WO2023216487A1 - 可光固化的纳米氧化锆分散液及其制备方法、光学膜 - Google Patents

可光固化的纳米氧化锆分散液及其制备方法、光学膜 Download PDF

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WO2023216487A1
WO2023216487A1 PCT/CN2022/119285 CN2022119285W WO2023216487A1 WO 2023216487 A1 WO2023216487 A1 WO 2023216487A1 CN 2022119285 W CN2022119285 W CN 2022119285W WO 2023216487 A1 WO2023216487 A1 WO 2023216487A1
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Prior art keywords
dispersion
zirconium oxide
silicon oxide
zirconia
dispersion liquid
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PCT/CN2022/119285
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English (en)
French (fr)
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朱恒
张栋
艾辽东
奚洪亮
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山东国瓷功能材料股份有限公司
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Publication of WO2023216487A1 publication Critical patent/WO2023216487A1/zh

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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
    • 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
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm

Definitions

  • the present disclosure relates to the field of fine chemical technology, and in particular to a photocurable nano-zirconia dispersion, a preparation method thereof, and an optical film.
  • Nano-zirconia has a high refractive index, is translucent in the visible light region, and has strong corrosion resistance. In recent years, it has been widely used in the optical field as a material to adjust the refractive index, such as camera lenses, automobile windows, photovoltaic glass, various types of Displays, optical filters, LED packaging resin and other fields.
  • nano-zirconia When nano-zirconia is directly added without treatment, agglomeration will occur due to the large surface active energy of the nanoparticles. On the other hand, the nanoparticles are not sufficiently dispersed and combined in the organic medium, which will directly affect Later use effects. Therefore, people have proposed using various methods to composite nano-zirconia with resin to prepare a dispersion and then use it.
  • Patent CN 112499678B discloses a nanometer zirconia powder, its preparation method, the resulting dispersion, and an optical film.
  • the modified zirconia is not purified, and the dispersion components are not purified.
  • the resin part in the film has not been selected and optimized, resulting in a relatively low refractive index of the dispersion.
  • the entire dispersion preparation process ignores the hardness properties of the dispersion after it is coated with the optical film, resulting in a later coating layer of the dispersion. The hardness is relatively low.
  • the purpose of the present disclosure includes providing a photocurable nano-zirconia dispersion and a preparation method thereof to alleviate at least one technical problem existing in the prior art.
  • the present disclosure provides a photocurable nano-zirconia dispersion, where the dispersion is an organic solvent-based dispersion;
  • the dispersion includes surface-modified zirconia, silicon oxide and acrylic resin;
  • the mass concentration of zirconium oxide in the dispersion is above 50%;
  • the content of the silicon oxide is 0.1-5% of the mass of the zirconium oxide
  • the average particle size of the silicon oxide is 2-3 nm, and the maximum particle size is less than 5 nm.
  • the preparation method of surface-modified zirconia includes the following steps:
  • step (C) removing the solvent from the modified mixed solution obtained in step (B) to obtain surface-coated zirconia powder
  • step (D) The surface-coated zirconia powder obtained in step (C) is alternately washed with a first polar solvent and a second polar solvent, and then dried to obtain the surface-modified zirconia;
  • the polarity of the first polar solvent is higher than the polarity of the second polar solvent.
  • the mass concentration of zirconium oxide in the zirconium oxide solution of the organic solvent phase described in step (A) is below 50%;
  • the particle size of zirconia is 1-30nm, preferably 1-10nm;
  • the amount of surface modifier described in step (B) is 1-30% of the mass of zirconia.
  • the first polar solvent in step (D) includes at least one of water, alcoholic organic solvents, and ketone organic solvents;
  • the second polar solvent includes at least one of benzene organic solvents, ester organic solvents and ether organic solvents;
  • the number of alternating washings is more than 4 times.
  • the silicon oxide includes surface-treated silicon oxide
  • the silicon oxide includes solid amorphous silicon oxide
  • the refractive index of the acrylic resin is above 1.55.
  • the dispersion also includes a dispersant
  • the dispersant includes a polymeric dispersant
  • the added amount of the polymeric dispersant is 1-20% of the mass of zirconia.
  • the refractive index of the dispersion is 1.65-1.75.
  • the present disclosure provides a method for preparing a nanometer zirconia dispersion with a photocurable resin, including the following steps:
  • the present disclosure provides an optical film obtained by curing the dispersion liquid.
  • the hardness of the optical film is above HB.
  • the present disclosure has at least the following beneficial effects:
  • the photocurable nano-zirconia dispersion provided by the present disclosure introduces a specific amount and specific particle size of silicon oxide into the zirconium oxide dispersion, effectively improving the oxidation rate without affecting the refractive index of the entire system.
  • the effect of the density and hardness of the later coating layer of the zirconium dispersion; the surface-modified zirconium oxide of the present disclosure is not easy to agglomerate in the dispersion, and can be more fully dispersed and combined in the organic medium; at the same time, the present disclosure adds
  • the acrylic resin has a high refractive index, which can increase the refractive index of the dispersion system and improve the application effect of the dispersion.
  • the preparation method of the photocurable nano-zirconia dispersion provided by the present disclosure has a simple and efficient process.
  • the optical film provided by the present disclosure has relatively high hardness.
  • a photocurable nano-zirconia dispersion is provided.
  • the dispersion of the present disclosure is an organic solvent-based dispersion, including surface-modified zirconia, silicon oxide and acrylic resin; Wherein, the mass concentration of zirconium oxide in the dispersion is above 50%, the content of silicon oxide is 0.1-5% of the mass of zirconium oxide, the average particle size of silicon oxide is 2-3 nm, and the maximum particle size is less than 5 nm.
  • the typical but non-limiting mass concentration of zirconia in the dispersion is, for example, 50%, 55%, 60%, 65%; the content of silicon oxide in the dispersion is 0.1-5% of the mass of zirconia, Its typical but non-limiting content is, for example, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%; silicon oxide is typical but non-limiting
  • the average particle diameter is, for example, 2 nm, 2.5 nm, or 3 nm.
  • the present disclosure introduces a trace amount of silicon oxide with a smaller particle size without affecting the refractive index of the entire system to improve the coating hardness after the zirconium oxide dispersion is coated; specifically, the present disclosure adds a smaller particle size than the zirconium oxide dispersion.
  • Silicon oxide due to the high hardness of silicon oxide, it can increase the coating hardness of the zirconium oxide dispersion.
  • the particle size of the silicon oxide is smaller, it can make the coating of the zirconium oxide dispersion more dense and dense. Harder.
