Zirconium oxide dispersion liquid, method for preparing same, and use thereof

Abstract

The application discloses a zirconium oxide dispersion liquid and a preparation method and application thereof, and belongs to the technical field of zirconium oxide materials. The zirconium oxide dispersion liquid comprises a zirconium oxide component, a dispersant and a resin component; the zirconium oxide raw material used in the zirconium oxide component has D 30 ≤20nm, D 80 ≤30nm and D 95 ≤100nm. By controlling the nano zirconium oxide D 30 ≤20nm and D 80 ≤30nm, the size of the nano particles in the system is relatively uniform, the entire particle size distribution is relatively narrow, the prepared dispersion liquid has relatively excellent rheological properties, the nano particles are arranged relatively uniformly and tightly during solidification and film formation, and the hardness after film formation is improved. By controlling the zirconium oxide D 95 ≤100nm, the large particles in the entire dispersion liquid system are controlled, and the light transmittance of the dispersion liquid is improved. The above-mentioned zirconium oxide dispersion liquid has relatively excellent rheological properties and light transmittance, the obtained film has relatively good film uniformity and film hardness, and can be used for adjusting a light path.

Description

Technical Field

[0001] This invention relates to the field of zirconia materials technology, and more specifically, to a zirconia dispersion, its preparation method, and its application. Background Technology

[0002] In recent years, high-refractive-index transparent materials have been applied in many fields, such as optical communication technology, photonic computers, display panels, lenses, optical films, optical waveguides, solar cells, and light-emitting diodes.

[0003] Optically transparent polymers are widely used due to their advantages such as low cost, good processability, and high visible light transmittance. However, most photocurable resins have relatively low refractive indices; for example, acrylate resins typically have a refractive index of 1.40–1.60. Although the refractive index can be further increased by changing the type and number of resin groups, such as increasing the amount of benzene rings, conjugated structures, and π-electron structures in the molecule, a large amount of these structures will cause the polymer to exhibit light scattering properties and a birefringence absorption coefficient, making it unsuitable as an optical material. Therefore, it is usually necessary to add a certain amount of inorganic nanoparticles to the photocurable resin to improve its refractive index.

[0004] Nano-zirconia possesses advantages such as high refractive index, high strength, thermal stability, and chemical inertness. Dispersing inorganic nano-zirconia in organic optical resins can significantly improve the optical properties of the resins and also enhance the mechanical properties after film formation. To ensure that this zirconia-resin dispersion performs its intended function in various optical fields, the dispersion needs not only high light transmittance but also good rheological properties to guarantee continuity and stability during subsequent adhesive applications (such as inkjet printing, spin coating, and roll coating), ensuring the uniformity and functionality of the cured coating.

[0005] In view of this, the present invention is proposed. Summary of the Invention

[0006] The purpose of this invention is to provide a zirconium oxide dispersion, its preparation method, and its application, so as to solve or improve the above-mentioned technical problems.

[0007] This invention can be implemented as follows:

[0008] In a first aspect, the present invention provides a zirconia dispersion comprising a zirconia component, a dispersant, and a resin component;

[0009] Among them, the zirconium oxide raw material used in the zirconium oxide component has a D 30 ≤20nm, D 80 ≤30nm and D 95 ≤100nm.

[0010] In an optional embodiment, the D of the zirconium oxide raw material used for the zirconium oxide component... 30 3nm~20nm, D 80 The wavelength range is 6nm to 30nm and D 95 The range is 30nm to 100nm.

[0011] In an optional embodiment, the D of the zirconium oxide raw material used for the zirconium oxide component... 30 The wavelength ranges from 3.87nm to 19.87nm, D 80 The wavelength ranges from 6.46nm to 29.55nm and D 95 The wavelength ranges from 30.05nm to 95.05nm.

[0012] In an optional embodiment, the content of the zirconium oxide raw material in the zirconium oxide dispersion is 40wt% to 75wt%.

[0013] In an optional embodiment, the content of the zirconium oxide raw material in the zirconium oxide dispersion is 45wt% to 70wt%.

[0014] In an optional embodiment, the content of the zirconium oxide raw material in the zirconium oxide dispersion is 50wt% to 65wt%.

[0015] In an optional embodiment, the zirconium oxide component is obtained by modifying zirconium oxide raw material with a surface modifier.

[0016] In an optional embodiment, the amount of surface modifier used is 1 wt% to 30 wt% of the zirconium oxide raw material.

[0017] In an optional embodiment, the amount of surface modifier used is 5 wt% to 20 wt% of the zirconium oxide raw material.

[0018] In optional embodiments, the surface modifier includes at least one of organic acid compounds, phosphonic acid compounds, coupling agents, and chelating agents.

[0019] In an optional embodiment, the coupling agent is a silane coupling agent.

[0020] In an optional embodiment, the amount of dispersant used is 1 wt% to 20 wt% of the zirconium oxide raw material.

