CN114656818B - metal oxide dispersion - Google Patents

metal oxide dispersion Download PDF

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CN114656818B
CN114656818B CN202111454326.8A CN202111454326A CN114656818B CN 114656818 B CN114656818 B CN 114656818B CN 202111454326 A CN202111454326 A CN 202111454326A CN 114656818 B CN114656818 B CN 114656818B
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acrylate
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metal oxide
methacrylate
oxide dispersion
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CN114656818A (en
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李慧映
郑佑永
金相现
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KCTech Co Ltd
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KCTech Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/027—Dispersing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium

Abstract

The present invention relates to a metal oxide dispersion liquid, and more particularly, to a metal oxide dispersion liquid comprising: zirconia nanoparticles; a monomer; and a surface modifier, and the peak intensity (I t ) Peak intensity of monoclinic system (I) m ) Is controlled.

Description

Metal oxide dispersion
Technical Field
The present invention relates to a metal oxide dispersion comprising zirconium oxide particles.
Background
The composition containing a metal oxide is useful for producing a thin film for display and the like. Films for display are required to have characteristics such as optical transmittance (optical transmittance), optical haze (optical haze), optical transparency (optical clarity), and refractive index. One example of a film for display is a brightness enhancement film.
Such a display film is used for improving the brightness of a display or the like. It can be used in word processor, desk display, television, video camera, automobile and airplane display, etc.
When such a film for display is used, optical characteristics and physical characteristics on the surface of a specific panel including refractive index can be preferably improved. For example, when a brightness enhancement film or the like is provided, by improving brightness, a display can be illuminated with less power, thereby reducing power consumption, reducing the degree of heat generation, and extending the life of a product, so that an electronic product can be used more effectively.
The materials of such display films have yet to be developed, and in order to produce such materials more efficiently, it is necessary to develop a metal oxide dispersion liquid which can include a metal oxide while maintaining a high refractive index, and which has high dispersibility of the metal oxide and low viscosity in the composition.
Disclosure of Invention
Technical problem to be solved
The present invention has been made to solve the above problems, and an object of the present invention is to provide a metal oxide dispersion liquid having a high refractive index and a low viscosity by adjusting the ratio of the crystal phases of zirconia nanopowder.
However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.
Technical method for solving the problems
The metal oxide dispersion liquid according to an embodiment of the present invention includes: zirconia nanoparticles; a monomer; and a surface modifier, and the tetragonal peak intensity (It) and the monoclinic peak intensity (Im) of the zirconia nanoparticles satisfy the following formulas:
[ 1]
3<It/I m <4。
According to an embodiment of the present invention, the zirconia nanoparticle may include: 30% to 40% of the monoclinic crystal structure; and 60 to 70% of the tetragonal crystal structure.
According to an embodiment of the present invention, the zirconia nanoparticles may account for 40wt% to 70 wt% of the metal oxide dispersion.
