WO2022105053A1 - 纳米氧化锆粉体、其制备方法及所得分散液、光学膜 - Google Patents

纳米氧化锆粉体、其制备方法及所得分散液、光学膜 Download PDF

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WO2022105053A1
WO2022105053A1 PCT/CN2021/072369 CN2021072369W WO2022105053A1 WO 2022105053 A1 WO2022105053 A1 WO 2022105053A1 CN 2021072369 W CN2021072369 W CN 2021072369W WO 2022105053 A1 WO2022105053 A1 WO 2022105053A1
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nano
zirconia
dispersion liquid
acid
zirconia powder
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French (fr)
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张曦
张兵
宋锡滨
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山东国瓷功能材料股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, 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
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Definitions

  • Nano zirconia powder, preparation method thereof and dispersion liquid and optical film prepared therefrom are nano zirconia powder, preparation method thereof and dispersion liquid and optical film prepared therefrom
  • the application belongs to the field of fine chemicals, and in particular relates to a nano-zirconia powder, a preparation method thereof, a dispersion liquid obtained therefrom, and an optical film.
  • zirconia particle dispersion In recent years, by combining zirconia particle dispersion with transparent resin or film, it has been well used in the field of optics by taking advantage of its high refractive index.
  • high-refractive zirconia dispersion is used to prepare optical films such as brightness enhancement film and anti-reflection film, which can be used on LCD displays to increase the brightness and clarity of the screen; it can also be used to improve the refractive index of LED sealing resin, which can more effectively The light emitted by the light-emitting body is extracted, and the brightness of the LED is further improved.
  • its high refractive properties can be used in high refractive coatings for applications in different fields.
  • the refractive index of the zirconia dispersion is closely related to the particle size, crystal structure, particle dispersion state and preparation process of the nano-zirconia in the system.
  • CN201810704465.3 discloses a preparation method of highly dispersed nano-zirconia particles and transparent dispersions thereof, which directly prepares nano-zirconia particles by pyrolyzing inorganic zirconium salts in a hypergravity environment. The agglomeration is greatly reduced, and after washing and modification, it is directly a transparent liquid dispersion of zirconia.
  • the zirconia prepared by this method has a small particle size and good dispersibility, its powder crystal structure is a monoclinic phase, and the refractive index of the powder is much lower than that of the tetragonal powder, and the corresponding liquid phase dispersion The refractive index of the bulk is also lower under the same conditions. Therefore, how to prepare nano-zirconia particles with excellent performance and zirconia dispersion with stable system, uniform dispersion and high refractive index is particularly important to better meet the performance requirements of transparent organic-inorganic composites.
  • the application provides a nano-zirconia powder, its preparation method, the obtained dispersion liquid, and an optical film.
  • the specific technical solutions are as follows:
  • a nano-zirconia powder characterized in that the particle size of the nano-zirconia powder is 3-10 nm, the specific surface area is 200-240 m 2 /g, and the nano-zirconia powder comprises a tetragonal crystal structure zirconia, and the proportion of zirconia with tetragonal crystal structure accounts for 60-95% of the powder.
  • the application also provides a method for preparing nano-zirconia powder according to the above technical solution, comprising the following steps:
  • solution B The base is dissolved in water to obtain solution B;
  • the solution A and the solution B are fully mixed under stirring to form a precipitate, wherein the mass of the precipitate accounts for 1-40% of the mass of the total mixed solution; after the precipitate is washed and filtered for many times, the precursor C is obtained;
  • the above obtained slurry is put into a reaction kettle, the filling amount is 60-90%, and the hydrothermal reaction is carried out at 180°C-220°C for 1-12 hours, and a reaction solution is obtained after the reaction;
  • the reaction solution is directly dried or concentrated, washed and then dried to obtain nano-zirconia powder.
  • the added zirconium salt is a water-soluble zirconium salt selected from at least one of basic carbonate, carbonate, nitrate, acetate, chloride and oxychloride; the added stability
  • the elemental salt is a chloride or nitrate of a stable element, wherein the stable element is selected from at least one of aluminum, magnesium, titanium and rare earth elements; the base is selected from ammonia water, sodium hydroxide, potassium hydroxide and at least one of lithium hydroxide.
  • the added zirconium salt concentration is less than or equal to 2 mol/L
  • the molar concentration ratio of the added stability element to the zirconium element is 2/98 to 30/70
  • the added alkali concentration is less than or equal to 8 mol/L.
  • the organic acid is selected from at least one of monocarboxylic acid, polycarboxylic acid and hydroxycarboxylic acid, wherein the monocarboxylic acid is selected from at least one of formic acid, acetic acid, propionic acid and butyric acid,
  • the polycarboxylic acid is selected from at least one of oxalic acid, malonic acid, succinic acid and phthalic acid, and the hydroxycarboxylic acid is selected from at least one of lactic acid, malic acid, tartaric acid and citric acid;
  • the salt of the organic acid Its alkali metal salt is at least one selected from potassium salt and sodium salt.
  • the molar concentration of the added organic acid or its salt is 10-100% of the total molar concentration of zirconium element and stabilizing element.
  • the reaction solution is directly dried to obtain nano-zirconia powder; when the boiling point of the organic acid added is greater than 150°C, the reaction solution is concentrated and washed several times before drying, A nano-zirconia powder is obtained.
  • the drying method is selected from any one of vacuum low-temperature drying, drying and spraying
  • the concentrated washing method is selected from any one of ultrafiltration, rotary evaporation and ceramic membrane concentrated washing.
  • the application also provides an organic solvent-based dispersion liquid containing the nano-zirconia powder described in the above technical solution, the content of the nano-zirconia in the dispersion liquid is 40-70 wt%, and the refractive index is 1.400-1.554.
  • the refractive index of the dispersion is not lower than 1.554.
  • the dispersion liquid is obtained by replacing the dispersion medium water in the reaction liquid obtained by the preparation method described in the above technical scheme with an organic solvent, or the nano zirconia powder prepared by the above technical scheme It is obtained by dispersing the body in an organic solvent, wherein the organic solvent is selected from at least one of alcohols, esters, aromatic hydrocarbons, ethers and amide organic solvents.
  • a modifier is added to the dispersion, and the amount of the modifier is 1-20 wt% of the content of the nano-zirconia.
  • the modifier is selected from at least one of silane coupling agents, titanate coupling agents, metal complexes, aromatic or highly conjugated chemical substances.
  • an oil-based dispersing aid is added to the dispersion liquid, and the amount of the oil-based dispersing aid is 1-20 wt % of the content of the nano-zirconia.
  • the present invention also provides a nano-zirconia dispersion liquid with a photocurable resin. Obtained after removing the organic solvent by distillation under reduced pressure;
  • the content of nano-zirconia in the dispersion liquid is 50-80 wt %, and the refractive index thereof is 1.60-1.70.
  • the added amount of the photocurable resin is 20-50% of the total mass of the zirconia and the photocurable resin.
  • the present application also provides an optical film, using the dispersion liquid containing nano-zirconia powder according to any one of the above technical solutions or the nano-oxide with photocurable resin described in any one of the above technical solutions.
  • Zirconium dispersion was prepared.
  • the present application also provides a nano zirconia powder according to the above technical solutions or a dispersion liquid containing nano zirconia powder according to any one of the above technical solutions or any one of the above technical solutions.
  • the nano-zirconia powder provided by the present invention has the characteristics of small particle size, large specific surface area, good particle monodispersion effect, and the main crystal phase is tetragonal;
  • the organic solvent type and photocurable resin type dispersion liquid prepared by using the nano zirconia powder obtained above has stable system, uniform dispersion, high dispersion liquid concentration and high refractive index.
  • the use of the dispersion liquid with the above characteristics can greatly increase the refractive index of the high-refractive coating and improve the performance of the film in the subsequent preparation of, for example, a brightness enhancement film or an anti-reflection film.