[0021] In an optional embodiment, the amount of dispersant used is 5 wt% to 10 wt% of the zirconium oxide raw material.

[0022] In an optional embodiment, the resin component is an optical resin.

[0023] In an optional embodiment, the resin component is a UV-curable acrylic resin.

[0024] In an optional embodiment, the zirconium oxide dispersion has at least one of the following characteristics:

[0025] Feature 1: Zirconia dispersion at a shear rate of 50 s -1 The viscosity value under the specified conditions is less than 6000 mPa·s;

[0026] Feature 2: Zirconia dispersion at a shear rate of 1000 s -1 The viscosity value under the specified conditions is less than 4000 mPa·s;

[0027] Feature 3: The rheological properties of the zirconium oxide dispersion are 1.1–2.5;

[0028] Feature 4: The transmittance of the zirconium oxide dispersion at a wavelength of 600 nm is not less than 50%;

[0029] Feature 5: The refractive index of the zirconium oxide dispersion is >1.65.

[0030] In a second aspect, the present invention provides a method for preparing a zirconia dispersion as described in any of the foregoing embodiments, comprising the following steps: mixing a mixed solution containing an organic solvent, a zirconia component and a dispersant with a resin component, and then removing the organic solvent.

[0031] In an optional embodiment, the content of the zirconium oxide raw material in the mixed solution is 10 wt% to 80 wt%.

[0032] In an optional embodiment, the content of the zirconium oxide raw material in the mixed solution is 20 wt% to 50 wt%.

[0033] In an optional embodiment, the content of the zirconium oxide raw material in the mixed solution is 20 wt% to 30 wt%.

[0034] In optional embodiments, the organic solvent includes at least one of alcohols, ketones, ethers, esters, aliphatic hydrocarbons, cycloaliphatic hydrocarbons, and aromatics.

[0035] In an optional embodiment, the organic solvent includes at least one of propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, toluene, butanone, and butyl acetate.

[0036] Thirdly, the present invention provides an optical path regulating coating, wherein the raw materials for preparing the optical path regulating coating include the zirconium oxide dispersion of any of the foregoing embodiments.

[0037] In an optional embodiment, the raw materials for preparing the optical path adjustment coating also include an initiator.

[0038] In an optional embodiment, when the resin component is a UV-curable acrylic resin, the initiator is a photoinitiator.

[0039] In an optional embodiment, the amount of initiator is 1 wt% to 5 wt% of the zirconium oxide dispersion.

[0040] In an optional implementation, the following steps are included: coating the raw materials for preparing the optical path adjustment coating onto the surface of the substrate and curing it.

[0041] In an optional embodiment, the light transmittance of the substrate is not less than 89%.

[0042] In an optional embodiment, the light transmittance of the substrate is not less than 90%.

[0043] In optional embodiments, the substrate includes polyethylene terephthalate, cellulose triacetate, polycarbonate, or polymethyl methacrylate.

[0044] In an optional implementation, the optical path adjustment coating is used to adjust the optical path.

[0045] In an alternative embodiment, the optical path conditioning coating is used in optical communication technologies, photonic computers, display panels, lenses, optical films, optical waveguides, solar cells, or light-emitting diodes.

[0046] The beneficial effects of this invention include:

[0047] This invention limits the D of nano-zirconia in a zirconia dispersion system. 30 ≤20nm and D 80 A particle size ≤30nm ensures relatively uniform particle size and narrow particle size distribution in the zirconia dispersion system, thereby achieving a zirconia dispersion with excellent rheological properties. Furthermore, satisfying the above-mentioned D... 30 and D 80 The presence of nano-zirconia within a certain range allows for a more uniform and dense arrangement of nanoparticles in the zirconia dispersion system during curing, thereby improving the hardness of the resulting coating. Through the aforementioned D... 30 and D 80 On the basis of this, the D of nano-zirconia is further limited. 95 This method effectively controls the content of large particles in the entire zirconia dispersion system, preventing them from affecting the light transmittance of the dispersion and thus improving its light transmittance. The resulting zirconia dispersion exhibits good rheological properties and light transmittance, with a high refractive index. The optical path adjustment coating further prepared from this zirconia dispersion has higher hardness, which is beneficial for maintaining the stability and functionality of the product. Detailed Implementation

[0048] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0049] The following is a detailed description of the zirconium oxide dispersion, its preparation method, and its application provided by the present invention.

[0050] This invention proposes a zirconia dispersion comprising a zirconia component, a dispersant, and a resin component.

[0051] Among them, the zirconium oxide raw material used in the zirconium oxide component has a D 30 ≤20nm, D 80 ≤30nm and D 95 ≤100nm. The above-mentioned zirconium oxide raw materials are nanoscale.