According to an embodiment of the present invention, the monomer is 1 to 50 wt% of the metal oxide dispersion, and, the monomers may be selected from the group consisting of methyl acrylate, lauryl acrylate, ethoxydiglycol acrylate, methoxytriglycol acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxyacrylate, neopentyl glycol diacrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, trimethylolpropane acrylate, trimethylolpropane benzoate, methyl methacrylate, 2-ethylhexyl methacrylate, n-stearyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, methoxypolyethylene methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl methacrylate, heptadecafluorodecyl methacrylate, trifluoromethyl methacrylate, trifluoroethyl acrylate, hexafluoropropylene methacrylate, 1, 6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, glycerol dimethacrylate hexamethylene diisocyanate, ethylene glycol dimethacrylate, urethane acrylate, epoxy acrylate, melamine acrylate, benzyl methacrylate, phenyl acrylate, diphenyl acrylate, biphenyl acrylate, 2-biphenylacrylate, ethyl 2- ([ 1,1' -biphenyl ] -2-aryloxy) acrylate, phenoxybenzyl acrylate, 3-phenoxybenzyl-3- (1-naphthyl) acrylate, ethyl (2E) -3-hydroxy-2- (3-phenoxybenzyl) acrylate, phenyl methacrylate, biphenyl methacrylate, 2-nitrophenylacrylate, 4-nitrophenylacrylate, 2-nitrophenylmethacrylate, 4-nitrophenylmethacrylate, 2-nitrobenzyl methacrylate, 4-nitrobenzyl methacrylate, 2-chlorophenyl acrylate, 4-chlorophenyl acrylate, 2-chlorophenyl methacrylate, 4-chlorophenyl methacrylate, ethylphenol, phenylphenol, biphenyl methacrylate, phenylphenol ethoxyacrylate, 1- (biphenyl-2-ylmethyl) -4-phenylpiperazine, 1- (biphenyl-2-ylmethyl) -4- (2-methoxyphenyl) piperazine, 1- (biphenyl-2-ylmethyl) -4- (2-ethoxyphenyl) piperazine, 1- (biphenyl-2-ylmethyl) -4- (2-isopropoxyphenyl) piperazine, at least one selected from the group consisting of 1- (biphenyl-2-ylmethyl) -4- (3-methoxyphenyl) piperazine, 1- (biphenyl-2-ylmethyl) -4- (4-methoxyphenyl) piperazine, and bisphenol diacrylate.
According to an embodiment of the present invention, the surface modifier includes a silane coupling agent, and the silane coupling agent may include at least one selected from the group consisting of an acrylate group, (meth) acrylic group, epoxy group (epoxy group), alkoxy group (alkoxy group), vinyl group (vinyl group), phenyl group (phenyl group), methacryloxy group (metacryloxy group), amino group (amino group), chlorosilane group (chlorosilanyl group), chloropropyl group (chloropropyl) and mercapto group (mercapto).
According to an embodiment of the present invention, the surface modifier may include a surfactant selected from the group consisting of (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 3, 4-epoxybutyltrimethoxysilane, 3, 4-epoxybutyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyl triethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxysilane, vinyltriisobutoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, phenylsilane, phenyltrimethoxysilane, phenylchlorosilane, phenyltrichlorosilane, gamma-glycidoxypropyl triphenoxysilane, gamma-dichlorophenyl-dimethoxysilane, dimethoxyphenyl-dimethoxysilane, and dimethoxysilane, at least one selected from the group consisting of methyl phenyl dichloro silane and phenoxy trimethyl silane.
According to an embodiment of the present invention, the surface modifier may account for 10 to 20 parts by weight with respect to the total weight of the zirconia nanoparticles in the metal oxide dispersion.
According to an embodiment of the present invention, the metal oxide dispersion liquid further includes a dispersant, and the dispersant may include at least one selected from the group consisting of a polyether acid compound, a polyether amine compound, a polyether acid/amine mixture, an ester compound including a phosphoric acid group, and a polyether compound including a phosphoric acid group.
According to an embodiment of the present invention, the refractive index of the metal oxide dispersion liquid may be 1.60 or more.
According to an embodiment of the present invention, the viscosity of the metal oxide dispersion may be 400CP or less.
According to an embodiment of the present invention, the metal oxide dispersion may be solvent-free.
An optical element for flexible display according to an embodiment of the present invention is manufactured using the metal oxide dispersion liquid according to the present invention.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a zirconia monomer dispersion having a low viscosity and a high refractive index by applying zirconia nanopowder having a controlled crystal phase ratio. Further, the dispersion is excellent in dispersibility of zirconia particles, provides relatively low viscosity, has excellent fluidity and plasticity, and can be suitably used as a display sol dispersion capable of improving the efficiency of a device (i.e., a display device).
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. In describing the present invention, when it is determined that detailed descriptions of related known functions or configurations unnecessarily obscure the gist of the present invention, detailed descriptions thereof will be omitted. Also, the terms used in the present specification are used to accurately express the preferred embodiments of the present invention, and can be varied according to the intention of a user, or a convention in the art to which the present invention pertains. Thus, the definition of the term should be defined according to the entire content of the present specification.
