WO2018143628A1 - Quantum dot dispersion, self-emission type photosensitive resin composition, color filter, and image display device - Google Patents

Quantum dot dispersion, self-emission type photosensitive resin composition, color filter, and image display device Download PDF

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Publication number
WO2018143628A1
WO2018143628A1 PCT/KR2018/001234 KR2018001234W WO2018143628A1 WO 2018143628 A1 WO2018143628 A1 WO 2018143628A1 KR 2018001234 W KR2018001234 W KR 2018001234W WO 2018143628 A1 WO2018143628 A1 WO 2018143628A1
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Prior art keywords
ester
acid
tetrahydro
ethyl ester
pyran
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PCT/KR2018/001234
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French (fr)
Korean (ko)
Inventor
김형주
김주호
왕현정
정성욱
이종수
Original Assignee
동우 화인켐 주식회사
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Priority to CN201880009840.0A priority Critical patent/CN110300791B/en
Priority to JP2019540631A priority patent/JP7072579B2/en
Publication of WO2018143628A1 publication Critical patent/WO2018143628A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Definitions

  • the present invention relates to a quantum dot dispersion, a self-luminous photosensitive resin composition, a color filter, and an image display device, and more particularly, to a quantum dot dispersion liquid, a self-luminous photosensitive resin composition, and a color filter without using a solvent harmful to a human body. And an image display apparatus.
  • 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 to shield the boundary between each pixel, and a plurality of colors (typically red (R), green (G) and The pixel units in which the three primary colors of blue (B) are arranged in a predetermined order are stacked in this order.
  • Korean Patent Laid-Open Publication No. 2006-0084668 relates to a quantum dot phosphor, and discloses a light emitting diode which maintains excellent light emission efficiency by including a quantum dot and a solid carrier supporting the quantum dot.
  • the patent uses a solvent harmful to the human body such as chloroform, toluene, hexane and the like excellent in dispersibility as a dispersing solvent for dispersing the quantum dot phosphor.
  • Solvents described above are highly volatile compounds (Volatile Organic Compound) or carcinogenic, neurotoxic, and may cause reproductive dysfunction, requiring strict control of the handling environment of the operator.
  • quantum dots it is not a highly volatile compound after removing the solvent harmful to the human body through drying or dispersing solvent, it is not carcinogenic, neurotoxic, and there is no risk or low risk of reproductive dysfunction. Subsequent to the process of substituting for a solvent, a phenomenon in which quantum efficiency is lowered in this process occurs, which causes a problem in that light emission characteristics of a manufactured color filter or an image display device are deteriorated.
  • One object of the present invention is to provide a quantum dot dispersion having excellent dispersibility without using a solvent harmful to the human body.
  • Another object of the present invention is to provide a self-luminous photosensitive resin composition comprising the quantum dot dispersion.
  • Still another object of the present invention is to provide a color filter formed using the self-luminous photosensitive resin composition.
  • the present invention is a quantum dot dispersion containing a quantum dot and a solvent
  • the solvent is C 3 -C 10 cycloalkyl group, C 2 -C 10 heterocycloalkyl group, C 5 -C 10 aromatic group and C 4-
  • a quantum dot dispersion comprising a compound having an ester bond with at least one member selected from the group consisting of C 10 heteroaromatic groups.
  • the solvent may include one or more selected from a compound represented by the following formula (1) and a compound represented by the following formula (2).
  • A is a C 3 -C 10 cycloalkyl group, C 2 -C 10 heterocycloalkyl group, C 5- , which is unsubstituted or substituted with one or more substituents selected from the group consisting of C 1 -C 10 alkyl groups and halogen.
  • L is a C 1 -C 6 alkylene group or absent
  • R is an alkyl group of C 1 -C 10 or an alkenyl group of C 2 -C 10 .
  • the solvent may have a dielectric constant of less than 12.0 at 20 °C.
  • this invention provides the self-luminous photosensitive resin composition containing the said quantum dot dispersion liquid, alkali-soluble resin, a photopolymerizable compound, and a photoinitiator.
  • this invention provides the color filter formed using the said self-luminous photosensitive resin composition.
  • the present invention provides an image display device characterized in that the color filter is provided.
  • the quantum dot dispersion according to the present invention is excellent in dispersibility without using a solvent harmful to the human body, and the color filter formed using the self-luminous photosensitive resin composition including the same may exhibit excellent light emission characteristics.
  • One embodiment of the present invention is a quantum dot dispersion containing a quantum dot and a solvent, wherein the solvent is a C 3 -C 10 cycloalkyl group, C 2 -C 10 heterocycloalkyl group, C 5 -C 10 aromatic group and C 4 It relates to a quantum dot dispersion comprising a compound having an ester bond with at least one member selected from the group consisting of -C 10 heteroaromatic groups.
  • the quantum dots may refer to a nano-sized semiconductor material. Atoms form molecules, and molecules form clusters of small molecules called clusters that form nanoparticles, which are called quantum dots when they are semiconducting. When the quantum dots reach the excited state from the outside, the quantum dots emit energy according to their corresponding energy bandgap.
  • the color filter made of the self-luminous photosensitive resin composition including the quantum dot dispersion liquid may emit light (light luminescence) by light irradiation by including the quantum dot.
  • a typical image display apparatus including a color filter
  • white light is transmitted through the color filter to implement color.
  • a part of the light is absorbed by the color filter, thereby degrading light efficiency.
  • the color filter made of the self-luminous photosensitive resin composition according to the present invention since the color filter is self-luminous by the light of the light source, it is possible to implement more excellent light efficiency, and also emit light with color Since the color reproducibility is excellent, and the light is emitted in all directions by the photoluminescence, the viewing angle is also improved.
  • the quantum dot is not particularly limited as long as it is a quantum dot particle capable of emitting light by stimulation caused by light.
  • 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 an elemental compound selected from the group consisting of CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnS, H
  • the group III-V semiconductor compound may be selected from the group consisting of GaN, 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, InAlNP, InAlNAs, InAlNSb, InAlPAs, In
  • the Group IV-VI semiconductor compound may be 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 one or more selected from the group consisting of an elemental compound selected from the group consisting of mixtures thereof, but are not limited thereto.
  • the group IV element or a compound including the same may be selected from the group consisting of Si, Ge, and mixtures thereof; And a binary element compound selected from the group consisting of SiC, SiGe, and mixtures thereof.
  • the quantum dots 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.
  • the quantum dots may be synthesized by a wet chemical process, a metal organic chemical vapor deposition (MOCVD), or a molecular beam epitaxy (MBE), but is not limited thereto. no.
  • MOCVD metal organic chemical vapor deposition
  • MBE molecular beam epitaxy
  • the wet chemical process is a method of growing a particle by adding a precursor material to an organic solvent.
  • the organic solvent naturally coordinates the surface of the quantum dot crystal and acts as a dispersant to control the growth of the crystal. Therefore, the nano solvent is easier and cheaper than the vapor deposition method such as the organometallic chemical vapor deposition process or molecular beam epitaxy. Since the growth of the particles can be controlled, it is desirable to produce the quantum dots using the wet chemical process.
  • the quantum dots may further include an organic ligand.
  • the organic ligand may be bound to the surface of the quantum dots to serve to stabilize the quantum dots.
  • the organic ligand is not limited in the present invention, for example, C5 to C20 alkyl carboxylic acid, alkenyl carboxylic acid or alkynyl carboxylic acid; Thiol, phosphoric acid, pyridine, mercapto alcohol, phosphine, phosphine oxide, and the like, and in terms of effectively protecting the surface of the quantum dot to improve stability, C5 to C20 alkyl carboxylic acid, alkenyl Carboxylic acid or alkynyl carboxylic acid; It is preferable to include one or more selected from the group consisting of thiol and phosphoric acid.
  • the organic ligand may cover 5% or more of the surface of the total area of the quantum dots.
  • the content of the organic ligand may be 0.1 to 10 moles with respect to 1 mole of the quantum dot.
  • the quantum dot may be included in an amount of 5 to 70 wt%, preferably 10 to 65 wt%, more preferably 15 to 60 wt%, based on 100 wt% of the total quantum dot dispersion.
  • the quantum dot is included in the above range, it is possible to provide a self-luminous photosensitive resin composition having excellent photosensitivity.
  • the solvent is an aromatic heterocyclic group the group consisting of C 3 -C 10 cycloalkyl group, C 2 -C 10 heterocycloalkyl group, C 5 -C 10 aromatic group, and a C 4 -C 10 of the It includes a compound having an ester bond with at least one member selected from.
  • the solvent may include at least one selected from a compound represented by Formula 1 and a compound represented by Formula 2.
  • A is a C 3 -C 10 cycloalkyl group, C 2 -C 10 heterocycloalkyl group, C 5- , which is unsubstituted or substituted with one or more substituents selected from the group consisting of C 1 -C 10 alkyl groups and halogen.
  • L is a C 1 -C 6 alkylene group or absent
  • R is an alkyl group of C 1 -C 10 or an alkenyl group of C 2 -C 10 .
  • an alkyl group of C 1 -C 10 refers to a straight or branched monovalent hydrocarbon having 1 to 10 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl And the like, but are not limited thereto.
  • a C 3 -C 10 cycloalkyl group means a simple or fused cyclic hydrocarbon composed of 3 to 10 carbon atoms, including but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. It doesn't happen.
  • a C 2 -C 10 heterocycloalkyl group means a functional group in which one or more of the ring carbons of a simple or fused cyclic hydrocarbon composed of 3 to 10 carbon atoms is replaced with oxygen, sulfur or nitrogen, for example Tetrahydrofuranyl, tetrahydropyranyl, thiazolidinyl, oxiranyl, and the like, but is not limited thereto.
  • an aromatic group of C 5 -C 10 refers to a simple or fused cyclic aromatic hydrocarbon of 5 to 10 members, for example phenyl, naphthyl, cyclopentadienyl, tetrahydronaphthyl And the like, but are not limited thereto.
  • a C 4 -C 10 heteroaromatic group means a functional group in which one or more of the ring carbons of a 5- to 10-membered simple or fused cyclic aromatic hydrocarbon is substituted with oxygen, sulfur or nitrogen, for example Pyridinyl, furanyl, thiophenyl, indolyl, quinolinyl, imidazolinyl, oxazolyl, thiazolyl And the like, but are not limited thereto.
  • an alkylene group of C 1 -C 6 refers to a straight or branched divalent hydrocarbon having 1 to 6 carbon atoms, and includes, for example, methylene, ethylene, propylene, butylene, pentylene, and the like. However, it is not limited thereto.
  • Alkenyl group of C 2 -C 10 as used herein means a straight or branched unsaturated hydrocarbon composed of 2 to 10 carbon atoms having one or more carbon-carbon double bonds, for example ethyleneyl, propenyl, moiety. Tenyls, pentenyls, allyls, and the like.
  • A is cyclopentyl, cyclohexyl, tetrahydrofuranyl, tetrahydropyranyl, phenyl, cyclopentadienyl or furanyl, substituted or unsubstituted with halogen
  • L is C 1- It may or may not be an alkylene group of C 6
  • R may be an alkyl group of C 1 -C 10 or an alkenyl group of C 2 -C 10 .
  • Examples of the compound represented by Formula 1 include phenyl-acetic acid ethyl ester, 3-phenyl-propionic acid methyl ester, 3-phenyl-propionic acid ethyl ester, 4-phenyl-butyric acid ethyl ester, 5-phenyl-pentanoic acid ethyl ester, 6- Phenyl-hexanoic acid ethyl ester, 4-phenyl-butyric acid propyl ester, 4- (4-chloro-phenyl) -butyric acid ethyl ester, 4- (3,4-dichloro-phenyl) -butyric acid ethyl ester, 3-cyclopenta- 1,3-dienyl-propionic acid methyl ester, 4-cyclopenta-1,3-dienyl-butyric acid ethyl ester, 5-cyclopenta-1,3-dienyl-pentanoic acid ethyl
  • Examples of the compound represented by Formula 2 include acetic acid benzyl ester, propionic acid phenethyl ester, propionic acid 3-phenyl-propyl ester, propionic acid 4-phenyl-butyl ester, butyric acid phenethyl ester, propionic acid 2- (4-chloro-phenyl)- Ethyl ester, propionic acid 2- (3,4-dichloro-phenyl) -ethyl ester, acetic acid cyclopenta-1,3-dienylmethyl ester, propionic acid 2-cyclopenta-1,3-dienyl-ethyl ester, propionic acid 3 -Cyclopenta-1,3-dienyl-propyl ester, propionic acid 4-cyclopenta-1,3-dienyl-butyl ester, butyric acid 2-cyclopenta-1,3-dienyl-ethyl ester, furan-2 a
  • the said solvent can be used individually or in mixture of 2 or more types, respectively.
  • the solvent may have a dielectric constant of less than 12.0, preferably less than 10 and even more preferably less than 6 at 20 ° C.
  • the solvent may have a dielectric constant of 2.0 to 5.5 at 20 ° C.
  • the dielectric constant of the solvent is less than 12.0, quantum dot aggregation does not occur during quantum dot dispersion and uniform dispersion is possible, and the light emission efficiency of the quantum dot dispersion may be excellent.
  • the content of the solvent may be 5 to 95% by weight, preferably 20 to 90% by weight, and more preferably 30 to 80% by weight based on 100% by weight of the total quantum dot dispersion.
  • the solvent is included in less than 5% by weight may cause a problem that the dispersibility is deteriorated, when it exceeds 95% by weight may be a problem that it is difficult to control the solid content of the resin composition.
  • the quantum dot dispersion may further comprise a dispersant.
  • the dispersant may be used to suppress the deagglomeration effect of the quantum dots and precipitation phenomenon due to the polarity difference when used in the self-luminous photosensitive resin composition, and to impart a protective layer role of the quantum dots in the color filter manufacturing process.
  • a phosphate ester dispersant, a urethane dispersant, an acrylic dispersant, or the like may be used as the resin type dispersant.
  • commercially available products of the dispersant include the brand names of BIC Chem Corporation: DISPER BYK-103, DISPER BYK-110, DISPER BYK-111, DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166 can be used.
  • the dispersant may be included in an amount of 1 to 300 parts by weight, preferably 3 to 250 parts by weight, and more preferably 5 to 200 parts by weight, based on 100 parts by weight of the total solids of the quantum dot dispersion.
  • the dispersant is included in the above range, the deagglomeration effect of the quantum dot is excellent, the precipitation phenomenon due to the polarity difference in the quantum dot dispersion liquid and the self-luminous photosensitive resin composition including the same according to the present invention is possible, the color filter manufacturing process It is preferable because it can act as a protective layer of the quantum dots.
  • the dispersant When the dispersant is included in the range below the deagglomeration effect of the quantum dot may be slightly reduced, and when included in the above range, the development characteristics of the self-luminous photosensitive resin composition including the quantum dot dispersion may be slightly lowered, It is preferable to be included in the said range.
  • One Embodiment of this invention relates to the self-luminous photosensitive resin composition containing a quantum dot dispersion liquid (A), alkali-soluble resin (B), a photopolymerizable compound (C), and a photoinitiator (D).
  • A quantum dot dispersion liquid
  • B alkali-soluble resin
  • C photopolymerizable compound
  • D photoinitiator
  • the quantum dot dispersion (A) uses the quantum dot dispersion described above.
  • the content of the quantum dot dispersion may be 3 to 80% by weight, preferably 5 to 70% by weight, and more preferably 10 to 60% by weight based on 100% by weight of the total self-luminous photosensitive resin composition.
  • the quantum dot dispersion is included in the above range, it is possible to manufacture a color filter having excellent light emission characteristics.
  • the quantum dot dispersion is included in less than the above range, the light emission characteristics may be slightly lowered.
  • the quantum dot dispersion is included in the above range, the formation of a pattern may be somewhat difficult as the content of other components is reduced. Since reliability may be degraded, it is preferable to be included in the above range.
  • Alkali-soluble resin (B) may play a role of making the non-exposed part of the color filter made of the self-luminous photosensitive resin composition alkali-soluble to be removed and leaving the exposure area.
  • the quantum dots may be evenly dispersed in the composition, and may serve to maintain the brightness by protecting the quantum dots during the process.
  • the alkali-soluble resin may be selected and used having an acid value of 10 to 200 (KOHmg / g).
  • the "acid value” is a value measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of the polymer and is involved in solubility.
  • the acid value of the alkali-soluble resin is less than the above range, it may be difficult to secure a sufficient developing speed, when the acid value of the alkali-soluble resin is exceeded, the adhesion to the substrate is reduced, the short circuit of the pattern is likely to occur, the storage stability of the entire composition is lowered viscosity The problem may arise.
  • the alkali-soluble resin may consider the limitation of the molecular weight and the molecular weight distribution (Mw / Mn) in order to improve the surface hardness for use as a color filter.
  • Mw / Mn molecular weight distribution
  • the weight average molecular weight is 3,000 to 30,000, preferably 5,000 to 20,000
  • the molecular weight distribution can be directly polymerized or purchased to have a range of 1.5 to 6.0, preferably 1.8 to 4.0.
  • Alkali-soluble resins having a molecular weight and a molecular weight distribution in the above range can be improved in hardness, and excellent solubility of the non-exposed portion in the developer as well as high residual film ratio can improve resolution.
  • the alkali-soluble resin may be a polymer of a carboxyl group-containing unsaturated monomer, or a copolymer with a monomer having an unsaturated bond copolymerizable therewith, or a combination thereof.
  • the carboxyl group-containing unsaturated monomer may be unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated tricarboxylic acid, and the like.
  • unsaturated monocarboxylic acid acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example.
  • unsaturated dicarboxylic acid maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example.
  • the unsaturated dicarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride and citraconic anhydride.
  • the unsaturated dicarboxylic acid may be mono (2- (meth) acryloyloxyalkyl) ester thereof, for example, succinic mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxy Ethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, and the like.
  • the unsaturated dicarboxylic acid may be mono (meth) acrylate of the sock end dicarboxy polymer, and examples thereof include? -Carboxypolycaprolactone monoacrylate and? -Carboxypolycaprolactone monomethacrylate.
  • carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively.
  • the monomer copolymerizable with the carboxyl group-containing unsaturated monomer may include an aromatic vinyl compound, an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid aminoalkyl ester compound, an unsaturated carboxylic acid glycidyl ester compound, a carboxylic acid vinyl ester compound, an unsaturated ether compound, a vinyl cyanide compound, and an unsaturated monomer.
  • It can be selected from the group consisting of an amide compound, an unsaturated imide compound, an aliphatic conjugated diene compound, a macromonomer having a monoacryloyl group or a monomethacryloyl group at the terminal of the molecular chain, a bulky monomer, and a combination thereof.
  • the copolymerizable monomer may be styrene, ⁇ -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- Methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl Aromatic vinyl compounds such as ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl g
  • Macromonomers having; Bulky monomers, such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton, which can lower the dielectric constant, can be used.
  • the alkali-soluble resin may be included in 5 to 80% by weight, specifically 10 to 70% by weight, more specifically 15 to 60% by weight based on 100% by weight of the total solids of the self-luminous 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 is prevented at the time of development, so that the dropping of the non-pixel portion is good, which is preferable.
  • the alkali-soluble resin is included in less than the above range, the non-pixel portion may be somewhat missing, and when the alkali-soluble resin is included in more than the above range, the solubility in the developing solution is slightly lowered may be somewhat difficult to form a pattern.
  • the photopolymerizable compound (C) is a compound that can be polymerized by the action of light and a photopolymerization initiator to be described later. Examples thereof include a monofunctional monomer, a bifunctional monomer, and other polyfunctional monomers. .
  • the kind of the monofunctional monomer is not particularly limited, and for example, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acryl
  • the rate, N-vinylpyrrolidone, etc. are mentioned.
  • the kind of the said bifunctional monomer is not specifically limited, For example, 1, 6- hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene Glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.
  • the kind of the polyfunctional monomer is not particularly limited, and examples thereof include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, and propoxylated trimethylolpropane tree (meth).
  • the photopolymerizable compound may be included in an amount of 5 to 70 wt%, specifically 10 to 60 wt%, and more specifically 15 to 50 wt%, based on 100 wt% of the total solids of the self-luminous photosensitive resin composition.
  • the photopolymerizable compound is included in the above range, there is a preferable advantage in terms of intensity or smoothness of the pixel portion.
  • the intensity of the pixel portion may be lowered slightly, and when the photopolymerizable compound is included in the above range, smoothness may be slightly lowered, so it is preferably included within the range. .
  • the photopolymerization initiator (D) can be used without particular limitation as long as it can polymerize the photopolymerizable compound.
  • the photopolymerization initiator may be an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound, or a thioxic acid from the viewpoint of polymerization characteristics, start efficiency, absorption wavelength, availability, and price. It is preferable to use at least one compound selected from the group consisting of ton compounds.
