광중합 개시제로서는, 예를 들면, 벤조인계 화합물, 벤조페논계 화합물, 티오크산톤계 화합물, 안트라센계 화합물 등을 들 수 있다. 이들은 각각 단독으로 또는 2종 이상 조합하여 사용할 수 있다. Moreover, as long as it does not impair the effect of this invention, the other photoinitiator etc. which are normally used in this field can also be used together. As another photoinitiator, 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.
벤조인계 화합물로서는, 예를 들면, 벤조인, 벤조인메틸에테르, 벤조인에틸에테르, 벤조인이소프로필에테르, 벤조인이소부틸에테르 등을 들 수 있다. As a benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.
벤조페논계 화합물로는, 예를 들면, 벤조페논, 0-벤조일벤조산 메틸, 4-페닐 벤조페논, 4-벤조일-4'-메틸디페닐술피드, 3,3',4,4'-테트라(tert-부틸퍼옥시카르보닐)벤조페논, 2,4,6-트리메틸벤조페논, 4,4'-디(N,N'-디메틸아미노)-벤조페논 등을 들 수 있다. As a 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.
티오크산톤계 화합물로는, 예를 들면, 2-이소프로필티오크산톤, 2,4-디에틸티오크산톤, 2,4-디클로로티오크산톤, 1-클로로-4-프로폭시티오크산톤 등을 들 수 있다. As a 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.
안트라센계 화합물로는, 예를 들면, 9,10-디메톡시안트라센, 2-에틸-9,10- 디메톡시안트라센, 9,10-디에톡시안트라센, 2-에틸-9,10-디에톡시안트라센 등을 들 수 있다. As an 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.
그 밖에 2,4,6-트리메틸벤조일디페닐포스핀옥시드, 10-부틸-2-클로로아크리돈, 2-에틸안트라퀴논, 9,10-페난트렌퀴논, 캄포퀴논, 페닐클리옥실산 메틸, 티타노센 화합물 등을 그 밖의 광중합 개시제로서 들 수 있다. In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, methyl phenyloxyoxylate, A titanocene compound etc. are mentioned as another photoinitiator.
또한, 본 발명에서 광중합 개시제(C)에 조합하여 사용할 수 있는 광중합 개시 보조제(C-1)로는 아민 화합물 및 카르복실산 화합물로 이루어진 군으로부터 선택되는 1종 이상의 화합물이 바람직하게 사용될 수 있다. In the present invention, 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).
광중합 개시 보조제 중 아민 화합물의 구체예로는 트리에탄올아민, 메틸디에탄올아민, 트리이소프로판올아민 등의 지방족 아민 화합물, 4-디메틸아미노벤조산 메틸, 4-디메틸아미노벤조산 에틸, 4-디메틸아미노벤조산 이소아밀, 4-디메틸아미노벤조산 2-에틸헥실, 벤조산 2-디메틸아미노에틸, N,N-디메틸파라톨루이딘, 4,4'-비스(디메틸아미노)벤조페논(통칭 : 미힐러 케톤), 4,4'-비스(디에틸아미노)벤조페논 등의 방향족 아민 화합물을 들 수 있다. 아민 화합물로서는 방향족 아민 화합물이 바람직하게 사용된다. Specific examples of the amine compound in the photopolymerization start adjuvant 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. As an amine compound, an aromatic amine compound is used preferably.
카르복실산 화합물의 구체예로서는 페닐티오아세트산, 메틸페닐티오아세트산, 에틸페닐티오아세트산, 메틸에틸페닐티오아세트산, 디메틸페닐티오아세트산, 메톡시페닐티오아세트산, 디메톡시페닐티오아세트산, 클로로페닐티오아세트산, 디클로로페닐티오아세트산, N-페닐글리신, 페녹시아세트산, 나프틸티오아세트산, N-나프틸글리신, 나프톡시아세트산 등의 방향족 헤테로아세트산류를 들 수 있다. Specific examples of the carboxylic acid compound 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.
상기 광중합 개시제(C)의 함량은 감광성 수지 조성물의 고형분 전체 100 중량%에 대하여 0.1 내지 20 중량%, 예를 들어 1 내지 10 중량%이며, 광중합 개시 보조제(C-1)의 함량은 감광성 수지 조성물의 고형분 전체 100 중량%에 대하여 통상 0.1 내지 20 중량%, 예를 들어 1 내지 10 중량%일 수 있다. 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.
상기 광중합 개시제(C)의 함량이 상기의 범위에 있으면 감광성 수지 조성물이 고감도화되어 화소부의 강도나, 이 화소부 표면에서의 평활성이 양호하게 되는 경향이 있기 때문에 바람직하다. 또한, 광중합 개시 보조제(C-1)의 함량이 상기의 범위에 있으면 감광성 수지 조성물의 감도 효율성이 더욱 높아지고, 이 조성물을 사용하여 형성되는 컬러필터의 생산성이 향상되는 경향이 있기 때문에 바람직하다.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.
알칼리 가용성 수지(D)Alkali-soluble resin (D)
알칼리 가용성 수지(D)는 카르복시기를 갖는 에틸렌성 불포화 단량체를 포함하여 중합된 것일 수 있다. 이는 패턴을 형성할 때의 현상 처리 공정에서 이용되는 알칼리 현상액에 대해서 가용성을 부여하는 성분이다.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.
카르복실기를 갖는 에틸렌성 불포화 단량체는 특별히 한정되지 않으며, 예를 들면 아크릴산, 메타아크릴산, 크로톤산 등의 모노카르복실산류; 푸마르산, 메사콘산, 이타콘산 등의 디카르복실산류 및 이들의 무수물; ω-카르복시폴리카프로락톤모노(메타)아크릴레이트 등의 양 말단에 카르복실기와 수산기를 갖는 폴리머의 모노(메타)아크릴레이트류 등을 들 수 있으며, 바람직하게는 아크릴산 및 메타아크릴산일 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.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.
본 발명에 따른 알칼리 가용성 수지는 상기 단량체와 공중합 가능한 적어도 1종의 다른 단량체를 더 포함하여 중합된 것일 수 있다. 예를 들면, 스티렌, 비닐톨루엔, 메틸스티렌, p-클로로스티렌, o-메톡시스티렌, m-메톡시스티렌, p-메톡시스티렌, o-비닐벤질메틸에테르, m-비닐벤질메틸에테르, p-비닐벤질메틸에테르, o-비닐벤질글리시딜에테르, m-비닐벤질글리시딜에테르, p-비닐벤질글리시딜에테르 등의 방향족 비닐 화합물; N-시클로헥실말레이미드, N-벤질말레이미드, N-페닐말레이미드, N-o-히드록시페닐말레이미드, N-m-히드록시페닐말레이미드, N-p-히드록시페닐말레이미드, N-o-메틸페닐말레이미드, N-m-메틸페닐말레이미드, N-p-메틸페닐말레이미드, N-o-메톡시페닐말레이미드, N-m-메톡시페닐말레이미드, N-p-메톡시페닐말레이미드 등의 N-치환 말레이미드계 화합물; 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, n-프로필(메타)아크릴레이트, i-프로필(메타)아크릴레이트, n-부틸(메타)아크릴레이트, i-부틸(메타)아크릴레이트, sec-부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트 등의 알킬(메타)아크릴레이트류; 시클로펜틸(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 2-메틸시클로헥실(메타)아크릴레이트, 트리시클로[5.2.1.02,6]데칸-8-일(메타)아크릴레이트, 2-디시클로펜타닐옥시에틸(메타)아크릴레이트, 이소보르닐(메타)아크릴레이트 등의 지환족(메타)아크릴레이트류; 페닐(메타)아크릴레이트, 벤질(메타)아크릴레이트 등의 아릴(메타)아크릴레이트류; 3-(메타크릴로일옥시메틸)옥세탄, 3-(메타크릴로일옥시메틸)-3-에틸옥세탄, 3-(메타크릴로일옥시메틸)-2-트리플루오로메틸옥세탄, 3-(메타크릴로일옥시메틸)-2-페닐옥세탄, 2-(메타크릴로일옥시메틸)옥세탄, 2-(메타크릴로일옥시메틸)-4-트리플루오로메틸옥세탄 등의 불포화 옥세탄 화합물 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Alkali-soluble resin according to the present invention may be polymerized further comprising at least one other monomer copolymerizable with the monomer. For example, 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-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide compounds such as -methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decane-8-yl (meth) acrylate, 2- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. And unsaturated oxetane compounds. These can be used individually or in mixture of 2 or more types.