  • the photocurable nano-zirconia dispersion provided by the present disclosure introduces a specific amount and specific particle size of silicon oxide into the zirconium oxide dispersion, and achieves an effective effect without affecting the refractive index of the entire system.
  • the preparation method of surface-modified zirconia includes the following steps:
  • the zirconium oxide aqueous solution and the organic solvent can be concentrated and replaced to obtain a zirconium oxide solution in the organic solvent phase;
  • the zirconium oxide mass concentration of the zirconium oxide solution in the organic solvent phase is less than 50%;
  • step (C) removing the solvent from the modified mixed solution obtained in step (B) to obtain surface-coated zirconia powder
  • step (D) The surface-coated zirconia powder obtained in step (C) is alternately washed with a first polar solvent and a second polar solvent, and then dried to obtain surface-modified zirconia;
  • the polarity of the first polar solvent is higher than the polarity of the second polar solvent.
  • the zirconium oxide aqueous solution in step (A) can be replaced with an organic solvent through repeated dilution and concentration processes using a rotary evaporator to obtain a zirconium oxide solution in the organic solvent phase, and the mass concentration of zirconium oxide is controlled to be less than 50%.
  • the typical However, non-limiting mass concentrations are, for example, 10%, 20%, 30%, 40%, and 50%;
  • the raw material of zirconia is not particularly limited and can be a zirconia aqueous solution or zirconia powder. In the case of zirconia powder, it can be The aqueous solution is obtained through various methods and then used. The specific method is not particularly limited.
  • the zirconium oxide aqueous solution can be obtained by grinding, ultrasonic, etc.; the present disclosure does not specifically limit the specific concentration of the zirconium oxide aqueous solution.
  • the mass concentration of the zirconium oxide aqueous solution can be controlled within 10% or more, for example, 15%, 20%, 25%, 30%, 35%, or 40%.
  • the zirconium oxide particle size in the zirconium oxide solution in the organic solvent phase in step (A) is controlled to be 1-30 nm, and its typical but non-limiting particle sizes are, for example, 1 nm, 5 nm, 10 nm, 15 nm, and 20 nm. , 25nm, 30nm, preferably zirconium oxide with a particle size less than 10nm.
  • the crystal form of zirconia is not particularly limited and may be a monoclinic phase, a tetragonal phase, a cubic phase, or a mixed phase.
  • the organic solvent in step (A) is not particularly limited. It can be any organic solvent that is miscible with water.
  • it can be alcohols, including but not limited to at least one of methanol, ethanol, propanol and n-butanol. species; for example, it can be ketones, including but not limited to at least one of acetone, methyl ethyl ketone, and methyl isobutyl ketone; for example, it can be esters, including but not limited to at least one of ethyl acetate and butyl acetate.
  • it can be aromatic hydrocarbons, including but not limited to at least one of toluene, xylene and ethylbenzene; for example, it can be ethers, including but not limited to propylene glycol methyl ether, ethylene glycol monomethyl ether and diethylene glycol. At least one of monobutyl ethers; for example, it can be amides, including but not limited to at least one of dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.
  • the surface modifier in step (B) is not particularly limited, including but not limited to carboxylic acid compounds with various types of organic groups, phosphonic acid compounds, various coupling agents, and various types of coupling agents. At least one of the chelating agents; the modification conditions of the present disclosure are not particularly limited and can be modified at a certain temperature, pressure, time or in the presence of a catalyst; the dosage of the surface modifier of the present disclosure is zirconia mass 1-30%, typical but non-limiting dosages are, for example, 1%, 5%, 10%, 15%, 20%, 25%, 30%.
  • the present disclosure uses specific types and amounts of surface modifiers to surface modify zirconium oxide in the organic solvent phase, which can make the surface modification effect of zirconium oxide more prominent, making it less likely to agglomerate in the dispersion, and can It is more fully dispersed and combined in organic media to improve the later use effect of the dispersion.
  • the method for removing the solvent from the modified mixed liquid is not particularly limited.
  • a rotary evaporator can be used to remove the solvent under negative pressure, or other vacuum distillation devices can be used.
  • the solvent is removed by evaporation under negative pressure.
  • the surface-coated zirconia powder is washed alternately with a high polarity solvent (first polar solvent) and a low polarity solvent (second polar solvent) at least 4 times, and then Dry to obtain pure surface-coated zirconia powder.
  • the drying method is not particularly limited. For example, it can be drying with natural volatile solvents and/or drying using drying equipment.
  • the drying device is not particularly limited. For example, it can be a vacuum oven.
  • the temperature conditions for drying are not particularly limited, and may be, for example, below 100°C; where the highly polar solvent (first polar solvent) includes but is not limited to at least one of water, alcoholic organic solvents, and ketone organic solvents.
  • Polar solvents (second polar solvents) include, but are not limited to, at least one of benzene organic solvents, ester organic solvents, and ether organic solvents.
  • This disclosure uses high polarity solvents and low polarity solvents to alternately wash the surface-modified zirconia powder.
  • the combination of specific high polarity solvents and low polarity solvents can effectively remove free particles on the zirconia surface.
  • the modifier makes the surface-modified zirconia powder more pure and achieves effective purification effect. Therefore, the dispersion prepared from the purified surface-modified zirconia powder has the characteristics of less free impurities. The refractive index of the zirconia dispersion is increased.
  • the silicon oxide of the present disclosure includes, but is not limited to, surface-treated silicon oxide; the silicon oxide includes, but is not limited to, solid amorphous silicon oxide.
  • Solid amorphous silicon oxide has high hardness and strong wear and corrosion resistance. After surface treatment, it is not easy to agglomerate in the dispersion, which is more conducive to mutual dispersion with zirconium oxide in the dispersion.
  • silicon oxide Surface modification preferentially uses groups containing active double bonds for modification, so that they can participate in the later curing of the entire coating, further increasing the cross-linking density of the later coating, and therefore improving the later coating properties of the zirconia dispersion. Density and hardness improve the application effect of dispersion.
  • the refractive index of the acrylic resin of the present disclosure is above 1.55, including but not limited to o-phenylphenoxyethyl acrylate, 2-(ethoxy) o-phenylphenoxyethyl acrylate Acrylate, 3-(ethoxy) o-phenylphenoxyethyl acrylate, biphenyl carbinol acrylate, (ethoxy) bisphenol fluorene diacrylate, (ethoxy) bisphenol fluorene diacrylate, At least one of 6-(ethoxy)bisphenolfluorene diacrylate, 10-(ethoxy)bisphenolfluorene diacrylate, and 3-phenylbenzyl acrylate.