In the entire specification, when a certain component is described as "including" a certain component, it is not meant to exclude other components, but other components may be included.
Hereinafter, the polishing slurry composition of the present invention will be specifically described with reference to examples. However, the present invention is not limited to the above-described embodiments.
The present invention relates to a metal oxide dispersion liquid, which may include, according to an embodiment of the present invention: zirconia nanoparticles; a monomer; and a surface modifier.
According to an embodiment of the present invention, the zirconia nanoparticles can reduce the viscosity of a metal oxide dispersion by adjusting the crystal phase ratio of a powder and exhibit a high refractive index. That is, the ratio of the crystalline phases may be adjusted to correspond to the peak intensity ratio of tetragonal and monoclinic, the ratio of tetragonal and monoclinic crystalline phases, or both in the XRD pattern.
As an example of the present invention, the peak intensity (I t ) Peak intensity of monoclinic system (I) m ) The following formula may be satisfied:
[ 1]
3<I t /I m <4。
As an example of the present invention, in the zirconia nanoparticle, the crystal structure of the monoclinic system may be 30% to 40% or 34% to 40%; and the tetragonal crystal structure may be 60% to 70% or 60% to 66%, and in combination with the peak intensity ratio according to formula 1, it is possible to facilitate lowering of the viscosity of the dispersion while having a high refractive index.
As an example of the present invention, the zirconia nanoparticles may constitute 40wt% to 70 wt% of the metal oxide dispersion. When included in the above range, the content of the zirconia is low, resulting in a low refractive index and brightness of the dispersion, thereby preventing the problem of difficulty in providing a cured film of high refractive index, and the dispersion interval between the zirconia particles is extremely short due to the excessive addition of the zirconia particles, which increases the viscosity of the dispersion, and suppresses the dispersibility due to aggregation occurring between the zirconia particles, and can reduce the deterioration of optical performance.
As an example of the present invention, the zirconia particles may have a size of 1nm or more; 10nm or more; or 50nm to 100nm.
According to an embodiment of the present invention, the monomer may include at least one selected from the group consisting of C1-C22 alkyl acrylate monomers, C1-C22 alkoxy acrylate monomers, C6-C24 aryl acrylate monomers, C1-C22 alkyl (meth) acrylate monomers, C1-C22 alkoxy (meth) acrylate monomers, C6-C24 aryl (meth) acrylate monomers, alkylene glycol di (meth) acrylate based monomers, alkylene glycol diacrylate monomers, alkylene glycol alkyl ether (meth) acrylate monomers, alkylene glycol alkyl ether acrylate monomers, derivatives incorporating methacrylate and/or acrylate substituents.
In addition, the monomer is further substituted with at least one or more of a hydroxyl group, an aliphatic ring, and an aromatic ring (6 to 30 carbon atoms) in the molecule, and the "alkylene" has 1 to 10 carbon atoms and is included as 1 to 20 (n) carbon atoms; the "alkyl ether" may include an alkyl group having 1 to 20 carbon atoms. The monomer may include 1 to 6 functional acrylates, e.g., difunctional, trifunctional, etc.