  • Figure 1a is a transmission electron microscope Figure 1 of the nano-zirconia powder provided in Example 1 of the application;
  • Figure 1b is a transmission electron microscope Figure 2 of the nano-zirconia powder provided in Example 1 of the application;
  • Fig. 2 is the XRD contrast pattern of the nano-zirconia powder provided by the embodiment 1 of the application and the standard tetragonal phase grain;
  • Example 3 is a particle size distribution diagram of the nano-zirconia powder provided in Example 1 of the present application.
  • An embodiment of the present application provides a nano-zirconia powder, the particle size of the nano-zirconia powder is 3-10 nm, the specific surface area is 200-240 m 2 /g, and the nano-zirconia powder includes a tetragonal The zirconia with phase crystal structure, and the proportion of zirconia with tetragonal crystal structure accounts for 60-95% of the powder.
  • the nano-zirconia powder provided by this embodiment has small particle size, large specific surface area, and high refractive index, and can prepare a nano-zirconia dispersion liquid with uniform dispersion and high refractive index.
  • the nano-zirconia powder provided by the above embodiment the synergistic effect of its particle size, specific surface area and the proportion of the tetragonal crystal structure can make the obtained nano-zirconia powder have the characteristics of uniform dispersion and high refractive index after dispersion, Specifically, when the particle size is small and the specific surface is large, the particle dispersibility is good, the prepared aqueous dispersion will be uniformly dispersed, and the refractive index will be higher; and when the zirconia crystal phase is a tetragonal phase and in the powder The higher the proportion of the tetragonal phase, the higher the corresponding refractive index (the refractive index of zirconia in the tetragonal phase is 2.40, which is significantly higher than the refractive
  • the particle size of the nano-zirconia powder can also be 4, 5, 6, 7, 8, 9 nm or any value within the above range
  • the specific surface area can also be 205, 210, 215, 220, 225 , 230, 235m2/g or any value within the above range
  • the proportion of the tetragonal crystal structure in the powder can also be 65, 70, 75, 80, 85, 90% or any value within the above range.
  • Another embodiment of the present application also provides the preparation method of the nano-zirconia powder described in the above embodiment, comprising the following steps:
  • solution B The base is dissolved in water to obtain solution B;
  • the solution A and the solution B are fully mixed under stirring to form a precipitate, wherein the mass of the precipitate accounts for 1-40% of the mass of the total mixed solution; after the precipitate is washed and filtered for many times, the precursor C is obtained;
  • the above obtained slurry is put into a reaction kettle, the filling amount is 60-90%, and the hydrothermal reaction is carried out at 180°C-220°C for 1-12 hours, and a reaction solution is obtained after the reaction;
  • the reaction solution is directly dried or concentrated, washed and then dried to obtain nano-zirconia powder.
  • the order of adding the organic acid or its salt is different from the prior art, that is, the organic acid or its salt needs to be introduced before pulping instead of after pulping. Because of the effect of electric charge before pulping, the viscosity of the precursor will be greatly reduced during the pulping process, which can not only improve the pulping and dispersion effect, but also increase the concentration of the precursor into the kettle, avoiding the poor pulping and dispersion effect. , resulting in high particle size of the prepared powder and agglomeration, not easy to disperse and other defects.
  • the hydrothermal reaction can be carried out above 170°C, and this embodiment limits its temperature within the range of 180-220°C, such as 190°C, 195°C, 200°C, 205°C, 210°C °C, 215 °C or any point within the above range.
  • the temperature of the hydrothermal reaction in the preparation method provided by this embodiment directly affects the crystal grain structure of the obtained powder, that is, if it is less than 180° C., for example, 170° C., the crystal form of the obtained powder is a monoclinic phase grain structure, while Unexpected tetragonal crystal structure; and if it is more than 220 ° C, the requirements for production equipment are strict, which is not conducive to scale-up production.
  • the added zirconium salt is a water-soluble zirconium salt, selected from at least one of basic carbonate, carbonate, nitrate, acetate, chloride, and oxychloride;
  • the added stabilizing element salt is chloride or nitrate of stabilizing element, wherein the stabilizing element is selected from at least one of aluminum, magnesium, titanium and rare earth elements; the alkali is selected from ammonia water, hydroxide At least one of sodium, potassium hydroxide and lithium hydroxide.
  • the concentration of the added zirconium salt is ⁇ 2mol/L
  • the molar concentration ratio of the added stability element and the zirconium element is 2/98 ⁇ 30/70
  • the concentration of the added alkali is ⁇ 8mol/L L.
  • the organic acid is selected from at least one of monocarboxylic acid, polycarboxylic acid and hydroxycarboxylic acid, wherein the monocarboxylic acid is selected from formic acid, acetic acid, propionic acid and butyric acid
  • the polycarboxylic acid is selected from at least one of oxalic acid, malonic acid, succinic acid, and phthalic acid
  • the hydroxycarboxylic acid is selected from at least one of lactic acid, malic acid, tartaric acid, and citric acid
  • the salt of the organic acid is an alkali metal salt, at least one selected from potassium salt and sodium salt.
  • the molar concentration of the added organic acid or its salt is 10-100% of the total molar concentration of zirconium element and stable element. It can be understood that the content of the organic acid and its salt is clearly defined in this embodiment, and the molar concentration of the organic acid and its salt is limited to 10-100% of the total molar concentration of zirconium element and stable element. The reason is that, in the prior art (for example, Chinese patent application CN102264645A), when preparing the zirconia dispersion, the amount of the organic acid added is usually more than 1 times the molar concentration of zirconium, but when the organic acid, especially the molecular weight, is added The amount is too large.
  • the acidity of the reaction slurry is highly corrosive to the reaction equipment.
  • the preparation of the aqueous dispersion in the later stage needs to be concentrated and washed with a large amount of water for many times, and the water waste is serious. More importantly, the larger the amount of acid The higher the probability of acid content remaining in the solvent-based dispersion prepared later, it is not conducive to industrial production. Therefore, in this embodiment, the amount is limited within the range of 10-100% through the optimization of the overall scheme.
  • the molar concentration of the organic acid and its salt can be 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% of the sum of the molar concentration of zirconium element and stable element, or within the above range any point value.
  • the reaction solution when the boiling point of the added organic acid is less than 150°C, the reaction solution is directly dried to obtain nano-zirconia powder; when the boiling point of the added organic acid is greater than 150°C, the reaction solution is concentrated for many times After washing, drying is performed to obtain nano-zirconia powder.
  • the organic acid with a boiling point of ⁇ 150°C can be selected from, for example, formic acid, acetic acid, propionic acid, etc.
  • the organic acid with a boiling point of >150°C can be selected from, for example, oleic acid, citric acid, isovaleric acid, etc., which are only listed here. There is no specific limitation.
  • the drying method is selected from any one of vacuum low-temperature drying, drying and spraying
  • the concentrated washing method is selected from any one of ultrafiltration, rotary evaporation and ceramic membrane concentrated washing. It can be understood that the above drying methods and concentrated washing methods are operation methods that are well known to those skilled in the art, and the specific requirements of the specific methods can be selected or adjusted according to the actual situation.
  • An embodiment of the present application also provides an organic solvent-based dispersion liquid containing the nano-zirconia powder described in the above embodiment, the content of the nano-zirconia in the dispersion liquid is 40-70wt%, and the refractive index is 1.400 -1.554. It can be understood that the content of nano-zirconia in the obtained organic solvent-type dispersion liquid has been significantly improved compared with the content of nano-zirconia in the prior art, which belongs to the organic solvent-type dispersion liquid of high-concentration nano-zirconia.
  • the content of nano-zirconia in the liquid can also be 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69 wt% or any value within the above range.
  • the dispersion liquid is obtained by replacing the dispersion medium (ie, water) in the reaction liquid obtained by the preparation method described in the above embodiment with an organic solvent, or by replacing the above
  • the nano-zirconia powder prepared by the method is dispersed in an organic solvent, wherein the organic solvent is selected from at least one of alcohols, esters, aromatic hydrocarbons, ethers and amide organic solvents.