  • the acrylic resin selected in this disclosure not only has a higher refractive index to improve the refractive index of the zirconium oxide dispersion, but also can better combine with the zirconium oxide, alleviate the agglomeration phenomenon in the zirconium oxide dispersion, and improve the refractive index of the zirconium oxide dispersion. Dispersion effect.
  • the refractive index of the nano-zirconia dispersion of the present disclosure is 1.65-1.75, and its typical but non-limiting refractive index is, for example, 1.65, 1.7, and 1.75.
  • the dispersion of the present disclosure also includes a dispersant;
  • the dispersant of the present disclosure includes but is not limited to polymeric dispersants, which are not particularly limited, and commercially available conventional models are sufficient; the dispersant of the present disclosure
  • the addition amount is 0-20% of the mass of zirconium oxide, preferably 1-20%, and typical but non-limiting addition amounts are, for example, 1%, 5%, 10%, 15%, and 20%.
  • the polymer dispersant has a high dispersion function and can effectively combine with the material particles in the dispersion system to improve the dispersion of the system. Therefore, it can effectively reduce the aggregation of zirconium oxide, silicon oxide and acrylic resin in the zirconium oxide dispersion. , and maintain the relative stability of the dispersed system.
  • a method for preparing a photocurable nano-zirconia dispersion including the following steps:
  • the dried surface-modified zirconia powder and silicon oxide powder are dissolved in an organic solvent in proportion, and a dispersant can be added to further disperse it, or auxiliary ultrasound and temperature rise (not higher than 80°C) can be used. Or grinding and other methods to accelerate dissolution and obtain better dispersion effect.
  • the preparation method of the photocurable nano-zirconia dispersion provided by the present disclosure has a simple and efficient process.
  • an optical film is provided, which is obtained by solidifying the above-mentioned dispersion liquid.
  • a preparation method for photocurable nano-zirconia dispersion including the following steps:
  • step S2 Add 6g isooctanoic acid and 6g silane KBM-503 to the propylene glycol methyl ether phase zirconium oxide solution obtained in step S1, and then reflux and stir for 4 hours at 120°C for surface modification to obtain a modified mixed solution;
  • step S3 The modified mixed liquid obtained in step S2 is used to remove propylene glycol methyl ether through a rotary evaporator to obtain modified zirconia powder;
  • step S4 The modified zirconia powder obtained in step S3 is washed alternately with ethanol and petroleum ether at least 4 times, and then dried in an oven at 60°C to obtain purified surface-modified zirconia powder;
  • step S5 Weigh 30g of the purified surface-modified zirconia powder obtained in step S4 and the surface-treated silicon oxide powder (wherein, the average particle size of silicon oxide is 3 nm, and the maximum particle size is less than 5 nm;
  • the surface treatment method uses an organic acid or silane coupling agent containing active double bonds for modification. Specifically, it can be KBM-503.
  • the modifier dose is 10% of the mass of silicon oxide.
  • Example 1 The difference between this embodiment and Example 1 is that the particle size of zirconium oxide in this embodiment is 8 nm, and step S5 of this embodiment:
  • Example 1 The difference between this embodiment and Example 1 is that the particle size of zirconium oxide in this embodiment is 5 nm, and step S5 of this embodiment:
  • Example 1 The difference between this embodiment and Example 1 is that the particle size of zirconium oxide in this embodiment is 8 nm, and step S5 of this embodiment:
  • Example 1 The difference between this embodiment and Example 1 is that the particle size of zirconium oxide in this embodiment is 8 nm, and step S2 of this embodiment:
  • step S5 of this embodiment is that step S5 of this embodiment:
  • Example 5 The difference between this embodiment and Example 5 is that the particle size of zirconium oxide in this embodiment is 5 nm, and step S5 of this embodiment:
  • the surface treatment method of silicon oxide is the same as in Example 1) Dissolve 1.5g in 150g butanone, then add 1.5g of BYK-111 dispersant, assist with ultrasonic or grinding, so that the powder is fully dissolved and dispersed, then add 17g of biphenyl methyl alcohol acrylate, and evaporate under reduced pressure to remove the butanone to obtain A zirconia dispersion with a mass concentration of 60% is a photocurable nano-zirconia dispersion;
  • Example 5 The difference between this embodiment and Example 5 is that the particle size of zirconium oxide in this embodiment is 5 nm, and step S5 of this embodiment:
  • Example 5 The difference between this embodiment and Example 5 is that the particle size of zirconium oxide in this embodiment is 5 nm, and step S5 of this embodiment:
  • Example 1 The difference between this example and Example 1 is that this example does not perform the purification process of step S4;
  • Example 2 Other steps are the same as in Example 1 to obtain a photocurable nano-zirconia dispersion.
  • Example 1 The difference between this embodiment and Example 1 is that no dispersant is added in this embodiment, and the rest are the same as in Example 1 to obtain a photocurable nano-zirconia dispersion.
  • step S5 of this comparative example is that step S5 of this comparative example:
  • step S5 of this comparative example is that step S5 of this comparative example:
  • step S5 of this embodiment is that step S5 of this embodiment:
  • step S5 of this embodiment is that step S5 of this embodiment:
  • Example 1 The difference between this comparative example and Example 1 is that the amount of silicon oxide added in step S5 of this comparative example is 1.8g, that is, the content of silicon oxide is 6% of the mass of zirconia.
  • the other steps are the same as in Example 1 to obtain dispersion. liquid.
  • Example 1 The difference between this comparative example and Example 1 is that the particle size of zirconium oxide in this comparative example is 5 nm, and the average particle size of silicon oxide is 10 nm. Other steps are the same as in Example 1 to obtain a dispersion.
  • Example 1 The difference between this comparative example and Example 1 is that the zirconium oxide was not modified in this comparative example. The other steps were the same as in Example 1, and the preparation of the dispersion failed.
  • the test method for refractive index is: use Abbe refractometer and test at room temperature.
  • the hardness test method is: test according to ASTM D3363-00 standard test method for coated pencil hardness.
  • Example 1 The refractive index of the dispersion Cured coating hardness
  • Example 2 1.6521 F
  • Example 3 1.7022 F
  • Example 4 1.7013 F
  • Example 5 1.6748 F
  • Example 6 1.6721 F
  • Example 7 1.7533 F
  • Example 8 1.7502 F
  • Example 9 1.6475 F
  • Example 10 1.6502 F Comparative example 1 1.6540 B Comparative example 2 1.7044 HB Comparative example 3 1.6756 B Comparative example 4 1.7541 HB Comparative example 5 1.6488 B Comparative example 6 1.6522 B Comparative example 7 / /
  • Example 1 and Comparative Example 5 it can be seen that when the added amount of silicon oxide of the present disclosure is too high, the refractive index of the system will decrease to a certain extent; according to the comparison between Example 1 and Comparative Example 6, it can be seen that the added oxide When the average particle size of silicon is too large, the filling effect will not be good and the hardness will not increase; according to the comparison between Example 1 and Comparative Example 7, it can be seen that the use of unmodified zirconia will reduce the refractive index of the dispersion and the coating.