For example, the number of the cells to be processed, the monomers may be methyl acrylate, lauryl acrylate, ethoxydiglycol acrylate, methoxytriethylene glycol acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxyacrylate, neopentyl glycol diacrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, trimethylolpropane acrylate benzoate, trimethylolpropane benzoate, methyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate phenoxyethyl methacrylate, methoxypolyethylene methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl methacrylate, heptadecafluorodecyl methacrylate, trifluoromethyl methacrylate, trifluoroethyl acrylate, hexafluoropropyl methacrylate, 1, 6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, glycerol dimethacrylate hexamethylene diisocyanate, ethylene glycol dimethacrylate, urethane acrylate, epoxy acrylate, melamine acrylate, benzyl methacrylate, phenyl acrylate, diphenyl acrylate, biphenyl acrylate, 2- ([ 1,1' -biphenyl ] -2-aryloxy) ethyl acrylate, phenoxybenzyl acrylate, 3-phenoxybenzyl-3- (1-naphthyl) acrylate, ethyl (2E) -3-hydroxy-2- (3-phenoxybenzyl) acrylate, phenyl methacrylate, biphenyl methacrylate, 2-nitrophenylacrylate, 4-nitrophenylacrylate, 2-nitrophenylmethacrylate, 4-nitrophenylmethacrylate, 2-nitrobenzyl methacrylate, 4-nitrobenzyl methacrylate, 2-chlorophenyl acrylate, 4-chlorophenyl acrylate, 2-chlorophenyl methacrylate, 4-chlorophenyl methacrylate, ethyl o-phenylphenol acrylate, phenylphenol, biphenyl methacrylate, phenylphenol ethoxyacrylate, 1- (biphenyl-2-ylmethyl) -4-phenylpiperazine, 1- (biphenyl-2-ylmethyl) -4- (2-methoxyphenyl) piperazine, 1- (biphenyl-2-ethoxyphenyl) -4- (2-ethoxyphenyl) piperazine, 1- (biphenyl-2-ylmethyl) -4- (2-isopropoxyphenyl) piperazine, 1- (biphenyl-2-ylmethyl) -4- (3-methoxyphenyl) piperazine, 1- (biphenyl-2-ylmethyl) -4- (4-methoxyphenyl) piperazine, bisphenol diacrylate, and the like.
As an example of the present invention, the monomer may account for 1 to 50 wt% of the metal oxide dispersion; or 10 to 50% by weight, and when it is included in the above range, it is possible to provide a coating layer having a high refractive index and flexibility by improving the dispersibility of the metal oxide and improving the curing in a subsequent process.
According to an embodiment of the present invention, when the surface modifier is included in the above range, the metal oxide sol dispersion can be used to effectively disperse zirconia seeds in the sol dispersion while maintaining a high refractive index, a low viscosity level suitable for forming a film, and effective light transmittance. Thus, even when the metal oxide dispersion liquid of the present invention is filled with zirconia particles at a high concentration, stable dispersibility is ensured, so that a metal oxide sol that maintains high transparency can be prepared.
As an example of the present invention, the surface modifier includes a silane coupling agent, and the silane coupling agent may include at least one selected from the group consisting of an acrylate group, (meth) acrylic group, epoxy group (epoxy group), alkoxy group (alkoxy group), vinyl group (vinyl group), phenyl group (phenyl group), methacryloxy group (metacryloxy group), amino group (amino group), chlorosilane group (chlorosilanyl group), chloropropyl group (chloropropyl) and mercapto group (mercapto). The acrylic monomer and the methacrylic monomer can be substituted by phenyl.
For example, the surface modifier may be (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 3, 4-epoxybutyltrimethoxysilane, 3, 4-epoxybutyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyl triethoxysilane, vinyltriethoxysilane, vinyltritibutoxysilane, vinyltriisobutoxysilane, vinyltriisopropoxysilane, aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, phenylsilane, phenyltrimethoxysilane, phenylchlorosilane, phenyltrichlorosilane, gamma-glycidoxypropyl triphenoxysilane, gamma-glycidoxypropyldiphenoxysilane, gamma-glycidoxypropyl methyldiphenoxysilane, dichlorophenyl, N-triphenoxysilane, dimethoxysilane, dimethoxyphenyl-dimethyl-dimethoxysilane, or the like.
As an example of the present invention, the surface modifier accounts for 10 to 20 parts by weight with respect to the total weight of the zirconia nanoparticles in the metal oxide dispersion, and when it is included in the above range, the progress speed of the surface treatment reaction of the zirconia particles can be appropriately maintained to increase the dispersibility of the zirconia particles in the dispersion composition, and the excessively used surface modifier adheres to the surface of the zirconia particles, and by inducing aggregation between the zirconia particles, deterioration of the dispersibility can be reduced.