  • acetophenone-based compound examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methylpropan-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, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.
  • benzophenone type compound for example, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.
  • triazine-based compound examples include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6 -(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
  • biimidazole compound examples include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4 And a biimidazole compound in which a phenyl group at a 4,4 ', 5,5' position is substituted by a carboalkoxy group, or the like.
  • oxime-based compound examples include o-ethoxycarbonyl- ⁇ -oxyimino-1-phenylpropan-1-one, and the like, and commercially available products include BASF's Irgacure OXE 01 and OXE 02.
  • thioxanthone type compound 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. There is this.
  • the photopolymerization initiator may be included in an amount of 0.1 to 20% by weight, preferably 0.5 to 15% by weight, and more preferably 1 to 10% by weight, based on 100% by weight of the total solid of the self-luminous photosensitive resin composition.
  • the self-luminous photosensitive resin composition is highly sensitive, so that the exposure time is shortened, so that productivity is improved and high resolution can be maintained.
  • the photopolymerization initiator may further include a photopolymerization initiation aid in order to improve the sensitivity of the self-luminous photosensitive resin composition of the present invention.
  • a photopolymerization initiation aid in order to improve the sensitivity of the self-luminous photosensitive resin composition of the present invention.
  • the photopolymerization initiation assistant may be preferably used, for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group, but is not limited thereto.
  • amine compound examples include aliphatic amine compounds such as triethanolamine, methyl diethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethyl.
  • the carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, Chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.
  • organic sulfur compound having the thiol group examples include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto Butyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) and the like Can be.
  • the photopolymerization start adjuvant may be appropriately added and used within a range that does not impair the effects of the present invention.
  • the self-luminous photosensitive resin composition according to one embodiment of the present invention may further include an additional solvent.
  • the additional solvent is not particularly limited, and may include an organic solvent commonly used in the art, which may be the same as or different from the solvent contained in the quantum dot dispersion of the present invention.
  • the additional solvent include alkylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol methylethyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; Alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl
  • the above additional solvent may preferably be an organic solvent having a boiling point of 100 ° C. to 200 ° C. in terms of coatability and dryness, and more preferably alkylene glycol alkyl ether acetates, ketones, and ethyl 3-ethoxypropionate.
  • Esters such as methyl 3-methoxypropionate can be used, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.
  • These additional solvents can be used individually or in mixture of 2 or more types, respectively.
  • the total solvent (solvent in quantum dot dispersion and additional solvent) contained in the self-luminous photosensitive resin composition of the present invention is 20 to 90% by weight, preferably 25 to 85% by weight, based on 100% by weight of the total of the self-luminous photosensitive resin composition, More preferably, it may be included in 30 to 80% by weight. If the total solvent content is within the above range, the applicability may be improved when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, or the like. It is preferable.
  • the self-luminous photosensitive resin composition according to the present invention may further include an additive such as an adhesion promoter and a surfactant to enhance the coating property or adhesion.
  • the adhesion promoter may include a silane coupling agent having a reactive substituent selected from the group consisting of carboxyl groups, methacryloyl groups, isocyanate groups, epoxy groups, and combinations thereof, which may be added to increase adhesion to the substrate. It is not limited to this.
  • the silane coupling agent may be trimethoxysilylbenzoic acid, ⁇ -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, ⁇ -isocyanatepropyl triethoxysilane, ⁇ -glycidoxy Propyl trimethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned, These can be used individually or in combination of 2 or more types.
  • the self-luminous photosensitive resin composition according to the present invention includes the surfactant
  • the surfactant is BM-1000, BM-1100 (BM Chemie Co., Ltd.), Proride FC-135 / FC-170C / FC-430 (Sumitomo 3M Co., Ltd.), SH-28PA / -190 / SZ-6032 (Dore Siri).
  • Fluorine-based surfactants such as Corn Co., Ltd. may be used, but is not limited thereto.
  • the self-luminous photosensitive resin composition according to the present invention may further include additives such as antioxidants, ultraviolet absorbers and anti-agglomerating agents in a range that does not impair the effects of the present invention, the additives also inhibit the effects of the present invention It can be used by those skilled in the art as long as it does not.
  • the additive may be used in an amount of 0.05 to 10% by weight, specifically 0.1 to 10% by weight, and more specifically 0.1 to 5% by weight, based on 100% by weight of the total self-luminous photosensitive resin composition.
  • One embodiment of the present invention relates to a color filter formed by using the above self-luminous photosensitive resin composition.
  • the color filter according to the present invention includes the cured product of the self-luminous photosensitive resin composition including the quantum dot dispersion liquid of the present invention, the quantum dot particles are uniformly dispersed, thereby providing excellent light emission characteristics.
  • the color filter includes a substrate and a pattern layer formed on the substrate.
  • the substrate may be the 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 self-luminous photosensitive resin composition of the present invention, and may be a layer formed by applying the self-luminous photosensitive resin composition and exposing, developing and thermosetting in a predetermined pattern.
  • the pattern layer may be formed by performing a method commonly known in the art.
  • the color filter including the substrate and the pattern layer may further include a partition wall or a black matrix formed between the patterns, but is not limited thereto.
  • a protective film formed on the pattern layer of the color filter may be further included.
  • the color filter may include at least one selected from the group consisting of a red pattern layer, a green pattern layer, and a blue pattern layer.
  • the color filter may include one or more selected from the group consisting of a red pattern layer including a red quantum dot, a green pattern layer including a green quantum dot, and a blue pattern layer including a blue quantum dot according to the present invention.
  • the red pattern layer, the green pattern layer, and the blue pattern layer may respectively emit red light, green light, and blue light when irradiated with light.
  • the emission light of the light source is not particularly limited, but blue light may be generated in terms of better color reproducibility.
  • a light source that emits can be used.
  • the color filter may include only a pattern layer of two colors among the red pattern layer, the green pattern layer, and the blue pattern layer, but is not limited thereto. However, when the color filter includes only the pattern layer of two colors, the pattern layer may further include a transparent pattern layer containing no quantum dot particles.
  • a light source emitting light having a wavelength representing a color other than the two colors may be used.
  • a light source emitting blue light may be used.
  • red quantum dots emit red light and green quantum dots emit green light
  • the transparent pattern layer may As the blue light transmitted by the light source is transmitted as it is, blue can be obtained.
  • 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.
  • the image display device includes the color filter made of the cured product of the self-luminous photosensitive resin composition containing the quantum dot dispersion liquid of the present invention, thereby exhibiting excellent light emission characteristics.
  • each component was mixed to prepare a self-luminous photosensitive resin composition (unit: wt%).
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 1 Comparative Example 2 Comparative Example 3 Quantum Dot Dispersion (A) Preparation Example 1 40 Preparation Example 2 40 Preparation Example 3 40 Preparation Example 4 40 Preparation Example 5 40 Preparation Example 6 40 Preparation Example 7 40 Preparation Example 8 40 Preparation Example 9 40 Preparation Example 10 40 Preparation Example 11 40 Preparation Example 12 40 Preparation Example 13 40 Preparation Example 14 40 Alkali-Soluble Resin (B) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20
  • Dispersion particle size of the quantum dot dispersion prepared in the above Preparation Example and the self-luminous photosensitive resin composition prepared in the Examples and Comparative Examples was measured using ELSZ-2000ZS (manufactured by Otsuka Co., Ltd.), and the results are shown in Table 3 below. .
  • ELSZ-2000ZS manufactured by Otsuka Co., Ltd.
  • Each self-luminous photosensitive resin composition was applied on a glass substrate by spin coating, then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. Subsequently, a test photomask having a square transmissive pattern having a width ⁇ length of 20 mm ⁇ 20 mm 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 ultra high 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 film coated glass plate 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 pattern.
  • the film thickness of the self-luminous color filter pattern prepared above was 3.0 ⁇ m.
  • the emission intensity in the 550 nm region of the color filter on which the self-luminous pixel was formed was measured using a spectrum meter (manufactured by Ocean Optics). It may be judged that the higher the measured light emission intensity is, the better the light emission characteristic is.
  • the quantum dot dispersion particle size in the quantum dot dispersion liquid of Preparation Examples 1 to 11 containing the specific solvent according to the present invention and the self-luminous photosensitive resin composition of Examples 1 to 11 including the same are prepared in Preparation Examples 12 to It was confirmed that it was smaller than the quantum dot dispersion particle size in the quantum dot dispersion liquid of 14 and the self-luminous photosensitive resin composition of Comparative Examples 1 to 3 including the same.
  • the color filter formed using the self-luminous photosensitive resin compositions of Examples 1 to 11 according to the present invention has superior emission intensity as compared to the color filter formed using the self-luminous photosensitive resin compositions of Comparative Examples 1 to 3. there was.

Abstract

The present invention provides: a quantum dot dispersion comprising quantum dots and a solvent, the solvent comprising a compound having an ester linkage with at least one selected from the group consisting of a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, a C5-C10 aromatic group, and a C4-C10 heteroaromatic group; a self-emission type photosensitive resin composition comprising the quantum dot dispersion; a color filter formed using the self-emission type photosensitive resin composition; and an image display device. The quantum dot dispersion according to the present invention has excellent dispersibility even without using a solvent harmful to the human body, and thus the color filter formed using the self-emission type photosensitive resin composition comprising the quantum dot dispersion can exhibit excellent emission characteristics.

Description

양자점 분산액, 자발광 감광성 수지 조성물, 컬러필터 및 화상표시장치Quantum dot dispersion, self-luminous photosensitive resin composition, color filter and image display device
본 발명은 양자점 분산액, 자발광 감광성 수지 조성물, 컬러필터 및 화상표시장치에 관한 것으로, 보다 상세하게는 인체에 유해한 용제를 사용하지 않으면서도 분산성이 우수한 양자점 분산액, 자발광 감광성 수지 조성물, 컬러필터 및 화상표시장치에 관한 것이다.The present invention relates to a quantum dot dispersion, a self-luminous photosensitive resin composition, a color filter, and an image display device, and more particularly, to a quantum dot dispersion liquid, a self-luminous photosensitive resin composition, and a color filter without using a solvent harmful to a human body. And an image display apparatus.
컬러필터는 백색광에서 적색, 녹색 및 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 위하여 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.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 to shield the boundary between each pixel, and a plurality of colors (typically red (R), green (G) and The pixel units in which the three primary colors of blue (B) are arranged in a predetermined order are stacked in this order.
최근에는 컬러필터를 구현하는 방법 중의 하나로서, 안료 분산형의 감광성 수지를 이용한 안료 분산법이 적용되고 있으나, 광원에서 조사된 광이 컬러필터를 투과하는 과정에서 광의 일부가 컬러필터에 흡수되어 광 효율이 저하되고, 또한 컬러필터에 포함되어 있는 안료의 특성으로 인하여 색재현이 저하되는 문제점이 발생하고 있다.Recently, as one of the methods of implementing a color filter, a pigment dispersion method using a pigment-dispersible photosensitive resin has been applied, but a part of the light is absorbed by the color filter while the light emitted from the light source passes through the color filter. The problem is that the efficiency is lowered and the color reproduction is lowered due to the characteristics of the pigment included in the color filter.
특히, 컬러필터가 각종 화상표시장치를 비롯한 다양한 분야에 사용됨에 따라 우수한 패턴 특성뿐만 아니라 높은 색재현율과 함께 고휘도, 고명암비와 같은 성능이 요구되고 있는 바, 이러한 문제를 해결하기 위하여, 양자점을 포함하는 자발광 감광성 수지 조성물을 이용한 컬러필터 제조 방법이 제안되었다.In particular, as color filters are used in various fields including various image display apparatuses, performances such as high brightness and high contrast ratio are required as well as high color reproduction ratio as well as excellent pattern characteristics. A color filter manufacturing method using a self-luminous photosensitive resin composition has been proposed.
대한민국 공개특허 제2006-0084668호는 양자점 형광체에 관한 것으로서, 양자점 및 상기 양자점을 고정시키는 고체상태의 담지체를 포함함으로써 우수한 발광 효율을 유지하는 발광 다이오드에 관한 내용을 개시하고 있다.Korean Patent Laid-Open Publication No. 2006-0084668 relates to a quantum dot phosphor, and discloses a light emitting diode which maintains excellent light emission efficiency by including a quantum dot and a solid carrier supporting the quantum dot.
하지만, 상기 특허에서는 상기 양자점 형광체를 분산시키기 위한 분산용제로서 분산성이 우수한 클로로포름, 톨루엔, 헥산 등과 같은 인체에 유해한 용제를 사용하고 있다. 앞서 기술한 용제의 경우 고휘발성 화합물(Volatile Organic Compound)이거나 또는 발암성, 신경독성을 띠고, 생식기능 이상을 유발할 수 있는 위험성이 있어 작업자의 취급환경에 대한 엄격한 관리가 필요하다. However, the patent uses a solvent harmful to the human body such as chloroform, toluene, hexane and the like excellent in dispersibility as a dispersing solvent for dispersing the quantum dot phosphor. Solvents described above are highly volatile compounds (Volatile Organic Compound) or carcinogenic, neurotoxic, and may cause reproductive dysfunction, requiring strict control of the handling environment of the operator.
따라서 이러한 양자점을 사용하기 위해서는 건조를 통하여 인체에 유해한 용제를 제거하거나, 분산 용제를 제거한 후 고휘발성 화합물이 아니며, 발암성, 신경독성을 띠지 않고, 생식기능 이상을 유발할 수 있는 위험성이 없거나 매우 낮은 용제로 치환하는 과정을 거치게 되는데, 이러한 과정에서 양자 효율이 저하되는 현상이 발생하고, 이 때문에 제조되는 컬러필터 또는 화상표시장치의 발광특성이 저하되는 문제가 발생하고 있다.Therefore, in order to use these quantum dots, it is not a highly volatile compound after removing the solvent harmful to the human body through drying or dispersing solvent, it is not carcinogenic, neurotoxic, and there is no risk or low risk of reproductive dysfunction. Subsequent to the process of substituting for a solvent, a phenomenon in which quantum efficiency is lowered in this process occurs, which causes a problem in that light emission characteristics of a manufactured color filter or an image display device are deteriorated.
그러므로, 양자점에 대한 우수한 분산성을 보이면서, 이를 이용하여 제조되는 컬러필터 또는 화상표시장치의 발광 특성 또한 우수하며, 인체에 유해한 성분을 함유하고 있지 않은 양자점 분산액의 개발이 요구되고 있다.Therefore, there is a demand for the development of a quantum dot dispersion liquid, which exhibits excellent dispersibility to quantum dots, is excellent in light emission characteristics of a color filter or an image display device manufactured using the same, and does not contain harmful components.
본 발명의 한 목적은 인체에 유해한 용제를 사용하지 않으면서도 분산성이 우수한 양자점 분산액을 제공하는 것이다.One object of the present invention is to provide a quantum dot dispersion having excellent dispersibility without using a solvent harmful to the human body.
본 발명의 다른 목적은 상기 양자점 분산액을 포함하는 자발광 감광성 수지 조성물을 제공하는 것이다.Another object of the present invention is to provide a self-luminous photosensitive resin composition comprising the quantum dot dispersion.
본 발명의 또 다른 목적은 상기 자발광 감광성 수지 조성물을 이용하여 형성되는 컬러필터를 제공하는 것이다.Still another object of the present invention is to provide a color filter formed using the self-luminous 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 양자점 및 용제를 포함하는 양자점 분산액으로서, 상기 용제는 C3-C10의 사이클로알킬기, C2-C10의 헤테로사이클로알킬기, C5-C10의 아로마틱기 및 C4-C10의 헤테로아로마틱기로 구성된 군으로부터 선택되는 1종 이상과 에스테르 결합을 갖는 화합물을 포함하는 양자점 분산액을 제공한다.On the other hand, the present invention is a quantum dot dispersion containing a quantum dot and a solvent, the solvent is C 3 -C 10 cycloalkyl group, C 2 -C 10 heterocycloalkyl group, C 5 -C 10 aromatic group and C 4- Provided is a quantum dot dispersion comprising a compound having an ester bond with at least one member selected from the group consisting of C 10 heteroaromatic groups.
본 발명의 일 실시형태에서, 상기 용제는 하기 화학식 1로 표시되는 화합물 및 하기 화학식 2로 표시되는 화합물 중에서 선택되는 1종 이상을 포함할 수 있다.In one embodiment of the present invention, the solvent may include one or more selected from a compound represented by the following formula (1) and a compound represented by the following formula (2).
[화학식 1][Formula 1]
Figure PCTKR2018001234-appb-I000001
Figure PCTKR2018001234-appb-I000001
[화학식 2][Formula 2]
Figure PCTKR2018001234-appb-I000002
Figure PCTKR2018001234-appb-I000002
상기 식에서,Where
A는 C1-C10의 알킬기 및 할로겐으로 구성된 군으로부터 선택되는 1종 이상의 치환기로 치환되거나 비치환된, C3-C10의 사이클로알킬기, C2-C10의 헤테로사이클로알킬기, C5-C10의 아로마틱기 또는 C4-C10의 헤테로아로마틱기이고,A is a C 3 -C 10 cycloalkyl group, C 2 -C 10 heterocycloalkyl group, C 5- , which is unsubstituted or substituted with one or more substituents selected from the group consisting of C 1 -C 10 alkyl groups and halogen. C 10 aromatic group or C 4 -C 10 heteroaromatic group,
L은 C1-C6의 알킬렌기이거나 존재하지 않고,L is a C 1 -C 6 alkylene group or absent,
R은 C1-C10의 알킬기 또는 C2-C10의 알케닐기이다.R is an alkyl group of C 1 -C 10 or an alkenyl group of C 2 -C 10 .
본 발명의 일 실시형태에서, 상기 용제는 유전상수가 20℃에서 12.0 미만일 수 있다.In one embodiment of the present invention, the solvent may have a dielectric constant of less than 12.0 at 20 ℃.
다른 한편으로, 본 발명은 상기 양자점 분산액, 알칼리 가용성 수지, 광중합성 화합물 및 광중합 개시제를 포함하는 자발광 감광성 수지 조성물을 제공한다.On the other hand, this invention provides the self-luminous photosensitive resin composition containing the said quantum dot dispersion liquid, alkali-soluble resin, a photopolymerizable compound, and a photoinitiator.
또 다른 한편으로, 본 발명은 상기 자발광 감광성 수지 조성물을 이용하여 형성되는 컬러필터를 제공한다.On the other hand, this invention provides the color filter formed using the said self-luminous 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 양자점 분산액은 인체에 유해한 용제를 사용하지 않으면서도 분산성이 우수하여, 이를 포함하는 자발광 감광성 수지 조성물을 이용하여 형성되는 컬러필터가 우수한 발광 특성을 나타낼 수 있다.The quantum dot dispersion according to the present invention is excellent in dispersibility without using a solvent harmful to the human body, and the color filter formed using the self-luminous photosensitive resin composition including the same may exhibit excellent light emission characteristics.
이하, 본 발명을 보다 상세히 설명한다. Hereinafter, the present invention will be described in more detail.
본 발명의 일 실시형태는 양자점 및 용제를 포함하는 양자점 분산액으로서, 상기 용제는 C3-C10의 사이클로알킬기, C2-C10의 헤테로사이클로알킬기, C5-C10의 아로마틱기 및 C4-C10의 헤테로아로마틱기로 구성된 군으로부터 선택되는 1종 이상과 에스테르 결합을 갖는 화합물을 포함하는 양자점 분산액에 관한 것이다.One embodiment of the present invention is a quantum dot dispersion containing a quantum dot and a solvent, wherein the solvent is a C 3 -C 10 cycloalkyl group, C 2 -C 10 heterocycloalkyl group, C 5 -C 10 aromatic group and C 4 It relates to a quantum dot dispersion comprising a compound having an ester bond with at least one member selected from the group consisting of -C 10 heteroaromatic groups.
본 발명의 일 실시형태에서, 상기 양자점은 나노 크기의 반도체 물질을 일컬을 수 있다. 원자가 분자를 이루고, 분자는 클러스터라고 하는 작은 분자들의 집합체를 구성하여 나노 입자를 이루게 되는데, 이러한 나노 입자들이 반도체 특성을 띠고 있을 때 양자점이라고 한다. 상기 양자점은 외부에서 에너지를 받아 들뜬 상태에 이르면, 상기 양자점의 자체적으로 해당하는 에너지 밴드갭에 따른 에너지를 방출하게 된다.In one embodiment of the invention, the quantum dots may refer to a nano-sized semiconductor material. Atoms form molecules, and molecules form clusters of small molecules called clusters that form nanoparticles, which are called quantum dots when they are semiconducting. When the quantum dots reach the excited state from the outside, the quantum dots emit energy according to their corresponding energy bandgap.