  • the above-mentioned alcohols can be selected from at least one of methanol, ethanol, propanol and n-butanol; ketones can be selected from at least one of acetone, methyl ethyl ketone, methyl isobutyl ketone; esters Can be selected from ethyl acetate or butyl acetate; aromatic hydrocarbons can be selected from at least one of toluene, xylene, ethylbenzene; ethers can be selected from propylene glycol methyl ether, ethylene glycol monomethyl ether, diethylene glycol At least one of monobutyl ether; amides can be selected from at least one of dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.
  • a modifier is added to the dispersion, and the addition amount of the modifier is 1-20 wt % of the content of the nano-zirconia.
  • the modifier is added for secondary dispersion, the purpose is to enable the nano-zirconia to be sufficiently dispersed through the sufficient combination of the modifier and the zirconia.
  • the addition amount of the modifier can also be 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt% of the nano-zirconia content , 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt% or any value within the above range.
  • the modifier is selected from at least one of silane coupling agents, titanate coupling agents, metal complexes, aromatic or highly conjugated chemical substances.
  • the silane coupling agent and titanate coupling agent are not specifically limited here, and can be commercially available coupling agents of various labels;
  • the metal complex can be selected from zirconium, titanium, aluminum, zinc, indium Metal complexes (such as titanium acetylacetonate, aluminum acetylacetonate) of at least one metal and tin and a ligand selected from at least one of acetylacetone, trifluoroacetylacetone and hexafluoroacetylacetone;
  • the modifier can also be an aromatic or highly conjugated substance, and can be selected from at least one of 1-styrene acetone, phenylacetylacetone, diphenylacetic acid, phenylphosphinic acid, and triphenyl phosphate .
  • an oily dispersing aid is added to the dispersion liquid, and the added amount of the oily dispersing aid is 1-20 wt % of the content of the nano-zirconia. It can be understood that the purpose of adding an oil-based dispersing aid in this embodiment is to further improve the stability and dispersibility of the dispersion.
  • the dispersing aid here is not specifically limited, and can be commercially available anionic dispersants, cationic dispersants At least one of dispersants, nonionic dispersants and polymer dispersants, preferably phosphate series dispersing aids.
  • the organic solvent-based dispersion of the nano-zirconia is obtained in the following manner: adding an organic solvent to the reaction solution obtained after the hydrothermal reaction of the method for preparing the nano-zirconia powder of the above-mentioned embodiment to carry out
  • the zirconia organic solvent-type dispersion liquid is obtained after the rotary evaporation treatment, concentration and removal of water and then adding an organic solvent, repeated dilution and concentration.
  • the dispersion liquid treated in this way has significant advantages.
  • Another embodiment of the present application also provides a nano-zirconia dispersion with a photocurable resin, wherein the dispersion is obtained by adding the photocurable resin to the nano-zirconia powder described in any one of the above embodiments After being in the dispersion liquid, the organic solvent is removed by distillation under reduced pressure; the content of nano-zirconia in the dispersion liquid is 50-80 wt%, and the refractive index is 1.60-1.70.
  • the photocurable resin used is one containing one or more radiation polymerizable double bonds
  • the photocurable resin may be selected from the group consisting of esters, urethanes, ethers, silicon, halogens and/or containing (meth)acrylic monomers or oligomers of phosphorus and other groups.
  • a photocurable resin with a higher refractive index such as an acrylate containing an alicyclic skeleton (dicyclopentyl methacrylate, cyclohexyl acrylate), is preferred.
  • light-curable resins with lower viscosity such as benzyl acrylate, methyl (meth)acrylate.
  • the photocurable resin may be a commercially available monomer or oligomer.
  • the added amount of the photocurable resin is 20-50% of the total mass of the zirconia and the photocurable resin.
  • the present application also provides an optical film, which is prepared by using the dispersion liquid containing nano-zirconia powder described in any of the above embodiments or using the nano-zirconia dispersion liquid with photocurable resin described in any of the above-mentioned embodiments get.
  • the optical films provided in this embodiment can mainly be brightness enhancement films, anti-reflection films, and other optical films with high-refractive coatings.
  • the slurry obtained above was put into a 10L reactor, and hydrothermally reacted at 200°C for 3h;
  • the reaction solution is directly dried to obtain nano-zirconia powder.
  • the particle size of the obtained nano-zirconia powder is 3-10nm, the specific surface area is 220m 2 /g, and the nano-zirconia powder is zirconia with tetragonal crystal structure, and zirconia with tetragonal crystal structure
  • the proportion accounts for more than 90% of the powder, as shown in Figure 1-3. It can be seen from Figure 1a and Figure 1b that the particle size of the obtained nano-zirconia powder is 3-10nm. It can be seen from Figure 2 that the diffraction peaks of the nano-zirconia powder above and the XRD characteristic peaks of the standard tetragonal phase grains below are Correspondingly, and the proportion of tetragonal crystal structure is relatively high. By analyzing and calculating the diffraction intensity data, it can be found that the proportion of the tetragonal crystal structure is more than 90%.
  • the reaction solution is directly dried to obtain nano-zirconia powder.
  • the obtained nano-zirconia powder has a particle size of 3-10 nm, a specific surface area of 200 m 2 /g, and the nano-zirconia powder includes zirconia with a tetragonal crystal structure, and zirconia with a tetragonal crystal structure. The proportion accounts for about 75% of the powder.
  • the slurry obtained above was put into a 10L reactor, and hydrothermally reacted at 220°C for 3h;
  • the reaction solution is directly dried to obtain nano-zirconia powder.
  • the particle size of the obtained nano-zirconia powder is 3-10 nm, and the specific surface area is 210 m 2 /g, and the nano-zirconia powder includes zirconia with tetragonal crystal structure and zirconia with tetragonal crystal structure. The proportion accounts for about 83% of the powder.
  • butanone (MEK) solvent was added to carry out rotary evaporation treatment, and then MEK was added after concentration to remove water. After repeated dilution and concentration, MEK dispersion of zirconia was obtained. Then, modifying agent triphenyl phosphate (addition amount is 10wt% of zirconium content) is added for modification, and then oil-based dispersing aid (addition amount is 5wt%) is added to obtain nano-zirconia organic MEK type dispersion.
  • MEK butanone
  • the refractive index is 1.458
  • the concentration is 60%
  • the refractive index is 1.516
  • the concentration is 70wt%
  • the refractive index is 1.554.
  • the method for preparing the nano-zirconia organic solvent-based dispersion liquid is the same as that in Example 4, except that the reaction liquid after the hydrothermal reaction in Example 2 is used, and the amount of the modifier added is 10% of the zirconium content , to obtain a nano-zirconia organic MEK-type dispersion.
  • the refractive index is 1.455
  • the concentration is 60wt%
  • the refractive index is 1.511
  • the concentration is 70wt%
  • the refractive index is 1.549.
  • the method for preparing the nano-zirconia organic solvent-based dispersion liquid is the same as that in Example 4, except that the reaction liquid after the hydrothermal reaction in Example 3 is used, and the amount of the modifier added is 15wt% of the zirconium content , to obtain a nano-zirconia organic MEK-type dispersion.
  • the refractive index is 1.439; when the concentration is 60wt%, the refractive index is 1.492; when the concentration is 70wt%, the refractive index is 1.545.
  • Benzyl acrylate (added according to the concentration of zirconia in the obtained monomer dispersion is 80wt%) is added to the organic MEK type dispersion of nano zirconia prepared in Example 4, and the mixed solution is subjected to vacuum distillation to remove the organic solvent , to obtain a nano-zirconia dispersion with photocurable benzyl acrylate;
  • the content of nano-zirconia in the dispersion liquid is 80wt%, and the refractive index thereof is 1.649.
  • Benzyl acrylate (added according to the concentration of zirconia in the obtained monomer dispersion is 60wt%) is added to the organic MEK type dispersion of nano zirconia prepared in Example 5, and the mixed solution is subjected to vacuum distillation to remove the organic solvent , to obtain a nano-zirconia dispersion with photocurable benzyl acrylate;
  • the content of nano-zirconia in the dispersion liquid is 60wt%, and the refractive index is 1.636.