  • the hardness of the coating in addition, from the comparison between Example 1 and Example 9, it can be seen that the specific purification treatment of the modified nano-zirconia powder in the present disclosure can further increase the refractive index of the dispersion system, thereby obtaining better results. Good application effect.
  • the photocurable nano-zirconia dispersion provided by the present disclosure introduces a specific amount and specific particle size of silicon oxide into the zirconium oxide dispersion, effectively improving the oxidation rate without affecting the refractive index of the entire system.
  • the effect of the density and hardness of the later coating layer of the zirconium dispersion; the surface-modified zirconium oxide of the present disclosure is not easy to agglomerate in the dispersion, and can be more fully dispersed and combined in the organic medium; at the same time, the present disclosure adds
  • the acrylic resin has a high refractive index, which can increase the refractive index of the dispersion system and improve the application effect of the dispersion.

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Abstract

本公开提供了一种可光固化的纳米氧化锆分散液及其制备方法、光学膜，涉及精细化工的技术领域，本公开的有机溶剂型分散液包括氧化锆、氧化硅以及光学丙烯酸类树脂单体；其中，氧化锆为表面改性的氧化锆，分散液中的氧化锆的质量浓度在50％以上，氧化硅的含量为氧化锆质量的0.1-5％，氧化硅的平均粒径为2-3nm，最大粒径小于5nm；其中，所述氧化硅的粒径小于氧化锆的粒径。本公开解决了分散液的折射率较低和后期涂覆层硬度低的技术问题，达到了提高分散液的折射率和后期涂覆层硬度的技术效果。

Description

可光固化的纳米氧化锆分散液及其制备方法、光学膜
相关申请的交叉引用
本申请要求于2022年05月13日提交中国专利局的申请号为202210521998.4、名称为“可光固化的纳米氧化锆分散液及其制备方法、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
本公开涉及精细化工技术领域，尤其是涉及一种可光固化的纳米氧化锆分散液及其制备方法、光学膜。
背景技术
纳米氧化锆的折射率高、可见光区域具有透光性，而且抗腐蚀性能较强，近年来被广泛应用于光学领域作为调节折射率的材料，例如照相机镜头、汽车车窗、光伏玻璃、各类型显示器、光学滤光片及LED封装树脂等领域。
纳米氧化锆在未经处理而直接添加应用时，一方面由于纳米颗粒表面活性能较大而会导致发生团聚现象，另一方面纳米粒子在有机介质中分散与结合的也不充分，会直接影响后期使用效果。因此，人们提出了利用各种方法将纳米氧化锆与树脂复合以制备分散液，之后再使用。
随着终端应用的发展，各类光学材料对分散液的折射率性能和分散液涂覆固化后的硬度性能提出了更高要求。氧化锆与树脂复合后制备的分散液折射率越高，其光学性能也就越优异，例如LED封装树脂折射率越高，其光提取率也就越高；分散液涂覆固化后的涂层硬度相对较高，高折射率涂层或薄膜越相对不容易变形，使应用的可靠性较高。
专利CN 112499678B公开了一种纳米氧化锆粉体、其制备方法及所得分散液、光学膜，其树脂分散液制备的过程中并没有对改性后的氧化锆进行纯化，同时对分散液组分中的树脂部分也没有进行选择及优化，导致分散液的折射率相对较低，而且整个分散液制备的过程忽略了分散液涂覆光膜后的硬度性能，导致制备的分散液后期涂覆层的硬度相对较低。
有鉴于此，特提出本公开。
公开内容
本公开的目的包括提供一种可光固化的纳米氧化锆分散液及其制备方法，以缓解现有技术中存在的至少一个技术问题。
为了实现本公开的上述目的，特采用以下技术方案：
第一方面，本公开提供了一种可光固化的纳米氧化锆分散液，所述分散液为有机溶剂型分散液；
所述分散液包括表面改性的氧化锆、氧化硅以及丙烯酸类树脂；
所述分散液中的氧化锆的质量浓度在50％以上；
所述氧化硅的含量为氧化锆质量的0.1-5％；
所述氧化硅的平均粒径为2-3nm，最大粒径小于5nm。
可选的，所述表面改性的氧化锆的制备方法包括以下步骤：
(A)提供有机溶剂相的氧化锆溶液；
(B)将表面改性剂加入到所述有机溶剂相的氧化锆溶液中改性氧化锆，得到改性后的混合液；
(C)步骤(B)得到的改性后的混合液除去溶剂，得到表面包覆的氧化锆粉体；
(D)步骤(C)得到的表面包覆的氧化锆粉体经第一极性溶剂和第二极性溶剂交替洗涤，再干燥，得到所述表面改性的氧化锆；
