WO2021080162A1 - Solvent-free curable composition, cured film produced using composition, and colour filter and display device comrising cured film - Google Patents
Solvent-free curable composition, cured film produced using composition, and colour filter and display device comrising cured film Download PDFInfo
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- WO2021080162A1 WO2021080162A1 PCT/KR2020/011809 KR2020011809W WO2021080162A1 WO 2021080162 A1 WO2021080162 A1 WO 2021080162A1 KR 2020011809 W KR2020011809 W KR 2020011809W WO 2021080162 A1 WO2021080162 A1 WO 2021080162A1
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- curable composition
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Images
Classifications
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
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- C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- 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
- G02F1/015—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 semiconductor elements having potential barriers, e.g. having a PN or PIN junction
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- G02F1/015—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 semiconductor elements having potential barriers, e.g. having a PN or PIN junction
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- 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
- 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
- G02F1/1336—Illuminating devices
- G02F1/133617—Illumination with ultraviolet light; Luminescent elements or materials associated to the cell
-
- 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
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
Definitions
- the present description relates to a solvent-free curable composition, a cured film prepared by using the composition, and a color filter including the cured film.
- the quantum dot ink is a solvent-free type that does not contain a solvent is the most preferable form to be applied to the actual process, the current technology of applying the quantum dot itself to the solvent-type composition is now evaluated to have reached a certain limit.
- quantum dots that are not surface-modified such as ligand substitution
- quantum dots that are not surface-modified such as ligand substitution
- a method of lowering the quantum dot content and increasing the content of the light diffusing agent (scattering body) has been attempted as another improvement direction, but this also fails to improve the sedimentation problem or the low light efficiency problem.
- One embodiment is to provide a solvent-free curable composition comprising quantum dots surface-modified with a compound having a polar portion and a non-polar portion at the same time.
- Another embodiment is to provide a cured film prepared using the solvent-free curable composition.
- Another embodiment is to provide a color filter including the cured film.
- One embodiment provides a solvent-free curable composition
- a solvent-free curable composition comprising a surface-modified quantum dot with a compound represented by the following Formula 1 and a polymerizable monomer having a carbon-carbon double bond at the terminal.
- L 1 , L 3 and L 5 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group or a substituted Or an unsubstituted C2 to C20 heteroarylene group,
- R 1 is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,
- n is an integer from 6 to 15,
- n is an integer from 1 to 10.
- Formula 1 may be represented by any one of Formulas 1-1 to 1-3 below.
- L 1 , L 3 and L 5 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group or a substituted Or an unsubstituted C2 to C20 heteroarylene group,
- R 1 and R 2 are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,
- n is an integer from 6 to 15,
- n 1 to 10
- p 0 to 4.
- Formula 1 may be represented by any one of Formulas 2 to 5 below.
- the quantum dots may have a maximum fluorescence emission wavelength in 500 nm to 680 nm.
- the polymerizable monomer may have a molecular weight of 220 g/mol to 1,000 g/mol.
- the polymerizable monomer may be represented by the following formula (6).
- R 3 and R 4 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group
- L 6 and L 8 are each independently a substituted or unsubstituted C1 to C10 alkylene group
- L 7 is a substituted or unsubstituted C1 to C10 alkylene group or an ether group (*-O-*).
- the solvent-free curable composition may include 1% to 60% by weight of the quantum dots and 40% to 99% by weight of the polymerizable monomer.
- the solvent-free curable composition may further include a polymerization initiator, a light diffusing agent, or a combination thereof.
- the light diffusing agent may include barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.
- the solvent-free curable composition may include a polymerization inhibitor; Malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine-based surfactant; Or it may further include a combination of these.
- Another embodiment provides a cured film prepared using the solvent-free curable composition.
- the cured film may have an emission wavelength of 540 nm or less.
- Another embodiment provides a color filter including the cured film.
- Another embodiment provides a display device including the color filter.
- One embodiment provides a solvent-free curable composition
- a solvent-free curable composition comprising quantum dots surface-modified with a compound having a polar portion and a non-polar portion at the same time, the surface-modifying compound by helping to form a constant gap between the quantum dots, the solvent-free curable composition It is possible to realize high color reproducibility by lowering the emission wavelength of the cured film prepared using the cured film, and at the same time, it is possible to prevent deterioration of physical properties such as light resistance and heat resistance of the cured film.
- 1 is a figure in which quantum dots surface-modified with a compound having a polar part and a non-polar part simultaneously exist in a monodisperse form in a solvent-free curable composition, and a quantum dot surface-modified with a compound having only a polar part in an aggregate form in a solvent-free curable composition. It is a drawing comparing existing pictures.
- alkyl group refers to a C1 to C20 alkyl group
- alkenyl group refers to a C2 to C20 alkenyl group
- cycloalkenyl group refers to a C3 to C20 cycloalkenyl group
- Heterocycloalkenyl group refers to a C3 to C20 heterocycloalkenyl group
- aryl group refers to a C6 to C20 aryl group
- arylalkyl group refers to a C6 to C20 arylalkyl group
- alkylene group Refers to a C1 to C20 alkylene group
- arylene group refers to a C6 to C20 arylene group
- alkylarylene group refers to a C6 to C20 alkylarylene group
- heteroarylene group refers to a C3 to C20 hetero It means an arylene group
- alkoxyl group means a C1 to C20 alkoxyl group.
- substituted means that at least one hydrogen atom is a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, Azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, ether group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C1 To C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C20 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocycloalkyl
- F, Cl, Br, I halogen
- hetero means that at least one hetero atom of at least one of N, O, S, and P is included in the formula.
- (meth)acrylate means that both “acrylate” and “methacrylate” are possible
- (meth)acrylic acid refers to “acrylic acid” and “methacrylic acid. “It means both are possible.
- the coated quantum dot single film (cured film obtained by curing the quantum dot curable composition) must have a light emission wavelength range of a range capable of achieving high color reproduction at a certain thickness, that is, a light emission wavelength (short wavelength) range of 540 nm or less.
- the emission wavelength of the quantum dot monolayer tends to have a long wavelength, and the shorter the emission wavelength of the quantum dot monolayer, the higher the blue light conversion rate and higher heat resistance, and the longer the wavelength, the lower the light conversion rate and the poorer heat resistance.
- the conventional quantum dot single film has a luminous wavelength in a long wavelength region, and thus high color reproducibility has not been achieved.
- the surface is modified to change the emission wavelength of the quantum dot to a short wavelength, so that the cured film emits light in the short wavelength region. It provides a solvent-free curable composition capable of maintaining excellent properties such as heat resistance and light resistance while realizing high color reproducibility by having a wavelength.
- the solvent-free curable composition according to an embodiment is surface-modified with a compound represented by Formula 1 below.
- L 1 , L 3 and L 5 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group or a substituted Or an unsubstituted C2 to C20 heteroarylene group,
- R 1 is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,
- n is an integer from 6 to 15,
- n is an integer from 1 to 10.
- the dispersibility of quantum dots and the degree of aggregation in the overall composition of the composition can be improved (see FIG. 1).
- the above-described problem can be improved by using the compound represented by Formula 1 as a surface-modifying material for quantum dots. have.
- the quantum dot surface-modified with the compound represented by Formula 1 has a high affinity with a ligand having a polar group, that is, a polymerizable monomer having a carbon-carbon double bond at the end, making it very easy to prepare a high concentration or highly concentrated quantum dot dispersion. (Improvement of dispersibility of quantum dots in a monomer), it can have a very positive effect on the realization of a solvent-free curable composition and improvement of light efficiency.
- the solvent-free curable composition includes a quantum dot surface-modified with the compound represented by Formula 1 and a polymerizable monomer having a carbon-carbon double bond at an end thereof.
- a highly hydrophobic alkyl chain is introduced in the structure adjacent to the thiol group, and an alkylene glycol chain having strong hydrophilicity is introduced at the opposite end, so that the compound represented by Formula 1 is generally amphiphilic.
- Quantum dots which are amphiphilic and used in monolayers that exhibit a luminous wavelength at a long wavelength, can also reduce the luminous wavelength and improve heat resistance by surface modification.
- n is an integer of 5 or less, it is difficult to lower the emission wavelength of the cured film containing quantum dots, making it difficult to implement high color reproducibility, and when n is an integer of 16 or more, the viscosity of the composition is too low, which may be disadvantageous for ink-jetting. In addition, it may be disadvantageous in terms of heat resistance and the like.
- Formula 1 may be represented by any one of Formulas 1-1 to 1-3 below.
- L 1 , L 3 and L 5 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group or a substituted Or an unsubstituted C2 to C20 heteroarylene group,
- R 1 and R 2 are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,
- n is an integer from 6 to 15,
- n 1 to 10
- p 0 to 4.
- n may be an integer of 6 to 11.
- R 1 may be represented by any one of Formulas R-1 to R-4, but is not limited thereto.
- Formula 1 may be represented by any one of Formulas 2 to 5 below.
- the curable composition (ink) containing quantum dots to date has been developed to specialize monomers having good compatibility with quantum dots, and furthermore, commercialization is being made.
- -ene-based monomers (vinyl-based monomers, acrylate-based monomers, methacrylate-based monomers, etc., and including monofunctional to polyfunctional), which are general and universally used polymerizable monomers, are used as quantum dots and It is true that it is difficult to develop a variety of applications for useful application to a curable composition containing quantum dots due to its low compatibility and limitations in the dispersibility of quantum dots. Above all, since the -ene-based monomer does not exhibit high-concentration quantum dot dispersibility, it is difficult to apply it to a curable composition containing quantum dots.
- the curable composition containing quantum dots has been developed as a composition containing a significant amount (50% by weight or more) of a solvent, but there is a problem in that ink jetting fairness is deteriorated when the solvent content is increased. Therefore, in order to satisfy ink jetting fairness, the demand for a solvent-free curable composition is increasing.
- the present application provides a solvent-free curable composition that is increasingly in demand, and by using a polymerizable monomer including a compound having a carbon-carbon double bond at the terminal together with a quantum dot surface-modified with a compound represented by Formula 1,
- a polymerizable monomer including a compound having a carbon-carbon double bond at the terminal together with a quantum dot surface-modified with a compound represented by Formula 1,
- By improving the affinity of the quantum dots to the curable composition it is possible to provide high-concentration dispersibility of the quantum dots even in a solvent-free system, while achieving a passivation effect that does not impair the natural optical properties of the quantum dots. .
- Quantum dots included in the solvent-free curable composition are quantum dots surface-modified with the compound represented by Formula 1.
- the quantum dot absorbs light in a wavelength region of 360 nm to 780 nm, such as 400 nm to 780 nm, and emits fluorescence in a wavelength region of 500 nm to 700 nm, such as 500 nm to 580 nm, or emits fluorescence at 600 nm to 680 nm.
- the quantum dot may have a maximum fluorescence emission wavelength (fluorescence ⁇ em ) at 500 nm to 680 nm.
- Each of the quantum dots may independently have a full width at half maximum (FWHM) of 20 nm to 100 nm, for example, 20 nm to 50 nm.
- FWHM full width at half maximum
- the quantum dots may each independently be an organic material, an inorganic material, or a hybrid (mixture) of an organic material and an inorganic material.
- the quantum dots may each independently consist of a core and a shell surrounding the core, and the core and shell are each independently a core, a core/shell, a core/first shell/ It may have a structure such as a second shell, an alloy, and an alloy/shell, but is not limited thereto.
- the core may include at least one material selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, and alloys thereof. , Is not necessarily limited thereto.
- the shell surrounding the core may include at least one material selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but is not limited thereto.
- the quantum yield is somewhat low, but environmentally friendly.
- a non-cadmium-based light emitting material InP/ZnS, InP/ZnSe/ZnS, etc. was used, it is not necessarily limited thereto.
- the size (average particle diameter) of each of the entire quantum dots including the shell may be 1 nm to 15 nm, for example, 5 nm to 15 nm.
- the quantum dots may each independently include red quantum dots, green quantum dots, or a combination thereof.
- Each of the red quantum dots may independently have an average particle diameter of 10 nm to 15 nm.
- Each of the green quantum dots may independently have an average particle diameter of 5 nm to 8 nm.
- the solvent-free curable composition according to an embodiment may further include a dispersant.
- the dispersant helps to uniformly disperse a light conversion material such as a quantum dot in a solvent-free curable composition, and nonionic, anionic, or cationic dispersants may be used.
- polyalkylene glycol or esters thereof polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid salt, alkyl amide alkylene oxide Adducts, alkyl amines, and the like may be used, and these may be used alone or in combination of two or more.
- the dispersant may be used in an amount of 0.1% to 100% by weight, such as 10% to 20% by weight, based on the solid content of a photo-conversion material such as a quantum dot.
- the quantum dots surface-modified by Formula 1 may be included in an amount of 1% to 60% by weight, such as 3% to 50% by weight, based on the total amount of the solvent-free curable composition.
- a light conversion rate is excellent and pattern characteristics and development characteristics are not impaired, so that excellent fairness may be obtained.
- the monomer having a carbon-carbon double bond at the terminal may be included in an amount of 40% to 99% by weight, such as 50% to 97% by weight, based on the total amount of the solvent-free curable composition. It is possible to prepare a solvent-free curable composition having a viscosity capable of ink jetting only when the content of the monomer having a carbon-carbon double bond at the terminal is within the above range, and also have excellent dispersibility in the prepared solvent-free curable composition. So that the optical properties can also be improved.
- a monomer having a carbon-carbon double bond at the terminal may have a molecular weight of 220 g/mol to 1,000 g/mol.
- the molecular weight of the monomer having a carbon-carbon double bond at the terminal is within the above range, the viscosity of the composition is not increased without impairing the optical properties of the quantum dots, which may be advantageous for ink-jetting.
- a monomer having a carbon-carbon double bond at the terminal may be represented by the following Formula 6, but is not limited thereto.
- R 3 and R 4 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group
- L 6 and L 8 are each independently a substituted or unsubstituted C1 to C10 alkylene group
- L 7 is a substituted or unsubstituted C1 to C10 alkylene group or an ether group (*-O-*).
- a monomer having a carbon-carbon double bond at the terminal may be represented by Formula 6-1 or 6-2, but is not limited thereto.
- the monomer having a carbon-carbon double bond at the terminal is, in addition to the compound represented by Formula 6-1 or Formula 6-2, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylic Rate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, di Pentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol Dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hex
- a monomer generally used in a conventional thermosetting or photocurable composition may be further included.
- the monomer is bis[1-ethyl(3-oxetanyl). )] may further include oxetane-based compounds such as methyl ether.
- the solvent-free curable composition according to an embodiment may further include a polymerization initiator, for example, a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.
- a polymerization initiator for example, a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.
- the photopolymerization initiator is an initiator generally used in the photosensitive resin composition, for example, acetophenone-based compound, benzophenone-based compound, thioxanthone-based compound, benzoin-based compound, triazine-based compound, oxime-based compound, aminoketone-based compound Such as may be used, but is not necessarily limited thereto.
- acetophenone-based compound examples include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloro acetophenone, pt-butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like.
- benzophenone-based compound examples include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4 '-Bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.
- thioxanthone compound examples include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- And chlorothioxanthone.
- benzoin-based compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyldimethylketal.
- triazine-based compound examples include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4' -Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine , 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)- 4,6-bis(trichlor
- Examples of the oxime-based compound include O-acyloxime-based compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime) -1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl- ⁇ -oxyamino-1-phenylpropan-1-one, etc. Can be used.
- O-acyloxime-based compound examples include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane- 1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione -2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-oneoxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime- O-acetate, etc. are mentioned.
- aminoketone-based compound examples include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone -1) etc. are mentioned.
- the photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, or a biimidazole compound.
- the photopolymerization initiator may be used together with a photosensitizer that causes a chemical reaction by absorbing light and becoming excited and then transferring the energy.
- photosensitizer examples include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, etc. Can be mentioned.
- thermal polymerization initiator examples include peroxide, specifically benzoyl peroxide, dibenzoyl peroxide, lauryl peroxide, dilauryl peroxide, di-tert-butyl peroxide, cyclohexane peroxide, methyl ethyl ketone peroxide.
- Oxide, hydroperoxide (e.g., tert-butyl hydroperoxide, cumene hydroperoxide), dicyclohexyl peroxydicarbonate, 2,2-azo-bis (isobutyronitrile), t-butyl perbenzo Eight, etc. may be mentioned, and 2,2'-azobis-2-methylpropionitrile, etc. may be mentioned, but the present invention is not limited thereto, and any one may be used as long as it is widely known in the art.
- the polymerization initiator may be included in an amount of 0.1% to 5% by weight, such as 1% to 4% by weight, based on the total amount of the solvent-free curable composition.