  • Benzyl acrylate (added according to the concentration of zirconia in the obtained monomer dispersion is 50wt%) is added to the organic MEK type dispersion of nano-zirconia prepared in Example 6, and the mixed solution is subjected to vacuum distillation to remove the organic solvent , to obtain nano-zirconia dispersion with photocurable resin;
  • the content of nano-zirconia in the dispersion is 50wt%, and the refractive index is 1.611.
  • the slurry obtained above was put into a 10L reactor, 270g of acetic acid was added, the total volume was controlled to be 8L, and the hydrothermal reaction was carried out at 200°C for 3h;
  • the reaction solution is directly dried to obtain nano-zirconia powder.
  • the obtained nano-zirconia powder has a particle size of about 30 nm and a specific surface area of 180 m 2 /g, and the nano-zirconia powder includes zirconia with a tetragonal crystal structure.
  • the reaction solution is directly dried to obtain nano-zirconia powder.
  • the obtained nano-zirconia powder had an average particle size of 30 nm and a specific surface area of 177 m 2 /g, and the nano-zirconia powder was zirconia with a monoclinic phase grain structure.
  • the method for preparing the organic solution type dispersion of nano-zirconia is the same as that in Example 4, the difference is that the solution after the hydrothermal reaction in Comparative Example 1 is used.
  • the refractive index is 1.445
  • the concentration is 60wt%
  • the refractive index is 1.491
  • the concentration is 70wt%
  • the refractive index is 1.530.
  • the method for preparing the butanone dispersion of nano-zirconia is the same as that in Example 4, the difference is that the solution after the hydrothermal reaction in Comparative Example 2 is adopted.
  • the refractive index is 1.439
  • the concentration is 60%
  • the refractive index is 1.480
  • the concentration is 70wt%
  • the refractive index is 1.532.
  • the method for preparing the organic solution-type dispersion of nano-zirconia is the same as that in Example 4, except that no modifier is added.
  • the method for preparing the organic solution-type dispersion of nano-zirconia is the same as that in Example 4, except that no oily dispersing aid is added.
  • the refractive index of Example 4-6 is 1.545-1.554, and the refractive index of Comparative Example 3-4 is 1.530-1.532, with a difference of 0.013-0.024;
  • the refractive index of Example 4-6 is 1.492-1.516, the refractive index of Comparative Example 3-4 is 1.480-1.491, and the maximum difference is 0.036;
  • the implementation The refractive index of Example 4-6 is 1.439-1.458, and the refractive index of Comparative Example 3-4 is 1.439-1.445, with a maximum difference of 0.013.
  • the particle size of the zirconia in the dispersion liquid in the comparative example is relatively large (Comparative Examples 3, 4), and the crystal form is a monoclinic phase (Comparative Example 4), so that the prepared dispersion liquid has a relatively low refractive index.
  • the refractive index difference is not much different from the numerical point of view, it is very different from the perspective of the optical properties of the refractive index of the dispersion liquid. Its transmittance is 89% and 93%, and this is the difference between A-level screen and B-level screen.

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Abstract