其中，所述第一极性溶剂的极性高于所述第二极性溶剂的极性。
可选的，步骤(A)中所述有机溶剂相的氧化锆溶液中氧化锆的质量浓度在50％以下；
优选的，氧化锆粒径为1-30nm，优选为1-10nm；
优选的，步骤(B)中所述表面改性剂的用量为氧化锆质量的1-30％。
可选的，步骤(D)中所述第一极性溶剂包括水、醇类有机溶剂以及酮类有机溶剂中的至少一种；
优选的，所述第二极性溶剂包括苯类有机溶剂、酯类有机溶剂以及醚类有机溶剂中的至少一种；
优选的，所述交替洗涤的次数在4次以上。
可选的，所述氧化硅包括表面处理后的氧化硅；
优选的，所述氧化硅包括实心无定型的氧化硅；
优选的，所述丙烯酸类树脂的折射率在1.55以上。
可选的，所述分散液还包括分散剂；
优选的，所述分散剂包括高分子型分散剂；
优选的，所述高分子型分散剂的添加量为氧化锆质量的1-20％。
可选的，所述分散液的折射率为1.65-1.75。
第二方面，本公开提供了一种具有可光固化树脂的纳米氧化锆分散液的制备方法，包括以下步骤：
将表面改性的氧化锆、氧化硅、丙烯酸类树脂以及任选的分散剂溶解在有机溶剂中，得到所述分散液。
第三方面，本公开提供了一种光学膜，由所述的分散液经固化得到的。
可选的，所述光学膜的硬度在HB以上。
与现有技术相比，本公开至少具有如下有益效果：
本公开提供的可光固化的纳米氧化锆分散液，在氧化锆的分散液中引入了特定用量和特定粒径的氧化硅，在不影响整个体系折射率的基础上，达到了有效地提高氧化锆分散液的后期涂覆层的致密度和硬度的效果；本公开表面改性的氧化锆在分散液中不易发生团聚，而且能够在有机介质中分散与结合地更加充分；同时，本公开添加的丙烯酸类树脂具有较高的折射率，能够增加分散液体系的折射率，提高分散液的应用效果。
本公开提供的可光固化的纳米氧化锆分散液的制备方法，工艺简单且高效。
本公开提供的光学膜，具有较高的硬度。
具体实施方式
下面将结合实施例对本公开的技术方案进行清楚、完整地描述，显然，所描述的实施例是本公开一部分实施例，而不是全部的实施例。基于本公开中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本公开保护的范围。
根据本公开的第一个方面，提供了一种可光固化的纳米氧化锆分散液，本公开的分散液为有机溶剂型分散液，包括表面改性的氧化锆、氧化硅以及丙烯酸类树脂；其中，分散液中的氧化锆的质量浓度在50％以上，氧化硅的含量为氧化锆质量的0.1-5％，氧化硅的平均粒径为2-3nm，最大粒径小于5nm。
在本公开中，分散液中的氧化锆典型但非限制性的质量浓度例如为50％、55％、60％、65％；分散液中氧化硅的含量为氧化锆质量的0.1-5％，其典型但非限制性的含量例如为 0.1％、0.5％、1％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％、5％；氧化硅典型但非限制性的平均粒径例如为2nm、2.5nm、3nm。
本公开在不影响整个体系折射率的基础上引入微量的粒径更小的氧化硅以提高氧化锆分散液涂覆后的涂层硬度；具体的，本公开添加相比氧化锆粒径更小的氧化硅，一方面由于氧化硅的硬度高，因此能够增加氧化锆分散液的涂层硬度，另一方面由于氧化硅的粒径更小，因此能够使氧化锆分散液的涂层更加致密和硬度更高。因此，本公开提供的可光固化的纳米氧化锆分散液，在氧化锆的分散液中引入了特定用量和特定粒径的氧化硅，在不影响整个体系折射率的基础上，达到了有效地提高氧化锆分散液的后期涂覆层的致密度和硬度的效果；同时，本公开表面改性的氧化锆在分散液中不易发生团聚，而且能够在有机介质中分散与结合地更加充分；此外，本公开添加的丙烯酸类树脂具有较高的折射率，能够增加分散液体系的折射率，提高分散液的应用效果。
在本公开中，表面改性的氧化锆的制备方法包括以下步骤：
(A)提供有机溶剂相的氧化锆溶液；
或者，还可以将氧化锆水溶液与有机溶剂通过浓缩置换，得到有机溶剂相的氧化锆溶液；
其中，有机溶剂相的氧化锆溶液的氧化锆质量浓度在50％以下；
(B)将表面改性剂加入到上述有机溶剂相的氧化锆溶液中改性氧化锆，得到改性后的混合液；
(C)步骤(B)得到的改性后的混合液除去溶剂，得到表面包覆的氧化锆粉体；
(D)步骤(C)得到的表面包覆的氧化锆粉体经第一极性溶剂和第二极性溶剂交替洗涤，再干燥，得到表面改性的氧化锆；
其中，第一极性溶剂的极性高于所述第二极性溶剂的极性。
在本公开中，步骤(A)中的氧化锆水溶液可以利用旋转蒸发器通过反复稀释浓缩工序置换成有机溶剂，得到有机溶剂相的氧化锆溶液，控制氧化锆的质量浓度小于50％，其典型但非限制性的质量浓度例如为10％、20％、30％、40％、50％；氧化锆原材料不作特别限定，可以为氧化锆水溶液或氧化锆粉体，如是氧化锆粉体，其可通过各种方式得到水溶液后使用，具体方式不作特别限定，可通过研磨、超声等方式得到氧化锆水溶液；本公开对氧化锆水溶液的具体浓度不作特别限定，可以将氧化锆水溶液的质量浓度控制在10％以上，例如可以为15％、20％、25％、30％、35％、40％。
在本公开中，步骤(A)中的有机溶剂相的氧化锆溶液中的氧化锆粒径控制在1-30nm，其典型但非限制性的粒径例如为1nm、5nm、10nm、15nm、20nm、25nm、30nm，优先选用小于10nm粒径的氧化锆。
在本公开中，氧化锆晶型不作特别限定，可以为单斜相或四方相或立方相或混合相。
在本公开中，步骤(A)中的有机溶剂不作特别限定，与水互溶的有机溶剂均可，例如可以为醇类，包括但不限于甲醇、乙醇、丙醇以及正丁醇中的至少一种；例如可以为酮类，包括但不限于丙酮、丁酮以及甲基异丁基甲酮中的至少一种；例如可以为酯类，包括但不限于乙酸乙酯和乙酸丁酯中的至少一种；例如可以为芳香烃类，包括但不限于甲苯、二甲苯以及乙苯中的至少一种；例如可以为醚类，包括但不限于丙二醇甲醚，乙二醇单甲醚以及二乙二醇单丁醚中的至少一种；例如可以为酰胺类，包括但不限于二甲基甲酰胺，N,N-二甲基乙酰胺以及N-甲基吡咯烷酮中的至少一种。