- the polymerization initiator is included within the above range, curing occurs sufficiently during exposure or thermal curing to obtain excellent reliability, and decreases in transmittance due to an unreacted initiator may be prevented, thereby preventing a decrease in optical properties of quantum dots.
- Light diffusing agent or light diffusing agent dispersion
- the solvent-free curable composition according to an embodiment may further include a light diffusing agent.
- the light diffusing agent may include barium sulfate (BaSO 4 ), calcium carbonate (CaCO 3 ), titanium dioxide (TiO 2 ), zirconia (ZrO 2 ), or a combination thereof.
- the light diffusing agent reflects light not absorbed by the above-described quantum dots, and allows the reflected light to be absorbed again. That is, the light diffusing agent may increase the amount of light absorbed by the quantum dots, thereby increasing the light conversion efficiency of the curable composition.
- the light diffusing agent may have an average particle diameter (D 50 ) of 150 nm to 250 nm, and specifically 180 nm to 230 nm.
- D 50 average particle diameter
- the light diffusing agent may be included in an amount of 1% to 20% by weight, such as 5% to 10% by weight, based on the total amount of the solvent-free curable composition.
- the light diffusing agent is included in an amount of less than 1% by weight based on the total amount of the solvent-free curable composition, it is difficult to expect the effect of improving the light conversion efficiency by using the light diffusing agent, and when it is included in more than 20% by weight, quantum dot sedimentation There is a risk of a problem occurring.
- the solvent-free curable composition according to an embodiment may further include a polymerization inhibitor.
- the polymerization inhibitor may include a hydroquinone compound, a catechol compound, or a combination thereof, but is not limited thereto.
- the solvent-free curable composition according to the embodiment further includes the hydroquinone-based compound, the catechol-based compound, or a combination thereof, after printing (coating) the solvent-free curable composition, it is possible to prevent crosslinking at room temperature during exposure. .
- the hydroquinone-based compound, the catechol-based compound, or a combination thereof is hydroquinone, methyl hydroquinone, methoxyhydroquinone, t-butyl hydroquinone, 2,5-di- t -butyl hydroquinone, 2,5- Bis(1,1-dimethylbutyl) hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl) hydroquinone, catechol, t-butyl catechol, 4-methoxyphenol, pyroga Roll, 2,6-di- t -butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitrosophenylaminato-O,O') aluminum (Tris(N-hydroxy-N -nitrosophenylaminato-O,O')aluminium) or a combination thereof, but is not limited thereto.
- the hydroquinone-based compound, catechol-based compound, or a combination thereof may be used in the form of a dispersion, and the polymerization inhibitor in the dispersion form is 0.001% by weight to 3% by weight, such as 0.1% by weight, based on the total amount of the solvent-free curable composition. It may be included in 2% by weight.
- the polymerization inhibitor is included within the above range, it is possible to solve the problem of room temperature aging and prevent sensitivity reduction and surface peeling.
- a solvent-free curable composition may include malonic acid for improving heat resistance and reliability; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine-based surfactant; Or it may further include a combination of these.
- the solvent-free curable composition according to an embodiment may further include a silane-based coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group to improve adhesion to the substrate.
- a silane-based coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group to improve adhesion to the substrate.
- silane coupling agent examples include trimethoxysilyl benzoic acid, ⁇ methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, ⁇ isocyanate propyl triethoxysilane, ⁇ glycidoxy propyl Trimethoxysilane, ⁇ epoxycyclohexyl)ethyltrimethoxysilane, and the like, and these may be used alone or in combination of two or more.
- the silane-based coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the solvent-free curable composition. When the silane-based coupling agent is included within the above range, adhesion and storage properties are excellent.
- the solvent-free curable composition may further include a surfactant, such as a fluorine-based surfactant, to improve coating properties and prevent defects, that is, to improve leveling performance, if necessary.
- a surfactant such as a fluorine-based surfactant
- the fluorine-based surfactant may have a low weight average molecular weight of 4,000 g/mol to 10,000 g/mol, and specifically, may have a weight average molecular weight of 6,000 g/mol to 10,000 g/mol.
- the fluorine-based surfactant may have a surface tension of 18 mN/m to 23 mN/m (measured in a 0.1% propylene glycol monomethyl ether acetate (PGMEA) solution).
- PMEA propylene glycol monomethyl ether acetate
- the fluorine is a surfactant, the BM Chemie ⁇ BM-1000 ®, BM-1100 ® , and the like; Mecha Pack F 142D ® , F 172 ® , F 173 ® , F 183 ®, etc. of Dai Nippon Inki Chemical High School Co., Ltd.; Sumitomo M.
- the solvent-free curable composition according to an embodiment may use a silicone-based surfactant together with the above-described fluorine-based surfactant.
- a silicone-based surfactant include TSF400, TSF401, TSF410, TSF4440 manufactured by Toshiba Silicone, but are not limited thereto.
- Surfactants including the fluorine-based surfactant and the like may be included in an amount of 0.01 parts by weight to 5 parts by weight, for example, 0.1 parts by weight to 2 parts by weight, based on 100 parts by weight of the solvent-free curable composition.
- the surfactant is included within the above range, the phenomenon that foreign substances are generated in the sprayed composition is reduced.
- a certain amount of other additives such as antioxidants may be further added within a range that does not impair physical properties.
- Another embodiment provides a cured film prepared using the above-described solvent-free curable composition.
- the cured film is prepared by curing the solvent-free curable composition according to an embodiment, it may have a luminous wavelength of 540 nm or less, thereby ultimately realizing high color reproducibility and maintaining excellent physical properties such as heat resistance and light resistance. have.
- One of the manufacturing methods of the cured film may include forming a pattern by applying the above-described solvent-free curable composition on a substrate by an ink jet spraying method (S1); And curing the pattern (S2).
- the solvent-free curable composition is applied on a substrate in a thickness of 0.5 to 20 ⁇ m in an ink jet dispersion method.
- the inkjet spraying can form a pattern by spraying only a single color for each nozzle and spraying repeatedly according to the number of required colors, and in order to reduce the process, the pattern can be simultaneously sprayed through each inkjet nozzle. It can also be formed.
- a pixel can be obtained by curing the obtained pattern.
- a thermal curing process or a photo curing process may be applied.
- the thermal curing process is preferably cured by heating at a temperature of 100° C. or higher, and more preferably cured by heating at 100° C. to 300° C., and a little more preferably heating to 160° C. to 250° C. I can.
- actinic rays such as UV rays of 190nm to 450nm, for example, 200nm to 500nm, are irradiated.
- a low-pressure mercury lamp As a light source used for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. may be used, and in some cases, an X-ray, an electron beam, and the like may be used.
- Another method of manufacturing the cured film is to prepare a cured film using a lithography method using the above-described solvent-free curable composition, and the manufacturing method is as follows.
- the above-described curable composition is applied on a substrate subjected to a predetermined pretreatment to a desired thickness, for example, 2 ⁇ m to 10 ⁇ m using a method such as spin or slit coating, roll coating, screen printing, and applicator method Then, the solvent is removed by heating at a temperature of 70° C. to 90° C. for 1 to 10 minutes to form a coating film.
- actinic rays such as UV rays of 190 nm to 450 nm, for example, 200 nm to 500 nm, are irradiated.
- a light source used for irradiation a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. may be used, and in some cases, an X-ray, an electron beam, and the like may be used.
- the exposure amount varies depending on the type, blending amount, and dry film thickness of each component of the curable composition, but is 500 mJ/cm 2 or less (by a 365 nm sensor), for example, when a high-pressure mercury lamp is used.
- an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary portions, so that only the exposed portions remain to form an image pattern. That is, when developing with an alkaline developer, the non-exposed portion is dissolved and an image color filter pattern is formed.
- the image pattern obtained by the above development may be cured by heating again or irradiating with actinic rays.
- Another embodiment provides a color filter including the cured film and a display device including the color filter.
- PH-4 one concentration 100g
- NaOH 22g is sufficiently dispersed in THF 500mL, H 2 O 100mL under a nitrogen atmosphere.
- the temperature of the dispersion is lowered to 0°C, and a THF solution in which p-toluenesulfonic acid (15g) is dissolved is added dropwise.
- p-toluenesulfonic acid 15g
- it is stirred at room temperature for 15 hours.
- ethyl acetate (EA) was added, followed by extraction, neutralization, and concentration, followed by purification and drying under vacuum.
- the mixture After mixing well for about 1 minute, the mixture is stirred in a nitrogen atmosphere at 80°C. After the reaction is completed, the reaction solution is cooled to room temperature, and then the quantum dot reaction solution is added to cyclohexane to capture precipitation. Separate the precipitated quantum dot powder and solvent through centrifugation. The solvent was decanted and discarded, and the precipitate was sufficiently dried for one day in a vacuum oven to obtain surface-modified quantum dots.
- the solvent-free curable composition including the quantum dots surface-modified with the compound represented by Formula 1 has a viscosity advantageous for ink jetting.
- the viscosity of the composition is 10 cPs to 35 cPs, it is advantageous for ink jetting.
- n in Formula 1 has an integer value of 5 or less or an integer value of 16 or more, the viscosity of the composition becomes too high. It can be seen that fairness is deteriorated due to disadvantages such as ink-jetting.
- the solvent-free curable compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were respectively coated on yellow photoresist (YPR) using a spin coater (Mikasa, Opticoat MS-A150, 800 rpm, 5 seconds). It was applied to a thickness of 15 ⁇ m, and exposed to 5000 mJ (83° C. for 10 seconds) with a 395 nm UV exposure machine in a nitrogen atmosphere. Thereafter, a 2cm x 2cm single film specimen was loaded into an integrating sphere equipment (QE-2100, otsuka electronics), and the light conversion rate was measured. Thereafter, the loaded single-film specimen was dried in a nitrogen atmosphere drying furnace at 180° C. for 2 hours, and the light retention rate until drying after exposure was measured. In addition, the maximum emission wavelength of each of the single films was measured in the range of 300 nm to 800 nm, and the measurement results are shown in Table 2 below.
- Example 1 90 538.7
- Example 2 95 539.9
- Example 3 97 540.0
- Example 4 92 539.7 Comparative Example 1 85
- Comparative Example 2 88
- Comparative Example 3 91 539.2 Comparative Example 4 94 538.5
- the cured film prepared using the solvent-free curable composition according to an embodiment can realize high color reproducibility by having a maximum light emission wavelength of 540 nm or less, and at the same time, the light retention rate is also very excellent, and properties such as heat resistance and light resistance. It can be seen that no deterioration of is also occurred.
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Abstract
Provided are: a solvent-free curable composition, and a cured film and colour filter produced using same, the composition comprising surface modified quantum dots and polymeric monomers having carbon-carbon double bonds at the terminals thereof.
Description
본 기재는 무용매형 경화성 조성물, 상기 조성물을 이용하여 제조된 경화막, 상기 경화막을 포함하는 컬러필터에 관한 것이다.The present description relates to a solvent-free curable composition, a cured film prepared by using the composition, and a color filter including the cured film.
일반적인 양자점의 경우, 소수성을 가지는 표면 특성으로 인해 분산되는 용매가 제한적이고, 그러다 보니 바인더나 경화성 모노머 등과 같은 극성 시스템으로의 도입에 많은 어려움을 겪고 있는 것이 사실이다. In the case of general quantum dots, it is true that the solvent to be dispersed is limited due to the hydrophobic surface property, and therefore, it is a fact that introduction into a polar system such as a binder or a curable monomer is difficult.
일 예로, 활발히 연구되고 있는 양자점 잉크 조성물의 경우에도 그 초기 단계에서는 상대적으로 극성도가 낮으며 소수성 정도가 높은 경화형 조성물에 사용되는 용매에 그나마 분산되는 수준이었다. 이 때문에 전체 조성물 총량 대비 20 중량% 이상의 양자점을 포함시키기 어려워 잉크의 광효율을 일정 수준 이상 증가시킬 수 없었고, 광효율을 증가시키기 위해 무리하게 양자점을 추가 투입해 분산시키더라도 잉크-젯팅(Ink-jetting)이 가능한 점도 범위(12cPs)를 넘어서게 되어, 공정성을 만족시킬 수 없었다. For example, even in the case of a quantum dot ink composition, which is being actively studied, at the initial stage, it was at a level that was only dispersed in a solvent used for a curable composition having a relatively low polarity and a high degree of hydrophobicity. Because of this, it was difficult to include more than 20% by weight of quantum dots relative to the total amount of the composition, so that the luminous efficiency of the ink could not be increased more than a certain level, and even if the quantum dots were forcefully added and dispersed to increase the luminous efficiency, ink-jetting This possible viscosity range (12 cPs) was exceeded, and fairness could not be satisfied.
또한, 젯팅(jetting)이 가능한 점도 범위를 구현하기 위해 전체 조성물 총량 대비 50 중량% 이상의 용매를 포함시켜 잉크 고형분 함량을 낮추는 방법을 사용해 왔는데, 이 방법 역시 점도 면에서는 어느정도 만족할 만한 결과를 제공하나, 젯팅(jetting) 시 용매 휘발에 의한 노즐 건조, 노즐 막힘 현상, 젯팅(jetting) 후 시간에 따른 단막 감소 등의 문제와 함께 경화 후 두께 편차가 심해지게 되어, 실제 공정에 적용하기 힘든 단점을 가진다.In addition, in order to realize the viscosity range in which jetting is possible, a method of lowering the ink solid content by including 50% by weight or more of a solvent relative to the total amount of the total composition has been used.This method also provides some satisfactory results in terms of viscosity. During jetting, there are problems such as drying of the nozzle due to volatilization of the solvent, clogging of the nozzle, and reduction of a single film over time after jetting, as well as the thickness deviation after hardening, which makes it difficult to apply to the actual process.
따라서, 양자점 잉크는 용매를 포함하지 않는 무용매 타입이 실제 공정에 적용하기에 가장 바람직한 형태이며, 현재의 양자점 자체를 용매형 조성물에 적용하는 기술은 이제 어느정도 한계에 다다랐다고 평가되고 있다.Therefore, the quantum dot ink is a solvent-free type that does not contain a solvent is the most preferable form to be applied to the actual process, the current technology of applying the quantum dot itself to the solvent-type composition is now evaluated to have reached a certain limit.
현재까지 보고된 바로는 용매형 조성물의 경우, 리간드 치환 등 표면 개질이 되지 않은 양자점이 용매형 조성물 총량 대비 약 20 중량% 내지 25 중량% 정도의 함량으로 포함되어 있고, 따라서 점도의 한계로 인해 광효율 및 흡수율을 증가시키기 어려운 상황이다. 한편, 다른 개선 방향으로 양자점 함량을 낮추고 광확산제(산란체)의 함량을 증가시키는 방법도 시도되고 있으나, 이 역시 침강 문제나 낮은 광효율 문제를 개선하지 못하고 있다. As reported so far, in the case of solvent-type compositions, quantum dots that are not surface-modified, such as ligand substitution, are contained in an amount of about 20% to 25% by weight relative to the total amount of the solvent-type composition. And it is difficult to increase the absorption rate. Meanwhile, a method of lowering the quantum dot content and increasing the content of the light diffusing agent (scattering body) has been attempted as another improvement direction, but this also fails to improve the sedimentation problem or the low light efficiency problem.
일 구현예는 극성부와 비극성부를 동시에 가지는 화합물로 표면개질된 양자점을 포함하는 무용매형 경화성 조성물을 제공하기 위한 것이다.One embodiment is to provide a solvent-free curable composition comprising quantum dots surface-modified with a compound having a polar portion and a non-polar portion at the same time.
다른 일 구현예는 상기 무용매형 경화성 조성물을 이용하여 제조된 경화막을 제공하기 위한 것이다.Another embodiment is to provide a cured film prepared using the solvent-free curable composition.
또 다른 일 구현예는 상기 경화막을 포함하는 컬러필터를 제공하기 위한 것이다.Another embodiment is to provide a color filter including the cured film.
일 구현예는 하기 화학식 1로 표시되는 화합물로 표면개질된 양자점 및 말단에 탄소-탄소 이중결합을 갖는 중합성 단량체를 포함하는 무용매형 경화성 조성물을 제공한다.One embodiment provides a solvent-free curable composition comprising a surface-modified quantum dot with a compound represented by the following Formula 1 and a polymerizable monomer having a carbon-carbon double bond at the terminal.