본 명세서에서 (메타)아크릴레이트는 아크릴레이트 또는 메타크릴레이트를 의미한다.As used herein, (meth) acrylate means acrylate or methacrylate.
상기 알칼리 가용성 수지의 함량은 특별히 한정되지 않으며, 예를 들면 감광성 수지 조성물의 고형분 전체 100 중량%에 대하여 5 내지 80 중량%, 예를 들어 10 내지 70 중량%로 포함될 수 있다. 알칼리 가용성 수지의 함량이 상기 범위 내인 경우, 현상액에의 용해성이 충분하여 패턴 형성이 용이하며, 현상시에 노광부의 화소 부분의 막 감소가 방지되어 비화소 부분의 누락성이 양호해질 수 있다.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. When the content of the alkali-soluble resin is within the above range, 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.
광안정제(E)Light stabilizer (E)
상기 광안정제는 입체장애아민 화합물을 포함한다. 본 발명의 감광성 수지 조성물은 입체장애아민(hindered amine) 화합물을 포함함으로써, 하드베이크 공정 중에 광루미네선스 양자점 입자가 산화되는 것을 억제하여 발광 특성의 저하 없이 높은 양자효율을 유지하고 발광 특성이 우수하다.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.
본 발명의 일 실시형태에서, 상기 입체장애아민 화합물은 하기 화학식 1로 표시되는 화합물일 수 있다.In one embodiment of the present invention, the hindered amine compound may be a compound represented by the following formula (1).
[화학식 1][Formula 1]
Figure PCTKR2017012621-appb-I000009
Figure PCTKR2017012621-appb-I000009
상기 식에서,Where
Ra 및 Rb는 각각 독립적으로 수소(hydrogen) 또는 메틸이고,R a and R b are each independently hydrogen or methyl,
Rc 및 Rd는 각각 독립적으로 수소(hydrogen), C1-4 알킬(alkyl) 또는 C6-10 아릴(aryl)이며,R c and R d are each independently hydrogen, C 1-4 alkyl, or C 6-10 aryl,
Re는 수소(hydrogen); C1-18 알킬(alkyl); C1-18 알콕시(alkoxy); 히드록시(hydroxy)로 치환된 C2-7 알킬(alkyl) 또는 C2-7 알콕시(alkoxy); C2-18 알케닐(alkenyl); C2-18 알케닐옥시(alkenyloxy); C3-18 알키닐(alkinyl); C3-18 알키닐옥시(alkinyloxy); C3-12 시클로알킬(cycloalkyl); C3-12 시클로알콕시(cycloalkoxy); C6-10 바이시클로알킬(bicycloalkyl); C6-10 바이시클로알콕시(bicycloalkoxy); C3-8 시클로알케닐(cycloalkenyl); C3-8 시클로알케닐옥시(cycloalkenyloxy); C1-4 알킬(alkyl), C1-4 알콕시(alkoxy) 또는 할로겐(halogen)으로 치환 또는 비치환된 C6-20 아릴; C1-4 알킬(alkyl), C1-4 알콕시(alkoxy) 또는 할로겐(halogen)으로 치환 또는 비치환된 C6-20 아릴옥시; -C(=O)-H, -C(=O)-C1-19 알킬(alkyl), -C(=O)-C2-19 알케닐(alkenyl), -C(=O)-C2-4 알케닐(alkenyl)-C6-10 아릴(aryl), -C(=O)-C6-10 아릴(aryl), -C(=O)-O-C1-6 알킬(alkyl), -C(=O)-O-C6-10 아릴(aryl), -C(=O)-NH-C1-6 알킬(alkyl), -C(=O)-NH-C6-10 아릴(aryl) 및 -C(=O)-N(C1-6 알킬)2로부터 선택되는 아실; 또는 -O-C(=O)-C1-19 알킬(alkyl), -O-C(=O)-C2-19 알케닐(alkenyl) 및 -OC(=O)-C6-10 아릴(aryl)로부터 선택되는 아실옥시이고,R e is hydrogen; C 1-18 alkyl; C 1-18 alkoxy; C 2-7 alkyl or C 2-7 alkoxy substituted with hydroxy; C 2-18 alkenyl; C 2-18 alkenyloxy; C 3-18 alkynyl; C 3-18 alkynyloxy; C 3-12 cycloalkyl; C 3-12 cycloalkoxy; C 6-10 bicycloalkyl; C 6-10 bicycloalkoxy; C 3-8 cycloalkenyl; C 3-8 cycloalkenyloxy; C 1-4 alkyl (alkyl), C 1-4 alkoxy (alkoxy), or a halogen-substituted or unsubstituted with (halogen) C 6-20 aryl; C 1-4 alkyl (alkyl), C 1-4 alkoxy (alkoxy) or halogen (halogen) substituted or unsubstituted C 6-20 aryloxy; -C (= 0) -H, -C (= 0) -C 1-19 alkyl, -C (= 0) -C 2-19 alkenyl, -C (= 0) -C 2-4 alkenyl-C 6-10 aryl, -C (= 0) -C 6-10 aryl, -C (= 0) -OC 1-6 alkyl, -C (= 0) -OC 6-10 aryl, -C (= 0) -NH-Ci_ 6 alkyl, -C (= 0) -NH-C 6-10 aryl ) And acyl selected from -C (= 0) -N (Ci_ 6 alkyl) 2 ; Or from —OC (═O) —C 1-19 alkyl, —OC (═O) —C 2-19 alkenyl and —OC (═O) —C 6-10 aryl Is acyloxy selected,
Y는 -O-C(=O)-R'-C(=O)-O-이며, Y is -O-C (= O) -R'-C (= O) -O-,
R'는 C1-10 알킬(alkyl), C3-12 시클로알킬(cycloalkyl), C6-15 아릴(aryl) 또는
Figure PCTKR2017012621-appb-I000010
이고,
R 'is C 1-10 alkyl, C 3-12 cycloalkyl, C 6-15 aryl or
Figure PCTKR2017012621-appb-I000010
ego,
R"는 C1-10 알킬(alkyl), C3-12 시클로알킬(cycloalkyl) 또는 C6-15 아릴(aryl)이다.R ″ is C 1-10 alkyl, C 3-12 cycloalkyl or C 6-15 aryl.
본 발명의 일 실시형태에서, 상기 입체장애아민 화합물은 하기 화학식 2로 표시되는 화합물일 수 있다.In one embodiment of the present invention, the hindered amine compound may be a compound represented by the following formula (2).