상기 양자점 분산액을 포함하는 자발광 감광성 수지 조성물로 제조된 컬러필터는 상기 양자점을 포함함으로써 광 조사에 의해 발광(광 루미네선스(luminescence))할 수 있다.The color filter made of the self-luminous photosensitive resin composition including the quantum dot dispersion liquid may emit light (light luminescence) by light irradiation by including the quantum dot.
컬러필터를 포함하는 통상의 화상표시장치에서는 백색광이 상기 컬러필터를 투과하여 컬러가 구현되는데, 이 과정에서 광의 일부가 컬러필터에 흡수되므로 광 효율이 저하된다. 그러나, 본 발명에 따른 자발광 감광성 수지 조성물로 제조된 컬러필터를 포함하는 경우에는, 컬러필터가 광원의 광에 의해 자체 발광하므로, 보다 뛰어난 광 효율을 구현할 수 있으며, 또한 색상을 가진 광이 방출되는 것이므로 색 재현성이 보다 우수하고, 광루미네선스에 의해 전 방향으로 광이 방출되므로 시야각도 개선될 수 있는 이점이 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 self-luminous photosensitive resin composition according to the present invention, since the color filter is self-luminous by the light of the light source, it is possible to implement more excellent light efficiency, and also emit light with color Since the color reproducibility is excellent, and the light is emitted in all directions by the photoluminescence, the viewing angle is also improved.
상기 양자점은 광에 의한 자극으로 발광할 수 있는 양자점 입자라면 특별히 한정되지 않는다. 예컨대, 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 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The quantum dot is not particularly limited as long as it is a quantum dot particle capable of emitting light by stimulation caused by light. For example, 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 it can be selected from the group consisting of these, these can be used alone or in combination of two or more.
구체적으로, 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 있으나, 이에 한정되는 것은 아니다.Specifically, 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 an elemental compound selected from the group consisting of CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof, but is not limited thereto.
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 있으나, 이에 한정되는 것은 아니다.The group III-V semiconductor compound may be selected from the group consisting of GaN, 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. However, the present invention is not limited thereto.
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 선택되는 하나 이상일 수 있으나, 역시 이에 한정되지 않는다.The Group IV-VI semiconductor compound may be 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 one or more selected from the group consisting of an elemental compound selected from the group consisting of mixtures thereof, but are not limited thereto.
이에 한정되지는 않으나, 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.Although not limited thereto, the group IV element or a compound including the same may be selected from the group consisting of Si, Ge, and mixtures thereof; And a binary element compound selected from the group consisting of SiC, SiGe, and mixtures thereof.
상기 양자점은 균질한(homogeneous) 단일 구조; 코어-쉘(core-shell), 그래디언트(gradient) 구조 등과 같은 이중 구조; 또는 이들의 혼합 구조일 수 있다.The quantum dots are homogeneous single structures; Dual structures such as core-shell, gradient structures, and the like; Or a mixed structure thereof.
구체적으로, 상기 코어-쉘의 이중 구조에서, 각각의 코어(core)와 쉘(shell)을 이루는 물질은 상기 언급된 서로 다른 반도체 화합물로 이루어질 수 있다. 예컨대, 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, 역시 이에 한정되는 것은 아니다.Specifically, 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.
상기 양자점은 습식 화학 공정(wet chemical process), 유기금속 화학증착 공정(MOCVD, metal organic chemical vapor deposition) 또는 분자선 에피텍시 공정(MBE, molecular beam epitaxy)에 의해 합성될 수 있으나, 이에 한정되는 것은 아니다.The quantum dots may be synthesized by a wet chemical process, a metal organic chemical vapor deposition (MOCVD), or a molecular beam epitaxy (MBE), but is not limited thereto. no.
상기 습식 화학 공정이란 유기용제에 전구체 물질을 넣어 입자를 성장시키는 방법이다. 결정이 성장될 때 유기용제가 자연스럽게 양자점 결정의 표면에 배위되어 분산제 역할을 하여 결정의 성장을 조절하게 되므로, 유기금속 화학증착 공정이나 분자선 에피텍시와 같은 기상증착법보다 더 쉽고 저렴한 공정을 통하여 나노 입자의 성장을 제어할 수 있으므로, 상기 습식 화학 공정을 사용하여 상기 양자점을 제조하는 것이 바람직하다.The wet chemical process is a method of growing a particle by adding a precursor material to an organic solvent. When the crystal grows, the organic solvent naturally coordinates the surface of the quantum dot crystal and acts as a dispersant to control the growth of the crystal. Therefore, the nano solvent is easier and cheaper than the vapor deposition method such as the organometallic chemical vapor deposition process or molecular beam epitaxy. Since the growth of the particles can be controlled, it is desirable to produce the quantum dots using the wet chemical process.
본 발명의 일 실시형태에 있어서, 상기 양자점은 유기 리간드를 더 포함하는 것일 수 있다. 상기 유기 리간드는 상기 양자점의 표면에 결합되어 상기 양자점을 안정화시키는 역할을 수행할 수 있다. 상기 유기 리간드는 본 발명에서 한정하는 것은 아니나, 예컨대 C5 내지 C20의 알킬 카르복실산, 알케닐 카르복실산 또는 알키닐 카르복실산; 티올(thiol), 인산, 피리딘, 메르캅토 알콜, 포스핀, 포스핀 산화물 등을 포함할 수 있으며, 양자점 표면을 효과적으로 보호하여 안정성을 향상시킨다는 측면에서, C5 내지 C20의 알킬 카르복실산, 알케닐 카르복실산 또는 알키닐 카르복실산; 티올 및 인산으로 이루어진 군으로부터 선택되는 1 종 이상을 포함하는 것이 바람직하다.In one embodiment of the present invention, the quantum dots may further include an organic ligand. The organic ligand may be bound to the surface of the quantum dots to serve to stabilize the quantum dots. The organic ligand is not limited in the present invention, for example, C5 to C20 alkyl carboxylic acid, alkenyl carboxylic acid or alkynyl carboxylic acid; Thiol, phosphoric acid, pyridine, mercapto alcohol, phosphine, phosphine oxide, and the like, and in terms of effectively protecting the surface of the quantum dot to improve stability, C5 to C20 alkyl carboxylic acid, alkenyl Carboxylic acid or alkynyl carboxylic acid; It is preferable to include one or more selected from the group consisting of thiol and phosphoric acid.
상기 유기 리간드는 상기 양자점의 총면적에 대하여 5% 이상의 표면을 덮고 있을 수 있다.The organic ligand may cover 5% or more of the surface of the total area of the quantum dots.
상기 유기 리간드의 함량은 양자점 1몰에 대하여 0.1 내지 10몰일 수 있다.The content of the organic ligand may be 0.1 to 10 moles with respect to 1 mole of the quantum dot.
상기 양자점은 상기 양자점 분산액 전체 100 중량%에 대하여, 5 내지 70 중량%, 바람직하게는 10 내지 65 중량%, 더욱 바람직하게는 15 내지 60 중량%의 양으로 포함될 수 있다. 상기 양자점이 상기 범위 내로 포함되는 경우 감광특성이 우수한 자발광 감광성 수지 조성물의 제공이 가능하다.The quantum dot may be included in an amount of 5 to 70 wt%, preferably 10 to 65 wt%, more preferably 15 to 60 wt%, based on 100 wt% of the total quantum dot dispersion. When the quantum dot is included in the above range, it is possible to provide a self-luminous photosensitive resin composition having excellent photosensitivity.
본 발명의 일 실시형태에서, 상기 용제는 C3-C10의 사이클로알킬기, C2-C10의 헤테로사이클로알킬기, C5-C10의 아로마틱기 및 C4-C10의 헤테로아로마틱기로 구성된 군으로부터 선택되는 1종 이상과 에스테르 결합을 갖는 화합물을 포함한다.In one embodiment of the invention, the solvent is an aromatic heterocyclic group the group consisting of C 3 -C 10 cycloalkyl group, C 2 -C 10 heterocycloalkyl group, C 5 -C 10 aromatic group, and a C 4 -C 10 of the It includes a compound having an ester bond with at least one member selected from.
구체적으로, 상기 용제는 하기 화학식 1로 표시되는 화합물 및 하기 화학식 2로 표시되는 화합물 중에서 선택되는 1종 이상을 포함할 수 있다.Specifically, the solvent may include at least one selected from a compound represented by Formula 1 and a compound represented by Formula 2.
[화학식 1][Formula 1]
Figure PCTKR2018001234-appb-I000003
Figure PCTKR2018001234-appb-I000003
[화학식 2][Formula 2]
Figure PCTKR2018001234-appb-I000004
Figure PCTKR2018001234-appb-I000004
상기 식에서,Where
A는 C1-C10의 알킬기 및 할로겐으로 구성된 군으로부터 선택되는 1종 이상의 치환기로 치환되거나 비치환된, C3-C10의 사이클로알킬기, C2-C10의 헤테로사이클로알킬기, C5-C10의 아로마틱기 또는 C4-C10의 헤테로아로마틱기이고,A is a C 3 -C 10 cycloalkyl group, C 2 -C 10 heterocycloalkyl group, C 5- , which is unsubstituted or substituted with one or more substituents selected from the group consisting of C 1 -C 10 alkyl groups and halogen. C 10 aromatic group or C 4 -C 10 heteroaromatic group,
L은 C1-C6의 알킬렌기이거나 존재하지 않고,L is a C 1 -C 6 alkylene group or absent,
R은 C1-C10의 알킬기 또는 C2-C10의 알케닐기이다.R is an alkyl group of C 1 -C 10 or an alkenyl group of C 2 -C 10 .
본 명세서에서 사용되는 C1-C10의 알킬기는 탄소수 1 내지 10개로 구성된 직쇄형 또는 분지형의 1가 탄화수소를 의미하며, 예를 들어 메틸, 에틸, 프로필, 부틸, 펜틸, 헥실, 헵틸, 옥틸 등이 포함되나 이에 한정되는 것은 아니다.As used herein, an alkyl group of C 1 -C 10 refers to a straight or branched monovalent hydrocarbon having 1 to 10 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl And the like, but are not limited thereto.
본 명세서에서 사용되는 C3-C10의 사이클로알킬기는 탄소수 3 내지 10개로 구성된 단순 또는 융합 고리형 탄화수소를 의미하며, 예를 들어 사이클로프로필, 사이클로부틸, 사이클로펜틸, 사이클로헥실 등이 포함되나 이에 한정되는 것은 아니다.As used herein, a C 3 -C 10 cycloalkyl group means a simple or fused cyclic hydrocarbon composed of 3 to 10 carbon atoms, including but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. It doesn't happen.
본 명세서에서 사용되는 C2-C10의 헤테로사이클로알킬기는 탄소수 3 내지 10개로 구성된 단순 또는 융합 고리형 탄화수소의 환 탄소 중 하나 이상이 산소, 황 또는 질소로 치환된 작용기를 의미하며, 예를 들어 테트라하이드로퓨라닐, 테트라하이드로피라닐, 티아졸리디닐, 옥시라닐 등이 포함되나 이에 한정되는 것은 아니다.As used herein, a C 2 -C 10 heterocycloalkyl group means a functional group in which one or more of the ring carbons of a simple or fused cyclic hydrocarbon composed of 3 to 10 carbon atoms is replaced with oxygen, sulfur or nitrogen, for example Tetrahydrofuranyl, tetrahydropyranyl, thiazolidinyl, oxiranyl, and the like, but is not limited thereto.
본 명세서에서 사용되는 C5-C10의 아로마틱기는 5원 내지 10원의 단순 또는 융합 고리형 방향족 탄화수소를 의미하며, 예를 들어 페닐, 나프틸, 사이클로펜타디에닐(cyclopentadienyl), 테트라히드로나프틸 등이 포함되나 이에 한정되는 것은 아니다.As used herein, an aromatic group of C 5 -C 10 refers to a simple or fused cyclic aromatic hydrocarbon of 5 to 10 members, for example phenyl, naphthyl, cyclopentadienyl, tetrahydronaphthyl And the like, but are not limited thereto.
본 명세서에서 사용되는 C4-C10의 헤테로아로마틱기는 5원 내지 10원의 단순 또는 융합 고리형 방향족 탄화수소의 환 탄소 중 하나 이상이 산소, 황 또는 질소로 치환된 작용기를 의미하며, 예를 들어 피리디닐(pyridinyl), 퓨라닐(furanyl), 티오페닐(thiophenyl), 인돌릴(indolyl), 퀴놀리닐(quinolinyl), 이미다졸리닐(imidazolinyl), 옥사졸릴(oxazolyl), 티아졸릴(thiazolyl) 등이 포함되나 이에 한정되는 것은 아니다.As used herein, a C 4 -C 10 heteroaromatic group means a functional group in which one or more of the ring carbons of a 5- to 10-membered simple or fused cyclic aromatic hydrocarbon is substituted with oxygen, sulfur or nitrogen, for example Pyridinyl, furanyl, thiophenyl, indolyl, quinolinyl, imidazolinyl, oxazolyl, thiazolyl And the like, but are not limited thereto.
본 명세서에서 사용되는 C1-C6의 알킬렌기는 탄소수 1 내지 6개로 구성된 직쇄형 또는 분지형의 2가 탄화수소를 의미하며, 예를 들어 메틸렌, 에틸렌, 프로필렌, 부틸렌, 펜틸렌 등이 포함되나 이에 한정되는 것은 아니다.As used herein, an alkylene group of C 1 -C 6 refers to a straight or branched divalent hydrocarbon having 1 to 6 carbon atoms, and includes, for example, methylene, ethylene, propylene, butylene, pentylene, and the like. However, it is not limited thereto.
본 명세서에서 사용되는 C2-C10의 알케닐기는 하나 이상의 탄소-탄소 이중결합을 갖는 탄소수 2 내지 10개로 구성된 직쇄형 또는 분지형 불포화 탄화수소를 의미하며, 예를 들어 에틸렌일, 프로펜일, 부텐일, 펜텐일, 알릴 등이 포함되나 이에 한정되는 것은 아니다.Alkenyl group of C 2 -C 10 as used herein means a straight or branched unsaturated hydrocarbon composed of 2 to 10 carbon atoms having one or more carbon-carbon double bonds, for example ethyleneyl, propenyl, moiety. Tenyls, pentenyls, allyls, and the like.
본 발명의 일 실시형태에서, A는 할로겐으로 치환되거나 비치환된, 사이클로펜틸, 사이클로헥실, 테트라하이드로퓨라닐, 테트라하이드로피라닐, 페닐, 사이클로펜타디에닐 또는 퓨라닐이고, L은 C1-C6의 알킬렌기이거나 존재하지 않고, R은 C1-C10의 알킬기 또는 C2-C10의 알케닐기일 수 있다.In one embodiment of the invention, A is cyclopentyl, cyclohexyl, tetrahydrofuranyl, tetrahydropyranyl, phenyl, cyclopentadienyl or furanyl, substituted or unsubstituted with halogen, and L is C 1- It may or may not be an alkylene group of C 6 , and R may be an alkyl group of C 1 -C 10 or an alkenyl group of C 2 -C 10 .
상기 화학식 1로 표시되는 화합물로는 페닐-아세트산 에틸 에스테르, 3-페닐-프로피온산 메틸 에스테르, 3-페닐-프로피온산 에틸 에스테르, 4-페닐-부티르산 에틸 에스테르, 5-페닐-펜타노산 에틸 에스테르, 6-페닐-헥사노산 에틸 에스테르, 4-페닐-부티르산 프로필 에스테르, 4-(4-클로로-페닐)-부티르산 에틸 에스테르, 4-(3,4-디클로로-페닐)-부티르산 에틸 에스테르, 3-사이클로펜타-1,3-디에닐-프로피온산 메틸 에스테르, 4-사이클로펜타-1,3-디에닐-부티르산 에틸 에스테르, 5-사이클로펜타-1,3-디에닐-펜타노산 에틸 에스테르, 6-사이클로펜타-1,3-디에닐-헥사노산 에틸 에스테르, 4-사이클로펜타-1,3-디에닐-부티르산 프로필 에스테르, 3-퓨란-2-일-프로피온산 메틸 에스테르, 4-퓨란-2-일-부티르산 에틸 에스테르, 5-퓨란-2-일-펜타노산 에틸 에스테르, 6-퓨란-2-일-헥사노산 에틸 에스테르, 4-퓨란-2-일-부티르산 프로필 에스테르, 퓨란-2-카르복실산 프로필 에스테르, 퓨란-2-카르복실산 부틸 에스테르, 3-사이클로펜틸-프로피온산 메틸 에스테르, 4-사이클로펜틸-부티르산 에틸 에스테르, 5-사이클로펜틸-펜타노산 에틸 에스테르, 6-사이클로펜틸-헥사노산 에틸 에스테르, 4-사이클로펜틸-부티르산 프로필 에스테르, 사이클로펜탄카르복실산 이소부틸 에스테르, 사이클로펜탄카르복실산 펜틸 에스테르, 3-(테트라하이드로-퓨란-3-일)-프로피온산 메틸 에스테르, 4-(테트라하이드로-퓨란-3-일)-부티르산 에틸 에스테르, 5-(테트라하이드로-퓨란-3-일)-펜타노산 에틸 에스테르, 6-(테트라하이드로-퓨란-3-일)-헥사노산 에틸 에스테르, 4-(테트라하이드로-퓨란-3-일)-부티르산 프로필 에스테르, 테트라하이드로-퓨란-3-카르복실산 프로필 에스테르, 테트라하이드로-퓨란-3-카르복실산 부틸 에스테르, 3-(테트라하이드로-퓨란-2-일)-프로피온산 메틸 에스테르, 4-(테트라하이드로-퓨란-2-일)-부티르산 에틸 에스테르, 5-(테트라하이드로-퓨란-2-일)-펜타노산 에틸 에스테르, 6-(테트라하이드로-퓨란-2-일)-헥사노산 에틸 에스테르, 4-(테트라하이드로-퓨란-2-일)-부티르산 프로필 에스테르, 테트라하이드로-퓨란-2-카르복실산 2-에틸-헥실 에스테르, 사이클로헥실-아세트산 에틸 에스테르, 3-사이클로헥실-프로피온산 메틸 에스테르, 4-사이클로헥실-부티르산 에틸 에스테르, 5-사이클로헥실-펜타노산 에틸 에스테르, 6-사이클로헥실-헥사노산 에틸 에스테르, 4-사이클로헥실-부티르산 프로필 에스테르, 사이클로헥산카르복실산 프로필 에스테르, 사이클로헥산카르복실산 헥실 에스테르, 사이클로헥실-아세트산 알릴 에스테르, 3-(테트라하이드로-피란-2-일)-프로피온산 메틸 에스테르, 4-(테트라하이드로-피란-2-일)-부티르산 에틸 에스테르, 5-(테트라하이드로-피란-2-일)-펜타노산 에틸 에스테르, 6-(테트라하이드로-피란-2-일)-헥사노산 에틸 에스테르, 4-(테트라하이드로-피란-2-일)-부티르산 프로필 에스테르, 테트라하이드로-피란-2-카르복실산 프로필 에스테르, 테트라하이드로-피란-2-카르복실산 부틸 에스테르, 3-(테트라하이드로-피란-3-일)-프로피온산 메틸 에스테르, 4-(테트라하이드로-피란-3-일)-부티르산 에틸 에스테르, 5-(테트라하이드로-피란-2-일)-펜타노산 에틸 에스테르, 6-(테트라하이드로-피란-3-일)-헥사노산 에틸 에스테르, 4-(테트라하이드로-피란-3-일)-부티르산 프로필 에스테르, 테트라하이드로-피란-3-카르복실산 이소부틸 에스테르, 테트라하이드로-피란-3-카르복실산 펜틸 에스테르, 3-(테트라하이드로-피란-4-일)-프로피온산 메틸 에스테르, 4-(테트라하이드로-피란-4-일)-부티르산 에틸 에스테르, 5-(테트라하이드로-피란-4-일)-펜타노산 에틸 에스테르, 6-(테트라하이드로-피란-4-일)-헥사노산 에틸 에스테르, 4-(테트라하이드로-피란-4-일)-부티르산 프로필 에스테르, 테트라하이드로-피란-4-카르복실산 부틸 에스테르 및 테트라하이드로-피란-4-카르복실산 프로필 에스테르 등을 예로 들 수 있다.Examples of the compound represented by Formula 1 include phenyl-acetic acid ethyl ester, 3-phenyl-propionic acid methyl ester, 3-phenyl-propionic acid ethyl ester, 4-phenyl-butyric acid ethyl ester, 5-phenyl-pentanoic acid ethyl ester, 6- Phenyl-hexanoic acid ethyl ester, 4-phenyl-butyric acid propyl ester, 4- (4-chloro-phenyl) -butyric acid ethyl ester, 4- (3,4-dichloro-phenyl) -butyric acid ethyl ester, 3-cyclopenta- 1,3-dienyl-propionic acid methyl ester, 4-cyclopenta-1,3-dienyl-butyric acid ethyl ester, 5-cyclopenta-1,3-dienyl-pentanoic acid ethyl ester, 6-cyclopenta-1 , 3-dienyl-hexanoic acid ethyl ester, 4-cyclopenta-1,3-dienyl-butyric acid propyl ester, 3-furan-2-yl-propionic acid methyl ester, 4-furan-2-yl-butyric acid ethyl ester , 5-furan-2-yl-pentanoic acid ethyl ester, 6-furan-2-yl-hexa No-acid ethyl ester, 4-furan-2-yl-butyric acid propyl ester, furan-2-carboxylic acid propyl ester, furan-2-carboxylic acid butyl ester, 3-cyclopentyl-propionic acid methyl ester, 4-cyclopentyl- Butyric acid ethyl ester, 5-cyclopentyl-pentanoic acid ethyl ester, 6-cyclopentyl-hexanoic acid ethyl ester, 4-cyclopentyl-butyric acid propyl ester, cyclopentanecarboxylic acid isobutyl ester, cyclopentanecarboxylic acid pentyl ester, 3- (tetrahydro-furan-3-yl) -propionic acid methyl ester, 4- (tetrahydro-furan-3-yl) -butyric acid ethyl ester, 5- (tetrahydro-furan-3-yl) -pentanoic acid ethyl Ester, 6- (tetrahydro-furan-3-yl) -hexanoic acid ethyl ester, 4- (tetrahydro-furan-3-yl) -butyric acid propyl ester, tetrahydro-furan-3-carboxylic acid propyl Ester, tetrahydro-furan-3-carboxylic acid butyl ester, 3- (tetrahydro-furan-2-yl) -propionic acid methyl ester, 4- (tetrahydro-furan-2-yl) -butyric acid ethyl ester, 5 -(Tetrahydro-furan-2-yl) -pentanoic acid ethyl ester, 6- (tetrahydro-furan-2-yl) -hexanoic acid ethyl ester, 4- (tetrahydro-furan-2-yl) -butyric acid profile Ester, tetrahydro-furan-2-carboxylic acid 2-ethyl-hexyl ester, cyclohexyl-acetic acid ethyl ester, 3-cyclohexyl-propionic acid methyl ester, 4-cyclohexyl-butyric acid ethyl ester, 5-cyclohexyl-penta No-acid ethyl ester, 6-cyclohexyl-hexanoic acid ethyl ester, 4-cyclohexyl-butyric acid propyl ester, cyclohexanecarboxylic acid propyl ester, cyclohexanecarboxylic acid hexyl ester, cyclohexyl-a Triacid allyl ester, 3- (tetrahydro-pyran-2-yl) -propionic acid methyl ester, 4- (tetrahydro-pyran-2-yl) -butyric acid ethyl ester, 5- (tetrahydro-pyran-2-yl) -Pentanoic acid ethyl ester, 6- (tetrahydro-pyran-2-yl) -hexanoic acid ethyl ester, 4- (tetrahydro-pyran-2-yl) -butyric acid propyl ester, tetrahydro-pyran-2-carboxyl Acid propyl ester, tetrahydro-pyran-2-carboxylic acid butyl ester, 3- (tetrahydro-pyran-3-yl) -propionic acid methyl ester, 4- (tetrahydro-pyran-3-yl) -butyric acid ethyl ester , 5- (tetrahydro-pyran-2-yl) -pentanoic acid ethyl ester, 6- (tetrahydro-pyran-3-yl) -hexanoic acid ethyl ester, 4- (tetrahydro-pyran-3-yl)- Butyric acid propyl ester, tetrahydro-pyran-3-carboxylic acid isobutyl ester, tetrahigh Dro-pyran-3-carboxylic acid pentyl ester, 3- (tetrahydro-pyran-4-yl) -propionic acid methyl ester, 4- (tetrahydro-pyran-4-yl) -butyric acid ethyl ester, 5- (tetra Hydro-pyran-4-yl) -pentanoic acid ethyl ester, 6- (tetrahydro-pyran-4-yl) -hexanoic acid ethyl ester, 4- (tetrahydro-pyran-4-yl) -butyric acid propyl ester, tetra Hydro-pyran-4-carboxylic acid butyl ester and tetrahydro-pyran-4-carboxylic acid propyl ester and the like.