在本公开中，步骤(B)中的表面改性剂不作特别限定，包括但不限于带有各种类型有机基团的羧酸类化合物、膦酸类化合物、各类偶联剂以及各类螯合剂中的至少一种；本公开的改性条件不作特别限定，可以在一定温度、压力、时间下或者催化剂存在的条件下进行改性；本公开表面改性剂的用量为氧化锆质量的1-30％，其典型但非限制性的用量例如为1％、5％、10％、15％、20％、25％、30％。
本公开利用特定种类及其用量的表面改性剂对有机溶剂相中的氧化锆进行表面改性，能够使氧化锆的表面改性效果更加突出，使其在分散液中不易发生团聚，能够在有机介质中更加充分地分散与结合，提高分散液的后期使用效果。
在本公开的步骤(C)中，改性后的混合液除去溶剂的方法不做特别限定，例如可以利用旋转蒸发器在负压的条件下旋除溶剂，也可以利用其他减压蒸馏装置在负压的条件下蒸发去除溶剂。
在本公开的步骤(D)中，将表面包覆的氧化锆粉体用高极性溶剂(第一极性溶剂)和低极性溶剂(第二极性溶剂)交替洗涤至少4遍，之后干燥，得到纯净的表面包覆的氧化锆粉体，干燥的方法不作特别限定，例如可以是自然挥发溶剂干燥和/或利用干燥设备进行干燥，干燥的装置不作特别限定，例如可以为真空烘箱，干燥的温度条件不作特别限制，例如可以在100℃以下；其中，高极性溶剂(第一极性溶剂)包括但不限于水、醇类有机溶剂以及酮类有机溶剂中的至少一种，低极性溶剂(第二极性溶剂)包括但不限于苯类有机溶剂、酯类有机溶剂以及醚类有机溶剂中的至少一种。
本公开利用高极性溶剂和低极性溶剂对表面改性后的氧化锆粉体进行了交替洗涤，特定的高极性溶剂和低极性溶剂的配合洗涤能够有效去除在氧化锆表面游离的改性剂，使表 面改性的氧化锆粉体的纯度更高，达到了有效纯化的效果，故由纯化后的表面改性的氧化锆粉体制备出的分散液具有游离杂质少的特点，提高了氧化锆分散液的折射率。
在一种优选的实施方式中，本公开的氧化硅包括但不限于表面处理后的氧化硅；氧化硅包括但不限于实心无定型的氧化硅。
实心无定型的氧化硅的硬度高，而且耐磨损和抗腐蚀性能强，其经表面处理后，在分散液中不易团聚，更有利于与氧化锆在分散液中的互相分散，同时氧化硅表面改性优先选用含有活性双键的基团进行改性，使其能够参与后期整个涂层固化，进一步增加后期涂层的交联密度，因此更能提高氧化锆分散液的后期涂覆层的致密度和硬度，提高分散液的应用效果。
在一种优选的实施方式中，本公开的丙烯酸类树脂的折射率在1.55以上，包括但不限于邻苯基苯氧乙基丙烯酸酯、2-(乙氧基)邻苯基苯氧乙基丙烯酸酯、3-(乙氧基)邻苯基苯氧乙基丙烯酸酯、联苯甲醇丙烯酸酯、(乙氧基)双酚芴二丙烯酸酯、(乙氧基)双酚芴二丙烯酸酯、6-(乙氧基)双酚芴二丙烯酸酯、10-(乙氧基)双酚芴二丙烯酸酯以及3-苯基苄基丙烯酸酯中的至少一种。
本公开所选用的丙烯酸类树脂不仅具有更高折射率以提高氧化锆分散液的折射率，而且能够与氧化锆更好地复合，缓解氧化锆分散液出现的团聚现象，提高氧化锆分散液的分散效果。
本公开的纳米氧化锆分散液的折射率为1.65-1.75，其典型但非限制性的折射率例如为1.65、1.7、1.75。
在一种优选的实施方式中，本公开的分散液还包括分散剂；本公开中的分散剂包括但不限于高分子型分散剂，不作特别限定，市售常规型号即可；本公开分散剂的添加量为氧化锆质量的0-20％，优选为1-20％，其典型但非限制性的添加量例如为1％、5％、10％、15％、20％。
高分子型分散剂具有高的分散功能，能够与分散体系中的物质粒子有效结合以提高体系的分散性，因此能够有效降低氧化锆分散液中的氧化锆、氧化硅以及丙烯酸类树脂的聚集情况，并且保持分散体系的相对稳定。
根据本公开的第二个方面，提供了一种可光固化的纳米氧化锆分散液的制备方法，包括以下步骤：
将表面改性的氧化锆、氧化硅、丙烯酸类树脂以及任选的分散剂溶解在有机溶剂中，得到分散液。
本公开将干燥后的表面改性的氧化锆粉体和氧化硅粉体按比例溶解在有机溶剂中，可以加入分散剂使其进一步分散，也可以利用辅助超声、升温(不高于80℃)或研磨等方式加速溶解，获得更好的分散效果。
本公开提供的可光固化的纳米氧化锆分散液的制备方法，工艺简单且高效。根据本公开的第三个方面，提供了一种光学膜，是由上述分散液经固化得到的。
在本公开的氧化锆分散液中加入光引发剂，再在PET或TAC薄膜上涂覆固化，得到涂层，其硬度在HB以上。
下面通过实施例对本公开作进一步说明。如无特别说明，实施例中的材料为根据现有方法制备而得，或直接从市场上购得。
实施例1
一种可光固化的纳米氧化锆分散液的制备方法，包括以下步骤：
S1：取质量浓度为20％的氧化锆水溶液400g(氧化锆的粒径为5nm)，利用旋转蒸发器浓缩除水至氧化锆的质量浓度在30％以上，然后加入丙二醇甲醚240g，再浓缩至氧化锆的质量浓度在30％以上，重复工序，将水与丙二醇甲醚置换，得到质量浓度为30％的丙二醇甲醚相的氧化锆溶液；
S2：将6g异辛酸和6g硅烷KBM-503加入到步骤S1得到的丙二醇甲醚相的氧化锆溶液中，再在120℃下回流搅拌4h进行表面改性，得到改性后的混合液；
S3：步骤S2得到的改性后的混合液经旋转蒸发器去除掉丙二醇甲醚后得到改性后的氧化锆粉体；
S4：步骤S3得到的改性后的氧化锆粉体用乙醇和石油醚交替洗涤至少4遍，再在60℃下的烘箱中干燥，得到纯化后的表面改性的氧化锆粉体；
S5：称取步骤S4得到的纯化后的表面改性的氧化锆粉体30g和表面处理后的氧化硅粉体(其中，氧化硅的平均粒径为3nm，最大粒径小于5nm；氧化硅的表面处理的方法采用含有活性双键的有机酸或硅烷偶联剂进行改性，具体可为KBM-503，改性剂量为氧化硅质量的10％)0.3g溶解在150g丁酮中，再加入型号为BYK-111分散剂1.5g，辅助超声或研磨，使粉体充分溶解分散，再加入18.2g邻苯基苯氧乙基丙烯酸酯，减压蒸发去除丁酮后得到质量浓度为60％的氧化锆分散液，即为可光固化的纳米氧化锆分散液。
实施例2
本实施例与实施例1的区别在于，本实施例氧化锆的粒径为8nm，而且本实施例的步骤S5：