According to an embodiment of the present invention, the metal oxide dispersion liquid further includes a dispersant, and the dispersant may include at least one selected from the group consisting of a polyether acid compound, a polyether amine compound, a polyether acid/amine mixture, an ester compound including a phosphoric acid group, and a polyether compound including a phosphoric acid group.
As an example of the present invention, the dispersant may constitute 1 to 20 wt% of the metal oxide dispersion. When the content of the dispersant is less than 1% by weight, compatibility with a resin composition made of an organic compound to be used in a subsequent treatment is lowered; when the content of the dispersant exceeds 20% by weight, the dispersant is excessively bonded to the surface of the zirconia particles, possibly resulting in a decrease in refractive index.
According to an embodiment of the present invention, the metal oxide dispersion may further include an organic solvent for easy dispersion, which may be 30 to 50 wt%. The solvent may be removed completely (almost) for subsequent treatment to form a solvent-free sol dispersion.
As an example of the present invention, when the organic solvent content is less than 30% by weight of the metal oxide dispersion, it exceeds the minimum range of the action of the dispersion medium, thereby reducing the dispersibility and suppressing the viscosity and optical properties, and increasing the solvent removal time by more than 50% by weight, thereby possibly reducing the refractive index and the brightness of the optical film made of the metal oxide dispersion, reducing the transmittance of the cured film, and increasing the haze.
According to an embodiment of the present invention, the refractive index of the metal oxide dispersion liquid is 1.60 or more; or 1.670 or more, which has excellent compatibility with components or compositions to be used in subsequent processes, and can form a coating layer having high brightness efficiency, high transmittance and high refractive index characteristics.
According to an embodiment of the present invention, the viscosity of the metal oxide dispersion liquid is 400CP or less; 100 to 400; or 100 to 300, the metal oxide dispersion is solvent-free, and may be a sol dispersion. When the viscosity is high, the viscosity becomes too high, so that it is difficult to prepare a liquid with an organic material, and the dispersibility of zirconia particles in the dispersion may be lowered, and it is difficult to form a uniform film layer when a film is produced, resulting in deterioration of optical characteristics. The viscosity can be measured using a DV2T LV spindle (manufactured by Brookfield). In addition, the viscosity can be measured at a temperature of 25℃and a shear rate of 1.0 (1/s).
An optical element for flexible display according to an embodiment of the present invention is manufactured using the metal oxide dispersion liquid according to the present invention.
As an example of the present invention, the optical element may be an optical element for display, for example, a diffusion film, an optical film, a polarizing film, a prism sheet, an AR sheet, a display film, or the like for an electronic device.
As an example of the present invention, the optical element may include a substrate; and a metal oxide dispersion according to the present invention or a coating (film or the like) prepared from a composition including the metal oxide dispersion formed on at least a portion of the substrate. When manufacturing the optical element, the metal oxide dispersion or the composition including the metal oxide dispersion may form a coating layer in a state of a trace amount of solvent or a near zero solvent or no (free) solvent.
As an example of the present invention, the substrate is appropriately selected according to the use of the optical film, and may be a transparent substrate. As long as the film has transparency, a transparent substrate can be applied without limitation. For example, a film including polyethylene (polyester) such as polyethylene terephthalate (PET, polyethylene terephthalate), polyethylene (EVA, ethylene vinyl acetate) such as polyethylene, cyclic olefin polymer (COP, cyclic olefin polymer), cyclic olefin copolymer (COC, cyclic olefin copolymer), polyacrylate (PAC), polycarbonate (PC), polyethylene (PE), polymethyl methacrylate (PMMA), polyether ether ketone (PEEK), polyethylene naphthalate (PEN, polyethylene Naphthalate), polyetherimide (PEI), polyimide (PI), triacetyl cellulose (TAC, triacetyl cellulose), methyl methacrylate (MMA, methyl methacrylate), or a fluorine-based resin may be used, and an inorganic substrate having flexibility may be used.