상기 화학식 2로 표시되는 화합물로는 아세트산 벤질 에스테르, 프로피온산 페네틸 에스테르, 프로피온산 3-페닐-프로필 에스테르, 프로피온산 4-페닐-부틸 에스테르, 부티르산 페네틸 에스테르, 프로피온산 2-(4-클로로-페닐)-에틸 에스테르, 프로피온산 2-(3,4-디클로로-페닐)-에틸 에스테르, 아세트산 사이클로펜타-1,3-디에닐메틸 에스테르, 프로피온산 2-사이클로펜타-1,3-디에닐-에틸 에스테르, 프로피온산 3-사이클로펜타-1,3-디에닐-프로필 에스테르, 프로피온산 4-사이클로펜타-1,3-디에닐-부틸 에스테르, 부티르산 2-사이클로펜타-1,3-디에닐-에틸 에스테르, 아세트산 퓨란-2-일메틸 에스테르, 프로피온산 2-퓨란-2-일-에틸 에스테르, 프로피온산 3-퓨란-2-일-프로필 에스테르, 프로피온산 4-퓨란-2-일-부틸 에스테르, 부티르산 2-퓨란-2-일-에틸 에스테르, 아세트산 사이클로펜틸메틸 에스테르, 프로피온산 2-사이클로펜틸-에틸 에스테르, 프로피온산 3-사이클로펜틸-프로필 에스테르, 프로피온산 4-사이클로펜틸-부틸 에스테르, 부티르산 2-사이클로펜틸-에틸 에스테르, 아세트산 테트라하이드로-퓨란-3-일메틸 에스테르, 프로피온산 2-(테트라하이드로-퓨란-3-일)-에틸 에스테르, 프로피온산 3-(테트라하이드로-퓨란-3-일)-프로필 에스테르, 프로피온산 4-(테트라하이드로-퓨란-3-일)-부틸 에스테르, 부티르산 2-(테트라하이드로-퓨란-3-일)-에틸 에스테르, 아세트산 테트라하이드로-퓨란-2-일메틸 에스테르, 프로피온산 2-(테트라하이드로-퓨란-2-일)-에틸 에스테르, 프로피온산 3-(테트라하이드로-퓨란-2-일)-프로필 에스테르, 프로피온산 4-(테트라하이드로-퓨란-2-일)-부틸 에스테르, 부티르산 2-(테트라하이드로-퓨란-2-일)-에틸 에스테르, 아세트산 사이클로헥실메틸 에스테르, 프로피온산 2-사이클로헥실-에틸 에스테르, 프로피온산 3-사이클로헥실-프로필 에스테르, 프로피온산 4-사이클로헥실-부틸 에스테르, 부티르산 2-사이클로헥실-에틸 에스테르, 부트-3-에노산 사이클로헥실메틸 에스테르, 아세트산 테트라하이드로-피란-2-일메틸 에스테르, 프로피온산 2-(테트라하이드로-피란-2-일)-에틸 에스테르, 프로피온산 3-(테트라하이드로-피란-2-일)-프로필 에스테르, 프로피온산 4-(테트라하이드로-피란-2-일)-부틸 에스테르, 부티르산 2-(테트라하이드로-피란-2-일)-에틸 에스테르, 아세트산 테트라하이드로-피란-3-일메틸 에스테르, 프로피온산 2-(테트라하이드로-피란-3-일)-에틸 에스테르, 프로피온산 3-(테트라하이드로-피란-2-일)-프로필 에스테르, 프로피온산 4-(테트라하이드로-피란-3-일)-부틸 에스테르, 부티르산 2-(테트라하이드로-피란-3-일)-에틸 에스테르, 아세트산 테트라하이드로-피란-4-일메틸 에스테르, 프로피온산 2-(테트라하이드로-피란-4-일)-에틸 에스테르, 프로피온산 3-(테트라하이드로-피란-4-일)-프로필 에스테르, 프로피온산 4-(테트라하이드로-피란-4-일)-부틸 에스테르 및 부티르산 2-(테트라하이드로-피란-4-일)-에틸 에스테르 등을 예로 들 수 있다.Examples of the compound represented by Formula 2 include acetic acid benzyl ester, propionic acid phenethyl ester, propionic acid 3-phenyl-propyl ester, propionic acid 4-phenyl-butyl ester, butyric acid phenethyl ester, propionic acid 2- (4-chloro-phenyl)- Ethyl ester, propionic acid 2- (3,4-dichloro-phenyl) -ethyl ester, acetic acid cyclopenta-1,3-dienylmethyl ester, propionic acid 2-cyclopenta-1,3-dienyl-ethyl ester, propionic acid 3 -Cyclopenta-1,3-dienyl-propyl ester, propionic acid 4-cyclopenta-1,3-dienyl-butyl ester, butyric acid 2-cyclopenta-1,3-dienyl-ethyl ester, furan-2 acetate -Ylmethyl ester, propionic acid 2-furan-2-yl-ethyl ester, propionic acid 3-furan-2-yl-propyl ester, propionic acid 4-furan-2-yl-butyl ester, butyric acid 2-furan-2-yl- Ethyl ester, acet Cyclopentylmethyl ester, propionic acid 2-cyclopentyl-ethyl ester, propionic acid 3-cyclopentyl-propyl ester, propionic acid 4-cyclopentyl-butyl ester, butyric acid 2-cyclopentyl-ethyl ester, tetrahydro-furan-3-yl acetate Methyl ester, propionic acid 2- (tetrahydro-furan-3-yl) -ethyl ester, propionic acid 3- (tetrahydro-furan-3-yl) -propyl ester, propionic acid 4- (tetrahydro-furan-3-yl) Butyl ester, butyric acid 2- (tetrahydro-furan-3-yl) -ethyl ester, acetic acid tetrahydro-furan-2-ylmethyl ester, propionic acid 2- (tetrahydro-furan-2-yl) -ethyl ester, Propionic acid 3- (tetrahydro-furan-2-yl) -propyl ester, propionic acid 4- (tetrahydro-furan-2-yl) -butyl ester, butyric acid 2- (tetrahydro-furan-2-yl)- Ethyl ester, acetic acid cyclohexylmethyl ester, propionic acid 2-cyclohexyl-ethyl ester, propionic acid 3-cyclohexyl-propyl ester, propionic acid 4-cyclohexyl-butyl ester, butyric acid 2-cyclohexyl-ethyl ester, but-3-eno Acid cyclohexylmethyl ester, acetic acid tetrahydro-pyran-2-ylmethyl ester, propionic acid 2- (tetrahydro-pyran-2-yl) -ethyl ester, propionic acid 3- (tetrahydro-pyran-2-yl) -propyl Ester, propionic acid 4- (tetrahydro-pyran-2-yl) -butyl ester, butyric acid 2- (tetrahydro-pyran-2-yl) -ethyl ester, acetic acid tetrahydro-pyran-3-ylmethyl ester, propionic acid 2 -(Tetrahydro-pyran-3-yl) -ethyl ester, propionic acid 3- (tetrahydro-pyran-2-yl) -propyl ester, propionic acid 4- (tetrahydro-py -3-yl) -butyl ester, butyric acid 2- (tetrahydro-pyran-3-yl) -ethyl ester, acetic acid tetrahydro-pyran-4-ylmethyl ester, propionic acid 2- (tetrahydro-pyran-4-yl ) -Ethyl ester, propionic acid 3- (tetrahydro-pyran-4-yl) -propyl ester, propionic acid 4- (tetrahydro-pyran-4-yl) -butyl ester and butyric acid 2- (tetrahydro-pyran-4- Il) -ethyl ester etc. are mentioned.
상기 용제는 각각 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다.The said solvent can be used individually or in mixture of 2 or more types, respectively.
상기 용제는 유전상수가 20℃에서 12.0 미만, 바람직하게는 10 미만, 더욱 더 바람직하게는 6 미만일 수 있다. 예를 들어, 상기 용제는 유전상수가 20℃에서 2.0 내지 5.5일 수 있다. 상기 용제의 유전상수가 12.0 미만인 경우, 양자점 분산 시 양자점 응집이 발생하지 않고 균일한 분산이 가능하며, 양자점 분산액의 광발광 효율이 우수할 수 있다.The solvent may have a dielectric constant of less than 12.0, preferably less than 10 and even more preferably less than 6 at 20 ° C. For example, the solvent may have a dielectric constant of 2.0 to 5.5 at 20 ° C. When the dielectric constant of the solvent is less than 12.0, quantum dot aggregation does not occur during quantum dot dispersion and uniform dispersion is possible, and the light emission efficiency of the quantum dot dispersion may be excellent.
상기 용제의 함량은 양자점 분산액 전체 100 중량%에 대하여 5 내지 95 중량%, 바람직하게는 20 내지 90 중량%, 보다 바람직하게는 30 내지 80 중량%일 수 있다. 상기 용제가 5 중량% 미만으로 포함될 경우 분산성이 악화되는 문제가 발생할 수 있으며, 95 중량%를 초과할 경우 수지 조성물의 고형분을 조절하기 어려운 문제가 발생할 수 있다.The content of the solvent may be 5 to 95% by weight, preferably 20 to 90% by weight, and more preferably 30 to 80% by weight based on 100% by weight of the total quantum dot dispersion. When the solvent is included in less than 5% by weight may cause a problem that the dispersibility is deteriorated, when it exceeds 95% by weight may be a problem that it is difficult to control the solid content of the resin composition.
본 발명의 일 실시형태에 있어서, 상기 양자점 분산액은 분산제를 더 포함할 수 있다.In one embodiment of the present invention, the quantum dot dispersion may further comprise a dispersant.
상기 분산제는 양자점의 탈응집 효과 및 자발광 감광성 수지 조성물에 이용시 극성 차이에 의한 석출현상을 억제하고, 컬러필터 제조공정 시 양자점의 보호층 역할을 부여하기 위해 사용될 수 있다.The dispersant may be used to suppress the deagglomeration effect of the quantum dots and precipitation phenomenon due to the polarity difference when used in the self-luminous photosensitive resin composition, and to impart a protective layer role of the quantum dots in the color filter manufacturing process.
상기 분산제로는 수지 타입의 분산제로서, 인산 에스테르계 분산제, 우레탄계 분산제, 아크릴계 분산제 등을 사용할 수 있다. 구체적으로, 상기 분산제의 시판품으로는 빅케미사의 상품명: DISPER BYK-103, DISPER BYK-110, DISPER BYK-111, DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166 등을 사용할 수 있다.As the dispersant, a phosphate ester dispersant, a urethane dispersant, an acrylic dispersant, or the like may be used as the resin type dispersant. Specifically, commercially available products of the dispersant include the brand names of BIC Chem Corporation: DISPER BYK-103, DISPER BYK-110, DISPER BYK-111, DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166 can be used.
상기 분산제는 상기 양자점 분산액의 고형분 전체 100 중량부에 대하여 1 내지 300 중량부로 포함될 수 있으며, 바람직하게는 3 내지 250 중량부, 더욱 바람직하게는 5 내지 200 중량부로 포함될 수 있다. 상기 분산제가 상기 범위 내로 포함될 경우 상기 양자점의 탈응집 효과가 우수하고, 본 발명에 따른 양자점 분산액 및 이를 포함하는 자발광 감광성 수지 조성물 내의 극성 차이에 의한 석출현상의 억제가 가능하며, 컬러필터 제조 공정 시 양자점의 보호층 역할을 수행할 수 있으므로 바람직하다.The dispersant may be included in an amount of 1 to 300 parts by weight, preferably 3 to 250 parts by weight, and more preferably 5 to 200 parts by weight, based on 100 parts by weight of the total solids of the quantum dot dispersion. When the dispersant is included in the above range, the deagglomeration effect of the quantum dot is excellent, the precipitation phenomenon due to the polarity difference in the quantum dot dispersion liquid and the self-luminous photosensitive resin composition including the same according to the present invention is possible, the color filter manufacturing process It is preferable because it can act as a protective layer of the quantum dots.
상기 분산제가 상기 범위 미만으로 포함될 경우 상기 양자점의 탈응집 효과가 다소 저하될 수 있으며, 상기 범위를 초과하여 포함될 경우 상기 양자점 분산액을 포함하는 자발광 감광성 수지 조성물의 현상 특성이 다소 저하될 수 있으므로, 상기 범위 내로 포함되는 것이 바람직하다.When the dispersant is included in the range below the deagglomeration effect of the quantum dot may be slightly reduced, and when included in the above range, the development characteristics of the self-luminous photosensitive resin composition including the quantum dot dispersion may be slightly lowered, It is preferable to be included in the said range.
본 발명의 일 실시형태는 양자점 분산액(A), 알칼리 가용성 수지(B), 광중합성 화합물(C) 및 광중합 개시제(D)를 포함하는 자발광 감광성 수지 조성물에 관한 것이다.One Embodiment of this invention relates to the self-luminous photosensitive resin composition containing a quantum dot dispersion liquid (A), alkali-soluble resin (B), a photopolymerizable compound (C), and a photoinitiator (D).
양자점 분산액(A)Quantum Dot Dispersion (A)
본 발명의 일 실시형태에서, 상기 양자점 분산액(A)은 전술한 양자점 분산액을 사용한다.In one embodiment of the present invention, the quantum dot dispersion (A) uses the quantum dot dispersion described above.
상기 양자점 분산액의 함량은 자발광 감광성 수지 조성물 전체 100 중량%에 대하여 3 내지 80 중량%, 바람직하게는 5 내지 70 중량%, 더욱 바람직하게는 10 내지 60 중량%일 수 있다. 상기 양자점 분산액이 상기 범위 내로 포함되는 경우 발광특성이 우수한 컬러필터의 제조가 가능하다. 상기 양자점 분산액이 상기 범위 미만으로 포함될 경우 발광특성이 다소 저하될 수 있으며, 상기 양자점 분산액이 상기 범위를 초과하여 포함될 경우 상대적으로 다른 구성성분의 함량이 줄어듦에 따라 패턴의 형성이 다소 어려울 수 있으며, 신뢰성이 저하될 수 있으므로 상기 범위 내로 포함되는 것이 바람직하다.The content of the quantum dot dispersion may be 3 to 80% by weight, preferably 5 to 70% by weight, and more preferably 10 to 60% by weight based on 100% by weight of the total self-luminous photosensitive resin composition. When the quantum dot dispersion is included in the above range, it is possible to manufacture a color filter having excellent light emission characteristics. When the quantum dot dispersion is included in less than the above range, the light emission characteristics may be slightly lowered. When the quantum dot dispersion is included in the above range, the formation of a pattern may be somewhat difficult as the content of other components is reduced. Since reliability may be degraded, it is preferable to be included in the above range.
알칼리 가용성 수지(B)Alkali-soluble resin (B)
본 발명의 일 실시형태에서, 상기 알칼리 가용성 수지(B)는 상기 자발광 감광성 수지 조성물로 제조하는 컬러필터의 비노광부를 알칼리 가용성으로 만들어 제거 가능하게 하고, 노광 영역을 잔류시키는 역할을 수행할 수 있다. 또한, 상기 자발광 감광성 수지 조성물이 상기 알칼리 가용성 수지를 포함하는 경우, 상기 양자점이 조성물 내에 고르게 분산될 수 있으며, 공정 중에 상기 양자점을 보호하여 휘도를 유지하도록 하는 역할을 수행할 수 있다.In one embodiment of the invention, Alkali-soluble resin (B) may play a role of making the non-exposed part of the color filter made of the self-luminous photosensitive resin composition alkali-soluble to be removed and leaving the exposure area. In addition, when the self-luminous photosensitive resin composition includes the alkali-soluble resin, the quantum dots may be evenly dispersed in the composition, and may serve to maintain the brightness by protecting the quantum dots during the process.
상기 알칼리 가용성 수지는 10 내지 200 (KOHmg/g)의 산가를 갖는 것을 선정하여 사용할 수 있다. 상기 “산가”란, 중합체 1g을 중화하는데 필요한 수산화칼륨의 양(mg)으로서 측정되는 값으로 용해성에 관여한다. 상기 알칼리 가용성 수지의 산가가 상기 범위 미만인 경우 충분한 현상속도를 확보하기 어려울 수 있으며, 상기 범위를 초과하면 기판과의 밀착성이 감소되어 패턴의 단락이 발생하기 쉽고, 전체 조성물의 저장 안정성이 저하되어 점도가 상승하는 문제가 발생할 수 있다.The alkali-soluble resin may be selected and used having an acid value of 10 to 200 (KOHmg / g). The "acid value" is a value measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of the polymer and is involved in solubility. When the acid value of the alkali-soluble resin is less than the above range, it may be difficult to secure a sufficient developing speed, when the acid value of the alkali-soluble resin is exceeded, the adhesion to the substrate is reduced, the short circuit of the pattern is likely to occur, the storage stability of the entire composition is lowered viscosity The problem may arise.