[화학식 2][Formula 2]
Figure PCTKR2017012621-appb-I000011
Figure PCTKR2017012621-appb-I000011
상기 식에서, Where
R은
Figure PCTKR2017012621-appb-I000012
이며,
R is
Figure PCTKR2017012621-appb-I000012
Is,
Ra 및 Rb는 각각 독립적으로 수소(hydrogen) 또는 메틸이고,R a and R b are each independently hydrogen or methyl,
Rc 및 Rd는 각각 독립적으로 수소(hydrogen), C1-4 알킬(alkyl) 또는 C6-10 아릴(aryl)이며,R c and R d are each independently hydrogen, C 1-4 alkyl, or C 6-10 aryl,
Re는 수소(hydrogen); C1-18 알킬(alkyl); C1-18 알콕시(alkoxy); 히드록시(hydroxy)로 치환된 C2-7 알킬(alkyl) 또는 C2-7 알콕시(alkoxy); C2-18 알케닐(alkenyl); C2-18 알케닐옥시(alkenyloxy); C3-18 알키닐(alkinyl); C3-18 알키닐옥시(alkinyloxy); C3-12 시클로알킬(cycloalkyl); C3-12 시클로알콕시(cycloalkoxy); C6-10 바이시클로알킬(bicycloalkyl); C6-10 바이시클로알콕시(bicycloalkoxy); C3-8 시클로알케닐(cycloalkenyl); C3-8 시클로알케닐옥시(cycloalkenyloxy); C1-4 알킬(alkyl), C1-4 알콕시(alkoxy) 또는 할로겐(halogen)으로 치환 또는 비치환된 C6-20 아릴기; C1-4 알킬(alkyl), C1-4 알콕시(alkoxy) 또는 할로겐(halogen)으로 치환 또는 비치환된 C6-20 아릴옥시; -C(=O)-H, -C(=O)-C1-19 알킬(alkyl), -C(=O)-C2-19 알케닐(alkenyl), -C(=O)-C2-4 알케닐(alkenyl)-C6-10 아릴(aryl), -C(=O)-C6-10 아릴(aryl), -C(=O)-O-C1-6 알킬(alkyl), -C(=O)-O-C6-10 아릴(aryl), -C(=O)-NH-C1-6 알킬(alkyl), -C(=O)-NH-C6-10 아릴(aryl) 및 -C(=O)-N(C1-6 알킬)2로부터 선택되는 아실; 또는 -O-C(=O)-C1-19 알킬(alkyl), -O-C(=O)-C2-19 알케닐(alkenyl) 및 -OC(=O)-C6-10 아릴(aryl)로부터 선택되는 아실옥시이다.R e is hydrogen; C 1-18 alkyl; C 1-18 alkoxy; C 2-7 alkyl or C 2-7 alkoxy substituted with hydroxy; C 2-18 alkenyl; C 2-18 alkenyloxy; C 3-18 alkynyl; C 3-18 alkynyloxy; C 3-12 cycloalkyl; C 3-12 cycloalkoxy; C 6-10 bicycloalkyl; C 6-10 bicycloalkoxy; C 3-8 cycloalkenyl; C 3-8 cycloalkenyloxy; Aryl C 1-4 alkyl (alkyl), C 1-4 alkoxy (alkoxy) or halogen (halogen) substituted or unsubstituted by C 6-20; C 1-4 alkyl (alkyl), C 1-4 alkoxy (alkoxy) or halogen (halogen) substituted or unsubstituted C 6-20 aryloxy; -C (= 0) -H, -C (= 0) -C 1-19 alkyl, -C (= 0) -C 2-19 alkenyl, -C (= 0) -C 2-4 alkenyl-C 6-10 aryl, -C (= 0) -C 6-10 aryl, -C (= 0) -OC 1-6 alkyl, -C (= 0) -OC 6-10 aryl, -C (= 0) -NH-Ci_ 6 alkyl, -C (= 0) -NH-C 6-10 aryl ) And acyl selected from -C (= 0) -N (Ci_ 6 alkyl) 2 ; Or from —OC (═O) —C 1-19 alkyl, —OC (═O) —C 2-19 alkenyl and —OC (═O) —C 6-10 aryl Is acyloxy selected.
본 발명에서 언급하는 알킬은 직쇄형 또는 분지형을 포함하고, 메틸, 에틸, n-프로필, i-프로필, n-부틸, i-부틸, t-부틸, n-펜틸, n-헥실, n-옥틸, n-데실 등을 포함한다.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.
또한, 알케닐은 하나 이상의 탄소-탄소 이중결합을 갖는 알킬이고, 알키닐은 하나 이상의 탄소-탄소 삼중결합을 갖는 알킬이다.Alkenyl is also alkyl having at least one carbon-carbon double bond, and alkynyl is alkyl having at least one carbon-carbon triple bond.
본 발명에서 언급하는 아릴은 페닐, 바이페닐, 터페닐, 스틸벤, 나프틸, 안트라세닐, 페난트릴, 파이레닐 등을 포함한다.Aryl mentioned in the present invention includes phenyl, biphenyl, terphenyl, stilbene, naphthyl, anthracenyl, phenanthryl, pyrenyl and the like.
본 발명에서 언급하는 시클로알킬은 시클로프로필, 시클로프로필메틸, 시클로펜틸, 시클로헥실, 아다만틸, 및 치환 및 비치환 보르닐, 노르보르닐 및 노르보르네닐 등을 포함한다.Cycloalkyl referred to in the present invention includes cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclohexyl, adamantyl, and substituted and unsubstituted bornyl, norbornyl and norbornenyl and the like.
본 발명에서 언급하는 알콕시는 메톡시, 에톡시, n-프로폭시, i-프로폭시, t-부톡시, n-부톡시, 펜톡시 등을 포함한다.Alkoxy mentioned in the present invention includes methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, pentoxy and the like.
상기 아실(acyl)은, 예를 들어 포밀(formyl), 아세틸(acetyl), 트리플루오로아세틸(trifluoroacetyl), 피발로일(pivaloyl), 아크릴로일(acryloyl), 메타크릴로일(methacryloyl), 올레오일(oleoyl), 시나모일(cinamoyl), 벤조일(benzoyl), 2,6-자일로일(xyloyl), 3급-부톡시카보닐(tert-butoxycarbonyl), 에틸카바모일(ethylcarbamoyl), 페닐카바모일(phenylcarbamoyl) 등일 수 있다.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.
상기 아실옥시는 아세톡시(acetoxy), 트리플루오로아세톡시(trifluoroacetoxy), 피발로일옥시(pivaloyloxy), 아크릴로일옥시(acryloyloxy), 메타크릴로일옥시(methacryloyloxy), 벤조일옥시(benzoyloxy) 등일 수 있다.The acyloxy is acetoxy, trifluoroacetoxy, pivaloyloxy, acryloyloxy, methacryloyloxy, benzoyloxy, and the like. Can be.
상기 화학식 1에서, Ra, Rb, Rc 및 Rd는 수소이고, Re는 수소 또는 C1-C18 알콕시이며, Y는 -O-C(=O)-R'-C(=O)-O-이고, R'는 C1-C10 알킬일 수 있다.In Formula 1, 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.
상기 화학식 2에서, Ra, Rb, Rc 및 Rd는 수소이고, Re는 수소 또는 C1-C18 알킬일 수 있다.In Formula 2, R a , R b , R c and R d may be hydrogen, and R e may be hydrogen or C 1 -C 18 alkyl.
상기 화학식 1로 표시되는 화합물의 시판품으로는 TINUVIN 123, TINUVIN 770DF, TINUVIN 292 (이상, BASF사) 등을 예로 들 수 있다.Commercially available products of the compound represented by Formula 1 include TINUVIN 123, TINUVIN 770DF, and TINUVIN 292 (above, BASF Corporation).
상기 화학식 2로 표시되는 화합물의 시판품으로는 LA-52, LA-57 (이상, 아데카사) 등을 예로 들 수 있다.As a commercial item of the compound represented by the said Formula (2), LA-52, LA-57 (above, Adeka Corporation) etc. are mentioned.