The present invention will be described in more detail by the following examples, which are, however, for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
Hydroxyl-zirconia nanoparticles were synthesized by a hydrothermal method, and at this time, the synthesized zirconia particles were 65.4% tetragonal, 34.6% monoclinic, and the peak ratio of monoclinic to monoclinic was 3.70 (XRD pattern).
In a 100mL container for a paint shaker flask, 28.9g of Tetrahydrofuran (hereinafter abbreviated as "THF") and 2.1g of silane with methylpropenyl group (3- (methacryloxy) propyltrimethoxysilane, particle solid content 10-20%) were placed and mixed at room temperature for 10 minutes using a stirring rod (stinrer bar). Next, 38g of a synthesized zirconia powder was added to the solution, and mixed for 30 minutes at room temperature using a stirring bar to form a mixed solution. Thereafter, 200g of 0.05mm beads were added to the mixture, and dispersed for 3 hours using a paint shaker to obtain a 40wt% zirconia-THF solvent dispersion. Thereafter, the zirconia-THF solvent dispersion was mixed with an acrylic monomer (biphenyl acrylate, 40 wt%) and the solvent was removed under reduced pressure to obtain a zirconia-monomer (40 wt%) dispersion. The viscosity and refractive index of the monomer dispersion prepared are shown in table 1.
Example 2
Hydroxyl-zirconia nano particles are synthesized by a hydrothermal method, at the moment, the synthesized zirconia particles are 64.2% of tetragonal system, 35.8% of monoclinic system and the peak ratio of monoclinic system to monoclinic system is 3.48. A monomer dispersion was prepared in the same manner as in example 1. The viscosity and refractive index of the monomer dispersion prepared are shown in table 1.
Example 3
Hydroxyl-zirconia nano particles are synthesized by a hydrothermal method, at the moment, the synthesized zirconia particles are 65.8% of tetragonal system, 34.2% of monoclinic system and the peak ratio of monoclinic system to monoclinic system is 3.36. A monomer dispersion was prepared in the same manner as in example 1. The viscosity and refractive index of the monomer dispersion prepared are shown in table 1.
Comparative example 1
Hydroxyl-zirconia nano particles are synthesized by a hydrothermal method, at the moment, the synthesized zirconia particles are 72.6% of tetragonal system, 27.4% of monoclinic system and the peak ratio of monoclinic system to monoclinic system is 5.90. A monomer dispersion was prepared in the same manner as in example 1. The viscosity and refractive index of the monomer dispersion prepared are shown in table 1.
Comparative example 2
Hydroxyl-zirconia nano particles are synthesized by a hydrothermal method, at the moment, the synthesized zirconia particles are 68.7% of tetragonal system, 31.3% of monoclinic system and the peak ratio of monoclinic system to monoclinic system is 5.65. A monomer dispersion was prepared in the same manner as in example 1. The viscosity and refractive index of the monomer dispersion prepared are shown in table 1.
Comparative example 3
Hydroxyl-zirconia nano particles are synthesized by a hydrothermal method, at the moment, the synthesized zirconia particles are 64.1% of tetragonal system, 35.9% of monoclinic system and the peak ratio of monoclinic system to monoclinic system is 4.01. A monomer dispersion was prepared in the same manner as in example 1. The viscosity and refractive index of the monomer dispersion prepared are shown in table 1.
Comparative example 4
Hydroxyl-zirconia nano particles are synthesized by a hydrothermal method, at the moment, the synthesized zirconia particles are 56.1% of tetragonal system, 43.9% of monoclinic system and the peak ratio of monoclinic system to monoclinic system is 2.923. A monomer dispersion was prepared in the same manner as in example 1. The viscosity and refractive index of the monomer dispersion prepared are shown in table 1.
Comparative example 5
Hydroxyl-zirconia nano particles are synthesized by a hydrothermal method, at the moment, the synthesized zirconia particles are 49.0% of tetragonal system, 51.0% of monoclinic system and the peak ratio of monoclinic system to monoclinic system is 1.62. A monomer dispersion was prepared in the same manner as in example 1. The viscosity and refractive index of the monomer dispersion prepared are shown in table 1.