또한, 상기 알칼리 가용성 수지는 컬러필터로 사용하기 위한 표면 경도 향상을 위해 분자량 및 분자량 분포도(Mw/Mn)의 한정을 고려할 수 있다. 바람직하기로 중량평균분자량이 3,000 내지 30,000, 바람직하게는 5,000 내지 20,000이 되도록 하고, 분자량 분포도는 1.5 내지 6.0, 바람직하기로 1.8 내지 4.0의 범위를 갖도록 직접 중합하거나 구입하여 사용할 수 있다. 상기 범위의 분자량 및 분자량 분포도를 갖는 알칼리 가용성 수지는 경도가 향상될 수 있고, 높은 잔막율 뿐만 아니라 현상액 중의 비-노출부의 용해성이 탁월하고 해상도를 향상시킬 수 있다.In addition, the alkali-soluble resin may consider the limitation of the molecular weight and the molecular weight distribution (Mw / Mn) in order to improve the surface hardness for use as a color filter. Preferably the weight average molecular weight is 3,000 to 30,000, preferably 5,000 to 20,000, the molecular weight distribution can be directly polymerized or purchased to have a range of 1.5 to 6.0, preferably 1.8 to 4.0. Alkali-soluble resins having a molecular weight and a molecular weight distribution in the above range can be improved in hardness, and excellent solubility of the non-exposed portion in the developer as well as high residual film ratio can improve resolution.
상기 알칼리 가용성 수지는 카르복실기 함유 불포화 단량체의 중합체, 또는 이와 공중합 가능한 불포화 결합을 갖는 단량체와의 공중합체, 또는 이들의 조합일 수 있다.The alkali-soluble resin may be a polymer of a carboxyl group-containing unsaturated monomer, or a copolymer with a monomer having an unsaturated bond copolymerizable therewith, or a combination thereof.
상기 카르복실기 함유 불포화 단량체는 불포화 모노카르복시산, 불포화 디카르복시산, 불포화 트리카르복시산 등이 가능하다. 구체적으로, 불포화 모노카르복시산으로서는, 예를 들면 아크릴산, 메타크릴산, 크로톤산, α-클로로아크릴산, 신남산 등을 들 수 있다. 불포화 디카르복시산으로서는, 예를 들면 말레산, 푸마르산, 이타콘산, 시트라콘산, 메사콘산 등을 들 수 있다. 불포화 디카르복시산은 산무수물일 수도 있으며, 구체적으로는 말레산 무수물, 이타콘산 무수물, 시트라콘산 무수물 등을 들 수 있다. 또한, 불포화 디카르복시산은 그의 모노(2-(메타)아크릴로일옥시알킬)에스테르일 수도 있으며, 예를 들면 숙신산 모노(2-아크릴로일옥시에틸), 숙신산 모노(2-메타크릴로일옥시에틸), 프탈산 모노(2-아크릴로일옥시에틸), 프탈산 모노(2-메타크릴로일옥시에틸) 등을 들 수 있다. 불포화 디카르복시산은 그 양말단 디카르복시 중합체의 모노(메타)아크릴레이트일 수도 있으며, 예를 들면 ω-카르복시폴리카프로락톤 모노아크릴레이트, ω-카르복시폴리카프로락톤 모노메타크릴레이트 등을 들 수 있다. 이들 카르복실기 함유 단량체는 각각 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다.The carboxyl group-containing unsaturated monomer may be unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated tricarboxylic acid, and the like. Specifically, as unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. As unsaturated dicarboxylic acid, maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example. The unsaturated dicarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride and citraconic anhydride. In addition, the unsaturated dicarboxylic acid may be mono (2- (meth) acryloyloxyalkyl) ester thereof, for example, succinic mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxy Ethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, and the like. The unsaturated dicarboxylic acid may be mono (meth) acrylate of the sock end dicarboxy polymer, and examples thereof include? -Carboxypolycaprolactone monoacrylate and? -Carboxypolycaprolactone monomethacrylate. These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively.
또한, 카르복실기 함유 불포화 단량체와 공중합이 가능한 단량체는 방향족 비닐 화합물, 불포화 카르복시산 에스테르 화합물, 불포화 카르복시산 아미노알킬에스테르 화합물, 불포화 카르복시산 글리시딜에스테르 화합물, 카르복시산 비닐에스테르 화합물, 불포화 에테르 화합물, 시안화 비닐 화합물, 불포화 아미드 화합물, 불포화 이미드 화합물, 지방족 공액 디엔 화합물, 분자쇄의 말단에 모노아크릴로일기 또는 모노메타크릴로일기를 갖는 거대 단량체, 벌키성 단량체 및 이들의 조합으로 이루어진 군에서 선택될 수 있다.In addition, the monomer copolymerizable with the carboxyl group-containing unsaturated monomer may include an aromatic vinyl compound, an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid aminoalkyl ester compound, an unsaturated carboxylic acid glycidyl ester compound, a carboxylic acid vinyl ester compound, an unsaturated ether compound, a vinyl cyanide compound, and an unsaturated monomer. It can be selected from the group consisting of an amide compound, an unsaturated imide compound, an aliphatic conjugated diene compound, a macromonomer having a monoacryloyl group or a monomethacryloyl group at the terminal of the molecular chain, a bulky monomer, and a combination thereof.
보다 구체적으로, 상기 공중합 가능한 단량체는 스티렌, α-메틸스티렌, o-비닐톨루엔, m-비닐톨루엔, p-비닐톨루엔, p-클로로스티렌, o-메톡시스티렌, m-메톡시스티렌, p-메톡시스티렌, o-비닐벤질메틸에테르, m-비닐벤질메틸에테르, p-비닐벤질메틸에테르, o-비닐벤질글리시딜에테르, m-비닐벤질글리시딜에테르, p-비닐벤질글리시딜에테르, 인덴 등의 방향족 비닐 화합물; 메틸아크릴레이트, 메틸메타크릴레이트, 에틸아크릴레이트, 에틸메타크릴레이트, n-프로필아크릴레이트, n-프로필메타크릴레이트, i-프로필아크릴레이트, i-프로필메타크릴레이트, n-부틸아크릴레이트, n-부틸메타크릴레이트, i-부틸아크릴레이트, i-부틸메타크릴레이트, sec-부틸아크릴레이트, sec-부틸메타크릴레이트, t-부틸아크릴레이트, t-부틸메타크릴레이트, 2-히드록시에틸아크릴레이트, 2-히드록시에틸메타크릴레이트, 2-히드록시프로필아크릴레이트, 2-히드록시프로필메타크릴레이트, 3-히드록시프로필아크릴레이트, 3-히드록시프로필메타크릴레이트, 2-히드록시부틸아크릴레이트, 2-히드록시부틸메타크릴레이트, 3-히드록시부틸아크릴레이트, 3-히드록시부틸메타크릴레이트, 4-히드록시부틸아크릴레이트, 4-히드록시부틸메타크릴레이트, 알릴아크릴레이트, 알릴메타크릴레이트, 벤질아크릴레이트, 벤질메타크릴레이트, 시클로헥실아크릴레이트, 시클로헥실메타크릴레이트, 페닐아크릴레이트, 페닐메타크릴레이트, 2-메톡시에틸아크릴레이트, 2-메톡시에틸메타크릴레이트, 2-페녹시에틸아크릴레이트, 2-페녹시에틸메타크릴레이트, 메톡시디에틸렌글리콜아크릴레이트, 메톡시디에틸렌글리콜메타크릴레이트, 메톡시트리에틸렌글리콜아크릴레이트, 메톡시트리에틸렌글리콜메타크릴레이트, 메톡시프로필렌글리콜아크릴레이트, 메톡시프로필렌글리콜메타크릴레이트, 메톡시디프로필렌글리콜아크릴레이트, 메톡시디프로필렌글리콜메타크릴레이트, 이소보르닐아크릴레이트, 이소보르닐메타크릴레이트, 디시클로펜타디에닐아크릴레이트, 디시클로펜타디에닐메타크릴레이트, 아다만틸(메타)아크릴레이트, 노르보르닐(메타)아크릴레이트, 2-히드록시-3-페녹시프로필아크릴레이트, 2-히드록시-3-페녹시프로필메타크릴레이트, 글리세롤모노아크릴레이트, 글리세롤모노메타크릴레이트 등의 불포화 카르복시산 에스테르; 2-아미노에틸아크릴레이트, 2-아미노에틸메타크릴레이트, 2-디메틸아미노에틸아크릴레이트, 2-디메틸아미노에틸메타크릴레이트, 2-아미노프로필아크릴레이트, 2-아미노프로필메타크릴레이트, 2-디메틸아미노프로필아크릴레이트, 2-디메틸아미노프로필메타크릴레이트, 3-아미노프로필아크릴레이트, 3-아미노프로필메타크릴레이트, 3-디메틸아미노프로필아크릴레이트, 3-디메틸아미노프로필메타크릴레이트 등의 불포화 카르복시산 아미노알킬에스테르 화합물; 글리시딜아크릴레이트, 글리시딜메타크릴레이트 등의 불포화 카르복시산 글리시딜에스테르 화합물; 아세트산 비닐, 프로피온산 비닐, 부티르산 비닐, 벤조산 비닐 등의 카르복시산 비닐에스테르 화합물; 비닐메틸에테르, 비닐에틸에테르, 알릴글리시딜에테르 등의 불포화 에테르 화합물; 아크릴로니트릴, 메타크릴로니트릴, α-클로로아크릴로니트릴, 시안화 비닐리덴 등의 시안화 비닐 화합물; 아크릴아미드, 메타크릴아미드, α-클로로아크릴아미드, N-2-히드록시에틸아크릴아미드, N-2-히드록시에틸메타크릴아미드 등의 불포화 아미드 화합물; 말레이미드, 벤질말레이미드, N-페닐말레이미드, N-시클로헥실말레이미드 등의 불포화 이미드 화합물; 1,3-부타디엔, 이소프렌, 클로로프렌 등의 지방족 공액 디엔 화합물; 및 폴리스티렌, 폴리메틸아크릴레이트, 폴리메틸메타크릴레이트, 폴리-n-부틸아크릴레이트, 폴리-n-부틸메타크릴레이트, 폴리실록산의 중합체 분자쇄의 말단에 모노아크릴로일기 또는 모노메타크릴로일기를 갖는 거대 단량체; 비유전 상수값을 낮출 수 있는 노르보닐 골격을 갖는 단량체, 아다만탄 골격을 갖는 단량체, 로진 골격을 갖는 단량체 등의 벌키성 단량체가 사용 가능하다.More specifically, the copolymerizable monomer may be styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- Methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl Aromatic vinyl compounds such as ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl Relate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol meth Methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadier Nyl acrylate, dicyclopentadienyl methacrylate, adamantyl (meth) a Relate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc. Unsaturated carboxylic acid esters of; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxylic acids such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate Alkyl ester compounds; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl ester compounds, such as vinyl acetate, a vinyl propionate, a vinyl butyrate, and a vinyl benzoate; Unsaturated ether compounds such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amide compounds such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethyl methacrylamide; Unsaturated imide compounds such as maleimide, benzylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; Aliphatic conjugated diene compounds such as 1,3-butadiene, isoprene and chloroprene; And monoacryloyl or monomethacryloyl groups at the terminal of the polymer molecular chain of polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, polysiloxane. Macromonomers having; Bulky monomers, such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton, which can lower the dielectric constant, can be used.
상기 알칼리 가용성 수지는 자발광 감광성 수지 조성물의 고형분 전체 100 중량%에 대하여 5 내지 80 중량%, 구체적으로 10 내지 70 중량%, 더욱 구체적으로 15 내지 60 중량%로 포함될 수 있다. 상기 알칼리 가용성 수지가 상기 범위 내로 포함될 경우 현상액에서의 용해성이 충분하여 패턴형성이 용이하며, 현상시에 노광부의 화소 부분의 막 감소가 방지되어 비화소 부분의 누락성이 양호해지므로 바람직하다. 상기 알칼리 가용성 수지가 상기 범위 미만으로 포함될 경우 비화소 부분이 다소 누락될 수 있으며, 상기 알칼리 가용성 수지가 상기 범위를 초과하여 포함될 경우 현상액에서의 용해성이 다소 저하되어 패턴형성이 다소 어려울 수 있다.The alkali-soluble resin may be included in 5 to 80% by weight, specifically 10 to 70% by weight, more specifically 15 to 60% by weight based on 100% by weight of the total solids of the self-luminous photosensitive resin composition. When the alkali-soluble resin is included in 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 is prevented at the time of development, so that the dropping of the non-pixel portion is good, which is preferable. If the alkali-soluble resin is included in less than the above range, the non-pixel portion may be somewhat missing, and when the alkali-soluble resin is included in more than the above range, the solubility in the developing solution is slightly lowered may be somewhat difficult to form a pattern.
광중합성 화합물(C)Photopolymerizable Compound (C)
본 발명의 일 실시형태에서, 상기 광중합성 화합물(C)은 광 및 후술할 광중합 개시제의 작용으로 중합할 수 있는 화합물로서, 단관능 단량체, 2관능 단량체, 그 밖의 다관능 단량체 등을 들 수 있다. In one embodiment of the present invention, the photopolymerizable compound (C) is a compound that can be polymerized by the action of light and a photopolymerization initiator to be described later. Examples thereof include a monofunctional monomer, a bifunctional monomer, and other polyfunctional monomers. .
상기 단관능 단량체의 종류는 특별히 한정되지 않으며, 예를 들면 노닐페닐카르비톨아크릴레이트, 2-히드록시-3-페녹시프로필아크릴레이트, 2-에틸헥실카르비톨아크릴레이트, 2-히드록시에틸아크릴레이트, N-비닐피롤리돈 등을 들 수 있다.The kind of the monofunctional monomer is not particularly limited, and for example, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acryl The rate, N-vinylpyrrolidone, etc. are mentioned.
상기 2관능 단량체의 종류는 특별히 한정되지 않으며, 예를 들면, 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.The kind of the said bifunctional monomer is not specifically limited, For example, 1, 6- hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene Glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.
상기 다관능 단량체의 종류는 특별히 한정되지 않으며, 예를 들면, 트리메틸올프로판트리(메타)아크릴레이트, 에톡실레이티드트리메틸올프로판트리(메타)아크릴레이트, 프로폭실레이티드트리메틸올프로판트리(메타)아크릴레이트, 펜타에리스리톨트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨트리(메타)아크릴레이트, 디펜타에리스리톨펜타(메타)아크릴레이트, 에톡실레이티드디펜타에리스리톨헥사(메타)아크릴레이트, 프로폭실레이티드디펜타에리스리톨헥사(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트 등을 들 수 있다. 이들 중에서 2관능 이상의 다관능 단량체가 바람직하게 사용된다.The kind of the polyfunctional monomer is not particularly limited, and examples thereof include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, and propoxylated trimethylolpropane tree (meth). ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned. Of these, bifunctional or higher polyfunctional monomers are preferably used.
상기 광중합성 화합물은 자발광 감광성 수지 조성물 고형분 전체 100 중량%에 대하여 5 내지 70 중량%, 구체적으로 10 내지 60 중량%, 더욱 구체적으로 15 내지 50 중량%로 포함될 수 있다. 상기 광중합성 화합물이 상기 범위 내로 포함될 경우 화소부의 강도나 평활성 측면에서 바람직한 이점이 있다. 상기 광중합성 화합물이 상기 범위 미만으로 포함되는 경우 화소부의 강도가 다소 저하될 수 있으며, 상기 광중합성 화합물이 상기 범위를 초과하여 포함되는 경우 평활성이 다소 저하될 수 있으므로 상기 범위 내로 포함되는 것이 바람직하다.The photopolymerizable compound may be included in an amount of 5 to 70 wt%, specifically 10 to 60 wt%, and more specifically 15 to 50 wt%, based on 100 wt% of the total solids of the self-luminous photosensitive resin composition. When the photopolymerizable compound is included in the above range, there is a preferable advantage in terms of intensity or smoothness of the pixel portion. When the photopolymerizable compound is included in the range below, the intensity of the pixel portion may be lowered slightly, and when the photopolymerizable compound is included in the above range, smoothness may be slightly lowered, so it is preferably included within the range. .
광중합 개시제(D)Photopolymerization Initiator (D)
본 발명의 일 실시형태에서, 상기 광중합 개시제(D)는 상기 광중합성 화합물을 중합시킬 수 있는 것이라면 그 종류를 특별히 제한하지 않고 사용할 수 있다. 특히, 상기 광중합 개시제는 중합특성, 개시효율, 흡수파장, 입수성, 가격 등의 관점에서 아세토페논계 화합물, 벤조페논계 화합물, 트리아진계 화합물, 비이미다졸계 화합물, 옥심계 화합물 및 티오크산톤계 화합물로 이루어지는 군으로부터 선택되는 1종 이상의 화합물을 사용하는 것이 바람직하다.In one embodiment of the present invention, the photopolymerization initiator (D) can be used without particular limitation as long as it can polymerize the photopolymerizable compound. In particular, the photopolymerization initiator may be an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound, or a thioxic acid from the viewpoint of polymerization characteristics, start efficiency, absorption wavelength, availability, and price. It is preferable to use at least one compound selected from the group consisting of ton compounds.
상기 아세토페논계 화합물의 구체적인 예로는 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-온, 2-(4-메틸벤질)-2-(디메틸아미노)-1-(4-모르폴리노페닐)부탄-1-온 등을 들 수 있다. Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methylpropan-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, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.
상기 벤조페논계 화합물로서는, 예를 들면 벤조페논, o-벤조일벤조산 메틸, 4-페닐벤조페논, 4-벤조일-4'-메틸디페닐술피드, 3,3',4,4'-테트라(tert-부틸퍼옥시카르보닐)벤조페논, 2,4,6-트리메틸벤조페논 등이 있다.As said benzophenone type compound, for example, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.
상기 트리아진계 화합물의 구체적인 예로는 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. Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6 -(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.
상기 비이미다졸계 화합물의 구체적인 예로는 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, 2,2-비스(2,6-디클로로페닐)-4,4',5,5'-테트라페닐-1,2'-비이미다졸 또는 4,4',5,5' 위치의 페닐기가 카르보알콕시기에 의해 치환되어 있는 비이미다졸 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'-테트라페닐비이미다졸, 2,2-비스(2,6-디클로로페닐)-4,4',5,5'-테트라페닐-1,2'-비이미다졸이 바람직하게 사용된다.Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4 And a biimidazole compound in which a phenyl group at a 4,4 ', 5,5' position is substituted by a carboalkoxy group, or the like. have. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole are preferred Used.
상기 옥심계 화합물의 구체적인 예로는 o-에톡시카르보닐-α-옥시이미노-1-페닐프로판-1-온 등을 들 수 있으며, 시판품으로 바스프사의 Irgacure OXE 01, OXE 02가 대표적이다.Specific examples of the oxime-based compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and the like, and commercially available products include BASF's Irgacure OXE 01 and OXE 02.
상기 티오크산톤계 화합물로서는, 예를 들면 2-이소프로필티오크산톤, 2,4-디에틸티오크산톤, 2,4-디클로로티오크산톤, 1-클로로-4-프로폭시티오크산톤 등이 있다. As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. There is this.
상기 광중합 개시제는 자발광 감광성 수지 조성물 고형분 전체 100 중량%에 대하여 0.1 내지 20 중량%, 바람직하게는 0.5 내지 15 중량%, 더욱 바람직하게는 1 내지 10 중량%로 포함될 수 있다. 상기 광중합 개시제가 상기 범위 내로 포함되는 경우 자발광 감광성 수지 조성물이 고감도화되어 노광 시간이 단축되므로 생산성이 향상되며 높은 해상도를 유지할 수 있기 때문에 바람직하다. 또한, 본 발명에 따른 자발광 감광성 수지 조성물을 사용하여 형성한 화소부의 강도와 상기 화소부의 표면에서의 평활성이 양호해지는 이점이 있다.The photopolymerization initiator may be included in an amount of 0.1 to 20% by weight, preferably 0.5 to 15% by weight, and more preferably 1 to 10% by weight, based on 100% by weight of the total solid of the self-luminous photosensitive resin composition. In the case where the photopolymerization initiator is included in the above range, the self-luminous photosensitive resin composition is highly sensitive, so that the exposure time is shortened, so that productivity is improved and high resolution can be maintained. Moreover, there exists an advantage that the intensity | strength of the pixel part formed using the self-luminous photosensitive resin composition concerning this invention, and smoothness in the surface of the said pixel part become favorable.