또한, 상기 광안정제는 상기 입체장애아민 화합물 이외에 공지의 광안정제를 추가로 포함할 수 있다. 예를 들어, 상기 광안정제는 벤조트리아졸계 광안정제, 트리아진계 광안정제 및 벤조페논계 광안정제로 구성된 군으로부터 선택되는 1종 이상의 광안정제를 더 포함할 수 있다.In addition, the light stabilizer may further include a known light stabilizer in addition to the sterically hindered amine compound. For example, 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.
상기 벤조트리아졸계 광안정제로는, 공지된 벤조트리아졸계 유도체를 사용할 수 있으며, 시판품으로부터 입수가능하다. 구체적으로 2-(2'-히드록시-5'-메틸페닐)벤조트리아졸, 2-(2'-히드록시-5'-tert-부틸페닐)벤조트리아졸, 2-(2'-히드록시-3',5-디-tert-부틸페닐)벤조트리아졸, 2-(2'-히드록시-5'-tert-옥틸페닐)벤조트리아졸 또는 2-(2'-히드록시-3',5'-디-tert-옥틸페닐)벤조트리아졸이나, 시판되는 TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUBIN 571, TINUVIN 900, TINUVIN 928 또는 TINUVIN 1130(이상, BASF사) 등이 예시될 수 있다.As the 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.
상기 트리아진계 광안정제로는, 히드록시페닐트리아진계 자외선 흡수제가 바람직하다. 시판의 것일 수 있고, 예를 들면 TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 또는 TINUVIN 1577 (이상, BASF사) 등을 들 수 있다.As said triazine type light stabilizer, 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).
상기 벤조페논계 광안정제로는, 광안정제로서 공지된 벤조페논계 유도체를 사용할 수 있으며, 시판품으로부터 입수 가능하다. 구체적으로 2,4-디히드록시벤조페논, 2-히드록시-4-메톡시 벤조페논, 2-히드록시-4-메톡시 벤조페논-5-술폰산, 2-히드록시-4-n-옥틸옥시 벤조페논, 2-히드록시-4-n-도데실옥시벤조페논, 2-히드록시-4-벤질옥시 벤조페논, 비스(5-벤조일-4-히드록시-2-메톡시페닐)메탄, 2,2'-디히드록시-4-메톡시 벤조페논 또는 2,2'-디히드록시-4,4'-디메톡시 벤조페논이나, 시판의 것으로는 CHIMASSORB81(이상, BASF사) 등을 들 수 있다.As said benzophenone light stabilizer, 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.
상기 추가의 광안정제는 입체장애아민 화합물 1 중량부 당 0.2 내지 2 중량부의 양으로 혼합하여 사용이 가능하다.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.
상기 광안정제의 함량은 감광성 수지 조성물의 고형분 전체 100 중량%에 대하여 0.025 내지 10 중량%, 예를 들어 0.01 내지 7 중량%일 수 있다. 상기 범위 내로 함유되는 경우, 감광성 수지 조성물의 광효율 저하를 방지할 수 있으며, 광중합 개시제의 작용을 방해하지 않고, 패턴을 잘 형성하게 할 수 있다.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. When contained in the said range, 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.
용제(F)Solvent (F)
상기 용제는 특별히 한정되지 않으며 당 분야에서 통상적으로 사용되는 유기 용제일 수 있다.The solvent is not particularly limited and may be an organic solvent commonly used in the art.
구체예로는, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노프로필에테르, 에틸렌글리콜모노부틸에테르 등의 에틸렌글리콜모노알킬에테르류; 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르, 디에틸렌글리콜디프로필에테르, 디에틸렌글리콜디부틸에테르 등의 디에틸렌글리콜디알킬에테르류; 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트 등의 에틸렌글리콜알킬에테르아세테이트류; 프로필렌글리콜모노메틸에테르 등의 프로필렌글리콜모노알킬에테르류; 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노프로필에테르아세테이트, 메톡시부틸아세테이트, 메톡시펜틸아세테이트 등의 알킬렌글리콜알킬에테르아세테이트류; 벤젠, 톨루엔, 크실렌, 메시틸렌 등의 방향족 탄화수소류; 메틸에틸케톤, 아세톤, 메틸아밀케톤, 메틸이소부틸케톤, 시클로헥사논 등의 케톤류; 에탄올, 프로판올, 부탄올, 헥사놀, 시클로헥사놀, 에틸렌글리콜, 글리세린 등의 알코올류; 3-에톡시프로피온산 에틸, 3-메톡시프로피온산 메틸 등의 에스테르류; γ-부티로락톤 등의 환상 에스테르류; 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다. Specific examples include 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 pentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as γ-butyrolactone; Etc. can be mentioned. These can be used individually or in mixture of 2 or more types.
상기 용제의 함량은 특별히 한정되지 않으며, 예를 들면 감광성 수지 조성물 총 중량 중 60 내지 90 중량%로 포함될 수 있고, 예를 들어 70 내지 85 중량%로 포함될 수 있다. 용제의 함량이 상기 범위 내인 경우, 도포성이 양호할 수 있다.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.
본 발명의 감광성 수지 조성물은 필요에 따라 충진제, 다른 고분자 화합물, 밀착 촉진제, 응집 방지제 등의 첨가제(G)를 병용할 수 있다. 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.
상기 충진제의 구체적인 예는 유리, 실리카, 알루미나 등이 예시된다.Specific examples of the filler include glass, silica, alumina and the like.
상기 다른 고분자 화합물로서는 구체적으로 에폭시 수지, 말레이미드 수지 등의 경화성 수지; 폴리비닐알코올, 폴리아크릴산, 폴리에틸렌글리콜모노알킬에테르, 폴리플루오로알킬아크릴레이트, 폴리에스테르, 폴리우레탄 등의 열가소성 수지 등을 들 수 있다. Specifically as said other high molecular compound, curable resin, such as an epoxy resin and a maleimide resin; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.
상기 밀착 촉진제로서, 예를 들면 비닐트리메톡시실란, 비닐트리에톡시실란, 비닐트리스(2-메톡시에톡시)실란, N-(2-아미노에틸)-3-아미노프로필메틸디메톡시실란, N-(2-아미노에틸)-3-아미노프로필트리메톡시실란, 3-아미노프로필트리에톡시실란, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필메틸디메톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, 3-클로로프로필메틸디메톡시실란, 3-클로로프로필트리메톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-머캅토프로필트리메톡시실란 등을 들 수 있다.As the 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.
상기 응집 방지제로서는 구체적으로 폴리아크릴산 나트륨 등을 들 수 있다.Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.
본 발명의 일 실시형태는 상술한 감광성 수지 조성물을 이용하여 형성되는 컬러필터에 관한 것이다.One embodiment of the present invention relates to a color filter formed by using the photosensitive resin composition described above.
본 발명의 컬러필터는 화상표시장치에 적용되는 경우에, 표시장치 광원의 광에 의해 발광하므로, 보다 뛰어난 광 효율을 구현할 수 있다. 또한, 색상을 가진 광이 방출되는 것이므로 색 재현성이 보다 우수하고, 광루미네선스에 의해 전 방향으로 광이 방출되므로 시야각도 개선될 수 있다.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.
컬러필터는 기판 및 상기 기판의 상부에 형성된 패턴층을 포함한다.The color filter includes a substrate and a pattern layer formed on the substrate.