本申请提供了一种纳米氧化锆粉体，粒径为3-10nm，比表面积为200-240m2/g，纳米氧化锆粉体包括四方相氧化锆，且四方相氧化锆的比例占粉体的60-95％。本申请提供的纳米氧化锆粉体具有粒径小、比表面积大、粒子单分散效果好、主晶相为四方相等特点，于水中分散后所得的水分散液在后续例如制备增亮膜或防反射膜中能够大幅提升高折射涂层的折射率，提升膜的性能。

Description

纳米氧化锆粉体、其制备方法及所得分散液、光学膜
Nano zirconia powder,preparation method thereof and dispersion liquid and optical film prepared therefrom
本申请要求在2020年11月23日提交中国专利局、申请号为202011320008.8、发明名称为“纳米氧化锆粉体、其制备方法及所得分散液、光学膜”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请属于精细化工领域，尤其涉及一种纳米氧化锆粉体、其制备方法及所得分散液、光学膜。
背景技术
近年来，通过氧化锆颗粒分散体与透明树脂或薄膜结合，利用它的高折射率，在光学领域中得到很好的应用。例如利用高折射的氧化锆分散液制备增亮膜和防反射膜等光学膜，可用在LCD显示器上，增加屏幕的亮度和清晰度；也可以用来提高LED密封树脂折射率，能够更有效地取出发光体放出的光，进而提高LED的亮度。总之，其高折射的特性可用在高折射涂层中，在不同领域得到应用。
氧化锆分散液折射率的高低与体系中纳米氧化锆的粒径、晶型结构、粒子分散状态和分散液制备工艺息息相关。CN201810704465.3公开了一种高分散纳米氧化锆颗粒及其透明分散体的制备方法，其采用在超重力环境下热解无机锆盐的方法直接制备纳米氧化锆颗粒，且随着超重力水平的提高团聚性大大减小，之后经过洗涤、改性后直接为透明的氧化锆液相分散体。该方 法制备的氧化锆虽然粒径小，分散性较好，但其粉体晶型结构为单斜相，粉体折射率远远低于四方相粉体的折射率，且对应的液相分散体的折射率在相同条件下折射率也较低。因此，如何制备得到性能优异的纳米氧化锆颗粒以及体系稳定、分散均匀、折射率高的氧化锆分散液对于更好地满足透明有机无机复合物的性能需求而言显得尤为重要。
发明内容
本申请提供了一种纳米氧化锆粉体、其制备方法及所得分散液、光学膜，具体技术方案如下：
一种纳米氧化锆粉体，其特征在于，所述纳米氧化锆粉体的粒径为3-10nm，比表面积为200-240m 2/g，所述纳米氧化锆粉体包括四方相晶型结构的氧化锆，且四方相晶型结构的氧化锆比例占粉体的60-95％。
本申请还提供了一种根据上述技术方案所述的纳米氧化锆粉体的制备方法，包括以下步骤：
将锆盐和稳定性元素盐共同溶解在水中，得到溶液A；
将碱溶解在水中，得到溶液B；
将溶液A和溶液B于搅拌下充分混合，生成有沉淀物，其中，沉淀物的质量占总混合液质量的1-40％；将沉淀物经过多次洗涤过滤后，得到前驱体C；
向前躯体C中加入水和有机酸或其盐制浆，所得浆料中的总固含量为6-20wt％；
将上述所得浆料投入到反应釜中，填充量为60-90％，于180℃-220℃下水热反应1-12h，反应后得到反应液；
将反应液直接干燥或浓缩洗涤后干燥，得到纳米氧化锆粉体。
作为优选，所加入的锆盐为水溶性锆盐，选自碱式碳酸盐、碳酸盐、硝酸盐、乙酸盐、氯化物、氧氯化物中的至少一种；所加入的稳定性元素盐为稳定性元素的氯化物或硝酸盐，其中所述稳定性元素选自铝、镁、钛和稀土类元素中的至少一种；所述碱选自氨水、氢氧化钠、氢氧化钾和氢氧化锂中的至少一种。
作为优选，所加入的锆盐浓度≤2mol/L，所加入的稳定性元素与锆元素的摩尔浓度比为2/98～30/70，所加入的碱的浓度为≤8mol/L。
作为优选，所述有机酸选自一元羧酸、多元羧酸和羟基羧酸中的至少一种，其中，所述一元羧酸选自甲酸、乙酸、丙酸、丁酸中的至少一种，多元羧酸选自草酸、丙二酸、琥珀酸、邻苯二甲酸中的至少一种，羟基羧酸选自乳酸、苹果酸、酒石酸、柠檬酸中的至少一种；所述有机酸的盐为其碱金属盐，选自钾盐、钠盐中的至少一种。
作为优选，所加入的有机酸或其盐的摩尔浓度为锆元素和稳定元素摩尔浓度总和的10-100％。
作为优选，当所加入的有机酸的沸点＜150℃时，将反应液直接进行干燥得到纳米氧化锆粉体；当所加入的有机酸沸点＞150℃时，将反应液多次浓缩洗涤后再干燥，得到纳米氧化锆粉体。
作为优选，所述干燥方式选自真空低温干燥、烘干和喷雾中的任意一种，所述浓缩洗涤方式选自超滤、旋蒸和陶瓷膜浓缩洗涤中的任意一种。
本申请还提供了一种包含上述技术方案所述纳米氧化锆粉体的有机溶剂型分散液，所述分散液中纳米氧化锆的含量为40-70wt％，其折射率为1.400-1.554。
作为优选，所述分散液在所含纳米氧化锆的含量为70wt％时，所述分散 液的折射率不低于1.554。
作为优选，所述分散液为通过将上述技术方案所述的制备方法在制备过程中得到的反应液中的分散介质水置换成有机溶剂得到，或通过将上述技术方案制备得到的纳米氧化锆粉体分散于有机溶剂中得到，其中所述有机溶剂选自醇类、酯类、芳香烃类、醚类以及酰胺类有机溶剂中的至少一种。
作为优选，所述分散液中添加有改性剂，所述改性剂的添加量为纳米氧化锆含量的1-20wt％。
作为优选，所述改性剂选自硅烷偶联剂、钛酸酯偶联剂、金属络合物、芳香型或高度共轭的化学物质中的至少一种。
作为优选，所述分散液中添加有油性分散助剂，所述油性分散助剂的添加量为纳米氧化锆含量的1-20wt％。
本发明还提供了一种具有可光固化树脂的纳米氧化锆分散液，所述分散液是将可光固化树脂添加到上述任一技术方案所述的纳米氧化锆粉体的分散液中后，通过减压蒸馏除去有机溶剂后得到的；
所述分散液中纳米氧化锆的含量为50-80wt％，其折射率为1.60-1.70。
作为优选，所述可光固化树脂的添加量为氧化锆和可光固化树脂总质量的20-50％。
本申请还提供了一种光学膜，采用上述技术方案中任一项所述的包含纳米氧化锆粉体的分散液或采用上述技术方案中任一项所述的具有可光固化树脂的纳米氧化锆分散液制备得到。
本申请还提供了一种根据上述技术方案所述的纳米氧化锆粉体或者上述技术方案中任一项所述的包含纳米氧化锆粉体的分散液或者上述技术方案中任一项所述的具有可光固化树脂的纳米氧化锆分散液在制备光学膜中的应用。
与现有技术相比，本申请的有益效果为：
1、本发明提供的纳米氧化锆粉体具有粒径小、比表面积大、粒子单分散效果好、主晶相为四方相等特点；
2、利用上述得到的纳米氧化锆粉体制备的有机溶剂型及光固化树脂型分散液具有体系稳定、分散均匀、分散液浓度高，折射率高。
3、利用具有上述特性的分散液在后续例如制备增亮膜或防反射膜中能够大幅提升高折射涂层的折射率，提升膜的性能。
附图说明
图1a为本申请实施例1提供的纳米氧化锆粉体的透射电镜图1；
图1b为本申请实施例1提供的纳米氧化锆粉体的透射电镜图2；
图2为本申请实施例1提供的纳米氧化锆粉体与标准四方相晶粒的XRD对比图谱；
图3为本申请实施例1提供的纳米氧化锆粉体的粒径分布图；
图4为本申请对比例1提供的纳米氧化锆粉体的扫描电镜图。
具体实施方式
以下结合具体实施方式对本申请的技术方案进行详实的阐述，然而应当理解，在没有进一步叙述的情况下，一个实施方式中的元件、结构和特征也可以有益地结合到其他实施方式中。
值得理解的是，尽管实施方式中可能示出了方法步骤的特定顺序，但是，这并非要求或者暗示必须按照该特定顺序来执行这些操作，或是必须执行全部所示的操作才能实现期望的结果，相反，步骤可以改变执行顺序。附加地或备选地，可以省略某些步骤，将多个步骤合并为一个步骤执行，和/或将一 个步骤分解为多个步骤执行。除非特别说明或步骤之间的关联性决定了执行顺序。这样的变型将取决于选择。所有这样的变型都在本公开的范围内。