상기 광중합 개시제는 본 발명의 자발광 감광성 수지 조성물의 감도를 향상시키기 위해서, 광중합 개시 보조제를 더 포함할 수 있다. 상기 광중합 개시 보조제가 포함되는 경우 감도가 더욱 높아져 생산성이 향상되는 이점이 있다.The photopolymerization initiator may further include a photopolymerization initiation aid in order to improve the sensitivity of the self-luminous photosensitive resin composition of the present invention. When the photopolymerization start adjuvant is included, there is an advantage in that the sensitivity is higher and the productivity is improved.
상기 광중합 개시 보조제는 예컨대, 아민 화합물, 카르복시산 화합물 및 티올기를 가지는 유기 황 화합물로 이루어진 군으로부터 선택되는 1종 이상의 화합물이 바람직하게 사용될 수 있으나, 이에 한정되지 않는다.The photopolymerization initiation assistant may be preferably used, for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group, but is not limited thereto.
상기 아민 화합물로는 구체적으로 트리에탄올아민, 메틸디에탄올아민, 트리이소프로판올아민 등의 지방족 아민 화합물, 4-디메틸아미노벤조산메틸, 4-디메틸아미노벤조산에틸, 4-디메틸아미노벤조산이소아밀, 4-디메틸아미노벤조산2-에틸헥실, 벤조산2-디메틸아미노에틸, N,N-디메틸파라톨루이딘, 4,4'-비스(디메틸아미노)벤조페논(통칭: 미힐러 케톤), 4,4'-비스(디에틸아미노)벤조페논 등의 방향족 아민 화합물을 사용할 수 있으며, 특히 방향족 아민 화합물을 사용하는 것이 바람직하다.Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyl diethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethyl. Aminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (di Aromatic amine compounds, such as ethylamino) benzophenone, can be used, It is especially preferable to use an aromatic amine compound.
상기 카르복시산 화합물은 방향족 헤테로아세트산류인 것이 바람직하며, 구체적으로 페닐티오아세트산, 메틸페닐티오아세트산, 에틸페닐티오아세트산, 메틸에틸페닐티오아세트산, 디메틸페닐티오아세트산, 메톡시페닐티오아세트산, 디메톡시페닐티오아세트산, 클로로페닐티오아세트산, 디클로로페닐티오아세트산, N-페닐글리신, 페녹시아세트산, 나프틸티오아세트산, N-나프틸글리신, 나프톡시아세트산 등을 들 수 있다. The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, Chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.
상기 티올기를 가지는 유기 황 화합물의 구체적인 예로서는 2-머캅토벤조티아졸, 1,4-비스(3-머캅토부티릴옥시)부탄, 1,3,5-트리스(3-머캅토부틸옥시에틸)-1,3,5-트리아진-2,4,6(1H,3H,5H)-트리온, 트리메틸올프로판트리스(3-머캅토프로피오네이트), 펜타에리트리톨테트라키스(3-머캅토부티레이트), 펜타에리트리톨테트라키스(3-머캅토프로피오네이트), 디펜타에리트리톨헥사키스(3-머캅토프로피오네이트), 테트라에틸렌글리콜비스(3-머캅토프로피오네이트) 등을 들 수 있다.Specific examples of the organic sulfur compound having the thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto Butyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) and the like Can be.
상기 광중합 개시 보조제는 본 발명의 효과를 해치지 않는 범위에서 적절히 추가하여 사용할 수 있다.The photopolymerization start adjuvant may be appropriately added and used within a range that does not impair the effects of the present invention.
용제(E)Solvent (E)
본 발명의 일 실시형태에 따른 자발광 감광성 수지 조성물은 추가 용제를 더 포함할 수 있다.The self-luminous photosensitive resin composition according to one embodiment of the present invention may further include an additional solvent.
상기 추가 용제는 특별히 한정되지 않으며, 당 분야에서 통상적으로 사용되는 유기 용제를 포함할 수 있으며, 이는 본 발명의 양자점 분산액에 포함되는 용제와 동일한 것일 수도, 상이한 것일 수도 있다.The additional solvent is not particularly limited, and may include an organic solvent commonly used in the art, which may be the same as or different from the solvent contained in the quantum dot dispersion of the present invention.
상기 추가 용제는 구체적으로 에틸렌글리콜 모노메틸에테르, 에틸렌글리콜 모노에틸에테르, 에틸렌글리콜 모노프로필에테르, 에틸렌글리콜 모노부틸에테르, 프로필렌글리콜 모노메틸에테르, 프로필렌글리콜 메틸에틸에테르 등의 알킬렌글리콜 알킬에테르류; 디에틸렌글리콜 디메틸에테르, 디에틸렌글리콜 디에틸에테르, 디에틸렌글리콜 디프로필에테르, 디에틸렌글리콜 디부틸에테르 등의 디에틸렌글리콜 디알킬에테르류; 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트, 프로필렌글리콜 모노메틸에테르아세테이트, 프로필렌글리콜 모노에틸에테르아세테이트, 프로필렌글리콜 모노프로필에테르아세테이트 등의 알킬렌글리콜 알킬에테르아세테이트류; 메톡시부틸아세테이트, 메톡시펜틸아세테이트 등의 알콕시알킬아세테이트류; 벤젠, 톨루엔, 크실렌, 메시틸렌 등의 방향족 탄화수소류; 메틸에틸케톤, 아세톤, 메틸아밀케톤, 메틸이소부틸케톤, 시클로헥사논 등의 케톤류; 에탄올, 프로판올, 부탄올, 헥산올, 시클로헥산올, 에틸렌글리콜, 글리세린 등의 알코올류; 3-에톡시프로피온산에틸, 3-메톡시프로피온산메틸 등의 에스테르류; γ-부티롤락톤 등의 환상 에스테르류 등을 들 수 있다.Specific examples of the additional solvent include alkylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol methylethyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; Alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl 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, glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.
상기의 추가 용제는 도포성 및 건조성 면에서 바람직하게는 비점이 100℃ 내지 200℃인 유기 용제를 사용할 수 있고, 보다 바람직하게는 알킬렌글리콜알킬에테르아세테이트류, 케톤류, 3-에톡시프로피온산 에틸이나, 3-메톡시프로피온산 메틸 등의 에스테르류를 사용할 수 있으며, 더욱 바람직하게는 프로필렌글리콜 모노메틸에테르아세테이트, 프로필렌글리콜 모노에틸에테르아세테이트, 3-에톡시프로피온산 에틸, 3-메톡시프로피온산 메틸 등을 들 수 있다. 이들 추가 용제는 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있다.The above additional solvent may preferably be an organic solvent having a boiling point of 100 ° C. to 200 ° C. in terms of coatability and dryness, and more preferably alkylene glycol alkyl ether acetates, ketones, and ethyl 3-ethoxypropionate. Esters such as methyl 3-methoxypropionate can be used, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like. Can be mentioned. These additional solvents can be used individually or in mixture of 2 or more types, respectively.
본 발명의 자발광 감광성 수지 조성물 내에 포함되는 전체 용제(양자점 분산액 내 용제 및 추가 용제)는 상기 자발광 감광성 수지 조성물 전체 100 중량%에 대하여 20 내지 90 중량%, 바람직하게는 25 내지 85 중량%, 보다 바람직하게는 30 내지 80 중량%로 포함될 수 있다. 상기 전체 용제의 함량이 상기 범위 이내로 포함될 경우에는 롤코터, 스핀 코터, 슬릿앤드 스핀 코터, 슬릿코터(다이 코터라고도 하는 경우가 있음), 잉크젯 등의 도포 장치로 도포했을 때 도포성이 양호해질 수 있어 바람직하다. 상기 전체 용제의 함량이 상기 범위 미만으로 포함될 경우 도포성이 다소 저하됨에 따라 공정이 다소 어려워질 수 있으며, 상기 범위를 초과하는 경우 상기 자발광 감광성 수지 조성물로 형성된 컬러필터의 성능이 다소 저하될 수 있는 문제가 발생할 수 있다.The total solvent (solvent in quantum dot dispersion and additional solvent) contained in the self-luminous photosensitive resin composition of the present invention is 20 to 90% by weight, preferably 25 to 85% by weight, based on 100% by weight of the total of the self-luminous photosensitive resin composition, More preferably, it may be included in 30 to 80% by weight. If the total solvent content is within the above range, the applicability may be improved when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, or the like. It is preferable. When the content of the total solvent is included in less than the above range may be a little difficult as the applicability is slightly reduced, if the content exceeds the above range, the performance of the color filter formed of the self-luminous photosensitive resin composition may be slightly lowered Problems can arise.
첨가제(F)Additive (F)
본 발명에 따른 자발광 감광성 수지 조성물은 코팅성 또는 밀착성을 증진 시키기 위해서 밀착촉진제, 계면활성제와 같은 첨가제를 추가로 포함할 수 있다.The self-luminous photosensitive resin composition according to the present invention may further include an additive such as an adhesion promoter and a surfactant to enhance the coating property or adhesion.
상기 밀착촉진제는 기판과의 밀착성을 높이기 위하여 첨가될 수 있는 것으로서 카르복실기, 메타크릴로일기, 이소시아네이트기, 에폭시기 및 이들의 조합으로 이루어진 군에서 선택되는 반응성 치환기를 갖는 실란 커플링제를 포함할 수 있으나, 이에 한정되는 것은 아니다. 예컨대, 상기 실란 커플링제는 트리메톡시실릴벤조산, γ-메타크릴옥시프로필트리메톡시실란, 비닐트리아세톡시실란, 비닐트리메톡시실란, γ-이소시아네이트프로필 트리에톡시실란, γ-글리시독시프로필트리메톡시실란, β-(3,4-에폭시시클로헥실)에틸트리메톡시실란 등을 들 수 있으며, 이들은 단독 또는 2종 이상 조합하여 사용할 수 있다.The adhesion promoter may include a silane coupling agent having a reactive substituent selected from the group consisting of carboxyl groups, methacryloyl groups, isocyanate groups, epoxy groups, and combinations thereof, which may be added to increase adhesion to the substrate. It is not limited to this. For example, the silane coupling agent may be trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyl triethoxysilane, γ-glycidoxy Propyl trimethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned, These can be used individually or in combination of 2 or more types.
본 발명에 따른 자발광 감광성 수지 조성물이 상기 계면활성제를 포함하는 경우 코팅성이 향상될 수 있는 이점이 있다. 예컨대 상기 계면활성제는 BM-1000, BM-1100(BM Chemie사), 프로라이드 FC-135/FC-170C/FC-430(스미토모 쓰리엠㈜), SH-28PA/-190/SZ-6032(도레 시리콘㈜) 등의 불소계 계면활성제를 사용할 수 있으나, 이에 한정되지는 않는다.When the self-luminous photosensitive resin composition according to the present invention includes the surfactant, there is an advantage that the coating property can be improved. For example, the surfactant is BM-1000, BM-1100 (BM Chemie Co., Ltd.), Proride FC-135 / FC-170C / FC-430 (Sumitomo 3M Co., Ltd.), SH-28PA / -190 / SZ-6032 (Dore Siri). Fluorine-based surfactants such as Corn Co., Ltd. may be used, but is not limited thereto.
이 외에도 본 발명에 따른 자발광 감광성 수지 조성물은 본 발명의 효과를 저해하지 않는 범위에서 산화 방지제, 자외선 흡수제, 응집 방지제와 같은 첨가제를 더 포함할 수도 있으며, 상기 첨가제는 역시 본 발명의 효과를 저해하지 않는 범위에서 당업자가 적절히 추가하여 사용이 가능하다. 예컨대 상기 첨가제는 상기 자발광 감광성 수지 조성물 전체 100 중량%를 기준으로 0.05 내지 10 중량%, 구체적으로 0.1 내지 10 중량%, 더욱 구체적으로 0.1 내지 5 중량%로 사용할 수 있으나 이에 한정되는 것은 아니다.In addition, the self-luminous photosensitive resin composition according to the present invention may further include additives such as antioxidants, ultraviolet absorbers and anti-agglomerating agents in a range that does not impair the effects of the present invention, the additives also inhibit the effects of the present invention It can be used by those skilled in the art as long as it does not. For example, the additive may be used in an amount of 0.05 to 10% by weight, specifically 0.1 to 10% by weight, and more specifically 0.1 to 5% by weight, based on 100% by weight of the total self-luminous photosensitive resin composition.
본 발명의 일 실시형태는 상술한 자발광 감광성 수지 조성물을 이용하여 형성되는 컬러필터에 관한 것이다.One embodiment of the present invention relates to a color filter formed by using the above self-luminous photosensitive resin composition.
본 발명에 따른 컬러필터는 본 발명의 양자점 분산액을 포함하는 자발광 감광성 수지 조성물의 경화물을 포함하기 때문에 양자점 입자가 고르게 분산되어 발광 특성이 우수한 이점이 있다.Since the color filter according to the present invention includes the cured product of the self-luminous photosensitive resin composition including the quantum dot dispersion liquid of the present invention, the quantum dot particles are uniformly dispersed, thereby providing excellent light emission characteristics.
상기 컬러필터는 기판 및 상기 기판의 상부에 형성된 패턴층을 포함한다.The color filter includes a substrate and a pattern layer formed on the substrate.
상기 기판은 상기 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 the 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).
상기 패턴층은 본 발명의 자발광 감광성 수지 조성물을 포함하는 층으로, 상기 자발광 감광성 수지 조성물을 도포하고 소정의 패턴으로 노광, 현상 및 열경화하여 형성된 층일 수 있다. 상기 패턴층은 당업계에서 통상적으로 알려진 방법을 수행함으로써 형성할 수 있다.The pattern layer is a layer including the self-luminous photosensitive resin composition of the present invention, and may be a layer formed by applying the self-luminous photosensitive resin composition and exposing, developing and thermosetting in a predetermined pattern. The pattern layer may be formed by performing a method commonly known in the art.
상기와 같은 기판 및 패턴층을 포함하는 컬러필터는 각 패턴 사이에 형성된 격벽 또는 블랙 매트릭스를 더 포함할 수 있으나 이에 한정되지 않는다.The color filter including the substrate and the pattern layer may further include a partition wall or a black matrix formed between the patterns, but is not limited thereto.
또한, 상기 컬러필터의 패턴층 상부에 형성된 보호막을 더 포함할 수도 있다.In addition, a protective film formed on the pattern layer of the color filter may be further included.
상기 컬러필터는 적색 패턴층, 녹색 패턴층 및 청색 패턴층으로 이루어진 군에서 선택되는 1종 이상을 포함할 수 있다. 구체적으로, 상기 컬러필터는 본 발명에 따른 적 양자점을 포함하는 적색 패턴층, 녹 양자점을 포함하는 녹색 패턴층 및 청 양자점을 포함하는 청색 패턴층으로 이루어진 군에서 선택되는 1 이상을 포함할 수 있다. 상기 적색 패턴층, 녹색 패턴층 및 청색 패턴층은 각각 광 조사시 적색광, 녹색광 및 청색광을 방출할 수 있으며, 이때, 상기 광원의 방출광은 특별히 한정되지는 않으나 보다 우수한 색 재현성의 측면에서 청색광을 방출하는 광원을 사용할 수 있다.The color filter may include at least one selected from the group consisting of a red pattern layer, a green pattern layer, and a blue pattern layer. Specifically, the color filter may include one or more selected from the group consisting of a red pattern layer including a red quantum dot, a green pattern layer including a green quantum dot, and a blue pattern layer including a blue quantum dot according to the present invention. . The red pattern layer, the green pattern layer, and the blue pattern layer may respectively emit red light, green light, and blue light when irradiated with light. In this case, the emission light of the light source is not particularly limited, but blue light may be generated in terms of better color reproducibility. A light source that emits can be used.
상기 컬러필터는 적색 패턴층, 녹색 패턴층 및 청색 패턴층 중 2종 색상의 패턴층만을 구비할 수도 있으나, 이에 한정되지 않는다. 다만, 상기 컬러필터가 2종 색상의 패턴층만을 구비하는 경우 상기 패턴층은 상기 양자점 입자를 함유하지 않는 투명 패턴층을 더 구비할 수 있다.The color filter may include only a pattern layer of two colors among the red pattern layer, the green pattern layer, and the blue pattern layer, but is not limited thereto. However, when the color filter includes only the pattern layer of two colors, the pattern layer may further include a transparent pattern layer containing no quantum dot particles.
상기 컬러필터가 상기 2종 색상의 패턴층만을 구비하는 경우에는 상기 2종 색상 외의 색상을 나타내는 파장의 빛을 방출하는 광원을 사용할 수 있다. 예컨대, 상기 컬러필터가 적색 패턴층 및 녹색 패턴층을 포함하는 경우에는 청색광을 방출하는 광원을 사용할 수 있으며, 이 경우 적 양자점은 적색광을, 녹 양자점은 녹색광을 방출하고, 상기 투명 패턴층은 상기 광원에 의한 청색광이 그대로 투과함에 따라 청색을 띨 수 있다.When the color filter includes only the pattern layers of the two colors, a light source emitting light having a wavelength representing a color other than the two colors may be used. For example, when the color filter includes a red pattern layer and a green pattern layer, a light source emitting blue light may be used. In this case, red quantum dots emit red light and green quantum dots emit green light, and the transparent pattern layer may As the blue light transmitted by the light source is transmitted as it is, blue can be obtained.
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, 전계발광 표시장치, 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.
본 발명에 따른 화상표시장치는 본 발명의 양자점 분산액을 포함하는 자발광 감광성 수지 조성물의 경화물로 제조된 컬러필터를 포함함으로써, 발광 특성이 우수한 효과가 있다. The image display device according to the present invention includes the color filter made of the cured product of the self-luminous photosensitive resin composition containing the quantum dot dispersion liquid of the present invention, thereby exhibiting excellent light emission characteristics.
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.
합성예 1: InP/ZnS 코어-쉘 양자점 입자의 합성Synthesis Example 1 Synthesis of InP / ZnS Core-Shell Quantum Dot Particles
InP 코어 양자점의 제조Fabrication of InP Core Quantum Dots
인듐 아세테이트(Indium acetate) 0.4 mmol (0.058g), 팔미트산(palmitic acid) 0.6mmol (0.15g) 및 1-옥타데센(octadecene) 20mL를 반응기에 넣고 진공 하에 120℃로 가열하였다. 1시간 후 반응기 내 분위기를 질소로 전환하였다. 280℃로 가열한 후, 트리스(트리메틸실릴)포스핀 (TMS3P) 0.2mmol (58㎕) 및 트리옥틸포스핀 1.0mL의 혼합 용액을 신속히 주입하고 20분간 반응시켰다. 상온으로 신속하게 식힌 반응 용액에 아세톤을 넣고 원심 분리하여 얻은 침전을 톨루엔에 분산시켰다. 얻어진 InP 반도체 나노 결정은, 흡수 최대 파장 560 내지 590nm를 나타내었다.0.4 mmol (0.058 g) of indium acetate, 0.6 mmol (0.15 g) of palmitic acid and 20 mL of 1-octadecene were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen. After heating to 280 ° C., a mixed solution of 0.2 mmol (58 μl) of tris (trimethylsilyl) phosphine (TMS 3 P) and 1.0 mL of trioctylphosphine was rapidly injected and reacted for 20 minutes. Acetone was added to the reaction solution cooled to room temperature rapidly, and the precipitate obtained by centrifugation was dispersed in toluene. The obtained InP semiconductor nanocrystal showed the absorption maximum wavelength of 560-590 nm.
InP/ZnS 코어-쉘 양자점의 제조Fabrication of InP / ZnS Core-Shell Quantum Dots
아연 아세테이트 2.4mmol (0.448g), 올레산 4.8mmol 및 트리옥틸아민 20mL를 반응기에 넣고 진공 하에 120℃로 가열하였다. 1시간 후 반응기 내 분위기를 질소로 전환하고 반응기를 280℃로 승온시켰다. 앞서 합성한 InP 코어 용액 2 ml를 넣고, 이어서 트리옥틸포스핀 중의 황(S/TOP) 4.8 mmol을 넣은 후, 최종 혼합물을 2시간 동안 반응시켰다. 상온으로 신속하게 식힌 반응 용액에 에탄올을 넣고 원심 분리하여 얻은 침전을 감압여과 후 감압 건조하여 InP/ZnS 코어-쉘 양자점을 수득하였다.2.4 mmol (0.448 g) of zinc acetate, 4.8 mmol of oleic acid and 20 mL of trioctylamine were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen and the reactor was warmed to 280 ° C. 2 ml of the synthesized InP core solution was added thereto, followed by 4.8 mmol of sulfur (S / TOP) in trioctylphosphine, and the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution cooled to room temperature rapidly, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to obtain an InP / ZnS core-shell quantum dot.
제조예Production Example 1 내지 14:  1 to 14: 양자점Quantum dots 분산액의 제조 Preparation of Dispersion
하기 표 1 에 기재된 바와 같이 각각의 성분을 혼합하여 양자점 분산액을 제조하였다(단위: 중량%).Each component was mixed as described in Table 1 below to prepare a quantum dot dispersion (unit: wt%).