기판은 컬러필터 자체 기판일 수 있으며, 또는 디스플레이 장치 등에 컬러필터가 위치되는 부위일 수도 있는 것으로, 특별히 제한되지 않는다. 상기 기판은 유리, 실리콘(Si), 실리콘 산화물(SiOx) 또는 고분자 기판일 수 있으며, 상기 고분자 기판은 폴리에테르설폰(polyethersulfone, PES) 또는 폴리카보네이트(polycarbonate, PC) 등일 수 있다. 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).
패턴층은 본 발명의 감광성 수지 조성물을 포함하는 층으로, 상기 감광성 수지 조성물을 도포하고 소정의 패턴으로 노광, 현상 및 열경화하여 형성된 층일 수 있다.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.
본 발명의 일 실시형태에서, 상기 감광성 수지 조성물로 형성된 패턴층은 적 양자점 입자를 함유한 적색 패턴층, 녹 양자점 입자를 함유한 녹색 패턴층, 및 청 양자점 입자를 함유한 청색 패턴층을 구비할 수 있다. 광 조사시 적색 패턴층은 적색광을, 녹색 패턴층은 녹색광을, 청색 패턴층은 청색광을 방출한다. 이러한 경우에 화상표시장치에 적용시 광원의 방출광이 특별히 한정되지 않으나, 보다 우수한 색 재현성의 측면에서 청색광을 방출하는 광원을 사용할 수 있다.In one embodiment of the present invention, 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. Can be. In the light irradiation, the red pattern layer emits red light, the green pattern layer emits green light, and the blue pattern layer emits blue light. In this case, 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.
본 발명의 일 실시형태에서, 상기 패턴층은 적색 패턴층, 녹색 패턴층 및 청색 패턴층 중 2종 색상의 패턴층만을 구비할 수도 있다. 이러한 경우에는 상기 패턴층은 양자점 입자를 함유하지 않는 투명 패턴층을 더 구비한다. 2종 색상의 패턴층만을 구비하는 경우에는 포함하지 않은 나머지 색상을 나타내는 파장의 빛을 방출하는 광원을 사용할 수 있다. 예를 들면, 적색 패턴층 및 녹색 패턴층을 포함하는 경우에는, 청색광을 방출하는 광원을 사용할 수 있다. 이러한 경우에 적 양자점 입자는 적색광을, 녹 양자점 입자는 녹색광을 방출하고, 투명 패턴층은 청색광이 그대로 투과하여 청색을 나타낸다.In one embodiment of the present invention, 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. In this case, the pattern layer further includes a transparent pattern layer containing no quantum dot particles. When only the pattern layer of two colors is provided, a light source that emits light having a wavelength representing the remaining colors not included can be used. For example, when including a red pattern layer and a green pattern layer, the light source which emits blue light can be used. In this case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer exhibits blue light as it is transmitted through as it is.
상기와 같은 기판 및 패턴층을 포함하는 컬러필터는, 각 패턴 사이에 형성된 격벽을 더 포함할 수 있으며, 블랙 매트릭스를 더 포함할 수도 있다. 또한, 컬러필터의 패턴층 상부에 형성된 보호막을 더 포함할 수도 있다. 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. In addition, a protective film formed on the pattern layer of the color filter may be further included.
본 발명의 일 실시형태는 상술한 컬러필터가 구비된 화상표시장치에 관한 것이다. One embodiment of the present invention relates to an image display apparatus equipped with the above-described color filter.
본 발명의 컬러필터는 통상의 액정표시장치뿐만 아니라, 전계발광표시장치, 플라스마표시장치, 전계방출표시장치 등 각종 화상표시장치에 적용이 가능하다.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.
이하, 실시예, 비교예 및 실험예에 의해 본 발명을 보다 구체적으로 설명하고자 한다. 이들 실시예, 비교예 및 실험예는 오직 본 발명을 설명하기 위한 것으로, 본 발명의 범위가 이들에 국한되지 않는다는 것은 당업자에게 있어서 자명하다.Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. These examples, comparative examples and experimental examples are only for illustrating the present invention, it is apparent to those skilled in the art that the scope of the present invention is not limited thereto.
제조예 1: CdSe(코어)/ZnS(쉘) 구조의 광루미네선스 녹 양자점 입자의 합성Preparation Example 1 Synthesis of Photoluminescent Green Quantum Dot Particles of CdSe (Core) / ZnS (Shell) Structure
CdO(0.4 mmol)과 아연 아세테이트(Zinc acetate)(4 mmol), 올레산(Oleic acid)(5.5 mL)을 1-옥타데센(1-Octadecene) (20 mL)과 함께 반응기에 넣고 150℃로 가열하여 반응시켰다. 이후에 아연에 올레산이 치환됨으로써 생성된 아세트산(acetic acid)을 제거하기 위해 상기 반응물을 100 mTorr의 진공 하에 20분간 방치하였다. 그리고 나서, 310℃의 열을 가하여 투명한 혼합물을 얻은 다음, 이를 20분간 310℃로 유지한 후, 0.4 mmol의 Se 분말과 2.3 mmol의 S 분말을 3mL의 트리옥틸포스핀(trioctylphosphine)에 용해시킨 Se 및 S 용액을 Cd(OA)2 및 Zn(OA)2 용액이 들어 있는 반응기에 빠르게 주입하였다. 이로부터 얻은 혼합물을 310℃에서 5분간 성장시킨 후 얼음물 배쓰(ice bath)를 이용하여 성장을 중단시켰다. 그리고 나서, 에탄올로 침전시켜 원심분리기를 이용하여 양자점을 분리하고 여분의 불순물은 클로로포름(chloroform)과 에탄올을 이용하여 씻어냄으로써, 올레인산으로 안정화된, 코어 입경과 쉘 두께의 합이 3 내지 5 nm인 입자들이 분포된 CdSe(코어)/ZnS(쉘) 구조의 양자점 입자를 수득하였다.CdO (0.4 mmol), zinc acetate (4 mmol) and oleic acid (5.5 mL) were added to the reactor together with 1-octadecene (20 mL) and heated to 150 ° C. Reacted. Thereafter, the reaction was allowed to stand for 20 minutes under vacuum of 100 mTorr to remove acetic acid produced by substitution of oleic acid with zinc. Then, 310 ° C. heat was applied to obtain a clear mixture, which was kept at 310 ° C. for 20 minutes, and 0.4 mmol of Se powder and 2.3 mmol of S powder were dissolved in 3 mL of trioctylphosphine. And S solution was injected rapidly into the reactor containing Cd (OA) 2 and Zn (OA) 2 solutions. The resulting mixture was grown at 310 ° C. for 5 minutes and then stopped using an ice bath. Then, precipitated with ethanol to separate the quantum dots using a centrifuge and the excess impurities are washed with chloroform and ethanol to stabilize the oleic acid, the sum of the core particle diameter and the shell thickness is 3 to 5 nm Quantum dot particles having a CdSe (core) / ZnS (shell) structure in which the particles were distributed were obtained.