所述的实施方式仅仅是对本申请的优选实施方式进行描述，并非对本申请的范围进行限定，在不脱离本申请设计精神的前提下，本领域普通技术人员对本申请的技术方案作出的各种变形和改进，均应落入本申请权利要求书确定的保护范围内。
本申请一种实施方式提供了一种纳米氧化锆粉体，所述纳米氧化锆粉体的粒径为3-10nm，比表面积为200-240m 2/g，所述纳米氧化锆粉体包括四方相晶型结构的氧化锆，且四方相晶型结构的氧化锆比例占粉体的60-95％。
该实施方式提供的纳米氧化锆粉体粒径小、比表面积大、折射率高，可制备出分散均匀、折射率高的纳米氧化锆分散液。上述实施方式提供的纳米氧化锆粉体，其粒径、比表面积以及四方相晶型结构占比三者的协同作用可使所得纳米氧化锆粉体在分散后具有分散均匀、折射率高等特点，具体为粒径小、比表面大时，其粒子分散性好，所制备得到的水分散液就会分散均匀，折射率就会越高；并且在当氧化锆晶相为四方相且粉体中四方相占比越高时，其对应的折射率就会越高(四方相的氧化锆折射率为2.40，比单斜相的氧化锆折射率2.02明显要高)。可以理解的是，纳米氧化锆粉体的粒径还可以为4、5、6、7、8、9nm或上述范围内的任一点值，比表面积还可以为205、210、215、220、225、230、235m2/g或上述范围内的任一点值，四方相晶型结构占粉体的比例还可以为65、70、75、80、85、90％或上述范围内的任一点值。
本申请另一种实施方式还提供了上述实施方式所述的纳米氧化锆粉体的制备方法，包括以下步骤：
将锆盐和稳定性元素盐共同溶解在水中，得到溶液A；
将碱溶解在水中，得到溶液B；
将溶液A和溶液B于搅拌下充分混合，生成有沉淀物，其中，沉淀物的质量占总混合液质量的1-40％；将沉淀物经过多次洗涤过滤后，得到前驱体C；
向前躯体C中加入水和有机酸或其盐制浆，所得浆料中的总固含量为6-20wt％；
将上述所得浆料投入到反应釜中，填充量为60-90％，于180℃-220℃下水热反应1-12h，反应后得到反应液；
将反应液直接干燥或浓缩洗涤后干燥，得到纳米氧化锆粉体。
上述实施方式限定的纳米氧化锆粉体的制备方法，有机酸或其盐的加入顺序不同于现有技术，即有机酸或其盐需要在制浆之前引入而非制浆之后再引入，这是因为制浆之前由于电荷的作用，会使得前驱体在制浆过程中粘度大幅度降低，这样不但可提高制浆分散效果，同时还可提高前驱体入釜的浓度，避免了制浆分散效果差、造成制备的粉体粒径偏高且团聚、不易分散等缺陷。另外，现有技术中已有报道水热反应可在170℃以上进行，该实施例将其温度限定在180-220℃范围内，例如可以为190℃、195℃、200℃、205℃、210℃、215℃或上述范围内的任一点值。本实施方式提供的制备方法中水热反应的温度直接影响了所得粉体的晶粒结构，即如果＜180℃，例如170℃，所得粉体的晶型则为单斜相晶粒结构，而非所预期的四方相晶型结构；而如果＞220℃，则对生产设备要求严苛，并不利于放大生产。
作为一种优选实施方式中，所加入的锆盐为水溶性锆盐，选自碱式碳酸盐、碳酸盐、硝酸盐、乙酸盐、氯化物、氧氯化物中的至少一种；所加入的 稳定性元素盐为稳定性元素的氯化物或硝酸盐，其中所述稳定性元素选自铝、镁、钛和稀土类元素中的至少一种；所述碱选自氨水、氢氧化钠、氢氧化钾和氢氧化锂中的至少一种。
作为一种优选实施方式，所加入的锆盐浓度≤2mol/L，所加入的稳定性元素与锆元素的摩尔浓度比为2/98～30/70，所加入的碱的浓度为≤8mol/L。可以理解的是，上述所加入的稳定性元素的量需进行严格控制，不宜过多或过少，这是因为过少易使制备得到的粉体的四方相占比较小甚至为单斜相，过多则易使制备得到的粉体中稳定性元素含量高而影响粉体本身折射率。通过控制所加入的锆盐浓度和稳定性元素盐的量，进而严格控制溶液A中稳定性元素与锆元素的摩尔浓度比。
作为一种优选实施方式，所述有机酸选自一元羧酸、多元羧酸和羟基羧酸中的至少一种，其中，所述一元羧酸选自甲酸、乙酸、丙酸、丁酸中的至少一种，多元羧酸选自草酸、丙二酸、琥珀酸、邻苯二甲酸中的至少一种，羟基羧酸选自乳酸、苹果酸、酒石酸、柠檬酸中的至少一种；所述有机酸的盐为其碱金属盐，选自钾盐、钠盐中的至少一种。
作为一种优选实施方式，所加入的有机酸或其盐的摩尔浓度为锆元素和稳定元素摩尔浓度总和的10-100％。可以理解的是，本实施例中对有机酸及其盐的含量做了明确限定，并将有机酸及其盐的摩尔浓度限定为锆元素和稳定元素摩尔浓度总和的10-100％。原因在于，现有技术(例如中国专利申请CN102264645A)中在制备氧化锆分散液时，所加入的有机酸的量通常为锆摩尔浓度1倍以上，但当有机酸尤其是分子量较大时其添加量太大，一方面造成反应浆液的酸性强对反应设备腐蚀性大，另一方面后期水分散液的制备需要用大量的水多次浓缩洗涤，水浪费严重，更重要的是酸量越大后期制备 的溶剂型分散液残留的酸量概率越大，并不利于工业化生产。因此，本实施方式通过整体方案的优化，将其量限定在10-100％范围内。优选的，有机酸及其盐的摩尔浓度可为锆元素和稳定元素摩尔浓度总和的20％、30％、40％、50％、60％、70％、80％、90％或上述范围内的任一点值。
作为一种优选实施方式中，当所加入的有机酸沸点＜150℃时，如将反应液直接进行干燥得到纳米氧化锆粉体；当所加入的有机酸沸点＞150℃时，将反应液多次浓缩洗涤后再干燥，得到纳米氧化锆粉体。可以理解的是，沸点＜150℃的有机酸例如可选自甲酸、乙酸、丙酸等，沸点＞150℃的有机酸例如可选自油酸、柠檬酸、异戊酸等，这里仅是列举并不做具体限定。
作为一种优选实施方式，所述干燥方式选自真空低温干燥、烘干和喷雾中的任意一种，所述浓缩洗涤方式选自超滤、旋蒸和陶瓷膜浓缩洗涤中的任意一种。可以理解的是，上述干燥方式和浓缩洗涤方式均为本领域技术人员已熟知的操作方式，具体方式下的具体要求可根据实际情况进行选择或调整。
本申请一种实施方式还提供了一种包含上述实施方式所述纳米氧化锆粉体的有机溶剂型分散液，所述分散液中纳米氧化锆的含量为40-70wt％，其折射率为1.400-1.554。可以理解的是，所得有机溶剂型分散液中的纳米氧化锆的含量相比于现有技术中纳米氧化锆的含量有了明显提升，属于高浓度纳米氧化锆的有机溶剂型分散液，该分散液中纳米氧化锆的含量还可以是41、42、43、44、45、46、47、48、49、50、51、52、53、54、55、56、57、58、59、60、61、62、63、64、65、66、67、68、69wt％或上述范围内的任一点值。
作为一种优选实施方式，所述分散液为通过将上述实施方式所述的制备方法在制备过程中得到的反应液中的分散介质(即，水)置换成有机溶剂得 到，或通过将上述实施方式制备得到的纳米氧化锆粉体分散于有机溶剂中得到，其中所述有机溶剂选自醇类、酯类、芳香烃类、醚类以及酰胺类有机溶剂中的至少一种。
可以理解的是，上述醇类可以选自甲醇、乙醇、丙醇、正丁醇中的至少一种；酮类可以选自丙酮、丁酮、甲基异丁基甲酮中的至少一种；酯类可以选自乙酸乙酯或乙酸丁酯；芳香烃类可以选自甲苯，二甲苯、乙苯中的至少一种；醚类可以选自丙二醇甲醚，乙二醇单甲醚、二乙二醇单丁醚中的至少一种；酰胺类可以选自二甲基甲酰胺，N，N-二甲基乙酰胺、N-甲基吡咯烷酮中的至少一种。
作为一种优选实施方式，所述分散液中添加有改性剂，所述改性剂的添加量为纳米氧化锆含量的1-20wt％。本实施方式中，加入改性剂对其进行二次分散，目的在于通过改性剂与氧化锆的充分结合使得纳米氧化锆能够得以充分的分散。可以理解的是，所述改性剂的添加量还可为纳米氧化锆含量的2wt％、3wt％、4wt％、5wt％、6wt％、7wt％、8wt％、9wt％、10wt％、11wt％、12wt％、13wt％、14wt％、15wt％、16wt％、17wt％、18wt％、19wt％或上述范围内的任一点值。