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
L1, L3 및 L5는 각각 독립적으로 단일결합, 치환 또는 비치환된 C1 내지 C20 알킬렌기, 치환 또는 비치환된 C3 내지 C20 사이클로알킬렌기, 치환 또는 비치환된 C6 내지 C20 아릴렌기 또는 치환 또는 비치환된 C2 내지 C20 헤테로아릴렌기이고,L 1 , L 3 and L 5 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group or a substituted Or an unsubstituted C2 to C20 heteroarylene group,
L2 및 L4는 각각 독립적으로 단일결합, *-O-*, *-S-*, *-C(=O)O-* 또는 *-OC(=O)-* 이고,L 2 and L 4 are each independently a single bond, *-O-*, *-S-*, *-C(=O)O-* or *-OC(=O)-*,
R1은 치환 또는 비치환된 C1 내지 C20 알킬기 또는 치환 또는 비치환된 C6 내지 C20 아릴기이고,R 1 is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,
n은 6 내지 15의 정수이고,n is an integer from 6 to 15,
m은 1 내지 10의 정수이다.m is an integer from 1 to 10.
상기 화학식 1은 하기 화학식 1-1 내지 화학식 1-3 중 어느 하나로 표시될 수 있다.Formula 1 may be represented by any one of Formulas 1-1 to 1-3 below.
[화학식 1-1][Formula 1-1]
[화학식 1-2][Formula 1-2]
[화학식 1-3][Formula 1-3]
상기 화학식 1-1 내지 화학식 1-3에서,In Formula 1-1 to Formula 1-3,
L1, L3 및 L5는 각각 독립적으로 단일결합, 치환 또는 비치환된 C1 내지 C20 알킬렌기, 치환 또는 비치환된 C3 내지 C20 사이클로알킬렌기, 치환 또는 비치환된 C6 내지 C20 아릴렌기 또는 치환 또는 비치환된 C2 내지 C20 헤테로아릴렌기이고,L 1 , L 3 and L 5 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group or a substituted Or an unsubstituted C2 to C20 heteroarylene group,
R1 및 R2는 각각 독립적으로 치환 또는 비치환된 C1 내지 C20 알킬기 또는 치환 또는 비치환된 C6 내지 C20 아릴기이고,R 1 and R 2 are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,
n은 6 내지 15의 정수이고,n is an integer from 6 to 15,
m은 1 내지 10의 정수이고,m is an integer from 1 to 10,
p는 0 내지 4이다.p is 0 to 4.
상기 화학식 1은 하기 화학식 2 내지 화학식 5 중 어느 하나로 표시될 수 있다.Formula 1 may be represented by any one of Formulas 2 to 5 below.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
상기 양자점은 500nm 내지 680nm에서 최대형광 발광파장을 가질 수 있다.The quantum dots may have a maximum fluorescence emission wavelength in 500 nm to 680 nm.
상기 중합성 단량체는 220 g/mol 내지 1,000 g/mol의 분자량을 가질 수 있다.The polymerizable monomer may have a molecular weight of 220 g/mol to 1,000 g/mol.
상기 중합성 단량체는 하기 화학식 6으로 표시될 수 있다.The polymerizable monomer may be represented by the following formula (6).
[화학식 6][Formula 6]
상기 화학식 6에서,In Chemical Formula 6,
R3 및 R4는 각각 독립적으로 수소 원자 또는 치환 또는 비치환된 C1 내지 C10 알킬기이고,R 3 and R 4 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
L6 및 L8은 각각 독립적으로 치환 또는 비치환된 C1 내지 C10 알킬렌기이고,L 6 and L 8 are each independently a substituted or unsubstituted C1 to C10 alkylene group,
L7은 치환 또는 비치환된 C1 내지 C10 알킬렌기 또는 에테르기(*-O-*)이다.L 7 is a substituted or unsubstituted C1 to C10 alkylene group or an ether group (*-O-*).
상기 무용매형 경화성 조성물은, 상기 양자점 1 중량% 내지 60 중량% 및 상기 중합성 단량체 40 중량% 내지 99 중량%를 포함할 수 있다.The solvent-free curable composition may include 1% to 60% by weight of the quantum dots and 40% to 99% by weight of the polymerizable monomer.
상기 무용매형 경화성 조성물은 중합개시제, 광확산제 또는 이들의 조합을 더 포함할 수 있다.The solvent-free curable composition may further include a polymerization initiator, a light diffusing agent, or a combination thereof.
상기 광확산제는 황산바륨, 탄산칼슘, 이산화티타늄, 지르코니아 또는 이들의 조합을 포함할 수 있다.The light diffusing agent may include barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.
상기 무용매형 경화성 조성물은 중합 금지제; 말론산; 3-아미노-1,2-프로판디올; 실란계 커플링제; 레벨링제; 불소계 계면활성제; 또는 이들의 조합을 더 포함할 수 있다.The solvent-free curable composition may include a polymerization inhibitor; Malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine-based surfactant; Or it may further include a combination of these.
다른 일 구현예는 상기 무용매형 경화성 조성물을 이용하여 제조된 경화막을 제공한다.Another embodiment provides a cured film prepared using the solvent-free curable composition.
상기 경화막은 540nm 이하의 발광파장을 가질 수 있다.The cured film may have an emission wavelength of 540 nm or less.
또 다른 일 구현예는 상기 경화막을 포함하는 컬러필터를 제공한다.Another embodiment provides a color filter including the cured film.
또 다른 일 구현예는 상기 컬러필터를 포함하는 디스플레이 장치를 제공한다.Another embodiment provides a display device including the color filter.
기타 본 발명의 측면들의 구체적인 사항은 이하의 상세한 설명에 포함되어 있다.Other specifics of aspects of the present invention are included in the detailed description below.
일 구현예는 극성부와 비극성부를 동시에 가지는 화합물로 표면개질된 양자점을 포함하는 무용매형 경화성 조성물을 제공하며, 상기 표면개질 화합물은 양자점 간에 일정한 간격이 형성되는 것을 도움으로써, 상기 무용매형 경화성 조성물을 이용하여 제조된 경화막의 발광파장이 낮아지도록 해 고색재현성을 구현할 수 있으며, 동시에 상기 경화막의 내광성, 내열성 등의 물성이 저하되는 것도 방지할 수 있다. One embodiment provides a solvent-free curable composition comprising quantum dots surface-modified with a compound having a polar portion and a non-polar portion at the same time, the surface-modifying compound by helping to form a constant gap between the quantum dots, the solvent-free curable composition It is possible to realize high color reproducibility by lowering the emission wavelength of the cured film prepared using the cured film, and at the same time, it is possible to prevent deterioration of physical properties such as light resistance and heat resistance of the cured film.
도 1은 극성부와 비극성부를 동시에 가지는 화합물로 표면개질된 양자점이 무용매형 경화성 조성물 내에 단분산된 형태로 존재하는 그림과 극성부만을 가지는 화합물로 표면개질된 양자점이 무용매형 경화성 조성물 내에 집합 형태로 존재하는 그림을 비교한 도면이다.1 is a figure in which quantum dots surface-modified with a compound having a polar part and a non-polar part simultaneously exist in a monodisperse form in a solvent-free curable composition, and a quantum dot surface-modified with a compound having only a polar part in an aggregate form in a solvent-free curable composition. It is a drawing comparing existing pictures.
이하, 본 발명의 구현예를 상세히 설명하기로 한다. 다만, 이는 예시로서 제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구범위의 범주에 의해 정의될 뿐이다. Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.
본 명세서에서 특별한 언급이 없는 한, "알킬기"란 C1 내지 C20 알킬기를 의미하고, "알케닐기"란 C2 내지 C20 알케닐기를 의미하고, "사이클로알케닐기"란 C3 내지 C20 사이클로알케닐기를 의미하고, "헤테로사이클로알케닐기"란 C3 내지 C20 헤테로사이클로알케닐기를 의미하고, "아릴기"란 C6 내지 C20 아릴기를 의미하고, "아릴알킬기"란 C6 내지 C20 아릴알킬기를 의미하며, "알킬렌기"란 C1 내지 C20 알킬렌기를 의미하고, "아릴렌기"란 C6 내지 C20 아릴렌기를 의미하고, "알킬아릴렌기"란 C6 내지 C20 알킬아릴렌기를 의미하고, "헤테로아릴렌기"란 C3 내지 C20 헤테로아릴렌기를 의미하고, "알콕실렌기"란 C1 내지 C20 알콕실렌기를 의미한다.Unless otherwise specified in the specification, "alkyl group" refers to a C1 to C20 alkyl group, "alkenyl group" refers to a C2 to C20 alkenyl group, and "cycloalkenyl group" refers to a C3 to C20 cycloalkenyl group. , "Heterocycloalkenyl group" refers to a C3 to C20 heterocycloalkenyl group, "aryl group" refers to a C6 to C20 aryl group, and "arylalkyl group" refers to a C6 to C20 arylalkyl group, and "alkylene group" Refers to a C1 to C20 alkylene group, "arylene group" refers to a C6 to C20 arylene group, "alkylarylene group" refers to a C6 to C20 alkylarylene group, and "heteroarylene group" refers to a C3 to C20 hetero It means an arylene group, and the "alkoxyl group" means a C1 to C20 alkoxyl group.
본 명세서에서 특별한 언급이 없는 한, "치환"이란 적어도 하나의 수소 원자가 할로겐 원자(F, Cl, Br, I), 히드록시기, C1 내지 C20 알콕시기, 니트로기, 시아노기, 아민기, 이미노기, 아지도기, 아미디노기, 히드라지노기, 히드라조노기, 카르보닐기, 카르바밀기, 티올기, 에스테르기, 에테르기, 카르복실기 또는 그것의 염, 술폰산기 또는 그것의 염, 인산이나 그것의 염, C1 내지 C20 알킬기, C2 내지 C20 알케닐기, C2 내지 C20 알키닐기, C6 내지 C20 아릴기, C3 내지 C20 사이클로알킬기, C3 내지 C20 사이클로알케닐기, C3 내지 C20 사이클로알키닐기, C2 내지 C20 헤테로사이클로알킬기, C2 내지 C20 헤테로사이클로알케닐기, C2 내지 C20 헤테로사이클로알키닐기, C3 내지 C20 헤테로아릴기 또는 이들의 조합의 치환기로 치환된 것을 의미한다.Unless otherwise specified in the specification, "substituted" means that at least one hydrogen atom is a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, Azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, ether group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C1 To C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C20 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocycloalkyl group, C2 To C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, C3 to C20 heteroaryl group, or a combination thereof.
또한 본 명세서에서 특별한 언급이 없는 한, "헤테로"란, 화학식 내에 N, O, S 및 P 중 적어도 하나의 헤테로 원자가 적어도 하나 포함된 것을 의미한다.In addition, unless otherwise specified in the specification, "hetero" means that at least one hetero atom of at least one of N, O, S, and P is included in the formula.
또한 본 명세서에서 특별한 언급이 없는 한, "(메타)아크릴레이트"는 "아크릴레이트"와 "메타크릴레이트" 둘 다 가능함을 의미하며, "(메타)아크릴산"은 "아크릴산"과 "메타크릴산" 둘 다 가능함을 의미한다. In addition, unless otherwise specified in the specification, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" refers to "acrylic acid" and "methacrylic acid. "It means both are possible.
본 명세서에서 특별한 언급이 없는 한, "조합"이란 혼합 또는 공중합을 의미한다.Unless otherwise specified in the specification, "combination" means mixing or copolymerization.
본 명세서 내 화학식에서 별도의 정의가 없는 한, 화학결합이 그려져야 하는 위치에 화학결합이 그려져있지 않은 경우는 상기 위치에 수소 원자가 결합되어 있음을 의미한다.Unless otherwise defined in the chemical formula in the present specification, when a chemical bond is not drawn at a position where a chemical bond is to be drawn, it means that a hydrogen atom is bonded at the position.
또한 본 명세서에서 특별한 언급이 없는 한, "*"는 동일하거나 상이한 원자 또는 화학식과 연결되는 부분을 의미한다.In addition, unless otherwise specified in the specification, "*" means a moiety connected with the same or different atom or chemical formula.
현재 활발히 개발 중인 양자점 디스플레이 제품에서 내세우는 가장 큰 장점은 넓은 시야각도 있지만, 100%에 가까운 높은 색재현율(고색재현성) 달성에 있다. 그러기 위해서는, 코팅된 양자점 단막(양자점 경화성 조성물을 경화시킨 경화막)이 일정 두께에서 고색재현율을 달성할 수 있는 범위의 발광 파장 영역, 즉 540nm 이하의 발광 파장(단파장) 영역을 가져야 한다. 그러나, 일반적인 양자점 합성의 방향 측면에서 보면 양자점 단막의 발광 파장은 장파장을 가지는 경향이 크며, 양자점 단막의 발광 파장이 단파장일수록 blue 광변환율이 높고 내열 안정성이 높으며, 장파장일수록 광변환율이 낮고 내열성이 취약하기에, 현재까지의 양자점 단막은 장파장 영역에서 발광파장을 가져, 고색재현성을 달성할 수 없었던 것이 사실이다. The biggest advantage of quantum dot display products that are currently being actively developed is in achieving a high color gamut (high color reproducibility) close to 100%, although it has a wide viewing angle. To do this, the coated quantum dot single film (cured film obtained by curing the quantum dot curable composition) must have a light emission wavelength range of a range capable of achieving high color reproduction at a certain thickness, that is, a light emission wavelength (short wavelength) range of 540 nm or less. However, from the perspective of general quantum dot synthesis, the emission wavelength of the quantum dot monolayer tends to have a long wavelength, and the shorter the emission wavelength of the quantum dot monolayer, the higher the blue light conversion rate and higher heat resistance, and the longer the wavelength, the lower the light conversion rate and the poorer heat resistance. Below, it is true that the conventional quantum dot single film has a luminous wavelength in a long wavelength region, and thus high color reproducibility has not been achieved.
일 구현예에서는 합성된 양자점 리간드 구조의 변경(양자점 표면개질)을 통해 비록 장파장 발광 특성을 갖는 양자점이라 할지라도 이를 표면개질하여 양자점의 발광 파장을 단파장으로 변경할 수 있도록 하여, 단파장 영역에서 경화막이 발광파장을 가져 고색재현성을 구현하면서 동시에 내열성, 내광성 등의 물성도 우수하게 유지할 수 있는 무용매형 경화성 조성물을 제공한다.In one embodiment, by changing the structure of the synthesized quantum dot ligand (quantum dot surface modification), even if the quantum dot has a long-wavelength emission characteristic, the surface is modified to change the emission wavelength of the quantum dot to a short wavelength, so that the cured film emits light in the short wavelength region. It provides a solvent-free curable composition capable of maintaining excellent properties such as heat resistance and light resistance while realizing high color reproducibility by having a wavelength.
구체적으로 일 구현예에 따른 무용매형 경화성 조성물은 하기 화학식 1로 표시되는 화합물로 표면개질된다.Specifically, the solvent-free curable composition according to an embodiment is surface-modified with a compound represented by Formula 1 below.
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
L1, L3 및 L5는 각각 독립적으로 단일결합, 치환 또는 비치환된 C1 내지 C20 알킬렌기, 치환 또는 비치환된 C3 내지 C20 사이클로알킬렌기, 치환 또는 비치환된 C6 내지 C20 아릴렌기 또는 치환 또는 비치환된 C2 내지 C20 헤테로아릴렌기이고,L 1 , L 3 and L 5 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group or a substituted Or an unsubstituted C2 to C20 heteroarylene group,
L2 및 L4는 각각 독립적으로 단일결합, *-O-*, *-S-*, *-C(=O)O-* 또는 *-OC(=O)-* 이고,L 2 and L 4 are each independently a single bond, *-O-*, *-S-*, *-C(=O)O-* or *-OC(=O)-*,
R1은 치환 또는 비치환된 C1 내지 C20 알킬기 또는 치환 또는 비치환된 C6 내지 C20 아릴기이고,R 1 is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,
n은 6 내지 15의 정수이고,n is an integer from 6 to 15,
m은 1 내지 10의 정수이다.m is an integer from 1 to 10.
상기 화학식 1로 표시되는 화합물은 극성부와 비극성부가 적절한 비율로 혼합되어 있어, 조성물전체 조성 내에서의 양자점 분산성 및 집합(aggregation) 정도를 개선할 수 있다(도 1 참조). 분산성이 떨어지고 집합(aggregation) 정도가 클수록 장파장에서의 발광 특성이 더 커질 수 있는데, 일 구현예에서는 상기 화학식 1로 표시되는 화합물을 양자점의 표면개질 물질로 사용함으로써, 전술한 문제점을 개선할 수 있다. In the compound represented by Formula 1, since the polar portion and the non-polar portion are mixed in an appropriate ratio, the dispersibility of quantum dots and the degree of aggregation in the overall composition of the composition can be improved (see FIG. 1). The lower the dispersibility and the greater the degree of aggregation, the greater the luminescence characteristic at a long wavelength.In one embodiment, the above-described problem can be improved by using the compound represented by Formula 1 as a surface-modifying material for quantum dots. have.