제조예 2: 알칼리 가용성 수지의 합성Preparation Example 2 Synthesis of Alkali-Soluble Resin
교반기, 온도계, 환류 냉각관, 적하 로트 및 질소 도입관을 구비한 플라스크를 준비하였다. 이와 별도로, N-벤질말레이미드 45중량부, 메타크릴산 45중량부, 트리시클로데실 메타크릴레이트 10중량부, t-부틸퍼옥시-2-에틸헥사노에이트 4중량부, 프로필렌글리콜모노메틸에테르아세테이트(이하, PGMEA) 40중량부를 투입후 교반 혼합하여 모노머 적하 로트를 준비하고, n-도데칸티올 6중량부 및 PGMEA 24중량부를 넣고 교반 혼합하여 연쇄 이동제 적하 로트를 준비하였다. 이후 플라스크에 PGMEA 395중량부를 도입하고 플라스크 내 분위기를 공기에서 질소로 한 후 교반하면서 플라스크의 온도를 90℃까지 승온했다. 이어서 모노머 및 연쇄 이동제를 적하 로트로부터 적하를 개시했다. 적하는 90℃를 유지하면서 각각 2시간 동안 진행하고 1시간 후에 110℃로 승온하여 3시간 유지한 뒤, 가스 도입관을 도입시켜, 산소/질소=5/95(v/v) 혼합 가스의 버블링을 개시했다. 이어서, 글리시딜메타크릴레이트 10중량부, 2,2'-메틸렌비스(4-메틸-6-t-부틸페놀) 0.4중량부, 트리에틸아민 0.8중량부를 플라스크 내에 투입하여 110℃에서 8시간 동안 반응을 계속하고, 그 후 실온까지 냉각하면서 고형분 29.1중량%, 중량평균분자량 32,000, 산가가 114㎎KOH/g인 알칼리 가용성 수지를 얻었다.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. Then, 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added thereto to prepare a chain transfer agent dropping lot. Thereafter, 395 parts by weight of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition proceeds for 2 hours each while maintaining 90 ° C, and after 1 hour, the temperature is raised to 110 ° C and maintained for 3 hours, and then a gas introduction tube is introduced to bubble oxygen / nitrogen = 5/95 (v / v) mixed gas. The ring started. Subsequently, 10 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 part by weight of triethylamine were added to the flask, followed by 8 hours at 110 ° C. The reaction was continued for a while, and an alkali-soluble resin having a solid content of 29.1 wt%, a weight average molecular weight of 32,000 and an acid value of 114 mgKOH / g was then cooled to room temperature.
실시예 1 내지 7 및 비교예 1 내지 2: 감광성 수지 조성물의 제조Examples 1-7 and Comparative Examples 1-2: Preparation of Photosensitive Resin Composition
하기 표 1에 기재된 바와 같이 각각 성분을 혼합(단위: 중량%)한 후, 전체 고형분이 20 중량%가 되도록 프로필렌글리콜모노메틸에테르아세테이트로 희석한 뒤, 충분히 교반하여 감광성 수지 조성물을 얻었다.As shown in Table 1 below, 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.
실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 실시예 5Example 5 실시예 6Example 6 실시예 7Example 7 비교예 1Comparative Example 1 비교예 2Comparative Example 2
양자점(A)Quantum Dots (A) A-1A-1 3030 3030 3030 3030 3030 3030 3030 3030 3030
광중합성 화합물(B)Photopolymerizable Compound (B) B-1B-1 99 99 99 99 99 99 99 1010 99
B-2B-2 2424 2424 2424 2424 2424 2424 2424 2525 2424
광중합 개시제(C)Photoinitiator (C) C-1C-1 55 55 55 55 55 55 55 55 55
알칼리 가용성 수지(D)Alkali-soluble resin (D) D-1D-1 3030 3030 3030 3030 3030 3030 3030 3030 3030
광안정제(E)Light stabilizer (E) E-1E-1 22 -- -- -- 1One 1One 0.50.5 -- --
E-2E-2 -- 22 -- -- -- --
E-3E-3 -- -- 22 -- 1One 0.50.5 -- --
E-4E-4 -- -- -- 22 -- --
E-5E-5 -- -- -- -- 1One 1One -- --
E-6E-6 -- -- -- -- -- -- -- -- 22
A-1: 제조예 1의 CdSe(코어)/ZnS(쉘) 구조 양자점A-1: CdSe (core) / ZnS (shell) structure quantum dots of Preparation Example 1
B-1: 디펜타에리트리톨펜타아크릴레이트숙신산모노에스테르 (카르복시산 함유 5관능 광중합성 화합물)(TO-1382, 동아합성 제조)B-1: dipentaerythritol pentaacrylate succinic acid monoester (carboxylic acid-containing 5-functional photopolymerizable compound) (TO-1382, manufactured by Dong-A Synthesis)
B-2: 디펜타에리트리톨헥사아크릴레이트(KAYARAD DPHA; 닛본 카야꾸 ㈜ 제조)B-2: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
C-1: Irgaqure-907 (BASF사 제조)C-1: Irgaqure-907 (manufactured by BASF Corporation)
D-1: 제조예 2의 알칼리 가용성 수지D-1: alkali-soluble resin of Preparation Example 2
E-1: TINUVIN 123 (BASF 제조) - 입체장애아민 화합물(Ra, Rb, Rc 및 Rd는 수소이고, Re는 옥톡시이며, Y는 -O-C(=O)-R'-C(=O)-O-이고, R'는 옥틸인 화학식 1의 화합물)E-1: TINUVIN 123 (made by BASF)-hindered amine compounds (R a , R b , R c and R d are hydrogen, R e is octoxy, Y is -OC (= O) -R'- A compound of Formula 1 wherein C (= 0) -O- and R 'is octyl)
E-2: TINUVIN 770DF (BASF 제조) - 입체장애아민 화합물(Ra, Rb, Rc 및 Rd는 수소이고, Re는 수소이며, Y는 -O-C(=O)-R'-C(=O)-O-이고, R'는 옥틸인 화학식 1의 화합물)E-2: TINUVIN 770DF (manufactured by BASF)-hindered amine compounds (R a , R b , R c and R d are hydrogen, R e is hydrogen, Y is -OC (= O) -R'-C (═O) —O—, wherein R ′ is octyl)
E-3: LA-52 (아데카 제조) - 입체장애아민 화합물(Ra, Rb, Rc 및 Rd는 수소이고, Re는 메틸인 화학식 2의 화합물)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 (아데카 제조) - 입체장애아민 화합물(Ra, Rb, Rc 및 Rd는 수소이고, Re는 수소인 화학식 2의 화합물)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)
E-5: TINUVIN 109 (BASF 제조) - 벤조트리아졸 화합물E-5: TINUVIN 109 (manufactured by BASF)-Benzotriazole Compound
E-6: DABCO (1,4-diazabicyclo[2,2,2]octane)E-6: DABCO (1,4-diazabicyclo [2,2,2] octane)
실험예 1Experimental Example 1
상기 실시예 및 비교예에서 제조된 감광성 수지 조성물을 이용하여 아래와 같이 컬러필터를 제조하였으며, 이때의 현상속도, 감도 및 밀착성을 하기와 같은 방법으로 측정하고, 그 결과를 하기 표 2에 나타내었다.Using the photosensitive resin composition prepared in the Examples and Comparative Examples to prepare a color filter as follows, the development speed, sensitivity and adhesion at this time was measured in the following manner, and the results are shown in Table 2 below.
<컬러필터의 제조><Production of color filter>
각각의 감광성 수지 조성물을 스핀 코팅법으로 유리 기판 위에 도포한 다음, 가열판 위에 놓고 100℃의 온도에서 3분간 유지하여 박막을 형성시켰다. 이어서 상기 박막 위에 가로×세로 20mm×20mm 정사각형의 투과 패턴과 1㎛ 내지 100㎛의 라인/스페이스 패턴을 갖는 시험 포토마스크를 올려놓고 시험 포토마스크와의 간격을 100㎛로 하여 자외선을 조사하였다. 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 μm to 100 μm was placed on the thin film and irradiated with ultraviolet rays at a distance of 100 μm from the test photomask.
이때, 자외선 광원은 우시오 덴끼㈜제의 초고압 수은 램프(상품명 USH-250D)를 이용하여 대기 분위기 하에 200mJ/㎠의 노광량(365㎚)으로 광조사하였으며, 특별한 광학 필터는 사용하지 않았다. 상기에서 자외선이 조사된 박막을 pH 10.5의 KOH 수용액 현상 용액에 80초 동안 담궈 현상하였다. 이 박막이 입혀진 유리 기판을 증류수를 사용하여 세척한 다음, 질소 가스를 불어서 건조하고, 150℃의 가열 오븐에서 10분 동안 가열하여 컬러필터를 제조하였다. 상기에서 제조된 컬러필터의 필름 두께는 3.0㎛이었다.At this time, 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 μm.