称取纯化后的表面改性的氧化锆粉体30g和表面处理后的氧化硅粉体(氧化硅的平均粒径为3nm，最大粒径小于5nm；氧化硅的表面处理方法同实施例1)1.5g溶解在150g丁酮中，再加入型号为BYK-111分散剂1.5g，辅助超声或研磨，使粉体充分溶解分散，再加入17g邻苯基苯氧乙基丙烯酸酯，减压蒸发去除丁酮后得到质量浓度为60％的氧化锆分散液，即为可光固化的纳米氧化锆分散液；
其他步骤均与实施例1相同。
实施例3
本实施例与实施例1的区别在于，本实施例氧化锆的粒径为5nm，而且本实施例的步骤S5：
称取纯化后的表面改性的氧化锆粉体30g和表面处理后的氧化硅粉体(氧化硅的平均粒径为3nm，最大粒径小于5nm；氧化硅的表面处理方法同实施例1)1g溶解在150g丁酮中，加入型号为BYK-111分散剂1.5g，辅助超声或研磨，使粉体充分溶解分散，再加入10.1g邻苯基苯氧乙基丙烯酸酯，减压蒸发去除丁酮后得到质量浓度为70％的氧化锆分散液，即为可光固化的纳米氧化锆分散液；
其他步骤均与实施例1相同。
实施例4
本实施例与实施例1的区别在于，本实施例氧化锆的粒径为8nm，而且本实施例的步骤S5：
称取纯化后的表面改性的氧化锆粉体30g和表面处理后的氧化硅粉体(氧化硅的平均粒径为2nm，最大粒径小于5nm；氧化硅的表面处理方法同实施例1)1.5g溶解在150g丁酮中，加入型号为BYK-111分散剂1.5g，辅助超声或研磨，使粉体充分溶解分散，再加入9.5g邻苯基苯氧乙基丙烯酸酯，减压蒸发去除丁酮后得到质量浓度为70％的氧化锆分散液，即为可光固化的纳米氧化锆分散液；
其他步骤均与实施例1相同。
实施例5
本实施例与实施例1的区别在于，本实施例氧化锆的粒径为8nm，而且本实施例的步骤S2：
将12g硅烷KBM-503加入到质量浓度为30％的丙二醇甲醚相的氧化锆溶液中，再在80℃下回流搅拌6h进行表面改性，得到改性后的混合液；
本实施例与实施例1的区别在于，本实施例的步骤S5：
称取纯化后的表面改性的氧化锆粉体30g和表面处理后的氧化硅粉体(氧化硅的平均粒径为2nm，最大粒径小于5nm；氧化硅的表面处理方法同实施例1)0.5g溶解在150g丁酮中，再加入型号为BYK-111分散剂1.5g，辅助超声或研磨，使粉体充分溶解分散，再加入18g联苯甲醇丙烯酸酯，减压蒸发去除丁酮后得到质量浓度为60％的氧化锆分散液，即为可光固化的纳米氧化锆分散液；
其他步骤均与实施例1相同。
实施例6
本实施例与实施例5的区别在于，本实施例氧化锆的粒径为5nm，而且本实施例的步骤S5：
称取纯化后的表面改性的氧化锆粉体30g和表面处理后的氧化硅粉体(氧化硅的平均粒径为2nm，最大粒径小于5nm；氧化硅的表面处理方法同实施例1)1.5g溶解在150g丁酮中，再加入型号为BYK-111分散剂1.5g，辅助超声或研磨，使粉体充分溶解分散，再加入17g联苯甲醇丙烯酸酯，减压蒸发去除丁酮后得到质量浓度为60％的氧化锆分散液，即为可光固化的纳米氧化锆分散液；
其他步骤均与实施例5相同。
实施例7
本实施例与实施例5的区别在于，本实施例氧化锆的粒径为5nm，而且本实施例的步骤S5：
称取纯化后的表面改性的氧化锆粉体30g和表面处理后的氧化硅粉体(氧化硅的平均粒径为3nm，最大粒径小于5nm；氧化硅的表面处理方法同实施例1)0.5g溶解在150g丁酮中，加入型号为BYK-111分散剂1.5g，辅助超声或研磨，使粉体充分溶解分散，再加入9.7g联苯甲醇丙烯酸酯，减压蒸发去除丁酮后得到质量浓度为72％的氧化锆分散液，即为可光固化的纳米氧化锆分散液；
其他步骤均与实施例5相同。
实施例8
本实施例与实施例5的区别在于，本实施例氧化锆的粒径为5nm，而且本实施例的步骤S5：
称取纯化后的表面改性的氧化锆粉体30g和表面处理后的氧化硅粉体(氧化硅的平均粒径为3nm，最大粒径小于5nm；氧化硅的表面处理方法同实施例1)1.5g溶解在150g丁酮中，加入型号为BYK-111分散剂1.5g，辅助超声或研磨，使粉体充分溶解分散，再加入 8.7g联苯甲醇丙烯酸酯，减压蒸发去除丁酮后得到质量浓度为72％的氧化锆分散液，即为可光固化的纳米氧化锆分散液；
其他步骤均与实施例5相同。
实施例9
本实施例与实施例1的区别在于，本实施例未进行步骤S4的纯化处理；
其他步骤均与实施例1相同，得到可光固化的纳米氧化锆分散液。
实施例10
本实施例与实施例1的区别在于，本实施例未加入分散剂，其余均与实施例1相同，得到可光固化的纳米氧化锆分散液。
对比例1
本对比例与实施例1的区别在于，本对比例的步骤S5：
称取纯化后的表面改性的氧化锆粉体30g溶解在150g丁酮中，加入型号为BYK-111分散剂1.5g，辅助超声或研磨，使粉体充分溶解分散，再加入18.5g邻苯基苯氧乙基丙烯酸酯，减压蒸发去除丁酮后得到质量浓度为60％的氧化锆分散液；
其他步骤均与实施例1相同。
对比例2
本对比例与实施例1的区别在于，本对比例的步骤S5：
称取纯化后的表面改性的氧化锆粉体30g溶解在150g丁酮中，加入型号为BYK-111分散剂1.5g，辅助超声或研磨，使粉体充分溶解分散，再加入11.1g邻苯基苯氧乙基丙烯酸酯，减压蒸发去除丁酮后得到质量浓度为70％的氧化锆分散液；
其他步骤均与实施例1相同。
对比例3
本对比例与实施例5的区别在于，本实施例的步骤S5：
称取纯化后的表面改性的氧化锆粉体30g溶解在150g丁酮中，加入型号为BYK-111分散剂1.5g，辅助超声或研磨，使粉体充分溶解分散，再加入18.5g邻苯基苯氧乙基丙烯酸酯，减压蒸发去除丁酮后得到质量浓度为60％的氧化锆分散液；
其他步骤均与实施例5相同。
对比例4
本对比例与实施例5的区别在于，本实施例的步骤S5：
称取纯化后的表面改性的氧化锆粉体30g溶解在150g丁酮中，加入型号为BYK-111分散剂1.5g，辅助超声或研磨，使粉体充分溶解分散，再加入10.2g联苯甲醇丙烯酸酯，减压蒸发去除丁酮后得到质量浓度为72％的氧化锆分散液；
其他步骤均与实施例1相同。
对比例5
本对比例与实施例1的区别在于，本对比例步骤S5中添加的氧化硅的为1.8g,即氧化硅的含量为氧化锆质量的6％，其他步骤均与实施例1相同，得到分散液。