양자점Quantum dots 용제solvent 분산제Dispersant
A-1A-1 B-1B-1 B-2B-2 B-3B-3 B-4B-4 B-5B-5 B-6B-6 B-7B-7 B-8B-8 C-1C-1 C-2C-2 C-3C-3 C-4C-4
제조예 1Preparation Example 1 3030 7070
제조예 2Preparation Example 2 3030 7070
제조예 3Preparation Example 3 3030 7070
제조예 4Preparation Example 4 3030 7070
제조예 5Preparation Example 5 3030 6565 55
제조예 6Preparation Example 6 3030 6565 55
제조예 7Preparation Example 7 3030 6565 55
제조예 8Preparation Example 8 3030 6565 55
제조예 9Preparation Example 9 3030 6565 55
제조예 10Preparation Example 10 3030 6565 55
제조예 11Preparation Example 11 3030 6565 55
제조예 12Preparation Example 12 3030 7070
제조예 13Preparation Example 13 3030 6565 55
제조예 14Preparation Example 14 3030 6565 55
A-1: 합성예 1에서 얻어진 InP/ZnS 코어-쉘 양자점A-1: InP / ZnS core-shell quantum dots obtained in Synthesis Example 1
B-1: 페닐-아세트산 에틸 에스테르 (20℃에서의 유전상수(ε): 5.11)B-1: Phenyl-acetic acid ethyl ester (dielectric constant (ε) at 20 ° C: 5.11)
B-2: 3-페닐-프로피온산 에틸 에스테르 (20℃에서의 유전상수(ε): 4.28)B-2: 3-phenyl-propionic acid ethyl ester (dielectric constant (ε) at 20 ° C: 4.28)
B-3: 사이클로헥실-아세트산 에틸 에스테르 (20℃에서의 유전상수(ε): 3.82)B-3: cyclohexyl-acetic acid ethyl ester (dielectric constant (ε) at 20 ° C: 3.82)
B-4: 사이클로헥실-아세트산 알릴 에스테르 (20℃에서의 유전상수(ε): 3.16)B-4: cyclohexyl-acetic acid allyl ester (dielectric constant (ε) at 20 ° C .: 3.16)
B-5: 프로피온산 페네틸 에스테르 (20℃에서의 유전상수(ε): 4.98)B-5: propionic acid phenethyl ester (dielectric constant (ε) at 20 ° C: 4.98)
B-6: 아세트산 사이클로헥실메틸 에스테르 (20℃에서의 유전상수(ε): 4.06)B-6: acetic acid cyclohexylmethyl ester (dielectric constant (ε) at 20 ° C .: 4.06)
B-7: 부트-3-에노산 사이클로헥실메틸 에스테르 (20℃에서의 유전상수(ε): 3.48)B-7: but-3-enoic acid cyclohexylmethyl ester (dielectric constant (ε) at 20 ° C: 3.48)
B-8: 프로필렌 글리콜 모노 메틸 에테르 (PGME) (20℃에서의 유전상수(ε): 12.3)B-8: Propylene Glycol Monomethyl Ether (PGME) (Dielectric Constant (ε) at 20 ° C: 12.3)
C-1: DISPER BYK-111 (빅케미사제, 인산에스테르계 분산제)C-1: DISPER BYK-111 (BIC Chemie Co., Phosphate ester dispersant)
C-2: DISPER BYK-103 (빅케미사제, 인산에스테르계 분산제)C-2: DISPER BYK-103 (manufactured by BIC Chem Corporation, phosphate ester dispersant)
C-3: DISPER BYK-161 (빅케미사제, 우레탄계 분산제)C-3: DISPER BYK-161 (manufactured by BICKEMI, urethane dispersant)
C-4: DISPER BYK-2001 (빅케미사제, 아크릴계 분산제)C-4: DISPER BYK-2001 (manufactured by BIC Chem Corporation, acrylic dispersant)
합성예 2: 알칼리 가용성 수지의 합성Synthesis Example 2: Synthesis of Alkali-Soluble Resin
교반기, 온도계, 환류 냉각관, 적하 로트 및 질소 도입관을 구비한 플라스크에 프로필렌글리콜모노메틸에테르 아세테이트 120중량부, 프로필렌글리콜모노메틸에테르 80중량부, AIBN 2중량부, 아크릴산 5.0중량부, 4-메틸스티렌 55.0중량부, 벤질메타아크릴레이트 20중량부, 메틸메타아크릴레이트 20중량부 및 n-도데실머캅탄 3중량부를 투입하고 질소 치환하였다. 그 후 교반하며 반응액의 온도를 80℃로 상승시키고 8시간 동안 반응시켰다. 이렇게 합성된 알칼리 가용성 수지의 고형분 산가는 17.4㎎KOH/g 이며 GPC로 측정한 중량 평균 분자량 Mw는 약 17,370이었다.120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 5.0 parts by weight of acrylic acid in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot and a nitrogen introduction tube. 55.0 parts by weight of methyl styrene, 20 parts by weight of benzyl methacrylate, 20 parts by weight of methyl methacrylate and 3 parts by weight of n-dodecyl mercaptan were added and nitrogen-substituted. After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. The solid acid value of the alkali-soluble resin thus synthesized was 17.4 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 17,370.
실시예 1 내지 11 및 비교예 1 내지 3: 자발광 감광성 수지 조성물의 제조Examples 1 to 11 and Comparative Examples 1 to 3: Preparation of self-luminous photosensitive resin composition
하기 표 2 에 기재된 바와 같이 각각의 성분을 혼합하여 자발광 감광성 수지 조성물을 제조하였다(단위: 중량%).As shown in Table 2 below, each component was mixed to prepare a self-luminous photosensitive resin composition (unit: wt%).
실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 실시예5Example 5 실시예6Example 6 실시예7Example 7 실시예8Example 8 실시예9Example 9 실시예10Example 10 실시예11Example 11 비교예1Comparative Example 1 비교예2Comparative Example 2 비교예3Comparative Example 3
양자점 분산액 (A)Quantum Dot Dispersion (A) 제조예1Preparation Example 1 4040
제조예2Preparation Example 2 4040
제조예3Preparation Example 3 4040
제조예4Preparation Example 4 4040
제조예5Preparation Example 5 4040
제조예6Preparation Example 6 4040
제조예7Preparation Example 7 4040
제조예8Preparation Example 8 4040
제조예9Preparation Example 9 4040
제조예10Preparation Example 10 4040
제조예11Preparation Example 11 4040
제조예12Preparation Example 12 4040
제조예13Preparation Example 13 4040
제조예14Preparation Example 14 4040
알칼리가용성 수지 (B)Alkali-Soluble Resin (B) 2020 2020 2020 2020 2020 2020 2020 2020 2020 2020 2020 2020 2020 2020
광중합성 화합물(C)Photopolymerizable Compound (C) 2020 2020 2020 2020 2020 2020 2020 2020 2020 2020 2020 2020 2020 2020
광중합 개시제(D)Photopolymerization Initiator (D) 55 55 55 55 55 55 55 55 55 55 55 55 55 55
용제(E)Solvent (E) 1515 1515 1515 1515 1515 1515 1515 1515 1515 1515 1515 1515 1515 1515
A: 각각의 제조예에서 얻어진 양자점 분산액A: Quantum dot dispersion liquid obtained by each manufacture example
B: 합성예 2에서 얻어진 알칼리 가용성 수지B: Alkali-soluble resin obtained in Synthesis Example 2
C: 디펜타에리트리톨헥사아크릴레이트(KAYARAD DPHA; 닛본 카야꾸 ㈜ 제조) C: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
D: Irgacure-907 (BASF사) D: Irgacure-907 (BASF Corporation)
E: 프로필렌글리콜모노메틸에테르아세테이트 E: Propylene Glycol Monomethyl Ether Acetate
실험예 1: Experimental Example 1:
(1) 분산 입도 측정(1) dispersion particle size measurement
상기 제조예에서 제조된 양자점 분산액과 상기 실시예 및 비교예에서 제조된 자발광 감광성 수지 조성물의 분산입도를 ELSZ-2000ZS(오츠카사 제)을 이용하여 측정하고, 그 결과를 하기 표 3에 나타내었다. 통상 양자점 입자가 응집되면 분산입도는 커지게 되고, 이에 따라 발광 특성이 떨어지는 문제를 야기할 수 있다.Dispersion particle size of the quantum dot dispersion prepared in the above Preparation Example and the self-luminous photosensitive resin composition prepared in the Examples and Comparative Examples was measured using ELSZ-2000ZS (manufactured by Otsuka Co., Ltd.), and the results are shown in Table 3 below. . In general, when the quantum dot particles are agglomerated, the dispersion particle size becomes large, which may cause a problem of deterioration of the light emission characteristics.
(2) 발광 강도 측정(2) emission intensity measurement
상기 실시예 및 비교예에서 제조된 자발광 감광성 수지 조성물을 이용하여 아래와 같이 컬러필터를 제조하였으며, 이때의 발광 강도를 하기와 같은 방법으로 측정하고, 그 결과를 하기 표 3에 나타내었다.Using the self-luminous photosensitive resin composition prepared in Examples and Comparative Examples to prepare a color filter as follows, the emission intensity at this time was measured by the following method, and the results are shown in Table 3 below.
<컬러필터의 제조><Production of color filter>
각각의 자발광 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×세로가 20mm × 20mm인 정사각형의 투과 패턴과 1㎛ 내지 100㎛의 라인/스페이스 패턴을 갖는 시험 포토마스크를 올려놓고 시험 포토마스크와의 간격을 100㎛로 하여 자외선을 조사하였다. Each self-luminous photosensitive resin composition was applied on a glass substrate by spin coating, then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. Subsequently, a test photomask having a square transmissive pattern having a width × length of 20 mm × 20 mm 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 하에서 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 유리판을 증류수를 사용하여 세척한 다음, 질소 가스를 불어서 건조하고, 150℃의 가열 오븐에서 10분 동안 가열하여 컬러필터 패턴을 제조하였다. 상기에서 제조된 자발광 컬러필터 패턴의 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 ultra high 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 film coated glass plate 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 pattern. The film thickness of the self-luminous color filter pattern prepared above was 3.0 μm.
<발광 강도 측정><Light emission intensity measurement>
상기 자발광 화소가 형성된 컬러필터에 대해 550nm 영역에서의 발광 강도를 스펙트럼 미터(Spectrum meter)(Ocean Optics사 제)를 이용하여 측정하였다. 측정된 발광 강도가 높을수록 우수한 발광 특성을 발휘하는 것으로 판단할 수 있다.The emission intensity in the 550 nm region of the color filter on which the self-luminous pixel was formed was measured using a spectrum meter (manufactured by Ocean Optics). It may be judged that the higher the measured light emission intensity is, the better the light emission characteristic is.
　 양자점 분산액 분산입도(nm)Quantum dot dispersion dispersion particle size (nm) 감광성 수지조성물 분산입도 (nm)Photosensitive resin composition dispersion particle size (nm) 발광 강도Luminous intensity
제조예1Preparation Example 1 실시예1Example 1 66 88 56,265 56,265
제조예2Preparation Example 2 실시예2Example 2 77 77 56,915 56,915
제조예3Preparation Example 3 실시예3Example 3 77 88 59,354 59,354
제조예4Preparation Example 4 실시예4Example 4 66 77 57,225 57,225
제조예5Preparation Example 5 실시예5Example 5 77 99 58,252 58,252
제조예6Preparation Example 6 실시예6Example 6 66 88 59,446 59,446
제조예7Preparation Example 7 실시예7Example 7 88 1010 58,243 58,243
제조예8Preparation Example 8 실시예8Example 8 66 88 57,65857,658
제조예9Preparation Example 9 실시예9Example 9 77 99 58,97558,975
제조예10Preparation Example 10 실시예10Example 10 88 88 59,45359,453
제조예11Preparation Example 11 실시예11Example 11 88 1010 58,82958,829
제조예12Preparation Example 12 비교예1Comparative Example 1 5050 12531253 12,542 12,542
제조예13Preparation Example 13 비교예2Comparative Example 2 2828 821821 26,654 26,654
제조예14Preparation Example 14 비교예3Comparative Example 3 4545 763763 25,569 25,569
상기 표 3에 나타낸 바와 같이, 본 발명에 따른 특정 용제를 포함하는 제조예 1 내지 11의 양자점 분산액 및 이를 포함하는 실시예 1 내지 11의 자발광 감광성 수지 조성물 중에서의 양자점 분산입도는 제조예 12 내지 14의 양자점 분산액 및 이를 포함하는 비교예 1 내지 3의 자발광 감광성 수지 조성물 중에서의 양자점 분산입도에 비해 더욱 작은 것을 확인할 수 있었다. 또한, 본 발명에 따른 실시예 1 내지 11의 자발광 감광성 수지 조성물을 이용하여 형성된 컬러필터가 비교예 1 내지 3의 자발광 감광성 수지 조성물을 이용하여 형성된 컬러필터에 비해 발광 강도가 우수한 것을 확인할 수 있었다. As shown in Table 3, the quantum dot dispersion particle size in the quantum dot dispersion liquid of Preparation Examples 1 to 11 containing the specific solvent according to the present invention and the self-luminous photosensitive resin composition of Examples 1 to 11 including the same are prepared in Preparation Examples 12 to It was confirmed that it was smaller than the quantum dot dispersion particle size in the quantum dot dispersion liquid of 14 and the self-luminous photosensitive resin composition of Comparative Examples 1 to 3 including the same. In addition, it can be seen that the color filter formed using the self-luminous photosensitive resin compositions of Examples 1 to 11 according to the present invention has superior emission intensity as compared to the color filter formed using the self-luminous photosensitive resin compositions of Comparative Examples 1 to 3. there was.
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 (10)

  1. 양자점 및 용제를 포함하는 양자점 분산액으로서, 상기 용제는 C3-C10의 사이클로알킬기, C2-C10의 헤테로사이클로알킬기, C5-C10의 아로마틱기 및 C4-C10의 헤테로아로마틱기로 구성된 군으로부터 선택되는 1종 이상과 에스테르 결합을 갖는 화합물을 포함하는 양자점 분산액.A quantum dot dispersion comprising a quantum dot and a solvent, wherein the solvent is a C 3 -C 10 cycloalkyl group, C 2 -C 10 heterocycloalkyl group, C 5 -C 10 aromatic group and C 4 -C 10 heteroaromatic group A quantum dot dispersion comprising a compound having an ester bond with at least one member selected from the group consisting of.
  2. 제1항에 있어서, 상기 용제는 하기 화학식 1로 표시되는 화합물 및 하기 화학식 2로 표시되는 화합물 중에서 선택되는 1종 이상을 포함하는 양자점 분산액:The quantum dot dispersion of claim 1, wherein the solvent comprises at least one selected from a compound represented by Formula 1 and a compound represented by Formula 2 below:
    [화학식 1][Formula 1]
    Figure PCTKR2018001234-appb-I000005
    Figure PCTKR2018001234-appb-I000005
    [화학식 2][Formula 2]
    Figure PCTKR2018001234-appb-I000006
    Figure PCTKR2018001234-appb-I000006
    상기 식에서,Where
    A는 C1-C10의 알킬기 및 할로겐으로 구성된 군으로부터 선택되는 1종 이상의 치환기로 치환되거나 비치환된, C3-C10의 사이클로알킬기, C2-C10의 헤테로사이클로알킬기, C5-C10의 아로마틱기 또는 C4-C10의 헤테로아로마틱기이고,A is a C 3 -C 10 cycloalkyl group, C 2 -C 10 heterocycloalkyl group, C 5- , which is unsubstituted or substituted with one or more substituents selected from the group consisting of C 1 -C 10 alkyl groups and halogen. C 10 aromatic group or C 4 -C 10 heteroaromatic group,
    L은 C1-C6의 알킬렌기이거나 존재하지 않고,L is a C 1 -C 6 alkylene group or absent,
    R은 C1-C10의 알킬기 또는 C2-C10의 알케닐기이다.R is an alkyl group of C 1 -C 10 or an alkenyl group of C 2 -C 10 .
  3. 제2항에 있어서, A는 할로겐으로 치환되거나 비치환된, 사이클로펜틸, 사이클로헥실, 테트라하이드로퓨라닐, 테트라하이드로피라닐, 페닐, 사이클로펜타디에닐 또는 퓨라닐이고, L은 C1-C6의 알킬렌기이거나 존재하지 않고, R은 C1-C10의 알킬기 또는 C2-C10의 알케닐인 양자점 분산액.The compound of claim 2, wherein A is cyclopentyl, cyclohexyl, tetrahydrofuranyl, tetrahydropyranyl, phenyl, cyclopentadienyl or furanyl, and L is C 1 -C 6 A quantum dot dispersion liquid wherein the alkylene group is or absent and R is a C 1 -C 10 alkyl group or a C 2 -C 10 alkenyl.