作为一种优选实施方式，所述改性剂选自硅烷偶联剂、钛酸酯偶联剂、金属络合物、芳香型或高度共轭的化学物质中的至少一种。其中，硅烷偶联剂和钛酸酯偶联剂在此不做具体限定，可为市售的各类标号的偶联剂；金属络合物可为选自锆、钛、铝、锌、铟和锡中至少一种的金属和选自乙酰丙酮、三氟乙酰丙酮和六氟乙酰丙酮中至少一种的配体的金属络合物(如乙酰丙酮合钛、乙酰丙酮合铝)；此外，所述改性剂也可为芳香型的或高度共轭的物质，可选自1-苯乙烯丙酮、苯乙酰丙酮、二苯乙酸、苯基次膦酸、磷酸三苯酯中 的至少一种。
作为一种优选实施方式，所述分散液中添加有油性分散助剂，所述油性分散助剂的添加量为纳米氧化锆含量的1-20wt％。可以理解的是，本实施方式中加入油性分散助剂的目的在于进一步提高分散液的稳定性及分散性，此处的分散助剂不作具体限定，可以为市售的阴离子型分散剂、阳离子型分散剂、非离子型分散剂和高分子型分散剂中的至少一种，优选磷酸酯系列分散助剂。
作为一种优选实施方式，所述纳米氧化锆的有机溶剂型分散液通过以下方式得到：向上述实施方式的纳米氧化锆粉体制备方法在水热反应后的得到的反应液中加入有机溶剂进行旋转蒸发处理，浓缩除水后再加入有机溶剂，重复稀释浓缩后得到氧化锆有机溶剂型分散液。
上述优选实施方式中，在将上述实施方式所述的制备方法在制备过程中得到的反应液中的分散介质的水置换成有机溶剂后，进一步加入改性剂对其进行亲油性改性处理，此外还加入油性分散助剂，以对分散液的稳定性及分散性进行强化。相对于现有技术中进行分散介质替换的分散液而言，这种方式处理后的分散液具有显著优势。
本申请另一种实施方式还提供了一种具有可光固化树脂的纳米氧化锆分散液，所述分散液是将可光固化树脂添加到上述任一实施方式所述的纳米氧化锆粉体的分散液中后，通过减压蒸馏除去有机溶剂后得到；所述分散液中纳米氧化锆的含量为50-80wt％，其折射率为1.60-1.70。可以理解的是，所采用的可光固化树脂为包含一个或多个可辐射聚合的双键，该可光固化树脂可选自包含酯、氨基甲酸乙酯、醚、硅、卤素和/或含磷等基团的(甲基)丙烯酸系的单体或其低聚物。优选折射率较高的光固化树脂，如含有脂环骨架的 丙烯酸酯(甲基丙烯酸二环戊基酯、丙烯酸环己酯)。或优选粘度较低的光固化树脂，如丙烯酸苄酯、(甲基)丙烯酸甲酯。该可光固化树脂可为市售的单体或低聚物。
作为一种优选实施方式，所述可光固化树脂的添加量为氧化锆和可光固化树脂总质量的20-50％。
本申请还提供了一种光学膜，采用上述任一实施方式所述的包含纳米氧化锆粉体的分散液或采用上述任一实施方式所述的具有可光固化树脂的纳米氧化锆分散液制备得到。可以理解的是，本实施方式中提供的光学膜主要可为增亮膜、防反射膜以及其他具有高折射涂层的光学膜。
以下结合实施例对本申请进行详细的阐述，值得理解的是，这些实施例仅仅是本申请的优选的一些实施例，并不能理解为对本申请的保护范围进行限制。
实施例1
称取1.47kg氧氯化锆和138g氯化钇溶于8kg水中，得到其混合溶液A；
将421g氢氧化钠溶于6kg水得到氢氧化钠溶液B；
将溶液A和溶液B于搅拌下充分混合后生成沉淀，将沉淀物经多次洗涤抽滤后得到前驱体C；
向前躯体C中加入水和270g乙酸(乙酸的物质的量为锆元素和稳定元素物质的量之和的90％，因此，乙酸的摩尔浓度为锆元素和稳定元素摩尔浓度之和的90％)，控制总体积在8L，搅拌制浆；
将上述所得浆料投入到10L反应釜中，于200℃下水热反应3h；
反应结束反应后将反应液直接干燥，得到纳米氧化锆粉体。
所得到的纳米氧化锆粉体的粒径为3-10nm，比表面积为220m 2/g，所 述纳米氧化锆粉体为四方相晶型结构的氧化锆，且四方相晶型结构的氧化锆比例占粉体的90％以上，如图1-3所示。由图1a和图1b可知，所得的纳米氧化锆粉体的粒径为3-10nm，由图2可知，上方的纳米氧化锆粉体的衍射峰与下方的标准四方相晶粒的XRD特征峰对应，而且四方相晶型结构的占比较高。对衍射强度数据进行分析计算，可得四方相晶型结构的占比为90％以上。
实施例2
称取1.47kg氧氯化锆和69g氯化钇溶于8kg水中，得到其混合溶液A；
将550g氢氧化钠溶于6kg水得到氢氧化钾溶液B；
将溶液A和溶液B于搅拌下充分混合后生成沉淀，将沉淀物经多次洗涤抽滤后得到前驱体C；
向前躯体C中加入水和160g乙酸(乙酸的物质的量为锆元素和稳定元素物质的量总和的56％)，控制总体积在8L，搅拌制浆；
将上述所得浆料投入到10L反应釜中，于180℃下水热反应4h；
反应结束反应后将反应液直接干燥，得到纳米氧化锆粉体。
所得到的纳米氧化锆粉体的粒径为3-10nm，比表面积为200m 2/g，所述纳米氧化锆粉体包括四方相晶型结构的氧化锆，且四方相晶型结构的氧化锆比例占粉体的约75％。
实施例3
称取1.47kg氧氯化锆和160g氯化钇溶于8kg水中，得到其混合溶液A；
将460g氢氧化钠溶于6kg水得到氢氧化钠溶液B；
将溶液A和溶液B于搅拌下充分混合后生成沉淀，将沉淀物经多次洗涤抽滤后得到前驱体C；
向前躯体C中加入水和337g丙酸(丙酸的物质的量为锆元素和稳定元素物质的量总和的90％)，控制总体积在8L，搅拌制浆；
将上述所得浆料投入到10L反应釜中，于220℃下水热反应3h；
反应结束反应后将反应液直接干燥，得到纳米氧化锆粉体。
所得到的纳米氧化锆粉体的粒径为3-10nm，比表面积为210m 2/g，所述纳米氧化锆粉体包括四方相晶型结构的氧化锆，且四方相晶型结构的氧化锆比例占粉体的约83％。
实施例4
向实施例1中水热反应后的反应液中加入丁酮(MEK)溶剂进行旋转蒸发处理，浓缩除水后再加入MEK，重复稀释浓缩后得到氧化锆的MEK分散液。然后，加入改性剂磷酸三苯酯(添加量为锆含量的10wt％)进行改性，再加入油性分散助剂(添加量为5wt％)，得到纳米氧化锆有机MEK型分散液。
所述纳米氧化锆有机MEK型分散液中，纳米氧化锆的浓度为40wt％时，折射率为1.458，浓度为60％时，折射率为1.516，浓度为70wt％，折射率为1.554。
实施例5
制备纳米氧化锆有机溶剂型分散液的方法与实施例4相同，区别之处在于采用是实施例2中水热反应后的反应液，以及所加入的改性剂的量为锆含量的10％，得到纳米氧化锆有机MEK型分散液。
所述纳米氧化锆有机MEK型分散液中，纳米氧化锆的浓度为40wt％时，折射率1.455，浓度为60wt％时，折射率为1.511，浓度为70wt％，折射率为1.549。
实施例6
制备纳米氧化锆有机溶剂型分散液的方法与实施例4相同，区别之处在于采用是实施例3中水热反应后的反应液，以及所加入的改性剂的量为锆含量的15wt％，得到纳米氧化锆有机MEK型分散液。
所述纳米氧化锆有机MEK型分散液中，纳米氧化锆的浓度为40wt％时，折射率为1.439，浓度为60wt％时，折射率为1.492，浓度为70wt％，折射率为1.545。
实施例7
将丙烯酸苄酯(按得到单体分散液中氧化锆浓度为80wt％添加)加入到实施例4制备得到的纳米氧化锆有机MEK型分散液中，对该混合液进行减压蒸馏，除去有机溶剂，获得具有可光固化丙烯酸苄酯纳米氧化锆分散液；
所述分散液中纳米氧化锆的含量为80wt％，其折射率为1.649。
实施例8
将丙烯酸苄酯(按得到单体分散液中氧化锆浓度为60wt％添加)加入到实施例5制备得到的纳米氧化锆有机MEK型分散液中，对该混合液进行减压蒸馏，除去有机溶剂，获得具有可光固化丙烯酸苄酯纳米氧化锆分散液；
所述分散液中纳米氧化锆的含量为60wt％，其折射率为1.636。
实施例9
将丙烯酸苄酯(按得到单体分散液中氧化锆浓度为50wt％添加)加入到实施例6制备得到的纳米氧化锆有机MEK型分散液中，对该混合液进行减压蒸馏，除去有机溶剂，获得具有可光固化树脂的纳米氧化锆分散液；
所述分散液中纳米氧化锆的含量50wt％，其折射率为1.611。
对比例1
称取1.47kg氧氯化锆和138g氯化钇溶于8kg水中，得到其混合溶液A；
将421g氢氧化钠溶于6kg水得到氢氧化钠溶液B；
将溶液A和溶液B于搅拌下充分混合后生成沉淀，将沉淀物经多次洗涤抽滤后得到前驱体C；
向前躯体C中加入水搅拌制浆；
将上述所得浆料投入到10L反应釜中，加入乙酸270g，控制总体积在8L，于200℃下水热反应3h；