Comparative example 6
Hydroxyl-zirconia nano particles are synthesized by a hydrothermal method, at this time, the synthesized zirconia particles are tetragonal 25.4%, monoclinic 74.6%, and the peak ratio of monoclinic to monoclinic is 0.61. A monomer dispersion was prepared in the same manner as in example 1. The viscosity and refractive index of the monomer dispersion prepared are shown in table 1.
< refractive index measurement method >
When the coating liquid sample prepared according to this example was dropped on the prism at room temperature (25 ℃) and reached the set temperature by pressing the start key, the measurement was automatically started. The values of the results are the refractive indices of the compositions and are shown in the following table.
Measuring equipment: agagogo (ATAGO)/japan
Model name: RX-5000 Alpha (Alpha)
< method of measuring viscosity >
The viscosity was measured using a DV2T LV spindle device.
TABLE 1
As can be seen from table 1, the ratio of peak intensities of tetragonal and monoclinic is more than 3 and less than 4, and the viscosity can be reduced while having a high refractive index by adjusting the ratio of the tetragonal and monoclinic mixed crystal phases (tetragonal ratio 60 to 66% and monoclinic ratio 34 to 40% crystal ratio) of zirconia and the like.
In summary, the embodiments have been described with limited examples, and those skilled in the art will be able to make numerous modifications and variations to the above disclosure. For example, the described techniques may be performed in a different order than the described methods, and/or the described components may be combined or combined in a different manner than the described methods, or other components or equivalents may be substituted or replaced to achieve the same effects. Thus, other embodiments, other implementations, and equivalents of the claims are intended to be within the scope of the patent claims.

Claims (9)

1. A metal oxide dispersion comprising: zirconia nanoparticles; a monomer; and a surface modifier, characterized in that,
the peak intensity (I t ) Peak intensity of monoclinic system (I) m ) Satisfies formula 1, as follows:
[ 1]
3<I t /I m <3.48，
The monomers include monomers selected from the group consisting of methyl acrylate, lauryl acrylate, ethoxydiglycol acrylate, methoxytriethylene glycol acrylate, isobornyl acrylate, 2-hydroxy-3-phenoxy acrylate, neopentyl glycol diacrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, trimethylolpropane acrylate benzoate, trimethylolpropane benzoate, 2-ethylhexyl methacrylate, stearyl n-methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, methoxypolyethylene methacrylate, 2-hydroxybutyl methacrylate-heptadecafluorodecyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, hexafluoropropyl methacrylate, glycerol dimethacrylate hexamethylene diisocyanate, urethane acrylate, epoxy acrylate, melamine acrylate, benzyl methacrylate, diphenyl acrylate, biphenyl acrylate, 2- ([ 1,1' -biphenyl ] -2-aryloxy) acrylic acid, phenoxy 3- (3-hydroxybenzyl) acrylate, 3-hydroxybenzyl (3-benzyl) acrylate, 3-nitrophenyl (3-benzyl) acrylate, 3-hydroxy-3-benzyl (3-benzyl) acrylate, 3-nitrophenyl acrylate, 3-hydroxy-methacrylate, 3-glycidyl acrylate, and (3-glycidyl) acrylate, and (3-hydroxy-3-glycidyl) acrylate, which is used as a solvent, at least one selected from the group consisting of 2-nitrophenyl methacrylate, 4-nitrophenyl methacrylate, 2-nitrobenzyl methacrylate, 4-nitrobenzyl methacrylate, 2-chlorophenyl acrylate, 4-chlorophenyl acrylate, 2-chlorophenyl methacrylate, 4-chlorophenyl methacrylate, o-phenylphenol ethyl acrylate, phenylphenol, biphenyl methacrylate, o-phenylphenol ethoxyacrylate, 1- (biphenyl-2-ylmethyl) -4-phenylpiperazine, 1- (biphenyl-2-ylmethyl) -4- (2-methoxyphenyl) piperazine, 1- (biphenyl-2-ylmethyl) -4- (2-ethoxyphenyl) piperazine, 1- (biphenyl-2-ylmethyl) -4- (2-isopropoxyphenyl) piperazine, 1- (biphenyl-2-ylmethyl) -4- (3-methoxyphenyl) piperazine, 1- (biphenyl-2-ylmethyl) -4- (4-methoxyphenyl) piperazine and bisphenol diacrylate,
the metal oxide dispersion liquid is solvent-free,
the refractive index of the metal oxide dispersion is 1.60 or more,
the viscosity of the metal oxide dispersion is 302.1CP or less.