그리고 상기 화학식 1로 표시되는 화합물로 표면개질된 양자점은 극성기를 갖는 리간드, 즉, 말단에 탄소-탄소 이중결합을 갖는 중합성 단량체와의 친화성이 높아, 고농도 혹은 고농축 양자점 분산액의 제조가 매우 용이(단량체에 대한 양자점의 분산성 향상)하여, 무용매형 경화성 조성물 구현 및 광효율 개선에 매우 긍정적인 영향을 미칠 수 있다.And the quantum dot surface-modified with the compound represented by Formula 1 has a high affinity with a ligand having a polar group, that is, a polymerizable monomer having a carbon-carbon double bond at the end, making it very easy to prepare a high concentration or highly concentrated quantum dot dispersion. (Improvement of dispersibility of quantum dots in a monomer), it can have a very positive effect on the realization of a solvent-free curable composition and improvement of light efficiency.
한편, 종래에는 양자점 합성 시 양자점을 구성하는 코어의 크기를 작게 만들어 양자점 함유 경화막의 발광파장을 단파장 쪽으로 이동시키려는 노력이 있었다. 그러나, 이 경우 양자점 함유 경화막의 발광파장을 단파장 쪽으로 이동시킬 수는 있으나, 내광성이나 내열성 등의 물성이 매우 저하되는 문제가 있어 고색재현성 구현과 함께 종래 물성(내광성, 내열성 등)을 동등 수준 이상으로 유지할 수 있는 방법에 대한 연구가 계속되었는데, 일 구현예는 상기 연구에 대한 결과물로서, 고색재현성 구현과 함께 종래 물성(내광성, 내열성)의 저하 또한 방지할 수 있는 무용매형 경화성 조성물을 제공한다.Meanwhile, in the prior art, there has been an effort to move the emission wavelength of the cured film containing the quantum dots toward a shorter wavelength by reducing the size of the core constituting the quantum dots during the synthesis of the quantum dots. However, in this case, it is possible to move the light emitting wavelength of the cured film containing quantum dots toward a shorter wavelength, but there is a problem that physical properties such as light resistance and heat resistance are very deteriorated, so that the conventional physical properties (light resistance, heat resistance, etc.) Research on a method that can be maintained has been continued, and one embodiment provides a solvent-free curable composition capable of preventing deterioration of conventional physical properties (light resistance, heat resistance) as well as implementation of high color reproducibility as a result of the above study.
보다 구체적으로 일 구현예에 따른 무용매형 경화성 조성물은 상기 화학식 1로 표시되는 화합물로 표면개질된 양자점 및 말단에 탄소-탄소 이중결합을 갖는 중합성 단량체를 포함한다.More specifically, the solvent-free curable composition according to an embodiment includes a quantum dot surface-modified with the compound represented by Formula 1 and a polymerizable monomer having a carbon-carbon double bond at an end thereof.
상기 화학식 1로 표시되는 화합물은 티올기 인접부 구조에 소수성이 강한 알킬 사슬이 도입되어 있고, 반대 말단부에는 친수성이 강한 알킬렌 글리콜 사슬이 도입되어 있어, 상기 화학식 1로 표시되는 화합물은 전체적으로 양친성(amphiphilic)을 띠며, 장파장에서 발광파장을 나타내는 단막에 사용되는 양자점도 표면개질하여 발광파장을 낮추고 내열성 등을 개선시킬 수 있다.In the compound represented by Formula 1, a highly hydrophobic alkyl chain is introduced in the structure adjacent to the thiol group, and an alkylene glycol chain having strong hydrophilicity is introduced at the opposite end, so that the compound represented by Formula 1 is generally amphiphilic. Quantum dots, which are amphiphilic and used in monolayers that exhibit a luminous wavelength at a long wavelength, can also reduce the luminous wavelength and improve heat resistance by surface modification.
상기 화학식 1에서, n이 5 이하의 정수일 경우 양자점 함유 경화막의 발광파장을 낮추기가 어려워 고색재현성 구현이 용이하지 않으며, 상기 n이 16 이상의 정수일 경우 조성물의 점도가 너무 낮아져 잉크-젯팅에 불리할 수 있으며, 내열성 등에 있어서도 불리할 수 있다.In Formula 1, when n is an integer of 5 or less, it is difficult to lower the emission wavelength of the cured film containing quantum dots, making it difficult to implement high color reproducibility, and when n is an integer of 16 or more, the viscosity of the composition is too low, which may be disadvantageous for ink-jetting. In addition, it may be disadvantageous in terms of heat resistance and the like.
예컨대, 상기 화학식 1은 하기 화학식 1-1 내지 화학식 1-3 중 어느 하나로 표시될 수 있다.For example, Formula 1 may be represented by any one of Formulas 1-1 to 1-3 below.
[화학식 1-1][Formula 1-1]
[화학식 1-2][Formula 1-2]
[화학식 1-3][Formula 1-3]
상기 화학식 1-1 내지 화학식 1-3에서,In Formula 1-1 to Formula 1-3,
L1, L3 및 L5는 각각 독립적으로 단일결합, 치환 또는 비치환된 C1 내지 C20 알킬렌기, 치환 또는 비치환된 C3 내지 C20 사이클로알킬렌기, 치환 또는 비치환된 C6 내지 C20 아릴렌기 또는 치환 또는 비치환된 C2 내지 C20 헤테로아릴렌기이고,L 1 , L 3 and L 5 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group or a substituted Or an unsubstituted C2 to C20 heteroarylene group,
R1 및 R2는 각각 독립적으로 치환 또는 비치환된 C1 내지 C20 알킬기 또는 치환 또는 비치환된 C6 내지 C20 아릴기이고,R 1 and R 2 are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,
n은 6 내지 15의 정수이고,n is an integer from 6 to 15,
m은 1 내지 10의 정수이고,m is an integer from 1 to 10,
p는 0 내지 4이다.p is 0 to 4.
예컨대, 상기 화학식 1에서, n은 6 내지 11의 정수일 수 있다.For example, in Formula 1, n may be an integer of 6 to 11.
예컨대, 상기 화학식 1에서, R1은 하기 화학식 R-1 내지 화학식 R-4 중 어느 하나로 표시될 수 있으나, 반드시 이에 한정되는 것은 아니다.For example, in Formula 1, R 1 may be represented by any one of Formulas R-1 to R-4, but is not limited thereto.
[화학식 R-1][Formula R-1]
[화학식 R-2][Formula R-2]
[화학식 R-3][Formula R-3]
[화학식 R-4][Formula R-4]
예컨대, 상기 화학식 1은 하기 화학식 2 내지 화학식 5 중 어느 하나로 표시될 수 있다.For example, Formula 1 may be represented by any one of Formulas 2 to 5 below.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
현재까지의 양자점 함유 경화성 조성물(잉크)은 양자점과의 상용성이 좋은 모노머를 특화시키는 쪽으로 개발이 이루어지고 있으며, 나아가 제품화까지 이루어지고 있다.The curable composition (ink) containing quantum dots to date has been developed to specialize monomers having good compatibility with quantum dots, and furthermore, commercialization is being made.
한편, 일반적이며 범용적으로 사용되고 있는 중합성 단량체인 -ene계 단량체(비닐계 단량체, 아크릴레이트계 단량체, 메타크릴레이트계 단량체 등을 모두 포함하며, 단관능에서부터 다관능까지 포함함)는 양자점과의 상용성이 적고, 양자점의 분산성에 있어서 한계가 있음으로 인해, 양자점 함유 경화성 조성물에 유용하게 적용시키기 위한 다양한 개발이 어려운 것이 사실이다. 무엇보다도 상기 -ene계 단량체는 고농축 양자점 분산성을 보이지 못한다는 점에서, 양자점 함유 경화성 조성물에 적용시키는 데 어려움이 있었다.Meanwhile, -ene-based monomers (vinyl-based monomers, acrylate-based monomers, methacrylate-based monomers, etc., and including monofunctional to polyfunctional), which are general and universally used polymerizable monomers, are used as quantum dots and It is true that it is difficult to develop a variety of applications for useful application to a curable composition containing quantum dots due to its low compatibility and limitations in the dispersibility of quantum dots. Above all, since the -ene-based monomer does not exhibit high-concentration quantum dot dispersibility, it is difficult to apply it to a curable composition containing quantum dots.
이러한 단점으로 인해 양자점 함유 경화성 조성물은 용매를 상당량(50 중량% 이상) 포함하는 조성으로 개발되어 왔으나, 용매 함량이 많아질 경우 잉크 젯팅(Ink jetting) 공정성이 저하되는 문제가 있다. 따라서 잉크 젯팅(Ink jetting) 공정성을 만족시키기 위해 무용매형 경화성 조성물에 대한 수요가 갈수록 증가하고 있다.Due to these disadvantages, the curable composition containing quantum dots has been developed as a composition containing a significant amount (50% by weight or more) of a solvent, but there is a problem in that ink jetting fairness is deteriorated when the solvent content is increased. Therefore, in order to satisfy ink jetting fairness, the demand for a solvent-free curable composition is increasing.
본원은 갈수록 수요가 증대되고 있는 무용매형 경화성 조성물을 제공하며, 말단에 탄소-탄소 이중결합을 가지는 화합물을 포함하는 중합성 단량체를 상기 화학식 1로 표시되는 화합물로 표면개질된 양자점과 함께 사용함으로써, 경화성 조성물에 대한 양자점의 친화성을 향상시켜 무용매 시스템(solvent-free system)에서도 양자점의 고농도 분산성을 줄 수 있으면서, 양자점 본연의 광특성을 저해하지 않는 패시베이션(passivation) 효과까지 달성할 수 있다. The present application provides a solvent-free curable composition that is increasingly in demand, and by using a polymerizable monomer including a compound having a carbon-carbon double bond at the terminal together with a quantum dot surface-modified with a compound represented by Formula 1, By improving the affinity of the quantum dots to the curable composition, it is possible to provide high-concentration dispersibility of the quantum dots even in a solvent-free system, while achieving a passivation effect that does not impair the natural optical properties of the quantum dots. .
이하에서 무용매형 경화성 조성물을 구성하는 각각의 성분에 대하여 구체적으로 설명한다.Hereinafter, each component constituting the solvent-free curable composition will be described in detail.
양자점Quantum dots
상기 무용매형 경화성 조성물에 포함되는 양자점은 상기 화학식 1로 표시되는 화합물로 표면개질된 양자점이다.Quantum dots included in the solvent-free curable composition are quantum dots surface-modified with the compound represented by Formula 1.
예컨대, 상기 양자점은 360nm 내지 780nm의 파장영역, 예컨대 400nm 내지 780nm의 파장영역의 광을 흡수하여, 500nm 내지 700nm의 파장영역, 예컨대 500nm 내지 580nm에서 형광을 방출하거나, 600nm 내지 680nm에서 형광을 방출할 수 있다. 즉, 상기 양자점은 500nm 내지 680nm에서 최대형광 발광파장(fluorescence λem)을 가질 수 있다. For example, the quantum dot absorbs light in a wavelength region of 360 nm to 780 nm, such as 400 nm to 780 nm, and emits fluorescence in a wavelength region of 500 nm to 700 nm, such as 500 nm to 580 nm, or emits fluorescence at 600 nm to 680 nm. I can. That is, the quantum dot may have a maximum fluorescence emission wavelength (fluorescence λ em ) at 500 nm to 680 nm.
상기 양자점은 각각 독립적으로 20nm 내지 100nm, 예컨대 20nm 내지 50nm의 반치폭(Full width at half maximum; FWHM)을 가질 수 있다. 상기 양자점이 상기 범위의 반치폭을 가질 경우, 색순도가 높음에 따라, 컬러필터 내 색재료로 사용 시 색재현율이 높아지는 효과가 있다.Each of the quantum dots may independently have a full width at half maximum (FWHM) of 20 nm to 100 nm, for example, 20 nm to 50 nm. When the quantum dots have a half width in the above range, as the color purity is high, there is an effect of increasing the color reproduction rate when used as a color material in a color filter.
상기 양자점은 각각 독립적으로 유기물이거나 무기물 또는 유기물과 무기물의 하이브리드(혼성물)일 수 있다.The quantum dots may each independently be an organic material, an inorganic material, or a hybrid (mixture) of an organic material and an inorganic material.
상기 양자점은 각각 독립적으로 코어 및 상기 코어를 감싸는 쉘로 구성될 수 있으며, 상기 코어 및 쉘은 각각 독립적으로 II-IV족, III-V족 등으로 이루어진 코어, 코어/쉘, 코어/제1쉘/제2쉘, 합금, 합금/쉘 등의 구조를 가질 수 있으며, 이에 한정되는 것은 아니다.The quantum dots may each independently consist of a core and a shell surrounding the core, and the core and shell are each independently a core, a core/shell, a core/first shell/ It may have a structure such as a second shell, an alloy, and an alloy/shell, but is not limited thereto.
예컨대, 상기 코어는 CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs 및 이들의 합금으로 이루어진 군으로부터 선택된 적어도 하나 이상의 물질을 포함할 수 있으나, 반드시 이에 한정되는 것은 아니다. 상기 코어를 둘러싼 쉘은 CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe 및 이들의 합금으로 이루어진 군으로부터 선택된 적어도 하나 이상의 물질을 포함할 수 있으나, 반드시 이에 한정되는 것은 아니다. For example, the core may include at least one material selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, and alloys thereof. , Is not necessarily limited thereto. The shell surrounding the core may include at least one material selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but is not limited thereto.
일 구현예에서는, 최근 전 세계적으로 환경에 대한 관심이 크게 증가하고 유독성 물질에 대한 규제가 강화되고 있으므로, 카드뮴계 코어를 갖는 발광물질을 대신하여, 양자 효율(quantum yield)은 다소 낮지만 친환경적인 비카드뮴계 발광소재(InP/ZnS, InP/ZnSe/ZnS 등)를 사용하였으나, 반드시 이에 한정되는 것은 아니다.In one embodiment, since interest in the environment has recently increased greatly around the world and regulations on toxic substances have been strengthened, instead of a light emitting material having a cadmium-based core, the quantum yield is somewhat low, but environmentally friendly. Although a non-cadmium-based light emitting material (InP/ZnS, InP/ZnSe/ZnS, etc.) was used, it is not necessarily limited thereto.
상기 코어/쉘 구조의 양자점의 경우, 쉘을 포함한 전체 양자점 각각의 크기(평균 입경)는 1nm 내지 15nm, 예컨대 5nm 내지 15nm 일 수 있다. In the case of the core/shell structured quantum dots, the size (average particle diameter) of each of the entire quantum dots including the shell may be 1 nm to 15 nm, for example, 5 nm to 15 nm.
예컨대, 상기 양자점은 각각 독립적으로 적색 양자점, 녹색 양자점 또는 이들의 조합을 포함할 수 있다. 상기 적색 양자점은 각각 독립적으로 10nm 내지 15nm의 평균 입경을 가질 수 있다. 상기 녹색 양자점은 각각 독립적으로 5nm 내지 8nm의 평균 입경을 가질 수 있다.For example, the quantum dots may each independently include red quantum dots, green quantum dots, or a combination thereof. Each of the red quantum dots may independently have an average particle diameter of 10 nm to 15 nm. Each of the green quantum dots may independently have an average particle diameter of 5 nm to 8 nm.
한편, 상기 양자점의 분산안정성을 위해, 일 구현예에 따른 무용매형 경화성 조성물은 분산제를 더 포함할 수도 있다. 상기 분산제는 양자점과 같은 광변환 물질이 무용매형 경화성 조성물 내에서 균일하게 분산되도록 도와주며, 비이온성, 음이온성 또는 양이온성 분산제 모두를 사용할 수 있다. 구체적으로는 폴리알킬렌 글리콜 또는 이의 에스테르류, 폴리옥시 알킬렌, 다가 알코올 에스테르 알킬렌 옥사이드 부가물, 알코올 알킬렌 옥사이드 부가물, 술폰산 에스테르, 술폰산 염, 카르복시산 에스테르, 카르복시산 염, 알킬 아미드 알킬렌 옥사이드 부가물, 알킬 아민 등을 사용할 수 있으며, 이들은 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다. 상기 분산제는 양자점과 같은 광변환 물질의 고형분 대비 0.1 중량% 내지 100 중량%, 예컨대 10 중량% 내지 20 중량%로 사용될 수 있다.On the other hand, for the dispersion stability of the quantum dots, the solvent-free curable composition according to an embodiment may further include a dispersant. The dispersant helps to uniformly disperse a light conversion material such as a quantum dot in a solvent-free curable composition, and nonionic, anionic, or cationic dispersants may be used. Specifically, polyalkylene glycol or esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid salt, alkyl amide alkylene oxide Adducts, alkyl amines, and the like may be used, and these may be used alone or in combination of two or more. The dispersant may be used in an amount of 0.1% to 100% by weight, such as 10% to 20% by weight, based on the solid content of a photo-conversion material such as a quantum dot.