(1) 패턴 정밀도(1) pattern precision
상기 감광성 수지 조성물을 사용하여 제조된 컬러필터 중 100㎛로 설계된 라인/스페이스 패턴마스크를 통해 얻어진, 패턴의 크기를 OM 장비 (ECLIPSE LV100POL 니콘사)를 통해 측정하였다. 패턴마스크에 형성된 광투과 패턴의 폭과 측정된 컬러필터 패턴의 폭(측정된 패턴 폭)을 비교하여 패턴오차를 계산하였다. 즉, 패턴오차는 하기 수학식 1로 구해진다.The size of the pattern, which was obtained through a line / space pattern mask designed to 100 μm 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.
[수학식 1][Equation 1]
패턴오차(Δ) = (광투과 패턴의 폭) - (측정된 패턴 폭)Pattern error (Δ) = (width of light transmission pattern)-(measured pattern width)
패턴오차의 값이 20㎛ 보다 크면 미세 패턴 구현이 어려워 미세 화소의 구현이 어렵고, 마이너스 값을 가지면 공정 불량이 초래될 수 있다.If the value of the pattern error is larger than 20 μm, it is difficult to implement the fine pattern, and thus, it is difficult to implement the fine pixel. If the value is negative, the process defect may be caused.
(2) 발광 강도 및 발광 강도 유지율(내열성)(2) luminescence intensity and luminescence intensity retention rate (heat resistance)
상기 컬러필터 중 20mm×20mm 정사각형의 패턴으로 형성된 패턴부에 365nm Tube형 4W UV조사기(VL-4LC, VILBER LOURMAT)로 광을 조사하여, 광루미네선스에 의해 방출되는 파장(550nm) 영역의 발광 강도(intensity)를 스펙트럼 미터(spectrum meter)(Ocean Optics사)를 이용하여 측정하였다.Light emission of a wavelength (550 nm) region emitted by photoluminescence by irradiating light with a 365 nm tube type 4W UV irradiator (VL-4LC, VILBER LOURMAT) to a pattern portion formed of a 20 mm × 20 mm square pattern among the color filters. Intensity was measured using a spectrum meter (Ocean Optics).
하드베이크(hard bake)를 230℃에서 60분 동안 진행하여, 하드베이크 전의 발광 강도와 이후의 강도를 측정하고 비교예 1 대비 발광 강도 유지율을 비교하여 표 2에 나타내었다.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.
패턴오차Pattern error 발광 강도Luminous intensity 발광 강도 유지율 (%)Luminous intensity retention rate (%)
비교예1Comparative Example 1 3030 2351223512 STDSTD
비교예2Comparative Example 2 2727 2445624456 104104
실시예1Example 1 1212 5213552135 130130
실시예2Example 2 1313 5325853258 135135
실시예3Example 3 1111 5895458954 133133
실시예4Example 4 1212 5487554875 138138
실시예5Example 5 1010 6042760427 142142
실시예6Example 6 1111 6032860328 141141
실시예7Example 7 99 6354263542 149149
상기 표 2에 나타낸 바와 같이, 본 발명에 따른 입체장애아민 화합물을 광안정제로서 포함하는 실시예 1 내지 7의 감광성 수지 조성물은 이를 포함하지 않는 비교예 1 내지 2의 감광성 수지 조성물과 비교하여 미세 패턴 구현이 가능하고, 하드베이크 후에도 양자점이 산화되는 것을 억제하여 더 높게 발광 강도를 유지할 수 있음을 확인할 수 있었다. As 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.
이상으로 본 발명의 특정한 부분을 상세히 기술하였는 바, 본 발명이 속한 기술분야에서 통상의 지식을 가진 자에게 있어서 이러한 구체적인 기술은 단지 바람직한 구현예일 뿐이며, 이에 본 발명의 범위가 제한되는 것이 아님은 명백하다. 본 발명이 속한 기술분야에서 통상의 지식을 가진 자라면 상기 내용을 바탕으로 본 발명의 범주 내에서 다양한 응용 및 변형을 행하는 것이 가능할 것이다. Having described the specific part of the present invention in detail, it is apparent to those skilled in the art that this specific technology is only a preferred embodiment, which is not intended to limit the scope of the present invention. Do. Those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above contents.
따라서, 본 발명의 실질적인 범위는 첨부된 특허청구범위와 그의 등가물에 의하여 정의된다고 할 것이다.Therefore, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

Claims (9)

  1. 광루미네선스 양자점 입자, 광중합성 화합물, 광중합 개시제, 알칼리 가용성 수지, 광안정제 및 용제를 포함하는 감광성 수지 조성물로서, 상기 광안정제는 입체장애아민 화합물을 포함하는 감광성 수지 조성물.A photosensitive resin composition comprising a photoluminescent quantum dot particle, a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, a light stabilizer, and a solvent, wherein the light stabilizer comprises a hindered amine compound.
  2. 제1항에 있어서, 상기 입체장애아민 화합물은 하기 화학식 1로 표시되는 화합물인 감광성 수지 조성물:The photosensitive resin composition of claim 1, wherein the sterically hindered amine compound is a compound represented by Formula 1 below:
    [화학식 1][Formula 1]
    Figure PCTKR2017012621-appb-I000013
    Figure PCTKR2017012621-appb-I000013
    상기 식에서,Where
    Ra 및 Rb는 각각 독립적으로 수소 또는 메틸이고,R a and R b are each independently hydrogen or methyl,
    Rc 및 Rd는 각각 독립적으로 수소, C1-4 알킬 또는 C6-10 아릴이며,R c and R d are each independently hydrogen, C 1-4 alkyl, or C 6-10 aryl,
    Re는 수소; C1-18 알킬; C1-18 알콕시; 히드록시로 치환된 C2-7 알킬 또는 C2-7 알콕시; C2-18 알케닐; C2-18 알케닐옥시; C3-18 알키닐; C3-18 알키닐옥시; C3-12 시클로알킬; C3-12 시클로알콕시; C6-10 바이시클로알킬; C6-10 바이시클로알콕시; C3-8 시클로알케닐; C3-8 시클로알케닐옥시; C1-4 알킬, C1-4 알콕시 또는 할로겐으로 치환 또는 비치환된 C6-20 아릴; C1-4 알킬, C1-4 알콕시 또는 할로겐으로 치환 또는 비치환된 C6-20 아릴옥시; -C(=O)-H, -C(=O)-C1-19 알킬, -C(=O)-C2-19 알케닐, -C(=O)-C2-4 알케닐-C6-10 아릴, -C(=O)-C6-10 아릴, -C(=O)-O-C1-6 알킬, -C(=O)-O-C6-10 아릴, -C(=O)-NH-C1-6 알킬, -C(=O)-NH-C6-10 아릴 및 -C(=O)-N(C1-6 알킬)2로부터 선택되는 아실; 또는 -O-C(=O)-C1-19 알킬, -O-C(=O)-C2-19 알케닐 및 -OC(=O)-C6-10 아릴로부터 선택되는 아실옥시이고,R e is hydrogen; C 1-18 alkyl; C 1-18 alkoxy; C 2-7 alkyl or C 2-7 alkoxy substituted with hydroxy; C 2-18 alkenyl; C 2-18 alkenyloxy; C 3-18 alkynyl; C 3-18 alkynyloxy; C 3-12 cycloalkyl; C 3-12 cycloalkoxy; C 6-10 bicycloalkyl; C 6-10 bicycloalkoxy; C 3-8 cycloalkenyl; C 3-8 cycloalkenyloxy; C 6-20 aryl unsubstituted or substituted with C 1-4 alkyl, C 1-4 alkoxy or halogen; C 6-20 aryloxy unsubstituted or substituted with C 1-4 alkyl, C 1-4 alkoxy or halogen; -C (= 0) -H, -C (= 0) -C 1-19 alkyl, -C (= 0) -C 2-19 alkenyl, -C (= 0) -C 2-4 alkenyl- C 6-10 aryl, -C (= 0) -C 6-10 aryl, -C (= 0) -OC 1-6 alkyl, -C (= 0) -OC 6-10 aryl, -C (= 0) Acyl selected from) -NH-C 1-6 alkyl, -C (= 0) -NH-C 6-10 aryl and -C (= 0) -N (C 1-6 alkyl) 2 ; Or an acyloxy selected from -OC (= 0) -C 1-19 alkyl, -OC (= 0) -C 2-19 alkenyl and -OC (= 0) -C 6-10 aryl,
    Y는 -O-C(=O)-R'-C(=O)-O-이며, Y is -O-C (= O) -R'-C (= O) -O-,
    R'는 C1-10 알킬, C3-12 시클로알킬, C6-15 아릴 또는
    Figure PCTKR2017012621-appb-I000014
    이고,
    R 'is C 1-10 alkyl, C 3-12 cycloalkyl, C 6-15 aryl or
    Figure PCTKR2017012621-appb-I000014
    ego,
    R"는 C1-10 알킬, C3-12 시클로알킬 또는 C6-15 아릴이다.R ″ is C 1-10 alkyl, C 3-12 cycloalkyl or C 6-15 aryl.