反应结束反应后将反应液直接干燥，得到纳米氧化锆粉体。
如图4所示，所得到的纳米氧化锆粉体的粒径约为30nm，比表面积为180m 2/g，所述纳米氧化锆粉体包括四方相晶型结构的氧化锆。
对比例2
称取1.47kg氧氯化锆和138g氯化钇溶于8kg水中，得到其混合溶液A；
将421g氢氧化钠溶于6kg水得到氢氧化钠溶液B；
将溶液A和溶液B于搅拌下充分混合后生成沉淀，将沉淀物经多次洗涤抽滤后得到前驱体C；
向前躯体C中加入水和270g乙酸，控制总体积在8L，搅拌制浆；
将上述所得浆料投入到10L反应釜中，于170℃下水热反应3h；
反应结束反应后将反应液直接干燥，得到纳米氧化锆粉体。
所得到的纳米氧化锆粉体的平均粒径为30nm，比表面积为177m 2/g，所述纳米氧化锆粉体为单斜相晶粒结构的氧化锆。
对比例3
制备纳米氧化锆的有机溶液型分散液的方法同实施例4，区别在于所采用的是对比例1中水热反应后的溶液。
所述纳米氧化锆有机MEK型分散液中，纳米氧化锆的浓度为40wt％时， 折射率为1.445，浓度为60wt％时，折射率为1.491，浓度为70wt％，折射率为1.530。
对比例4
制备纳米氧化锆的丁酮分散液的方法同实施例4，区别在于所采用的是对比例2中水热反应后的溶液。
所述纳米氧化锆有机MEK型分散液中，纳米氧化锆的浓度为40wt％时，折射率为1.439，浓度为60％时，折射率为1.480，浓度为70wt％，折射率为1.532。
对比例5
制备纳米氧化锆的有机溶液型分散液的方法同实施例4，区别在于未加入改性剂。
所述纳米氧化锆有机MEK型分散液中，纳米氧化锆的浓度为40wt％时，折射率为1.416，但无法获得浓度为70wt％的分散液。
对比例6
制备纳米氧化锆的有机溶液型分散液的方法同实施例4，区别在于未加入油性分散助剂。
所述纳米氧化锆有机MEK型分散液中，纳米氧化锆的浓度为40wt％时，折射率为1.411，但无法获得浓度为70wt％的分散液。
从以上可以看到纳米氧化锆的浓度为70wt％条件下，实施例4-6的折射率为1.545～1.554，对比例3-4的折射率为1.530～1.532，相差0.013～0.024；纳米氧化锆的浓度为60wt％条件下，实施例4-6的折射率为1.492～1.516，对比例3-4的折射率为1.480～1.491，最高相差0.036；纳米氧化锆的浓度为40wt％条件下，实施例4-6的折射率为1.439～1.458，对比例3-4的折射率为 1.439～1.445，最高相差0.013。这是因为对比例中分散液中的氧化锆粒径较大(对比例3、4)，晶型为单斜相(对比例4)，使得制备的分散液折射率相对较低。虽然从数值上看折射率相差不大，但是从分散液折射率的光学特性这个角度看其差别天壤之别，比如利用相差为0.01折射率的分散液分别制备增亮膜应用在显示屏上，其透光率为89％和93％，而这也正是A级屏与B级屏的区别。此外，在制备有机溶剂型分散液时，由对比例5和对比例6可知，不加油性分散助剂或改性剂时，分散液中的纳米氧化锆的含量最多只能到40wt％，并无法获得浓度为70wt％的分散液，更不必说获得70wt％下的高折射率。

Claims (18)

  1. 纳米氧化锆粉体，其特征在于，所述纳米氧化锆粉体的粒径为3-10nm，比表面积为200-240m 2/g，所述纳米氧化锆粉体包括四方相晶型结构的氧化锆，且四方相晶型结构的氧化锆比例占粉体的60-95％。
  2. 根据权利要求1所述的纳米氧化锆粉体的制备方法，其特征在于，包括以下步骤：
    将锆盐和稳定性元素盐共同溶解在水中，得到溶液A；
    将碱溶解在水中，得到溶液B；
    将溶液A和溶液B于搅拌下充分混合，生成有沉淀物，其中，沉淀物的质量占总混合液质量的1-40％；将沉淀物经过多次洗涤过滤后，得到前驱体C；
    向前躯体C中加入水和有机酸或其盐制浆，所得浆料中的总固含量为6-20wt％；
    将上述所得浆料投入到反应釜中，填充量为60-90％，于180℃-220℃下水热反应1-12h，反应后得到反应液；
    将反应液直接干燥或浓缩洗涤后干燥，得到纳米氧化锆粉体。
  3. 根据权利要求2所述的制备方法，其特征在于，所加入的锆盐为水溶性锆盐，选自碱式碳酸盐、碳酸盐、硝酸盐、乙酸盐、氯化物、氧氯化物中的至少一种；所加入的稳定性元素盐为稳定性元素的氯化物或硝酸盐，其中所述稳定性元素选自铝、镁、钛和稀土类元素中的至少一种；所述碱选自氨水、氢氧化钠、氢氧化钾和氢氧化锂中的至少一种。
  4. 根据权利要求3所述的制备方法，其特征在于，所加入的锆盐浓度≤2mol/L，所加入的稳定性元素与锆元素的摩尔浓度比为2/98～30/70，所加入 的碱的浓度为≤8mol/L。
  5. 根据权利要求2所述的制备方法，其特征在于，所述有机酸选自一元羧酸、多元羧酸和羟基羧酸中的至少一种，其中，所述一元羧酸选自甲酸、乙酸、丙酸、丁酸中的至少一种，多元羧酸选自草酸、丙二酸、琥珀酸、邻苯二甲酸中的至少一种，羟基羧酸选自乳酸、苹果酸、酒石酸、柠檬酸中的至少一种；所述有机酸的盐为其碱金属盐，选自钾盐、钠盐中的至少一种。
  6. 根据权利要求5所述的制备方法，其特征在于，所加入的有机酸或其盐的摩尔浓度为锆元素和稳定元素摩尔浓度总和的10-100％。
  7. 根据权利要求2所述的制备方法，其特征在于，当所加入的有机酸的沸点＜150℃时，将反应液直接进行干燥得到纳米氧化锆粉体；当所加入的有机酸沸点＞150℃时，将反应液多次浓缩洗涤后再干燥，得到纳米氧化锆粉体。
  8. 根据权利要求7所述的制备方法，其特征在于，所述干燥方式选自真空低温干燥、烘干和喷雾中的任意一种，所述浓缩洗涤方式选自超滤、旋蒸和陶瓷膜浓缩洗涤中的任意一种。
  9. 包含权利要求1所述的纳米氧化锆粉体的分散液，其特征在于，所述分散液为有机溶剂型分散液，所述分散液中纳米氧化锆的含量为40-70wt％，其折射率为1.400-1.554。
  10. 包含权利要求9所述的纳米氧化锆粉体的分散液，其特征在于，所述分散液在所含纳米氧化锆的含量为70wt％时，所述分散液的折射率不低于1.554。
  11. 根据权利要求9所述的分散液，其特征在于，所述分散液为通过将权利要求2所述的制备方法在制备过程中得到的反应液中的分散介质水置换成有机溶剂得到，其中所述有机溶剂选自醇类、酯类、芳香烃类、醚类以及 酰胺类有机溶剂中的至少一种。
  12. 根据权利要求9所述的分散液，其特征在于，所述分散液中添加有改性剂，所述改性剂的添加量为纳米氧化锆含量的1-20wt％。
  13. 根据权利要求12所述的分散液，其特征在于，所述改性剂选自硅烷偶联剂、钛酸酯偶联剂、金属络合物、芳香型或高度共轭的化学物质中的至少一种。
  14. 根据权利要求9所述的分散液，其特征在于，所述分散液中添加有油性分散助剂，所述油性分散助剂的添加量为纳米氧化锆含量的1-20wt％。
  15. 具有可光固化树脂的纳米氧化锆分散液，其特征在于，所述分散液是将可光固化树脂添加到权利要求9-14中任一项所述的纳米氧化锆粉体的分散液中后，通过减压蒸馏除去有机溶剂后得到；
    所述分散液中纳米氧化锆的含量为50-80wt％，其折射率为1.60-1.70。
  16. 根据权利要求15所述的具有可光固化树脂的纳米氧化锆分散液，其特征在于，所述可光固化树脂的添加量为氧化锆和可光固化树脂总质量的20-50％。
  17. 光学膜，其特征在于，采用权利要求9-14任一项所述的包含纳米氧化锆粉体的分散液或采用权利要求15或16所述的具有可光固化树脂的纳米氧化锆分散液制备得到。
  18. 根据权利要求1所述的纳米氧化锆粉体或者权利要求9-14任一项所述的包含纳米氧化锆粉体的分散液或者权利要求15或16所述的具有可光固化树脂的纳米氧化锆分散液在制备光学膜中的应用。
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