상기 화학식 1로 표면 개질된 양자점은 상기 무용매형 경화성 조성물 총량에 대해 1 중량% 내지 60 중량%, 예컨대 3 중량% 내지 50 중량% 포함될 수 있다. 상기 표면 개질된 양자점이 상기 범위 내로 포함될 경우, 광변환률이 우수하며 패턴특성과 현상특성을 저해하지 않아 우수한 공정성을 가질 수 있다. The quantum dots surface-modified by Formula 1 may be included in an amount of 1% to 60% by weight, such as 3% to 50% by weight, based on the total amount of the solvent-free curable composition. When the surface-modified quantum dots are included within the above range, a light conversion rate is excellent and pattern characteristics and development characteristics are not impaired, so that excellent fairness may be obtained.
말단에 탄소-탄소 이중결합을 갖는 중합성 단량체Polymerizable monomer having a carbon-carbon double bond at the terminal
상기 말단에 탄소-탄소 이중결합을 갖는 단량체는 상기 무용매형 경화성 조성물 총량에 대하여 40 중량% 내지 99 중량%, 예컨대 50 중량% 내지 97 중량%로 포함될 수 있다. 상기 말단에 탄소-탄소 이중결합을 갖는 단량체의 함량이 상기 범위 내이어야 잉크 젯팅이 가능한 점도를 가지는 무용매형 경화성 조성물의 제조가 가능하며, 또한 제조된 무용매형 경화성 조성물 내 양자점이 우수한 분산성을 가질 수 있어, 광특성 또한 향상될 수 있다. The monomer having a carbon-carbon double bond at the terminal may be included in an amount of 40% to 99% by weight, such as 50% to 97% by weight, based on the total amount of the solvent-free curable composition. It is possible to prepare a solvent-free curable composition having a viscosity capable of ink jetting only when the content of the monomer having a carbon-carbon double bond at the terminal is within the above range, and also have excellent dispersibility in the prepared solvent-free curable composition. So that the optical properties can also be improved.
예컨대, 상기 말단에 탄소-탄소 이중결합을 갖는 단량체는 220 g/mol 내지 1,000 g/mol의 분자량을 가질 수 있다. 상기 말단에 탄소-탄소 이중결합을 갖는 단량체의 분자량이 상기 범위일 경우 양자점의 광특성을 저해하지 않으면서 조성물의 점도를 높이지 않아 잉크-젯팅에 유리할 수 있다.For example, a monomer having a carbon-carbon double bond at the terminal may have a molecular weight of 220 g/mol to 1,000 g/mol. When the molecular weight of the monomer having a carbon-carbon double bond at the terminal is within the above range, the viscosity of the composition is not increased without impairing the optical properties of the quantum dots, which may be advantageous for ink-jetting.
예컨대, 상기 말단에 탄소-탄소 이중결합을 갖는 단량체는 하기 화학식 6으로 표시될 수 있으나, 반드시 이에 한정되는 것은 아니다.For example, a monomer having a carbon-carbon double bond at the terminal may be represented by the following Formula 6, but is not limited thereto.
[화학식 6][Formula 6]
상기 화학식 6에서,In Chemical Formula 6,
R3 및 R4는 각각 독립적으로 수소 원자 또는 치환 또는 비치환된 C1 내지 C10 알킬기이고,R 3 and R 4 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
L6 및 L8은 각각 독립적으로 치환 또는 비치환된 C1 내지 C10 알킬렌기이고,L 6 and L 8 are each independently a substituted or unsubstituted C1 to C10 alkylene group,
L7은 치환 또는 비치환된 C1 내지 C10 알킬렌기 또는 에테르기(*-O-*)이다.L 7 is a substituted or unsubstituted C1 to C10 alkylene group or an ether group (*-O-*).
예컨대, 상기 말단에 탄소-탄소 이중결합을 가지는 단량체는 하기 화학식 6-1 또는 6-2로 표시될 수 있으나, 반드시 이에 한정되는 것은 아니다.For example, a monomer having a carbon-carbon double bond at the terminal may be represented by Formula 6-1 or 6-2, but is not limited thereto.
[화학식 6-1][Chemical Formula 6-1]
[화학식 6-2][Formula 6-2]
예컨대, 상기 말단에 탄소-탄소 이중결합을 갖는 단량체는 상기 화학식 6-1 또는 화학식 6-2로 표시되는 화합물 외에도, 에틸렌글리콜디아크릴레이트, 트리에틸렌글리콜디아크릴레이트, 1,4-부탄디올디아크릴레이트, 1,6-헥산디올디아크릴레이트, 네오펜틸글리콜디아크릴레이트, 펜타에리트리톨디아크릴레이트, 펜타에리트리톨트리아크릴레이트, 디펜타에리트리톨디아크릴레이트, 디펜타에리트리톨트리아크릴레이트, 디펜타에리트리톨펜타아크릴레이트, 펜타에리트리톨헥사아크릴레이트, 비스페놀 A 디아크릴레이트, 트리메틸올프로판트리아크릴레이트, 노볼락에폭시아크릴레이트, 에틸렌글리콜디메타크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 프로필렌글리콜디메타크릴레이트, 1,4-부탄디올디메타크릴레이트, 1,6-헥산디올디메타크릴레이트 또는 이들의 조합을 더 포함할 수 있다.For example, the monomer having a carbon-carbon double bond at the terminal is, in addition to the compound represented by Formula 6-1 or Formula 6-2, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylic Rate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, di Pentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol Dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, or a combination thereof may be further included.
또한, 상기 말단에 탄소-탄소 이중결합을 가지는 단량체와 더불어 종래의 열경화성 또는 광경화성 조성물에 일반적으로 사용되는 단량체를 더 포함할 수 있으며, 예컨대 상기 단량체는 비스[1-에틸(3-옥세타닐)]메틸 에테르 등의 옥세탄계 화합물 등을 더 포함할 수 있다.In addition, in addition to a monomer having a carbon-carbon double bond at the terminal, a monomer generally used in a conventional thermosetting or photocurable composition may be further included. For example, the monomer is bis[1-ethyl(3-oxetanyl). )] may further include oxetane-based compounds such as methyl ether.
중합개시제Polymerization initiator
일 구현예에 따른 무용매형 경화성 조성물은 중합개시제를 더 포함할 수 있으며, 예컨대, 광중합 개시제, 열중합 개시제 또는 이들의 조합을 포함할 수 있다. The solvent-free curable composition according to an embodiment may further include a polymerization initiator, for example, a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.
상기 광중합 개시제는 감광성 수지 조성물에 일반적으로 사용되는 개시제로서, 예를 들어 아세토페논계 화합물, 벤조페논계 화합물, 티오크산톤계 화합물, 벤조인계 화합물, 트리아진계 화합물, 옥심계 화합물, 아미노케톤계 화합물 등을 사용할 수 있으나, 반드시 이에 한정되는 것은 아니다.The photopolymerization initiator is an initiator generally used in the photosensitive resin composition, for example, acetophenone-based compound, benzophenone-based compound, thioxanthone-based compound, benzoin-based compound, triazine-based compound, oxime-based compound, aminoketone-based compound Such as may be used, but is not necessarily limited thereto.
상기 아세토페논계의 화합물의 예로는, 2,2'-디에톡시 아세토페논, 2,2'-디부톡시 아세토페논, 2-히드록시-2-메틸프로피오페논, p-t-부틸트리클로로 아세토페논, p-t-부틸디클로로 아세토페논, 4-클로로 아세토페논, 2,2'-디클로로-4-페녹시 아세토페논, 2-메틸-1-(4-(메틸티오)페닐)-2-모폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모폴리노페닐)-부탄-1-온 등을 들 수 있다.Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloro acetophenone, pt-butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like.
상기 벤조페논계 화합물의 예로는, 벤조페논, 벤조일 안식향산, 벤조일 안식향산 메틸, 4-페닐 벤조페논, 히드록시벤조페논, 아크릴화 벤조페논, 4,4'-비스(디메틸 아미노)벤조페논, 4,4'-비스(디에틸아미노)벤조페논, 4,4'-디메틸아미노벤조페논, 4,4'-디클로로벤조페논, 3,3'-디메틸-2-메톡시벤조페논등을 들 수 있다.Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4 '-Bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.
상기 티오크산톤계 화합물의 예로는, 티오크산톤, 2-메틸티오크산톤, 이소프로필 티오크산톤, 2,4-디에틸 티오크산톤, 2,4-디이소프로필 티오크산톤, 2-클로로티오크산톤 등을 들 수 있다.Examples of the thioxanthone compound include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- And chlorothioxanthone.
상기 벤조인계 화합물의 예로는, 벤조인, 벤조인 메틸 에테르, 벤조인 에틸 에테르, 벤조인 이소프로필 에테르, 벤조인 이소부틸 에테르, 벤질디메틸케탈 등을 들 수 있다.Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyldimethylketal.
상기 트리아진계 화합물의 예로는, 2,4,6-트리클로로-s-트리아진, 2-페닐-4,6-비스(트리클로로메틸)-s-트리아진, 2-(3',4'-디메톡시스티릴)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(4'-메톡시나프틸)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(p-메톡시페닐)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(p-톨릴)-4,6-비스(트리클로로 메틸)-s-트리아진, 2-비페닐-4,6-비스(트리클로로 메틸)-s-트리아진, 비스(트리클로로메틸)-6-스티릴-s-트리아진, 2-(나프토-1-일)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(4-메톡시나프토-1-일)-4,6-비스(트리클로로메틸)-s-트리아진, 2-4-비스(트리클로로메틸)-6-피페로닐-s-트리아진, 2-4-비스(트리클로로메틸)-6-(4-메톡시스티릴)-s-트리아진 등을 들 수 있다.Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4' -Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine , 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)- 4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4 -Bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc. are mentioned. .
상기 옥심계 화합물의 예로는 O-아실옥심계 화합물, 2-(O-벤조일옥심)-1-[4-(페닐티오)페닐]-1,2-옥탄디온, 1-(O-아세틸옥심)-1-[9-에틸-6-(2-메틸벤조일)-9H-카르바졸-3-일]에탄온, O-에톡시카르보닐-α-옥시아미노-1-페닐프로판-1-온 등을 사용할 수 있다. 상기 O-아실옥심계 화합물의 구체적인 예로는, 1,2-옥탄디온, 2-디메틸아미노-2-(4-메틸벤질)-1-(4-모르폴린-4-일-페닐)-부탄-1-온, 1-(4-페닐술파닐페닐)-부탄-1,2-디온-2-옥심-O-벤조에이트, 1-(4-페닐술파닐페닐)-옥탄-1,2-디온-2-옥심-O-벤조에이트, 1-(4-페닐술파닐페닐)-옥탄-1-온옥심-O-아세테이트 및 1-(4-페닐술파닐페닐)-부탄-1-온옥심-O-아세테이트 등을 들 수 있다. Examples of the oxime-based compound include O-acyloxime-based compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime) -1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, etc. Can be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane- 1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione -2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-oneoxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime- O-acetate, etc. are mentioned.
상기 아미노케톤계 화합물의 예로는 2-벤질-2-디메틸아미노-1-(4-모폴리노페닐)-부탄온-1 (2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1) 등을 들 수 있다.Examples of the aminoketone-based compound include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone -1) etc. are mentioned.
상기 광중합 개시제는 상기 화합물 이외에도 카바졸계 화합물, 디케톤류 화합물, 술포늄 보레이트계 화합물, 디아조계 화합물, 이미다졸계 화합물, 비이미다졸계 화합물 등을 사용할 수 있다.In addition to the above compounds, the photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, or a biimidazole compound.
상기 광중합 개시제는 빛을 흡수하여 들뜬 상태가 된 후 그 에너지를 전달함으로써 화학반응을 일으키는 광 증감제와 함께 사용될 수도 있다.The photopolymerization initiator may be used together with a photosensitizer that causes a chemical reaction by absorbing light and becoming excited and then transferring the energy.
상기 광 증감제의 예로는, 테트라에틸렌글리콜 비스-3-머캡토 프로피오네이트, 펜타에리트리톨 테트라키스-3-머캡토 프로피오네이트, 디펜타에리트리톨 테트라키스-3-머캡토 프로피오네이트 등을 들 수 있다. Examples of the photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, etc. Can be mentioned.
상기 열중합 개시제의 예로는, 퍼옥사이드, 구체적으로 벤조일 퍼옥사이드, 다이벤조일 퍼옥사이드, 라우릴 퍼옥사이드, 다이라우릴 퍼옥사이드, 다이-tert-부틸 퍼옥사이드, 사이클로헥산 퍼옥사이드, 메틸 에틸 케톤 퍼옥사이드, 하이드로퍼옥사이드(예컨대, tert-부틸 하이드로퍼옥사이드, 쿠멘 하이드로퍼옥사이드), 다이사이클로헥실 퍼옥시다이카르보네이트, 2,2-아조-비스(아이소부티로니트릴), t-부틸 퍼벤조에이트 등을 들 수 있고, 2,2'-아조비스-2-메틸프로피오니트릴 등을 들 수도 있으나, 반드시 이에 한정되는 것은 아니고, 당업계에 널리 알려진 것이면 어느 것이든 사용할 수 있다.Examples of the thermal polymerization initiator include peroxide, specifically benzoyl peroxide, dibenzoyl peroxide, lauryl peroxide, dilauryl peroxide, di-tert-butyl peroxide, cyclohexane peroxide, methyl ethyl ketone peroxide. Oxide, hydroperoxide (e.g., tert-butyl hydroperoxide, cumene hydroperoxide), dicyclohexyl peroxydicarbonate, 2,2-azo-bis (isobutyronitrile), t-butyl perbenzo Eight, etc. may be mentioned, and 2,2'-azobis-2-methylpropionitrile, etc. may be mentioned, but the present invention is not limited thereto, and any one may be used as long as it is widely known in the art.
상기 중합 개시제는 상기 무용매형 경화성 조성물 총량에 대해 0.1 중량% 내지 5 중량%, 예컨대 1 중량% 내지 4 중량%로 포함될 수 있다. 중합 개시제가 상기 범위 내로 포함될 경우, 노광 또는 열경화 시 경화가 충분히 일어나 우수한 신뢰성을 얻을 수 있으며, 미반응 개시제로 인한 투과율의 저하를 막아 양자점의 광특성 저하를 방지할 수 있다. The polymerization initiator may be included in an amount of 0.1% to 5% by weight, such as 1% to 4% by weight, based on the total amount of the solvent-free curable composition. When the polymerization initiator is included within the above range, curing occurs sufficiently during exposure or thermal curing to obtain excellent reliability, and decreases in transmittance due to an unreacted initiator may be prevented, thereby preventing a decrease in optical properties of quantum dots.
광확산제 (또는 광확산제 분산액)Light diffusing agent (or light diffusing agent dispersion)
일 구현예에 따른 무용매형 경화성 조성물은 광확산제를 더 포함할 수 있다.The solvent-free curable composition according to an embodiment may further include a light diffusing agent.
예컨대, 상기 광확산제는 황산바륨(BaSO4), 탄산칼슘(CaCO3), 이산화티타늄(TiO2), 지르코니아(ZrO2) 또는 이들의 조합을 포함할 수 있다.For example, the light diffusing agent may include barium sulfate (BaSO 4 ), calcium carbonate (CaCO 3 ), titanium dioxide (TiO 2 ), zirconia (ZrO 2 ), or a combination thereof.
상기 광확산제는 전술한 양자점에 흡수되지 않은 광을 반사시키고, 상기 반사된 광을 양자점이 다시 흡수할 수 있도록 한다. 즉, 상기 광확산제는 양자점에 흡수되는 광의 양을 증가시켜, 경화성 조성물의 광변환 효율을 증가시킬 수 있다.The light diffusing agent reflects light not absorbed by the above-described quantum dots, and allows the reflected light to be absorbed again. That is, the light diffusing agent may increase the amount of light absorbed by the quantum dots, thereby increasing the light conversion efficiency of the curable composition.
상기 광확산제는 평균 입경(D50)이 150nm 내지 250nm 일 수 있으며, 구체적으로는 180nm 내지 230nm일 수 있다. 상기 광확산제의 평균 입경이 상기 범위 내일 경우, 보다 우수한 광확산 효과를 가질 수 있으며, 광변환 효율을 증가시킬 수 있다.The light diffusing agent may have an average particle diameter (D 50 ) of 150 nm to 250 nm, and specifically 180 nm to 230 nm. When the average particle diameter of the light diffusing agent is within the above range, a better light diffusing effect may be obtained, and light conversion efficiency may be increased.