2. The metal oxide dispersion according to claim 1, characterized in that,
the zirconia nanoparticle includes:
30% to 40% of the monoclinic crystal structure; and
the tetragonal crystal structure is 60 to 70%.
3. The metal oxide dispersion according to claim 1, characterized in that,
the zirconia nanoparticles comprise 40% to 70% by weight of the metal oxide dispersion.
4. The metal oxide dispersion according to claim 1, characterized in that,
the monomer comprises 1 to 50 wt% of the metal oxide dispersion.
5. The metal oxide dispersion according to claim 1, characterized in that,
the surface modifying agent comprises a silane coupling agent,
the silane coupling agent includes at least one selected from the group consisting of an acrylate group, (meth) acrylic group, epoxy group, alkoxy group, vinyl group, phenyl group, methacryloxy group, amino group, chlorosilane group, chloropropyl group, and mercapto group.
6. The metal oxide dispersion according to claim 1, characterized in that,
the surface modifier includes a silane selected from the group consisting of (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 3, 4-epoxybutyltrimethoxysilane, 3, 4-epoxybutyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyl triethoxysilane, vinyltriethoxysilane, vinyltritutoxysilane, vinyltriisobutoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, phenylsilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylchlorosilane, phenyltrichlorosilane, gamma-glycidoxypropyl triphenoxysilane, gamma-glycidoxypropylmethylphenoxysilane, dichlorodiphenylsilane, N-aminophenyltrimethoxysilane, dimethoxysilane, dimethoxyphenyl-dimethyl silane, and at least one of the group of diphenol, and diethoxysilanes.
7. The metal oxide dispersion according to claim 1, characterized in that,
the surface modifier comprises 10 to 20 parts by weight based on the total weight of the zirconia nanoparticles in the metal oxide dispersion.
8. The metal oxide dispersion according to claim 1, characterized in that,
the metal oxide dispersion also includes a dispersant,
the dispersant includes at least one selected from the group consisting of a polyether acid compound, a polyether amine compound, a polyether acid/amine mixture, an ester compound including a phosphoric acid group, and a polyether compound including a phosphoric acid group.
9. An optical element for flexible display, characterized in that,
manufactured using the metal oxide dispersion of claim 1.
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JP4559004B2 (en) * 1999-10-28 2010-10-06 スリーエム イノベイティブ プロパティズ カンパニー Zirconia sol and method for producing the same
CN107001067A (en) * 2014-12-12 2017-08-01 Dic株式会社 The manufacture method of inorganic microparticle-dispersed liquid, solidification compound and its solidfied material comprising the dispersion liquid
CN109641759A (en) * 2016-12-22 2019-04-16 第稀元素化学工业株式会社 Zirconia sol and preparation method thereof

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JP4559004B2 (en) * 1999-10-28 2010-10-06 スリーエム イノベイティブ プロパティズ カンパニー Zirconia sol and method for producing the same
CN107001067A (en) * 2014-12-12 2017-08-01 Dic株式会社 The manufacture method of inorganic microparticle-dispersed liquid, solidification compound and its solidfied material comprising the dispersion liquid
CN109641759A (en) * 2016-12-22 2019-04-16 第稀元素化学工业株式会社 Zirconia sol and preparation method thereof

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