  3. 제1항에 있어서, 상기 입체장애아민 화합물은 하기 화학식 2로 표시되는 화합물인 감광성 수지 조성물:The photosensitive resin composition of claim 1, wherein the hindered amine compound is a compound represented by the following Chemical Formula 2:
    [화학식 2][Formula 2]
    Figure PCTKR2017012621-appb-I000015
    Figure PCTKR2017012621-appb-I000015
    상기 식에서, Where
    R은
    Figure PCTKR2017012621-appb-I000016
    이며,
    R is
    Figure PCTKR2017012621-appb-I000016
    Is,
    Ra 및 Rb는 각각 독립적으로 수소 또는 메틸이고,R a and R b are each independently hydrogen or methyl,
    Rc 및 Rd는 각각 독립적으로 수소, C1-4 알킬 또는 C6-10 아릴이며,R c and R d are each independently hydrogen, C 1-4 alkyl, or C 6-10 aryl,
    Re는 수소; C1-18 알킬; C1-18 알콕시; 히드록시로 치환된 C2-7 알킬 또는 C2-7 알콕시; C2-18 알케닐; C2-18 알케닐옥시; C3-18 알키닐; C3-18 알키닐옥시; C3-12 시클로알킬; C3-12 시클로알콕시; C6-10 바이시클로알킬; C6-10 바이시클로알콕시; C3-8 시클로알케닐; C3-8 시클로알케닐옥시; C1-4 알킬, C1-4 알콕시 또는 할로겐으로 치환 또는 비치환된 C6-20 아릴; C1-4 알킬, C1-4 알콕시 또는 할로겐으로 치환 또는 비치환된 C6-20 아릴옥시; -C(=O)-H, -C(=O)-C1-19 알킬, -C(=O)-C2-19 알케닐, -C(=O)-C2-4 알케닐-C6-10 아릴, -C(=O)-C6-10 아릴, -C(=O)-O-C1-6 알킬, -C(=O)-O-C6-10 아릴, -C(=O)-NH-C1-6 알킬, -C(=O)-NH-C6-10 아릴 및 -C(=O)-N(C1-6 알킬)2로부터 선택되는 아실; 또는 -O-C(=O)-C1-19 알킬, -O-C(=O)-C2-19 알케닐 및 -OC(=O)-C6-10 아릴로부터 선택되는 아실옥시이다.R e is hydrogen; C 1-18 alkyl; C 1-18 alkoxy; C 2-7 alkyl or C 2-7 alkoxy substituted with hydroxy; C 2-18 alkenyl; C 2-18 alkenyloxy; C 3-18 alkynyl; C 3-18 alkynyloxy; C 3-12 cycloalkyl; C 3-12 cycloalkoxy; C 6-10 bicycloalkyl; C 6-10 bicycloalkoxy; C 3-8 cycloalkenyl; C 3-8 cycloalkenyloxy; C 6-20 aryl unsubstituted or substituted with C 1-4 alkyl, C 1-4 alkoxy or halogen; C 6-20 aryloxy unsubstituted or substituted with C 1-4 alkyl, C 1-4 alkoxy or halogen; -C (= 0) -H, -C (= 0) -C 1-19 alkyl, -C (= 0) -C 2-19 alkenyl, -C (= 0) -C 2-4 alkenyl- C 6-10 aryl, -C (= 0) -C 6-10 aryl, -C (= 0) -OC 1-6 alkyl, -C (= 0) -OC 6-10 aryl, -C (= 0) Acyl selected from) -NH-C 1-6 alkyl, -C (= 0) -NH-C 6-10 aryl and -C (= 0) -N (C 1-6 alkyl) 2 ; Or an acyloxy selected from -OC (= 0) -C 1-19 alkyl, -OC (= 0) -C 2-19 alkenyl and -OC (= 0) -C 6-10 aryl.
  4. 제2항에 있어서, Ra, Rb, Rc 및 Rd는 수소이고, Re는 수소 또는 C1-C18 알콕시이며, Y는 -O-C(=O)-R'-C(=O)-O-이고, R'는 C1-C10 알킬인 감광성 수지 조성물.The compound of claim 2, wherein R a , R b , R c and R d are hydrogen, R e is hydrogen or C 1 -C 18 alkoxy, and Y is —OC (═O) —R′—C (═O ) -O- and R 'is C 1 -C 10 alkyl.
  5. 제3항에 있어서, Ra, Rb, Rc 및 Rd는 수소이고, Re는 수소 또는 C1-C18 알킬인 감광성 수지 조성물.The photosensitive resin composition of claim 3, wherein R a , R b , R c and R d are hydrogen and R e is hydrogen or C 1 -C 18 alkyl.
  6. 제1항에 있어서, 상기 광안정제는 벤조트리아졸계 광안정제, 트리아진계 광안정제 및 벤조페논계 광안정제로 구성된 군으로부터 선택되는 1종 이상의 광안정제를 더 포함하는 감광성 수지 조성물.The photosensitive resin composition of claim 1, wherein the light stabilizer further comprises at least one light stabilizer selected from the group consisting of a benzotriazole light stabilizer, a triazine light stabilizer, and a benzophenone light stabilizer.
  7. 제1항에 있어서, 상기 광안정제의 함량은 감광성 수지 조성물의 고형분 전체 100 중량%에 대하여 0.025 내지 10 중량%인 감광성 수지 조성물.The photosensitive resin composition of claim 1, wherein the light stabilizer is present in an amount of 0.025 to 10 wt% based on 100 wt% of the total solids of the photosensitive resin composition.
  8. 제1항 내지 제7항 중 어느 한 항에 따른 감광성 수지 조성물을 이용하여 형성되는 컬러필터.The color filter formed using the photosensitive resin composition of any one of Claims 1-7.
  9. 제8항에 따른 컬러필터가 구비된 것을 특징으로 하는 화상표시장치.An image display apparatus comprising a color filter according to claim 8.
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