상기 광확산제는 상기 무용매형 경화성 조성물 총량에 대해 1 중량% 내지 20 중량%, 예컨대 5 중량% 내지 10 중량%로 포함될 수 있다. 상기 광확산제가 상기 무용매형 경화성 조성물 총량에 대해 1 중량% 미만으로 포함될 경우, 광확산제를 사용함에 따른 광변환 효율 향상 효과를 기대하기가 어렵고, 20 중량%를 초과하여 포함할 경우에는 양자점 침강 문제가 발생될 우려가 있다. The light diffusing agent may be included in an amount of 1% to 20% by weight, such as 5% to 10% by weight, based on the total amount of the solvent-free curable composition. When the light diffusing agent is included in an amount of less than 1% by weight based on the total amount of the solvent-free curable composition, it is difficult to expect the effect of improving the light conversion efficiency by using the light diffusing agent, and when it is included in more than 20% by weight, quantum dot sedimentation There is a risk of a problem occurring.
기타 첨가제Other additives
상기 양자점의 안정성 및 분산성 향상을 위해, 일 구현예에 따른 무용매형 경화성 조성물은 중합금지제를 더 포함할 수 있다.In order to improve the stability and dispersibility of the quantum dots, the solvent-free curable composition according to an embodiment may further include a polymerization inhibitor.
상기 중합 금지제는 하이드로퀴논계 화합물, 카테콜계 화합물 또는 이들의 조합을 포함할 수 있으나, 반드시 이에 한정되는 것은 아니다. 일 구현예에 따른 무용매형 경화성 조성물이 상기 하이드로퀴논계 화합물, 카테콜계 화합물 또는 이들의 조합을 더 포함함에 따라, 무용매형 경화성 조성물을 인쇄(코팅) 후, 노광하는 동안 상온 가교를 방지할 수 있다.The polymerization inhibitor may include a hydroquinone compound, a catechol compound, or a combination thereof, but is not limited thereto. As the solvent-free curable composition according to the embodiment further includes the hydroquinone-based compound, the catechol-based compound, or a combination thereof, after printing (coating) the solvent-free curable composition, it is possible to prevent crosslinking at room temperature during exposure. .
예컨대, 상기 하이드로퀴논계 화합물, 카테콜계 화합물 또는 이들의 조합은 하이드로퀴논, 메틸 하이드로퀴논, 메톡시하이드로퀴논, t-부틸 하이드로퀴논, 2,5-디-t-부틸 하이드로퀴논, 2,5-비스(1,1-디메틸부틸) 하이드로퀴논, 2,5-비스(1,1,3,3-테트라메틸부틸) 하이드로퀴논, 카테콜, t-부틸 카테콜, 4-메톡시페놀, 피로가롤, 2,6-디-t-부틸-4-메틸페놀, 2-나프톨, 트리스(N-하이드록시-N-니트로소페닐아미나토-O,O')알루미늄(Tris(N-hydroxy-N-nitrosophenylaminato-O,O')aluminium) 또는 이들의 조합을 포함할 수 있으나, 반드시 이에 한정되는 것은 아니다.For example, the hydroquinone-based compound, the catechol-based compound, or a combination thereof is hydroquinone, methyl hydroquinone, methoxyhydroquinone, t-butyl hydroquinone, 2,5-di- t -butyl hydroquinone, 2,5- Bis(1,1-dimethylbutyl) hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl) hydroquinone, catechol, t-butyl catechol, 4-methoxyphenol, pyroga Roll, 2,6-di- t -butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitrosophenylaminato-O,O') aluminum (Tris(N-hydroxy-N -nitrosophenylaminato-O,O')aluminium) or a combination thereof, but is not limited thereto.
상기 하이드로퀴논계 화합물, 카테콜계 화합물 또는 이들의 조합은 분산액의 형태로 사용될 수 있으며, 상기 분산액 형태의 중합 금지제는 무용매형 경화성 조성물 총량에 대하여 0.001 중량% 내지 3 중량%, 예컨대 0.1 중량% 내지 2 중량%로 포함될 수 있다. 상기 중합 금지제가 상기 범위 내로 포함될 경우, 상온 경시 문제를 해결함과 동시에, 감도 저하 및 표면 박리 현상을 방지할 수 있다.The hydroquinone-based compound, catechol-based compound, or a combination thereof may be used in the form of a dispersion, and the polymerization inhibitor in the dispersion form is 0.001% by weight to 3% by weight, such as 0.1% by weight, based on the total amount of the solvent-free curable composition. It may be included in 2% by weight. When the polymerization inhibitor is included within the above range, it is possible to solve the problem of room temperature aging and prevent sensitivity reduction and surface peeling.
또한, 일 구현예에 따른 무용매형 경화성 조성물은 내열성 및 신뢰성 향상을 위해, 말론산; 3-아미노-1,2-프로판디올; 실란계 커플링제; 레벨링제; 불소계 계면활성제; 또는 이들의 조합을 더 포함할 수 있다.In addition, a solvent-free curable composition according to an embodiment may include malonic acid for improving heat resistance and reliability; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine-based surfactant; Or it may further include a combination of these.
예컨대, 일 구현예에 따른 무용매형 경화성 조성물은 기판과의 밀착성 등을 개선하기 위해 비닐기, 카르복실기, 메타크릴옥시기, 이소시아네이트기, 에폭시기 등의 반응성 치환기를 갖는 실란계 커플링제를 더 포함할 수 있다.For example, the solvent-free curable composition according to an embodiment may further include a silane-based coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group to improve adhesion to the substrate. have.
상기 실란계 커플링제의 예로는, 트리메톡시실릴 벤조산, γ메타크릴 옥시프로필 트리메톡시실란, 비닐 트리아세톡시실란, 비닐 트리메톡시실란, γ이소시아네이트 프로필 트리에톡시실란, γ글리시독시 프로필 트리메톡시실란, β에폭시사이클로헥실)에틸트리메톡시실란 등을 들 수 있으며, 이들을 단독 또는 2종 이상 혼합하여 사용할 수 있다. Examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ isocyanate propyl triethoxysilane, γ glycidoxy propyl Trimethoxysilane, βepoxycyclohexyl)ethyltrimethoxysilane, and the like, and these may be used alone or in combination of two or more.
상기 실란계 커플링제는 상기 무용매형 경화성 조성물 100 중량부에 대하여 0.01 중량부 내지 10 중량부로 포함될 수 있다. 실란계 커플링제가 상기 범위 내로 포함될 경우 밀착성, 저장성 등이 우수하다. The silane-based coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the solvent-free curable composition. When the silane-based coupling agent is included within the above range, adhesion and storage properties are excellent.
또한 상기 무용매형 경화성 조성물은 필요에 따라 코팅성 향상 및 결점 생성 방지 효과를 위해, 즉 레벨링(leveling) 성능을 개선시키기 위해 계면 활성제, 예컨대 불소계 계면활성제를 더 포함할 수 있다. In addition, the solvent-free curable composition may further include a surfactant, such as a fluorine-based surfactant, to improve coating properties and prevent defects, that is, to improve leveling performance, if necessary.
상기 불소계 계면활성제는 4,000 g/mol 내지 10,000 g/mol의 낮은 중량평균 분자량을 가질 수 있으며, 구체적으로는 6,000 g/mol 내지 10,000g/mol의 중량평균 분자량을 가질 수 있다. 또한 상기 불소계 계면활성제는 표면장력이 18 mN/m 내지 23 mN/m(0.1% 프로필렌글리콜 모노메틸에테르 아세테이트(PGMEA) 용액에서 측정)일 수 있다. 상기 불소계 계면활성제의 중량평균 분자량 및 표면장력이 상기 범위 내일 경우 레벨링 성능을 더욱 개선할 수 있으며, 고속 코팅(high speed coating)시 얼룩 발생을 방지할 수 있고, 기포 발생이 적어 막 결함이 적기 때문에, 고속 코팅법인 슬릿 코팅(slit coating)에 우수한 특성을 부여한다. The fluorine-based surfactant may have a low weight average molecular weight of 4,000 g/mol to 10,000 g/mol, and specifically, may have a weight average molecular weight of 6,000 g/mol to 10,000 g/mol. In addition, the fluorine-based surfactant may have a surface tension of 18 mN/m to 23 mN/m (measured in a 0.1% propylene glycol monomethyl ether acetate (PGMEA) solution). When the weight average molecular weight and surface tension of the fluorine-based surfactant are within the above ranges, leveling performance can be further improved, stains can be prevented during high speed coating, and there are few film defects due to fewer bubbles. , It gives excellent properties to slit coating, a high-speed coating method.
상기 불소계 계면활성제로는, BM Chemie社의 BM-1000®, BM-1100® 등; 다이 닛폰 잉키 가가꾸 고교(주)社의 메카 팩 F 142D®, 동 F 172®, 동 F 173®, 동 F 183® 등; 스미토모 스리엠(주)社의 프로라드 FC-135®, 동 FC-170C®, 동 FC-430®, 동 FC-431® 등; 아사히 그라스(주)社의 사프론 S-112®, 동 S-113®, 동 S-131®, 동 S-141®, 동 S-145® 등; 도레이 실리콘(주)社의 SH-28PA®, 동-190®, 동-193®, SZ-6032®, SF-8428® 등; DIC(주)社의 F-482, F-484, F-478, F-554 등의 명칭으로 시판되고 있는 불소계 계면활성제를 사용할 수 있다.The fluorine is a surfactant, the BM Chemie社BM-1000 ®, BM-1100 ® , and the like; Mecha Pack F 142D ® , F 172 ® , F 173 ® , F 183 ®, etc. of Dai Nippon Inki Chemical High School Co., Ltd.; Sumitomo M. (Note)社Pro rod FC-135 ®, the same FC-170C ®, copper FC-430 ®, the same FC-431 ®, and the like; Asahi Grass Co., Saffron S-112 ® of社, such S-113 ®, the same S-131 ®, the same S-141 ®, the same S-145 ®, and the like; Toray silicone (Note)社SH-28PA ®, ® -190 copper, copper -193 ®, SZ-6032 ®, SF-8428 ® , and the like; It is possible to use a fluorine-based surfactant marketed under the names of DIC Corporation's F-482, F-484, F-478, F-554, and the like.
또한, 일 구현예에 따른 무용매형 경화성 조성물은 전술한 불소계 계면활성제와 함께 실리콘계 계면활성제를 사용할 수도 있다. 상기 실리콘계 계면활성제의 구체적인 예로는 도시바 실리콘社의 TSF400, TSF401, TSF410, TSF4440 등이 있으나, 이에 한정되는 것은 아니다. In addition, the solvent-free curable composition according to an embodiment may use a silicone-based surfactant together with the above-described fluorine-based surfactant. Specific examples of the silicone-based surfactant include TSF400, TSF401, TSF410, TSF4440 manufactured by Toshiba Silicone, but are not limited thereto.
상기 불소계 계면활성제 등을 포함하는 계면활성제는 상기 무용매형 경화성 조성물 100 중량부에 대하여 0.01 중량부 내지 5 중량부, 예컨대 0.1 중량부 내지 2 중량부로 포함될 수 있다. 상기 계면활성제가 상기 범위 내로 포함될 경우 분사된 조성물 내에 이물이 발생되는 현상이 줄어들게 된다.Surfactants including the fluorine-based surfactant and the like may be included in an amount of 0.01 parts by weight to 5 parts by weight, for example, 0.1 parts by weight to 2 parts by weight, based on 100 parts by weight of the solvent-free curable composition. When the surfactant is included within the above range, the phenomenon that foreign substances are generated in the sprayed composition is reduced.
또한 일 구현예에 따른 무용매형 경화성 조성물은 물성을 저해하지 않는 범위 내에서 산화방지제 등의 기타 첨가제가 일정량 더 첨가될 수도 있다.In addition, in the solvent-free curable composition according to an embodiment, a certain amount of other additives such as antioxidants may be further added within a range that does not impair physical properties.
다른 일 구현예는 전술한 무용매형 경화성 조성물을 이용하여 제조된 경화막을 제공한다.Another embodiment provides a cured film prepared using the above-described solvent-free curable composition.
상기 경화막은 일 구현예에 따른 무용매형 경화성 조성물을 경화하여 제조되기에 540nm 이하의 발광파장을 가질 수 있고, 이로 인해 궁극적으로 고색재현성을 구현함과 동시에 내열성, 내광성 등의 물성 또한 우수하게 유지할 수 있다. Since the cured film is prepared by curing the solvent-free curable composition according to an embodiment, it may have a luminous wavelength of 540 nm or less, thereby ultimately realizing high color reproducibility and maintaining excellent physical properties such as heat resistance and light resistance. have.
상기 경화막의 제조방법 중 하나는, 전술한 무용매형 경화성 조성물을 기판 위에 잉크젯 분사 방법으로 도포하여 패턴을 형성하는 단계(S1); 및 상기 패턴을 경화하는 단계(S2)를 포함한다.One of the manufacturing methods of the cured film may include forming a pattern by applying the above-described solvent-free curable composition on a substrate by an ink jet spraying method (S1); And curing the pattern (S2).
(S1) 패턴을 형성하는 단계(S1) forming a pattern
상기 무용매형 경화성 조성물은 잉크젯 분산 방식으로 0.5 내지 20 ㎛의 두께로 기판 위에 도포하는 것이 바람직하다. 상기 잉크젯 분사는 각 노즐당 단일 컬러만 분사하여 필요한 색의 수에 따라 반복적으로 분사함으로써 패턴을 형성할 수 있으며, 공정을 줄이기 위하여 필요한 색의 수를 각 잉크젯 노즐을 통해 동시에 분사하는 방식으로 패턴을 형성할 수도 있다. It is preferable that the solvent-free curable composition is applied on a substrate in a thickness of 0.5 to 20 µm in an ink jet dispersion method. The inkjet spraying can form a pattern by spraying only a single color for each nozzle and spraying repeatedly according to the number of required colors, and in order to reduce the process, the pattern can be simultaneously sprayed through each inkjet nozzle. It can also be formed.
(S2) 경화하는 단계(S2) curing step
상기 수득된 패턴을 경화시켜 화소를 얻을 수 있다. 이때 경화시키는 방법으로는 열경화 공정 또는 광경화 공정을 모두 적용할 수 있다. 상기 열경화 공정은 100℃이상의 온도로 가열하여 경화시키는 것이 바람직하고, 더욱 바람직하게는 100℃ 내지 300℃로 가열하여 경화시킬 수 있으며, 조금 더 바람직하게는 160℃내지 250℃로 가열하여 경화시킬 수 있다. 상기 광경화 공정은 190nm 내지 450nm, 예컨대 200nm 내지 500nm의 UV 광선 등의 활성선을 조사한다. 조사에 사용되는 광원으로는 저압 수은등, 고압 수은등, 초고압 수은등, 금속 할로겐화물 램프, 아르곤 가스 레이저 등을 사용할 수 있으며, 경우에 따라 X선, 전자선 등도 이용할 수 있다. A pixel can be obtained by curing the obtained pattern. At this time, as a curing method, both a thermal curing process or a photo curing process may be applied. The thermal curing process is preferably cured by heating at a temperature of 100° C. or higher, and more preferably cured by heating at 100° C. to 300° C., and a little more preferably heating to 160° C. to 250° C. I can. In the photocuring process, actinic rays such as UV rays of 190nm to 450nm, for example, 200nm to 500nm, are irradiated. As a light source used for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. may be used, and in some cases, an X-ray, an electron beam, and the like may be used.
상기 경화막의 제조방법 중 또 다른 하나는 전술한 무용매형 경화성 조성물을 이용하여 리소그래피법을 이용하여 경화막을 제조하는 것으로, 제조방법은 다음과 같다.Another method of manufacturing the cured film is to prepare a cured film using a lithography method using the above-described solvent-free curable composition, and the manufacturing method is as follows.
(1) 도포 및 도막 형성 단계(1) Application and film formation step
전술한 경화성 조성물을 소정의 전처리를 한 기판 상에 스핀 또는 슬릿 코트법, 롤 코트법, 스크린 인쇄법, 어플리케이터법 등의 방법을 사용하여 원하는 두께, 예를 들어 2㎛ 내지 10㎛의 두께로 도포한 후, 70℃내지 90℃의 온도에서 1분 내지 10분 동안 가열하여 용매를 제거함으로써 도막을 형성한다. The above-described curable composition is applied on a substrate subjected to a predetermined pretreatment to a desired thickness, for example, 2 μm to 10 μm using a method such as spin or slit coating, roll coating, screen printing, and applicator method Then, the solvent is removed by heating at a temperature of 70° C. to 90° C. for 1 to 10 minutes to form a coating film.