  4. 제2항에 있어서, 상기 화학식 1로 표시되는 화합물은 페닐-아세트산 에틸 에스테르, 3-페닐-프로피온산 메틸 에스테르, 3-페닐-프로피온산 에틸 에스테르, 4-페닐-부티르산 에틸 에스테르, 5-페닐-펜타노산 에틸 에스테르, 6-페닐-헥사노산 에틸 에스테르, 4-페닐-부티르산 프로필 에스테르, 4-(4-클로로-페닐)-부티르산 에틸 에스테르, 4-(3,4-디클로로-페닐)-부티르산 에틸 에스테르, 3-사이클로펜타-1,3-디에닐-프로피온산 메틸 에스테르, 4-사이클로펜타-1,3-디에닐-부티르산 에틸 에스테르, 5-사이클로펜타-1,3-디에닐-펜타노산 에틸 에스테르, 6-사이클로펜타-1,3-디에닐-헥사노산 에틸 에스테르, 4-사이클로펜타-1,3-디에닐-부티르산 프로필 에스테르, 3-퓨란-2-일-프로피온산 메틸 에스테르, 4-퓨란-2-일-부티르산 에틸 에스테르, 5-퓨란-2-일-펜타노산 에틸 에스테르, 6-퓨란-2-일-헥사노산 에틸 에스테르, 4-퓨란-2-일-부티르산 프로필 에스테르, 퓨란-2-카르복실산 프로필 에스테르, 퓨란-2-카르복실산 부틸 에스테르, 3-사이클로펜틸-프로피온산 메틸 에스테르, 4-사이클로펜틸-부티르산 에틸 에스테르, 5-사이클로펜틸-펜타노산 에틸 에스테르, 6-사이클로펜틸-헥사노산 에틸 에스테르, 4-사이클로펜틸-부티르산 프로필 에스테르, 사이클로펜탄카르복실산 이소부틸 에스테르, 사이클로펜탄카르복실산 펜틸 에스테르, 3-(테트라하이드로-퓨란-3-일)-프로피온산 메틸 에스테르, 4-(테트라하이드로-퓨란-3-일)-부티르산 에틸 에스테르, 5-(테트라하이드로-퓨란-3-일)-펜타노산 에틸 에스테르, 6-(테트라하이드로-퓨란-3-일)-헥사노산 에틸 에스테르, 4-(테트라하이드로-퓨란-3-일)-부티르산 프로필 에스테르, 테트라하이드로-퓨란-3-카르복실산 프로필 에스테르, 테트라하이드로-퓨란-3-카르복실산 부틸 에스테르, 3-(테트라하이드로-퓨란-2-일)-프로피온산 메틸 에스테르, 4-(테트라하이드로-퓨란-2-일)-부티르산 에틸 에스테르, 5-(테트라하이드로-퓨란-2-일)-펜타노산 에틸 에스테르, 6-(테트라하이드로-퓨란-2-일)-헥사노산 에틸 에스테르, 4-(테트라하이드로-퓨란-2-일)-부티르산 프로필 에스테르, 테트라하이드로-퓨란-2-카르복실산 2-에틸-헥실 에스테르, 사이클로헥실-아세트산 에틸 에스테르, 3-사이클로헥실-프로피온산 메틸 에스테르, 4-사이클로헥실-부티르산 에틸 에스테르, 5-사이클로헥실-펜타노산 에틸 에스테르, 6-사이클로헥실-헥사노산 에틸 에스테르, 4-사이클로헥실-부티르산 프로필 에스테르, 사이클로헥산카르복실산 프로필 에스테르, 사이클로헥산카르복실산 헥실 에스테르, 사이클로헥실-아세트산 알릴 에스테르, 3-(테트라하이드로-피란-2-일)-프로피온산 메틸 에스테르, 4-(테트라하이드로-피란-2-일)-부티르산 에틸 에스테르, 5-(테트라하이드로-피란-2-일)-펜타노산 에틸 에스테르, 6-(테트라하이드로-피란-2-일)-헥사노산 에틸 에스테르, 4-(테트라하이드로-피란-2-일)-부티르산 프로필 에스테르, 테트라하이드로-피란-2-카르복실산 프로필 에스테르, 테트라하이드로-피란-2-카르복실산 부틸 에스테르, 3-(테트라하이드로-피란-3-일)-프로피온산 메틸 에스테르, 4-(테트라하이드로-피란-3-일)-부티르산 에틸 에스테르, 5-(테트라하이드로-피란-2-일)-펜타노산 에틸 에스테르, 6-(테트라하이드로-피란-3-일)-헥사노산 에틸 에스테르, 4-(테트라하이드로-피란-3-일)-부티르산 프로필 에스테르, 테트라하이드로-피란-3-카르복실산 이소부틸 에스테르, 테트라하이드로-피란-3-카르복실산 펜틸 에스테르, 3-(테트라하이드로-피란-4-일)-프로피온산 메틸 에스테르, 4-(테트라하이드로-피란-4-일)-부티르산 에틸 에스테르, 5-(테트라하이드로-피란-4-일)-펜타노산 에틸 에스테르, 6-(테트라하이드로-피란-4-일)-헥사노산 에틸 에스테르, 4-(테트라하이드로-피란-4-일)-부티르산 프로필 에스테르, 테트라하이드로-피란-4-카르복실산 부틸 에스테르 및 테트라하이드로-피란-4-카르복실산 프로필 에스테르로 구성된 군으로부터 선택되는 1종 이상인 양자점 분산액.According to claim 2, wherein the compound represented by Formula 1 is phenyl- acetic acid ethyl ester, 3-phenyl- propionic acid methyl ester, 3-phenyl- propionic acid ethyl ester, 4-phenyl-butyric acid ethyl ester, 5-phenyl-pentanoic acid Ethyl ester, 6-phenyl-hexanoic acid ethyl ester, 4-phenyl-butyric acid propyl ester, 4- (4-chloro-phenyl) -butyric acid ethyl ester, 4- (3,4-dichloro-phenyl) -butyric acid ethyl ester, 3-cyclopenta-1,3-dienyl-propionic acid methyl ester, 4-cyclopenta-1,3-dienyl-butyric acid ethyl ester, 5-cyclopenta-1,3-dienyl-pentanoic acid ethyl ester, 6 -Cyclopenta-1,3-dienyl-hexanoic acid ethyl ester, 4-cyclopenta-1,3-dienyl-butyric acid propyl ester, 3-furan-2-yl-propionic acid methyl ester, 4-furan-2- Mono-butyric acid ethyl ester, 5-furan-2-yl-pentanoic acid ethyl ester, 6- Furan-2-yl-hexanoic acid ethyl ester, 4-furan-2-yl-butyric acid propyl ester, furan-2-carboxylic acid propyl ester, furan-2-carboxylic acid butyl ester, 3-cyclopentyl-propionic acid methyl Ester, 4-cyclopentyl-butyric acid ethyl ester, 5-cyclopentyl-pentanoic acid ethyl ester, 6-cyclopentyl-hexanoic acid ethyl ester, 4-cyclopentyl-butyric acid propyl ester, cyclopentanecarboxylic acid isobutyl ester, cyclo Pentanecarboxylic acid pentyl ester, 3- (tetrahydro-furan-3-yl) -propionic acid methyl ester, 4- (tetrahydro-furan-3-yl) -butyric acid ethyl ester, 5- (tetrahydro-furan-3 -Yl) -pentanoic acid ethyl ester, 6- (tetrahydro-furan-3-yl) -hexanoic acid ethyl ester, 4- (tetrahydro-furan-3-yl) -butyric acid propyl ester, tetrahydro-furan-3 Carr Real acid propyl ester, tetrahydro-furan-3-carboxylic acid butyl ester, 3- (tetrahydro-furan-2-yl) -propionic acid methyl ester, 4- (tetrahydro-furan-2-yl) -butyric acid ethyl ester , 5- (tetrahydro-furan-2-yl) -pentanoic acid ethyl ester, 6- (tetrahydro-furan-2-yl) -hexanoic acid ethyl ester, 4- (tetrahydro-furan-2-yl)- Butyric acid propyl ester, tetrahydro-furan-2-carboxylic acid 2-ethyl-hexyl ester, cyclohexyl-acetic acid ethyl ester, 3-cyclohexyl-propionic acid methyl ester, 4-cyclohexyl-butyric acid ethyl ester, 5-cyclohexyl -Pentanoic acid ethyl ester, 6-cyclohexyl-hexanoic acid ethyl ester, 4-cyclohexyl-butyric acid propyl ester, cyclohexanecarboxylic acid propyl ester, cyclohexanecarboxylic acid hexyl ester, Clohexyl-acetic acid allyl ester, 3- (tetrahydro-pyran-2-yl) -propionic acid methyl ester, 4- (tetrahydro-pyran-2-yl) -butyric acid ethyl ester, 5- (tetrahydro-pyran-2 -Yl) -pentanoic acid ethyl ester, 6- (tetrahydro-pyran-2-yl) -hexanoic acid ethyl ester, 4- (tetrahydro-pyran-2-yl) -butyric acid propyl ester, tetrahydro-pyran-2 -Carboxylic acid propyl ester, tetrahydro-pyran-2-carboxylic acid butyl ester, 3- (tetrahydro-pyran-3-yl) -propionic acid methyl ester, 4- (tetrahydro-pyran-3-yl)- Butyric acid ethyl ester, 5- (tetrahydro-pyran-2-yl) -pentanoic acid ethyl ester, 6- (tetrahydro-pyran-3-yl) -hexanoic acid ethyl ester, 4- (tetrahydro-pyran-3- Yl) -butyric acid propyl ester, tetrahydro-pyran-3-carboxylic acid isobutyl ester , Tetrahydro-pyran-3-carboxylic acid pentyl ester, 3- (tetrahydro-pyran-4-yl) -propionic acid methyl ester, 4- (tetrahydro-pyran-4-yl) -butyric acid ethyl ester, 5- (Tetrahydro-pyran-4-yl) -pentanoic acid ethyl ester, 6- (tetrahydro-pyran-4-yl) -hexanoic acid ethyl ester, 4- (tetrahydro-pyran-4-yl) -butyric acid propyl ester And at least one quantum dot dispersion selected from the group consisting of tetrahydro-pyran-4-carboxylic acid butyl ester and tetrahydro-pyran-4-carboxylic acid propyl ester.
  5. 제2항에 있어서, 상기 화학식 2로 표시되는 화합물은 아세트산 벤질 에스테르, 프로피온산 페네틸 에스테르, 프로피온산 3-페닐-프로필 에스테르, 프로피온산 4-페닐-부틸 에스테르, 부티르산 페네틸 에스테르, 프로피온산 2-(4-클로로-페닐)-에틸 에스테르, 프로피온산 2-(3,4-디클로로-페닐)-에틸 에스테르, 아세트산 사이클로펜타-1,3-디에닐메틸 에스테르, 프로피온산 2-사이클로펜타-1,3-디에닐-에틸 에스테르, 프로피온산 3-사이클로펜타-1,3-디에닐-프로필 에스테르, 프로피온산 4-사이클로펜타-1,3-디에닐-부틸 에스테르, 부티르산 2-사이클로펜타-1,3-디에닐-에틸 에스테르, 아세트산 퓨란-2-일메틸 에스테르, 프로피온산 2-퓨란-2-일-에틸 에스테르, 프로피온산 3-퓨란-2-일-프로필 에스테르, 프로피온산 4-퓨란-2-일-부틸 에스테르, 부티르산 2-퓨란-2-일-에틸 에스테르, 아세트산 사이클로펜틸메틸 에스테르, 프로피온산 2-사이클로펜틸-에틸 에스테르, 프로피온산 3-사이클로펜틸-프로필 에스테르, 프로피온산 4-사이클로펜틸-부틸 에스테르, 부티르산 2-사이클로펜틸-에틸 에스테르, 아세트산 테트라하이드로-퓨란-3-일메틸 에스테르, 프로피온산 2-(테트라하이드로-퓨란-3-일)-에틸 에스테르, 프로피온산 3-(테트라하이드로-퓨란-3-일)-프로필 에스테르, 프로피온산 4-(테트라하이드로-퓨란-3-일)-부틸 에스테르, 부티르산 2-(테트라하이드로-퓨란-3-일)-에틸 에스테르, 아세트산 테트라하이드로-퓨란-2-일메틸 에스테르, 프로피온산 2-(테트라하이드로-퓨란-2-일)-에틸 에스테르, 프로피온산 3-(테트라하이드로-퓨란-2-일)-프로필 에스테르, 프로피온산 4-(테트라하이드로-퓨란-2-일)-부틸 에스테르, 부티르산 2-(테트라하이드로-퓨란-2-일)-에틸 에스테르, 아세트산 사이클로헥실메틸 에스테르, 프로피온산 2-사이클로헥실-에틸 에스테르, 프로피온산 3-사이클로헥실-프로필 에스테르, 프로피온산 4-사이클로헥실-부틸 에스테르, 부티르산 2-사이클로헥실-에틸 에스테르, 부트-3-에노산 사이클로헥실메틸 에스테르, 아세트산 테트라하이드로-피란-2-일메틸 에스테르, 프로피온산 2-(테트라하이드로-피란-2-일)-에틸 에스테르, 프로피온산 3-(테트라하이드로-피란-2-일)-프로필 에스테르, 프로피온산 4-(테트라하이드로-피란-2-일)-부틸 에스테르, 부티르산 2-(테트라하이드로-피란-2-일)-에틸 에스테르, 아세트산 테트라하이드로-피란-3-일메틸 에스테르, 프로피온산 2-(테트라하이드로-피란-3-일)-에틸 에스테르, 프로피온산 3-(테트라하이드로-피란-2-일)-프로필 에스테르, 프로피온산 4-(테트라하이드로-피란-3-일)-부틸 에스테르, 부티르산 2-(테트라하이드로-피란-3-일)-에틸 에스테르, 아세트산 테트라하이드로-피란-4-일메틸 에스테르, 프로피온산 2-(테트라하이드로-피란-4-일)-에틸 에스테르, 프로피온산 3-(테트라하이드로-피란-4-일)-프로필 에스테르, 프로피온산 4-(테트라하이드로-피란-4-일)-부틸 에스테르 및 부티르산 2-(테트라하이드로-피란-4-일)-에틸 에스테르로 구성된 군으로부터 선택되는 1종 이상인 양자점 분산액.The compound represented by the formula (2) is acetic acid benzyl ester, propionic acid phenethyl ester, propionic acid 3-phenyl-propyl ester, propionic acid 4-phenyl-butyl ester, butyric acid phenethyl ester, propionic acid 2- (4- Chloro-phenyl) -ethyl ester, propionic acid 2- (3,4-dichloro-phenyl) -ethyl ester, acetic acid cyclopenta-1,3-dienylmethyl ester, propionic acid 2-cyclopenta-1,3-dienyl- Ethyl ester, propionic acid 3-cyclopenta-1,3-dienyl-propyl ester, propionic acid 4-cyclopenta-1,3-dienyl-butyl ester, butyric acid 2-cyclopenta-1,3-dienyl-ethyl ester , Furan-2-ylmethyl ester, propionic acid 2-furan-2-yl-ethyl ester, propionic acid 3-furan-2-yl-propyl ester, propionic acid 4-furan-2-yl-butyl ester, butyric acid 2-furan 2-yl-ethyl on Tereacetic acid cyclopentylmethyl ester, propionic acid 2-cyclopentyl-ethyl ester, propionic acid 3-cyclopentyl-propyl ester, propionic acid 4-cyclopentyl-butyl ester, butyric acid 2-cyclopentyl-ethyl ester, acetic acid tetrahydro-furan- 3-ylmethyl ester, propionic acid 2- (tetrahydro-furan-3-yl) -ethyl ester, propionic acid 3- (tetrahydro-furan-3-yl) -propyl ester, propionic acid 4- (tetrahydro-furan-3 -Yl) -butyl ester, butyric acid 2- (tetrahydro-furan-3-yl) -ethyl ester, acetic acid tetrahydro-furan-2-ylmethyl ester, propionic acid 2- (tetrahydro-furan-2-yl)- Ethyl ester, propionic acid 3- (tetrahydro-furan-2-yl) -propyl ester, propionic acid 4- (tetrahydro-furan-2-yl) -butyl ester, butyric acid 2- (tetrahydro -Furan-2-yl) -ethyl ester, acetic acid cyclohexylmethyl ester, propionic acid 2-cyclohexyl-ethyl ester, propionic acid 3-cyclohexyl-propyl ester, propionic acid 4-cyclohexyl-butyl ester, butyric acid 2-cyclohexyl- Ethyl ester, but-3-enoic acid cyclohexylmethyl ester, acetic acid tetrahydro-pyran-2-ylmethyl ester, propionic acid 2- (tetrahydro-pyran-2-yl) -ethyl ester, propionic acid 3- (tetrahydro- Pyran-2-yl) -propyl ester, propionic acid 4- (tetrahydro-pyran-2-yl) -butyl ester, butyric acid 2- (tetrahydro-pyran-2-yl) -ethyl ester, acetic acid tetrahydro-pyran- 3-ylmethyl ester, propionic acid 2- (tetrahydro-pyran-3-yl) -ethyl ester, propionic acid 3- (tetrahydro-pyran-2-yl) -propyl ester, propionic acid 4- (tet Hydro-pyran-3-yl) -butyl ester, butyric acid 2- (tetrahydro-pyran-3-yl) -ethyl ester, acetic acid tetrahydro-pyran-4-ylmethyl ester, propionic acid 2- (tetrahydro-pyran- 4-yl) -ethyl ester, propionic acid 3- (tetrahydro-pyran-4-yl) -propyl ester, propionic acid 4- (tetrahydro-pyran-4-yl) -butyl ester and butyric acid 2- (tetrahydro-pyran At least one quantum dot dispersion selected from the group consisting of -4-yl) -ethyl ester.
  6. 제1항에 있어서, 상기 용제는 유전상수가 20℃에서 12.0 미만인 양자점 분산액.The quantum dot dispersion of claim 1, wherein the solvent has a dielectric constant of less than 12.0 at 20 ° C.
  7. 제1항에 있어서, 분산제를 더 포함하는 양자점 분산액.The quantum dot dispersion of claim 1, further comprising a dispersant.
  8. 제1항 내지 제7항 중 어느 한 항에 따른 양자점 분산액, 알칼리 가용성 수지, 광중합성 화합물 및 광중합 개시제를 포함하는 자발광 감광성 수지 조성물.The self-luminous photosensitive resin composition containing the quantum dot dispersion liquid, alkali-soluble resin, a photopolymerizable compound, and a photoinitiator of any one of Claims 1-7.
  9. 제8항에 따른 자발광 감광성 수지 조성물을 이용하여 형성되는 컬러필터.The color filter formed using the self-luminous photosensitive resin composition of Claim 8.
  10. 제9항에 따른 컬러필터가 구비된 것을 특징으로 하는 화상표시장치.An image display apparatus comprising a color filter according to claim 9.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020166131A (en) * 2019-03-29 2020-10-08 山陽色素株式会社 Quantum dot dispersion and composition for coating film formation including quantum dot dispersion

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102153965B1 (en) * 2019-02-28 2020-09-09 동우 화인켐 주식회사 Light Conversion Ink Composition, Color Filter and Display Device
EP3763801B1 (en) 2019-07-12 2022-05-04 Samsung Display Co., Ltd. Quantum dot-containing material, method of preparing the same, and optical member and appapratus including the quantum dot-containing material
KR102609622B1 (en) * 2019-10-14 2023-12-01 삼성에스디아이 주식회사 Quantum dot, curable composition comprising the same, cured layer using the composition and color filter including the cured layer
WO2022153443A1 (en) * 2021-01-14 2022-07-21 シャープ株式会社 Method for manufacturing quantum dot dispersion, quantum dot dispersion, and light-emitting device
JP2023152725A (en) * 2022-03-31 2023-10-17 住友化学株式会社 Composition, membrane and display device
JP2023152726A (en) * 2022-03-31 2023-10-17 住友化学株式会社 Composition, membrane and display device

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110128264A (en) * 2011-11-15 2011-11-29 삼성에스디아이 주식회사 Metal oxide paste composition and preparaton method of a semiconductor electrode using the same
JP2014077046A (en) * 2012-10-10 2014-05-01 Konica Minolta Inc Ink composition for forming light-emitting layer, method for preparing light-emitting device and electroluminescence device
KR20160000915A (en) * 2014-06-25 2016-01-06 엘지디스플레이 주식회사 Display device
US20160011506A1 (en) * 2013-12-30 2016-01-14 Boe Technology Group Co., Ltd. Photosensitive resin composition and method for forming quantum dot pattern using the same
KR20160111142A (en) * 2015-03-16 2016-09-26 엘지전자 주식회사 Method for mamufactuing quantum dot-resin complex, quantum dot-resin complex, light conversion film, backlight unit and display device comprising the same

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0915859A (en) * 1995-06-30 1997-01-17 Hitachi Chem Co Ltd Colored image forming photoensitive solution, manufacture of color filter using it, and color filter
KR100678285B1 (en) 2005-01-20 2007-02-02 삼성전자주식회사 Quantum Dot Phosphor for Light Emitting Diode and Method of Preparing Thereof
JP2008111985A (en) 2006-10-30 2008-05-15 Sekisui Chem Co Ltd Spacer particle dispersion liquid and liquid crystal display device
JP4959411B2 (en) 2007-04-27 2012-06-20 富士フイルム株式会社 Colored photopolymerizable composition, color filter using the same, and method for producing color filter
JP2010009995A (en) * 2008-06-27 2010-01-14 Seiko Epson Corp Discharge liquid, discharge liquid set, thin film pattern forming method, thin film, light emitting element, image display device, and electronic equipment
US10358569B2 (en) 2013-03-15 2019-07-23 South Dakota Board Of Regents Systems and methods for printing patterns using near infrared upconverting inks
JP6171923B2 (en) 2013-12-24 2017-08-02 Jsr株式会社 Curable resin composition, cured film, light emitting element, wavelength conversion film, and method for forming light emitting layer
KR101879016B1 (en) * 2014-11-21 2018-07-16 동우 화인켐 주식회사 Self emission type photosensitive resin composition, color filter manufactured using thereof and image display device having the same
WO2016098570A1 (en) * 2014-12-15 2016-06-23 Jsr株式会社 Organic el element, curable resin composition, method for forming wavelength conversion unit, and organic el device
KR101878421B1 (en) * 2015-07-07 2018-07-13 동우 화인켐 주식회사 Quantum dot dispersion, self emission type photosensitive resin composition comprising the same, color filter and image display device manufactured using the same
CN105062218A (en) * 2015-08-21 2015-11-18 Tcl集团股份有限公司 Quantum dot printing ink for ink-jet printing and preparation method thereof
CN105907179A (en) * 2016-04-26 2016-08-31 Tcl集团股份有限公司 Quantum dot printing oil and preparation method thereof
KR102028968B1 (en) 2016-10-20 2019-10-07 동우 화인켐 주식회사 Quantum dot dispersion, self emission type photosensitive resin composition comprising the same, color filter and image display device produced using the same
KR102028969B1 (en) 2016-11-15 2019-10-07 동우 화인켐 주식회사 Quantum dot dispersion, self emission type photosensitive resin composition, color filter manufactured using thereof and image display device having the same
JP6856367B2 (en) 2016-11-30 2021-04-07 東京応化工業株式会社 A method for forming a photosensitive composition, a cured film, a light emitting layer for a light emitting display element, a light emitting display element, and a light emitting layer.
JP7152854B2 (en) * 2016-12-28 2022-10-13 東京応化工業株式会社 Silicon-containing resin composition, silicon-containing resin film, silica film, light-emitting display element panel, and light-emitting display device
CN106654068B (en) 2017-01-20 2018-10-02 京东方科技集团股份有限公司 A kind of production method and related device of organic electroluminescence device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110128264A (en) * 2011-11-15 2011-11-29 삼성에스디아이 주식회사 Metal oxide paste composition and preparaton method of a semiconductor electrode using the same
JP2014077046A (en) * 2012-10-10 2014-05-01 Konica Minolta Inc Ink composition for forming light-emitting layer, method for preparing light-emitting device and electroluminescence device
US20160011506A1 (en) * 2013-12-30 2016-01-14 Boe Technology Group Co., Ltd. Photosensitive resin composition and method for forming quantum dot pattern using the same
KR20160000915A (en) * 2014-06-25 2016-01-06 엘지디스플레이 주식회사 Display device
KR20160111142A (en) * 2015-03-16 2016-09-26 엘지전자 주식회사 Method for mamufactuing quantum dot-resin complex, quantum dot-resin complex, light conversion film, backlight unit and display device comprising the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020166131A (en) * 2019-03-29 2020-10-08 山陽色素株式会社 Quantum dot dispersion and composition for coating film formation including quantum dot dispersion

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