对比例6
本对比例与实施例1的区别在于，本对比例氧化锆的粒径为5nm，氧化硅的平均粒径为10nm,其他步骤均与实施例1相同，得到分散液。
对比例7
本对比例与实施例1的区别在于，本对比例对氧化锆未进行改性，其他步骤均与实施例1相同，分散液制备失败。
试验例1
对实施例1-10和对比例1-7得到的分散液进行折射率的测试，结果见表1。
折射率的测试方法为：利用阿贝折仪，室温下测试。
分别添加光引发剂到实施例1-10和对比例1-7得到的分散液中，在PET膜上涂覆UV固化后得到涂层，测试其硬度，结果见表1。
硬度的测试方法为：按ASTM D3363-00涂层铅笔硬度的标准测试方法测试。
表1
样品 分散液的折射率 固化的涂层硬度
实施例1 1.6536 F
实施例2 1.6521 F
实施例3 1.7022 F
实施例4 1.7013 F
实施例5 1.6748 F
实施例6 1.6721 F
实施例7 1.7533 F
实施例8 1.7502 F
实施例9 1.6475 F
实施例10 1.6502 F
对比例1 1.6540 B
对比例2 1.7044 HB
对比例3 1.6756 B
对比例4 1.7541 HB
对比例5 1.6488 B
对比例6 1.6522 B
对比例7 / /
由表1的数据可知，本公开在纳米氧化锆的分散液中引入微量的粒径更小的氧化硅，在不影响整个体系折射率的基础上，能够有效提高分散液涂覆后的涂层硬度；同时，根据实施例1与对比例5的对比可知，本公开氧化硅的添加量过高时，体系折射率会一定程度降低；根据实施例1与对比例6的对比可知，添加的氧化硅的平均粒径过大时，起不到很好地填充效果，硬度没有增加；根据实施例1与对比例7的对比可知，使用未改性的氧化锆会降低分散液的折射率和涂覆层的硬度；此外，由实施例1与实施例9的对比可知，本公开对改性后的纳米氧化锆粉体进行的特定纯化处理，能够进一步提高分散液体系的折射率，进而获得更好的应用效果。
尽管已用具体实施例来说明和描述了本公开，然而应意识到，在不背离本公开的精神和范围的情况下可以作出许多其它的更改和修改。因此，这意味着在所附权利要求中包括属于本公开范围内的所有这些变化和修改。
工业实用性
本公开提供的可光固化的纳米氧化锆分散液，在氧化锆的分散液中引入了特定用量和特定粒径的氧化硅，在不影响整个体系折射率的基础上，达到了有效地提高氧化锆分散液的后期涂覆层的致密度和硬度的效果；本公开表面改性的氧化锆在分散液中不易发生团聚，而且能够在有机介质中分散与结合地更加充分；同时，本公开添加的丙烯酸类树脂具有较高的折射率，能够增加分散液体系的折射率，提高分散液的应用效果。

Claims (19)

  1. 一种可光固化的纳米氧化锆分散液，其特征在于，所述分散液为有机溶剂型分散液；
    所述分散液包括表面改性的氧化锆、氧化硅以及丙烯酸类树脂；
    所述分散液中的氧化锆的质量浓度在50％以上；
    所述氧化硅的含量为氧化锆质量的0.1-5％；
    所述氧化硅的平均粒径为2-3nm，最大粒径小于5nm。
  2. 根据权利要求1所述的分散液，其特征在于，所述表面改性的氧化锆的制备方法包括以下步骤：
    (A)提供有机溶剂相的氧化锆溶液；
    (B)将表面改性剂加入到所述有机溶剂相的氧化锆溶液中改性氧化锆，得到改性后的混合液；
    (C)步骤(B)得到的改性后的混合液除去溶剂，得到表面包覆的氧化锆粉体；
    (D)步骤(C)得到的表面包覆的氧化锆粉体经第一极性溶剂和第二极性溶剂交替洗涤，再干燥，得到所述表面改性的氧化锆；
    其中，所述第一极性溶剂的极性高于所述第二极性溶剂的极性。
  3. 根据权利要求2所述的分散液，其特征在于，步骤(A)中所述有机溶剂相的氧化锆溶液中氧化锆的质量浓度在50％以下。
  4. 根据权利要求3所述的分散液，其特征在于，氧化锆的粒径为1-30nm。
  5. 根据权利要求3所述的分散液，其特征在于，氧化锆的粒径为1-10nm。
  6. 根据权利要求2所述的分散液，其特征在于，步骤(B)中所述表面改性剂的用量为氧化锆质量的1-30％。
  7. 根据权利要求2所述的分散液，其特征在于，步骤(D)中所述第一极性溶剂包括水、醇类有机溶剂以及酮类有机溶剂中的至少一种。
  8. 根据权利要求7所述的分散液，其特征在于，所述第二极性溶剂包括苯类有机溶剂、酯类有机溶剂以及醚类有机溶剂中的至少一种。
  9. 根据权利要求2所述的分散液，其特征在于，所述交替洗涤的次数在4次以上。
  10. 根据权利要求1所述的分散液，其特征在于，所述氧化硅包括表面处理后的氧化硅。
  11. 根据权利要求10所述的分散液，其特征在于，所述氧化硅包括实心无定型的氧化硅。
  12. 根据权利要求1所述的分散液，其特征在于，所述丙烯酸类树脂的折射率在1.55以上。
  13. 根据权利要求1-12任一项所述的分散液，其特征在于，所述分散液还包括分散剂。
  14. 根据权利要求13所述的分散液，其特征在于，所述分散剂包括高分子型分散剂。
  15. 根据权利要求14所述的分散液，其特征在于，所述高分子型分散剂的添加量为氧化锆质量的1-20％。
  16. 根据权利要求1-12任一项所述的分散液，其特征在于，所述分散液的折射率为1.65-1.75。
  17. 一种权利要求1-16任一项所述的分散液的制备方法，其特征在于，包括以下步骤：
    将表面改性的氧化锆、氧化硅、丙烯酸类树脂以及任选的分散剂溶解在有机溶剂中，得到所述分散液。
  18. 一种光学膜，其特征在于，由权利要求1-16任一项所述的分散液经固化得到的。
  19. 根据权利要求18所述的光学膜，其特征在于，所述光学膜的硬度在HB以上。
PCT/CN2022/119285 2022-05-13 2022-09-16 可光固化的纳米氧化锆分散液及其制备方法、光学膜 WO2023216487A1 (zh)

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