(2) 노광 단계(2) exposure step
상기 얻어진 도막에 필요한 패턴 형성을 위해 소정 형태의 마스크를 개재한 뒤, 190nm 내지 450nm, 예컨대 200nm 내지 500nm의 UV 광선 등의 활성선을 조사한다. 조사에 사용되는 광원으로는 저압 수은등, 고압 수은등, 초고압 수은등, 금속 할로겐화물 램프, 아르곤 가스 레이저 등을 사용할 수 있으며, 경우에 따라 X선, 전자선 등도 이용할 수 있다. After a mask of a predetermined shape is interposed in order to form a pattern required for the obtained coating film, actinic rays such as UV rays of 190 nm to 450 nm, for example, 200 nm to 500 nm, are irradiated. As a light source used for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. may be used, and in some cases, an X-ray, an electron beam, and the like may be used.
노광량은 상기 경화성 조성물 각 성분의 종류, 배합량 및 건조 막 두께에 따라 다르지만, 예를 들어 고압 수은등을 사용할 경우 500 mJ/cm2 이하(365 nm 센서에 의함)이다.The exposure amount varies depending on the type, blending amount, and dry film thickness of each component of the curable composition, but is 500 mJ/cm 2 or less (by a 365 nm sensor), for example, when a high-pressure mercury lamp is used.
(3) 현상 단계(3) development stage
상기 노광 단계에 이어, 알칼리성 수용액을 현상액으로 이용하여 불필요한 부분을 용해, 제거함으로써 노광 부분만을 잔존시켜 화상 패턴을 형성시킨다. 즉, 알칼리 현상액으로 현상하는 경우, 비노광부는 용해되고, 이미지 컬러필터 패턴이 형성되게 된다.Following the exposure step, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary portions, so that only the exposed portions remain to form an image pattern. That is, when developing with an alkaline developer, the non-exposed portion is dissolved and an image color filter pattern is formed.
(4) 후처리 단계(4) Post-processing step
상기 현상에 의해 수득된 화상 패턴을 내열성, 내광성, 밀착성, 내크랙성, 내화학성, 고강도, 저장 안정성 등의 면에서 우수한 패턴을 얻기 위해, 다시 가열하거나 활성선 조사 등을 행하여 경화시킬 수 있다.In order to obtain an excellent pattern in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, storage stability, and the like, the image pattern obtained by the above development may be cured by heating again or irradiating with actinic rays.
또 다른 일 구현예는 상기 경화막을 포함하는 컬러필터 및 상기 컬러필터를 포함하는 디스플레이 장치를 제공한다.Another embodiment provides a color filter including the cured film and a display device including the color filter.
이하, 본 발명의 바람직한 실시예를 기재한다. 다만, 하기의 실시예는 본 발명의 바람직한 일 실시예일뿐, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only preferred examples of the present invention, and the present invention is not limited by the following examples.
(리간드 화합물 합성)(Ligand compound synthesis)
합성예 1Synthesis Example 1
6-mercapto-1-hexanol 30g, [2-(2-methoxyethoxy)ethoxy]acetic acid 40g, p-toluenesulfonic acid 6.4g을 반응 플라스크에 넣고, cyclohexane 300mL에서 분산한다. 반응 플라스크에 dean stark condensor를 설치하고 reflux 및 교반한다. 이론 H2O 수득량이 확인되면 1시간 후에 반응을 종료하고 상온으로 온도를 낮춘다. 과량의 물을 넣고 반응을 quenching한 다음, ethyle acetate (EA) 용매를 넣어 extraction, neutralization, concentration 순으로 정제를 진행한다. 농축된 수득물을 진공 건조하여 하기 화학식 2로 표시되는 화합물을 얻는다. 30 g of 6-mercapto-1-hexanol, 40 g of [2-(2-methoxyethoxy)ethoxy]acetic acid, and 6.4 g of p-toluenesulfonic acid were added to the reaction flask, and dispersed in 300 ml of cyclohexane. Install the dean stark condensor in the reaction flask, reflux and stir. When the theoretical H 2 O yield is confirmed, the reaction is terminated after 1 hour and the temperature is lowered to room temperature. After quenching the reaction with an excess of water, ethyle acetate (EA) solvent is added to purify in the order of extraction, neutralization, and concentration. The concentrated product was dried under vacuum to obtain a compound represented by the following formula (2).
[화학식 2][Formula 2]
합성예 2Synthesis Example 2
6-mercapto-1-hexanol 대신 11-mercapto-1-undecanol을 사용한 것을 제외하고는 합성예 1과 동일하게 실시하여 하기 화학식 3으로 표시되는 화합물을 얻는다.Except that 11-mercapto-1-undecanol was used instead of 6-mercapto-1-hexanol, it was carried out in the same manner as in Synthesis Example 1 to obtain a compound represented by the following formula (3).
[화학식 3][Formula 3]
합성예 3Synthesis Example 3
p-toluenesulfonic (p-Ts), poly(ethylene glycol)n methyl ether (n=9; PEG9ME, 한농화성) 30g, 3-mercaptopropionic acid 7.5g을 혼합하고 5시간 동안 교반하여 carboxylic acid compound를 준비한다. 여기에 6-mercapto-1-hexanol 9.4g, p-toluenesulfonic acid 2g을 넣고 cyclohexane 300mL에서 분산한다. 이 후에는 합성예 1과 동일한 방법으로 합성을 진행하여 하기 화학식 4로 표시되는 화합물을 얻는다. 30 g of p-toluenesulfonic (p-Ts), poly(ethylene glycol) n methyl ether (n=9; PEG9ME, Hahn Hwaseong) and 7.5 g of 3-mercaptopropionic acid are mixed and stirred for 5 hours to prepare a carboxylic acid compound. Here, 9.4 g of 6-mercapto-1-hexanol and 2 g of p-toluenesulfonic acid are added and dispersed in 300 mL of cyclohexane. After that, synthesis is performed in the same manner as in Synthesis Example 1 to obtain a compound represented by the following formula (4).
[화학식 4][Formula 4]
합성예 4Synthesis Example 4
Phthalic anhydride 20g, (Ethylene oxide)n methyl ether (n=9; EO9-ME, 한농화성) 115.7g을 질소 분위기 하에서 혼합하고 5시간 동안 교반하여 하기 화학식 5로 표시되는 화합물을 얻는다. Phthalic anhydride 20g, (Ethylene oxide) n methyl ether (n=9; EO9-ME, concentrated) 115.7g was mixed under a nitrogen atmosphere and stirred for 5 hours to obtain a compound represented by the following formula (5).
[화학식 5][Formula 5]
비교합성예 1Comparative Synthesis Example 1
PH-4 (한농화성) 100g, NaOH 22g을 THF 500mL, H2O 100mL에 질소 분위기 하에서 충분히 분산한다. 분산액을 0℃까지 온도를 낮추고 p-toluenesulfonic acid (15g)가 용해된 THF 용액을 dropwise 투입한다. 투입이 끝나면 이를 상온에서 15시간 동안 교반한다. 과량의 물을 넣고 반응을 종료하고 ethyl acetate (EA)를 넣고 extraction, neutralization, concentration을 거쳐 정제 후 진공에서 건조한다. 이 수득물 중 50 g 을 ethyl acohol 300 mL에 녹인 다음 thiourea 12.5 g을 넣고, 15시간 동안 reflux 교반한다. 여기에 NaOH solution을 투입하고 5시간 추가 교반한다. 반응 종료 후 extraction, neutralization, concentration을 거쳐 정제한다. 진공 오븐에서 24시간 동안 건조하여 하기 화학식 C-1로 표시되는 화합물을 얻는다. PH-4 (one concentration) 100g, NaOH 22g is sufficiently dispersed in THF 500mL, H 2 O 100mL under a nitrogen atmosphere. The temperature of the dispersion is lowered to 0°C, and a THF solution in which p-toluenesulfonic acid (15g) is dissolved is added dropwise. When the addition is finished, it is stirred at room temperature for 15 hours. After adding excess water to complete the reaction, ethyl acetate (EA) was added, followed by extraction, neutralization, and concentration, followed by purification and drying under vacuum. 50 g of this product was dissolved in 300 mL of ethyl acohol, and 12.5 g of thiourea was added, followed by reflux stirring for 15 hours. Add NaOH solution and stir for 5 hours. After completion of the reaction, it is purified through extraction, neutralization, and concentration. Drying in a vacuum oven for 24 hours to obtain a compound represented by the following formula (C-1).
[화학식 C-1][Chemical Formula C-1]
비교합성예 2Comparative Synthesis Example 2
2구 환저 플라스크에 2-mercapto-1-ethanol 5.82g, 2-2-(2-methoxyethoxy)ethoxy acetic acid 13.3g, p-toluenesulfonic acid monohydrate 2.1g을 각각 넣고 cyclohexane 300mL에 용해한다. 주입구에 dean stark을 채결하고 여기에 condensor를 연결한다. 8시간 동안 reflux 후 반응을 종료한다. (dean stark에 모인 물 최종 수득량 확인). Separating funnel로 반응물을 옮기고 추출(extraction), 중화 단계를 거쳐 용매를 제거한 다음, 진공 오븐 건조해, 하기 화학식 C-2로 표시되는 화합물을 얻는다.In a 2-neck round bottom flask, add 5.82 g of 2-mercapto-1-ethanol, 13.3 g of 2-2-(2-methoxyethoxy) ethoxy acetic acid, and 2.1 g of p-toluenesulfonic acid monohydrate, respectively, and dissolve in 300 ml of cyclohexane. Attach a dean stark to the inlet and connect the condensor to it. After refluxing for 8 hours, the reaction was terminated. (Check the final yield of water collected in dean stark). The reactant is transferred to a separating funnel, extraction and neutralization are performed to remove the solvent, followed by drying in a vacuum oven to obtain a compound represented by the following formula (C-2).
[화학식 C-2][Chemical Formula C-2]
비교합성예 3Comparative Synthesis Example 3
6-mercapto-1-hexanol 대신 5-mercapto-1-pentanol을 사용한 것을 제외하고는 합성예 1과 동일하게 실시하여 하기 화학식 C-3으로 표시되는 화합물을 얻는다. Except for using 5-mercapto-1-pentanol instead of 6-mercapto-1-hexanol, it was carried out in the same manner as in Synthesis Example 1 to obtain a compound represented by the following formula (C-3).
[화학식 C-3][Chemical Formula C-3]
비교합성예 4Comparative Synthesis Example 4
6-mercapto-1-hexanol 대신 16-mercapto-1-hexanol을 사용한 것을 제외하고 합성예 1과 동일하게 실시하여, 하기 화학식 C-4로 표시되는 화합물을 얻는다. In the same manner as in Synthesis Example 1, except that 16-mercapto-1-hexanol was used instead of 6-mercapto-1-hexanol, a compound represented by the following formula (C-4) was obtained.
[화학식 C-4][Chemical Formula C-4]
(리간드로 표면개질된 양자점 분산액 제조)(Preparation of a surface-modified quantum dot dispersion with a ligand)
제조예 1Manufacturing Example 1
3구 환저 플라스크에 마그네틱바를 넣고, 양자점-CHA(cyclohexyl acetate) 용액(고형분 26wt%)을 계량 투입한다. 여기에 상기 화학식 2로 표시되는 화합물을 투입한다. Insert a magnetic bar into a 3-neck round bottom flask, and measure and add a quantum dot-CHA (cyclohexyl acetate) solution (solid content 26wt%). Here, the compound represented by Chemical Formula 2 is added.
1분 정도 잘 혼합하여 준 다음 80℃질소 분위기에서 교반한다. 반응 종료 후 상온으로 cooling한 다음 cyclohexane에 양자점 반응액을 넣어 침전을 잡는다. 원심분리를 통해 침전된 양자점 파우더와 용매를 분리한다. 용매는 따라내서 폐기하고 침전은 진공 오븐에서 하루 간 충분히 건조하여, 표면개질된 양자점을 수득한다. After mixing well for about 1 minute, the mixture is stirred in a nitrogen atmosphere at 80°C. After the reaction is completed, the reaction solution is cooled to room temperature, and then the quantum dot reaction solution is added to cyclohexane to capture precipitation. Separate the precipitated quantum dot powder and solvent through centrifugation. The solvent was decanted and discarded, and the precipitate was sufficiently dried for one day in a vacuum oven to obtain surface-modified quantum dots.
상기 표면개질된 양자점 40 g을 하기 화학식 6-2로 표시되는 단량체(1,6-hexanediol diacrylate; 미원상사) 52.999 g에 12시간 동안 교반하여 표면개질된 양자점 분산액을 수득하였다. 40 g of the surface-modified quantum dots were stirred in 52.999 g of a monomer (1,6-hexanediol diacrylate; Miwon Sangsa) represented by the following Formula 6-2 for 12 hours to obtain a surface-modified quantum dot dispersion.
[화학식 6-2] [Formula 6-2]
제조예 2Manufacturing Example 2
상기 화학식 2로 표시되는 화합물 대신 상기 화학식 3으로 표시되는 화합물을 사용한 것을 제외하고는 제조예 1과 동일하게 하였다.It was carried out in the same manner as in Preparation Example 1, except that the compound represented by Formula 3 was used instead of the compound represented by Formula 2.
제조예 3Manufacturing Example 3
상기 화학식 2로 표시되는 화합물 대신 상기 화학식 4로 표시되는 화합물을 사용한 것을 제외하고는 제조예 1과 동일하게 하였다.It was carried out in the same manner as in Preparation Example 1, except that the compound represented by Formula 4 was used instead of the compound represented by Formula 2.
제조예 4Manufacturing Example 4
상기 화학식 2로 표시되는 화합물 대신 상기 화학식 5로 표시되는 화합물을 사용한 것을 제외하고는 제조예 1과 동일하게 하였다.It was carried out in the same manner as in Preparation Example 1, except that the compound represented by Formula 5 was used instead of the compound represented by Formula 2.
비교제조예 1Comparative Production Example 1
상기 화학식 2로 표시되는 화합물 대신 상기 화학식 C-1로 표시되는 화합물을 사용한 것을 제외하고는 제조예 1과 동일하게 하였다.In the same manner as in Preparation Example 1, except that the compound represented by Formula C-1 was used instead of the compound represented by Formula 2 above.
비교제조예 2Comparative Production Example 2
상기 화학식 2로 표시되는 화합물 대신 상기 화학식 C-2로 표시되는 화합물을 사용한 것을 제외하고는 제조예 1과 동일하게 하였다.In the same manner as in Preparation Example 1, except that the compound represented by Formula C-2 was used instead of the compound represented by Formula 2 above.
비교제조예 3Comparative Production Example 3
상기 화학식 2로 표시되는 화합물 대신 상기 화학식 C-3으로 표시되는 화합물을 사용한 것을 제외하고는 제조예 1과 동일하게 하였다.In the same manner as in Preparation Example 1, except that the compound represented by Formula C-3 was used instead of the compound represented by Formula 2 above.
비교제조예 4Comparative Production Example 4
상기 화학식 2로 표시되는 화합물 대신 상기 화학식 C-4로 표시되는 화합물을 사용한 것을 제외하고는 제조예 1과 동일하게 하였다.In the same manner as in Preparation Example 1, except that the compound represented by Formula C-4 was used instead of the compound represented by Formula 2 above.
(무용매형 경화성 조성물 제조)(Preparation of solvent-free curable composition)
실시예 1Example 1
상기 제조예 1에서 얻어진 분산액 92.999 g에 중합금지제(메틸하이드로퀴논, TOKYO CHEMICAL社) 0.001 g을 넣고 5분 간 교반한다. 이어서 광개시제(TPO-L, 폴리네트론社) 3 g을 투입하고 난 후, 광확산제(TiO2; SDT89, 이리도스社) 4 g을 넣는다. 전체 분산액을 1시간 동안 교반하여 무용매형 경화성 조성물을 제조한다.To 92.999 g of the dispersion obtained in Preparation Example 1, 0.001 g of a polymerization inhibitor (methylhydroquinone, TOKYO CHEMICAL) was added and stirred for 5 minutes. Subsequently, 3 g of a photoinitiator (TPO-L, Polynetron) was added, followed by 4 g of a light diffusing agent (TiO 2; SDT89, Iridos). The entire dispersion is stirred for 1 hour to prepare a solvent-free curable composition.
실시예 2Example 2
상기 제조예 1에서 얻어진 분산액 대신 상기 제조예 2에서 얻어진 분산액을 사용한 것을 제외하고는 실시예 1과 동일하게 하였다.In the same manner as in Example 1, except that the dispersion obtained in Preparation Example 2 was used instead of the dispersion obtained in Preparation Example 1 above.
실시예 3Example 3
상기 제조예 1에서 얻어진 분산액 대신 상기 제조예 3에서 얻어진 분산액을 사용한 것을 제외하고는 실시예 1과 동일하게 하였다.In the same manner as in Example 1, except that the dispersion obtained in Preparation Example 3 was used instead of the dispersion obtained in Preparation Example 1.
실시예 4Example 4
상기 제조예 1에서 얻어진 분산액 대신 상기 제조예 4에서 얻어진 분산액을 사용한 것을 제외하고는 실시예 1과 동일하게 하였다.In the same manner as in Example 1, except that the dispersion obtained in Preparation Example 4 was used instead of the dispersion obtained in Preparation Example 1 above.
비교예 1Comparative Example 1
상기 제조예 1에서 얻어진 분산액 대신 상기 비교제조예 1에서 얻어진 분산액을 사용한 것을 제외하고는 실시예 1과 동일하게 하였다.In the same manner as in Example 1, except that the dispersion obtained in Comparative Preparation Example 1 was used instead of the dispersion obtained in Preparation Example 1 above.
비교예 2Comparative Example 2
상기 제조예 1에서 얻어진 분산액 대신 상기 비교제조예 2에서 얻어진 분산액을 사용한 것을 제외하고는 실시예 1과 동일하게 하였다.In the same manner as in Example 1, except that the dispersion obtained in Comparative Preparation Example 2 was used instead of the dispersion obtained in Preparation Example 1 above.
비교예 3Comparative Example 3
상기 제조예 1에서 얻어진 분산액 대신 상기 비교제조예 3에서 얻어진 분산액을 사용한 것을 제외하고는 실시예 1과 동일하게 하였다.It was the same as in Example 1, except that the dispersion obtained in Comparative Preparation Example 3 was used instead of the dispersion obtained in Preparation Example 1.
비교예 4Comparative Example 4
상기 제조예 1에서 얻어진 분산액 대신 상기 비교제조예 4에서 얻어진 분산액을 사용한 것을 제외하고는 실시예 1과 동일하게 하였다.In the same manner as in Example 1, except that the dispersion obtained in Comparative Preparation Example 4 was used instead of the dispersion obtained in Preparation Example 1 above.
평가 1Evaluation 1
실시예 1 내지 실시예 4 및 비교예 1 내지 비교예 4에서 제조된 무용매형 경화성 조성물에 점도계(RheoStress 6000, HAAKE社)를 이용하여 상온(25℃에서 100rpm으로 2분 간 측정 후 측정한 점도값을 하기 표 1에 나타내었다.Viscosity value measured after 2 minutes at room temperature (100 rpm at 25°C) using a viscometer (RheoStress 6000, HAAKE) on the solvent-free curable compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 4 It is shown in Table 1 below.
| 점도Viscosity | |
| 실시예 1Example 1 | 2828 |
| 실시예 2Example 2 | 24.424.4 |
| 실시예 3Example 3 | 34.834.8 |
| 실시예 4Example 4 | 33.533.5 |
| 비교예 1Comparative Example 1 | 24.924.9 |
| 비교예 2Comparative Example 2 | 29.829.8 |
| 비교예 3Comparative Example 3 | 35.435.4 |
| 비교예 4Comparative Example 4 | 64.164.1 |
상기 표 1로부터, 화학식 1로 표시되는 화합물로 표면개질된 양자점을 포함하는 무용매형 경화성조성물은 잉크젯팅에 유리한 점도를 가짐을 확인할 수 있다. (일반적으로 조성물의 점도가 10 cPs 내지 35cPs인 경우 잉크젯팅에 유리하다.) 구체적으로, 화학식 1에서 n이 5 이하의 정수값을 가지거나 16 이상의 정수값을 가질 경우, 조성물의 점도가 너무 높아져 잉크-젯팅 등에 불리해 공정성이 저하됨을 확인할 수 있다.From Table 1, it can be seen that the solvent-free curable composition including the quantum dots surface-modified with the compound represented by Formula 1 has a viscosity advantageous for ink jetting. (In general, when the viscosity of the composition is 10 cPs to 35 cPs, it is advantageous for ink jetting.) Specifically, when n in Formula 1 has an integer value of 5 or less or an integer value of 16 or more, the viscosity of the composition becomes too high. It can be seen that fairness is deteriorated due to disadvantages such as ink-jetting.
평가 2Evaluation 2
실시예 1 내지 실시예 4 및 비교예 1 내지 비교예 4에서 제조된 무용매형 경화성 조성물을 각각 옐로우 포토레지스트(YPR) 위에 스핀 코팅기(Mikasa社, Opticoat MS-A150, 800rpm, 5초)를 사용하여 15㎛의 두께로 도포하고, 질소 분위기 하 395nm UV 노광기로 5000mJ(83℃10초)로 노광하였다. 이 후, 적분구 장비(QE-2100, otsuka electronics)에 2cm x 2cm 단막 시편을 로딩하여, 광변환율을 측정하였다. 이 후, 상기 로딩된 단막 시편을 180℃질소 분위기 건조로 안에서 2시간 동안 건조한 후, 노광 후 건조되기까지의 광유지율을 측정하였다. 또한, 상기 단막 각각의 최대발광파장을 300nm 내지 800nm으로 측정하였고, 측정결과를 하기 표 2에 나타내었다. The solvent-free curable compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were respectively coated on yellow photoresist (YPR) using a spin coater (Mikasa, Opticoat MS-A150, 800 rpm, 5 seconds). It was applied to a thickness of 15 μm, and exposed to 5000 mJ (83° C. for 10 seconds) with a 395 nm UV exposure machine in a nitrogen atmosphere. Thereafter, a 2cm x 2cm single film specimen was loaded into an integrating sphere equipment (QE-2100, otsuka electronics), and the light conversion rate was measured. Thereafter, the loaded single-film specimen was dried in a nitrogen atmosphere drying furnace at 180° C. for 2 hours, and the light retention rate until drying after exposure was measured. In addition, the maximum emission wavelength of each of the single films was measured in the range of 300 nm to 800 nm, and the measurement results are shown in Table 2 below.
| 광유지율(%)Mineral retention rate (%) | 최대발광파장(nm)Maximum emission wavelength (nm) | |
| 실시예 1Example 1 | 9090 | 538.7538.7 |
| 실시예 2Example 2 | 9595 | 539.9539.9 |
| 실시예 3Example 3 | 9797 | 540.0540.0 |
| 실시예 4Example 4 | 9292 | 539.7539.7 |
| 비교예 1Comparative Example 1 | 8585 | 542.0542.0 |
| 비교예 2Comparative Example 2 | 8888 | 543.1543.1 |
| 비교예 3Comparative Example 3 | 9191 | 539.2539.2 |
| 비교예 4Comparative Example 4 | 9494 | 538.5538.5 |
상기 표 2로부터, 일 구현예에 따른 무용매형 경화성 조성물을 이용하여 제조된 경화막은 540nm 이하의 최대발광파장을 가짐으로써 고색재현성을 구현할 수 있으며, 동시에 광유지율 또한 매우 우수하여 내열성, 내광성 등의 특성의 저하도 발생하지 않음을 확인할 수 있다. From Table 2 above, the cured film prepared using the solvent-free curable composition according to an embodiment can realize high color reproducibility by having a maximum light emission wavelength of 540 nm or less, and at the same time, the light retention rate is also very excellent, and properties such as heat resistance and light resistance. It can be seen that no deterioration of is also occurred.
본 발명은 상기 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 제조될 수 있으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다.The present invention is not limited to the above embodiments, but may be manufactured in a variety of different forms, and those of ordinary skill in the art to which the present invention pertains, other specific forms without changing the technical spirit or essential features of the present invention. It will be appreciated that it can be implemented with Therefore, it should be understood that the embodiments described above are illustrative and non-limiting in all respects.
Claims (13)
- 하기 화학식 1로 표시되는 화합물로 표면개질된 양자점 및Quantum dots surface-modified with a compound represented by the following formula (1), and말단에 탄소-탄소 이중결합을 갖는 중합성 단량체Polymerizable monomer having a carbon-carbon double bond at the terminal를 포함하는 무용매형 경화성 조성물:Solvent-free curable composition comprising:[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,L1, L3 및 L5는 각각 독립적으로 단일결합, 치환 또는 비치환된 C1 내지 C20 알킬렌기, 치환 또는 비치환된 C3 내지 C20 사이클로알킬렌기, 치환 또는 비치환된 C6 내지 C20 아릴렌기 또는 치환 또는 비치환된 C2 내지 C20 헤테로아릴렌기이고,L 1 , L 3 and L 5 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group or a substituted Or an unsubstituted C2 to C20 heteroarylene group,L2 및 L4는 각각 독립적으로 단일결합, *-O-*, *-S-*, *-C(=O)O-* 또는 *-OC(=O)-* 이고,L 2 and L 4 are each independently a single bond, *-O-*, *-S-*, *-C(=O)O-* or *-OC(=O)-*,R1은 치환 또는 비치환된 C1 내지 C20 알킬기 또는 치환 또는 비치환된 C6 내지 C20 아릴기이고,R 1 is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,n은 6 내지 15의 정수이고,n is an integer from 6 to 15,m은 1 내지 10의 정수이다.m is an integer from 1 to 10. - 제1항에 있어서,The method of claim 1,상기 화학식 1은 하기 화학식 1-1 내지 화학식 1-3 중 어느 하나로 표시되는 무용매형 경화성 조성물:Formula 1 is a solvent-free curable composition represented by any one of the following Formulas 1-1 to 1-3:[화학식 1-1][Formula 1-1]
[화학식 1-2][Formula 1-2]
[화학식 1-3][Formula 1-3]
상기 화학식 1-1 내지 화학식 1-3에서,In Formula 1-1 to Formula 1-3,L1, L3 및 L5는 각각 독립적으로 단일결합, 치환 또는 비치환된 C1 내지 C20 알킬렌기, 치환 또는 비치환된 C3 내지 C20 사이클로알킬렌기, 치환 또는 비치환된 C6 내지 C20 아릴렌기 또는 치환 또는 비치환된 C2 내지 C20 헤테로아릴렌기이고,L 1 , L 3 and L 5 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group or a substituted Or an unsubstituted C2 to C20 heteroarylene group,R1 및 R2는 각각 독립적으로 치환 또는 비치환된 C1 내지 C20 알킬기 또는 치환 또는 비치환된 C6 내지 C20 아릴기이고,R 1 and R 2 are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,n은 6 내지 15의 정수이고,n is an integer from 6 to 15,m은 1 내지 10의 정수이고,m is an integer from 1 to 10,p는 0 내지 4이다.p is 0 to 4. - 제1항에 있어서,The method of claim 1,상기 화학식 1은 하기 화학식 2 내지 화학식 5 중 어느 하나로 표시되는 무용매형 경화성 조성물.Formula 1 is a solvent-free curable composition represented by any one of the following Formulas 2 to 5.[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
- 제1항에 있어서,The method of claim 1,상기 양자점은 500nm 내지 680nm에서 최대형광 발광파장을 가지는 무용매형 경화성 조성물.The quantum dot is a solvent-free curable composition having a maximum fluorescence emission wavelength at 500nm to 680nm.
- 제1항에 있어서,The method of claim 1,상기 중합성 단량체는 220 g/mol 내지 1,000 g/mol의 분자량을 가지는 무용매형 경화성 조성물.The polymerizable monomer is a solvent-free curable composition having a molecular weight of 220 g / mol to 1,000 g / mol.
- 제1항에 있어서,The method of claim 1,상기 중합성 단량체는 하기 화학식 6으로 표시되는 무용매형 경화성 조성물:The polymerizable monomer is a solvent-free curable composition represented by the following formula (6):[화학식 6][Formula 6]
상기 화학식 6에서,In Chemical Formula 6,R3 및 R4는 각각 독립적으로 수소 원자 또는 치환 또는 비치환된 C1 내지 C10 알킬기이고,R 3 and R 4 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,L6 및 L8은 각각 독립적으로 치환 또는 비치환된 C1 내지 C10 알킬렌기이고,L 6 and L 8 are each independently a substituted or unsubstituted C1 to C10 alkylene group,L7은 치환 또는 비치환된 C1 내지 C10 알킬렌기 또는 에테르기(*-O-*)이다.L 7 is a substituted or unsubstituted C1 to C10 alkylene group or an ether group (*-O-*). - 제1항에 있어서,The method of claim 1,상기 무용매형 경화성 조성물은, The solvent-free curable composition,상기 양자점 1 중량% 내지 60 중량% 및1% to 60% by weight of the quantum dots, and상기 중합성 단량체 40 중량% 내지 99 중량%40% to 99% by weight of the polymerizable monomer를 포함하는 무용매형 경화성 조성물.Solvent-free curable composition comprising a.
- 제1항에 있어서,The method of claim 1,상기 무용매형 경화성 조성물은 중합개시제, 광확산제 또는 이들의 조합을 더 포함하는 무용매형 경화성 조성물.The solvent-free curable composition further comprises a polymerization initiator, a light diffusing agent, or a combination thereof.
- 제8항에 있어서,The method of claim 8,상기 광확산제는 황산바륨, 탄산칼슘, 이산화티타늄, 지르코니아 또는 이들의 조합을 포함하는 무용매형 경화성 조성물.The light diffusing agent is a solvent-free curable composition comprising barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.
- 제1항에 있어서,The method of claim 1,상기 무용매형 경화성 조성물은 중합 금지제; 말론산; 3-아미노-1,2-프로판디올; 실란계 커플링제; 레벨링제; 불소계 계면활성제; 또는 이들의 조합을 더 포함하는 무용매형 경화성 조성물.The solvent-free curable composition may include a polymerization inhibitor; Malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine-based surfactant; Or a solvent-free curable composition further comprising a combination thereof.
- 제1항 내지 제10항 중 어느 한 항에 따른 조성물을 이용하여 제조된 경화막.A cured film prepared using the composition according to any one of claims 1 to 10.
- 제11항에 있어서,The method of claim 11,상기 경화막은 540nm 이하의 발광파장을 가지는 경화막.The cured film is a cured film having an emission wavelength of 540 nm or less.
- 제11항의 경화막을 포함하는 컬러필터.A color filter comprising the cured film of claim 11.
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| KR1020190133235A KR102485991B1 (en) | 2019-10-24 | 2019-10-24 | Solvent-free curable composition, cured layer using the composition and color filter including the cured layer |
| KR10-2019-0133235 | 2019-10-24 |
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| CN (1) | CN114127636A (en) |
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| JP2002121548A (en) * | 2000-10-13 | 2002-04-26 | Mitsubishi Chemicals Corp | Production method for ethanol-soluble ultrafine semiconductor particle |
| JP2017032918A (en) * | 2015-08-05 | 2017-02-09 | Jsr株式会社 | Composition for forming cured film, cured film, light-emitting display element, film and method for forming cured film |
| KR20170022951A (en) * | 2015-08-21 | 2017-03-02 | 삼성전자주식회사 | Photosensitive compositions, preparation methods thereof, quantum dot polymer composite produced therefrom, and electronic devices including the same |
| KR101815344B1 (en) * | 2014-08-14 | 2018-01-04 | 주식회사 엘지화학 | Light-emitting film |
| KR20190047573A (en) * | 2017-10-27 | 2019-05-08 | 삼성에스디아이 주식회사 | Photosensitive resin composition including quantum dot, manufacturing method quantum dot and color filter |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6361260B2 (en) * | 2014-04-18 | 2018-07-25 | 大日本印刷株式会社 | LAMINATE MANUFACTURING METHOD, COLOR FILTER MANUFACTURING METHOD, LAMINATE, AND COLOR FILTER |
| JP7011055B2 (en) * | 2017-10-27 | 2022-01-26 | サムスン エスディアイ カンパニー，リミテッド | Quantum dot-containing composition, quantum dot manufacturing method and color filter |
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Patent Citations (5)
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|---|---|---|---|---|
| JP2002121548A (en) * | 2000-10-13 | 2002-04-26 | Mitsubishi Chemicals Corp | Production method for ethanol-soluble ultrafine semiconductor particle |
| KR101815344B1 (en) * | 2014-08-14 | 2018-01-04 | 주식회사 엘지화학 | Light-emitting film |
| JP2017032918A (en) * | 2015-08-05 | 2017-02-09 | Jsr株式会社 | Composition for forming cured film, cured film, light-emitting display element, film and method for forming cured film |
| KR20170022951A (en) * | 2015-08-21 | 2017-03-02 | 삼성전자주식회사 | Photosensitive compositions, preparation methods thereof, quantum dot polymer composite produced therefrom, and electronic devices including the same |
| KR20190047573A (en) * | 2017-10-27 | 2019-05-08 | 삼성에스디아이 주식회사 | Photosensitive resin composition including quantum dot, manufacturing method quantum dot and color filter |
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| CN114127636A (en) | 2022-03-01 |
| KR102485991B1 (en) | 2023-01-05 |
| TWI756819B (en) | 2022-03-01 |
| KR20210048934A (en) | 2021-05-04 |
| TW202122555A (en) | 2021-06-16 |
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