[0052] As an example, the D of the zirconium oxide raw material used in the zirconium oxide composition 30 The wavelength can be 20nm, 18nm, 16nm, 14nm, 12nm, 10nm, 8nm, 6nm, 4nm, 2nm, or 1nm, or other values ​​within the range of ≤20nm and >0. The D of this zirconium oxide raw material... 80 The wavelength can be 30nm, 25nm, 20nm, 18nm, 16nm, 14nm, 12nm, 10nm, 8nm, 6nm, 4nm, 2nm, or 1nm, or other values ​​within the range of ≤30nm and >0. The D of this zirconium oxide raw material... 95 It can be 100nm, 90nm, 80nm, 70nm, 60nm, 50nm, 40nm, 30nm, 20nm or 10nm, or other values ​​within the range of ≤100nm and >0.

[0053] It should be emphasized that, in the case of D 30 D 80 and D 95 When setting it up, D must be satisfied simultaneously. 30 ≤20nm, D 80 ≤30nm and D 95 ≤100nm.

[0054] In some embodiments, the zirconium oxide component uses zirconium oxide raw materials with a D... 30 3nm~20nm, D 80 The wavelength range is 6nm to 30nm and D 95 The wavelength range is 30nm to 100nm. In some preferred embodiments, the zirconium oxide raw material used for the zirconium oxide composition has a D... 30The wavelength ranges from 3.87nm to 19.87nm, D 80 The wavelength ranges from 6.46nm to 29.55nm and D 95 The wavelength ranges from 30.05nm to 95.05nm.

[0055] Continuing from the above, this invention limits the D of nano-zirconia in the zirconia dispersion system. 30 ≤20nm and D 80 A particle size ≤30nm ensures relatively uniform particle size and narrow particle size distribution in the zirconia dispersion system, thereby achieving a zirconia dispersion with excellent rheological properties. Furthermore, satisfying the above-mentioned D... 30 and D 80 The presence of nano-zirconia within a certain range allows for a more uniform and dense arrangement of nanoparticles in the zirconia dispersion system during curing, thereby improving the hardness of the resulting coating. Through the aforementioned D... 30 and D 80 On the basis of this, the D of nano-zirconia is further limited. 95 It can effectively control the content of large particles in the entire zirconia dispersion system, avoid large particles from affecting the light transmittance of the dispersion, and thus help improve the light transmittance of the dispersion.

[0056] In this invention, the crystal form of the zirconium oxide raw material is not limited. When using it, zirconium oxide raw materials with monoclinic, tetragonal or mixed-phase crystal forms can be used.

[0057] In some embodiments, the content of the zirconia raw material in the zirconia dispersion can be 40 wt% to 75 wt%, such as 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, or 75 wt%, or other values ​​within the range of 40 wt% to 75 wt%. In some preferred embodiments, the content of the zirconia raw material in the zirconia dispersion is 45 wt% to 70 wt%. In some even more preferred embodiments, the content of the zirconia raw material in the zirconia dispersion is 50 wt% to 65 wt%.

[0058] If the content of zirconia raw material in the zirconia dispersion is less than 45 wt%, the prepared dispersion has a low refractive index, which is not conducive to optical path adjustment; if the content of zirconia raw material in the zirconia dispersion is higher than 75 wt%, a dispersion cannot be prepared.

[0059] Continuing from the above, it also satisfies D in this invention. 30 D 80 and D 95 The zirconia dispersion prepared from the zirconia raw materials in the above-mentioned proportions exhibits superior rheological properties and high light transmittance.

[0060] In some embodiments, the above-mentioned zirconium oxide component is obtained by modifying zirconium oxide raw material with a surface modifier.

[0061] By modifying the surface of zirconia raw materials, the surface properties of zirconia raw materials can be improved, allowing resin-compatible groups to be grafted onto their surface.

[0062] The surface modification method is not limited, and can include grinding, heating or mixing.

[0063] The type of surface modifier is not limited, as long as it can act as an affinity agent for the resin. In some embodiments, the surface modifier may include at least one of organic acid compounds with various types of groups, phosphonic acid compounds, coupling agents, and chelating agents.

[0064] In some preferred embodiments, the surface modifier is a silane coupling agent, such as a silane containing acrylate, (meth)acrylate, epoxy, alkyl, alkoxy, vinyl, phenyl, methacryloyloxy, amino, chlorosilyl, chloropropyl, or mercapto groups.

[0065] The amount of surface modifier can be 1 wt% to 30 wt% of the zirconium oxide raw material, such as 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, or 30 wt%, or other values ​​within the range of 1 wt% to 30 wt%. In some preferred embodiments, the amount of surface modifier is 5 wt% to 20 wt% of the zirconium oxide raw material.

[0066] In this invention, the dispersant plays an auxiliary role in dispersion and wetting. The dispersant can be any commercially available type or model; each dispersant can be used individually or in combination. Exemplarily, the dispersant may include at least one of polyether acid compounds, polyether amine compounds, polyether acid / amine mixtures, ester compounds with phosphate groups, and polyether compounds including phosphate groups. The dispersion method can be ultrasonication, stirring, grinding, etc., without specific limitations.

[0067] In some embodiments, the amount of dispersant used is 1 wt% to 20 wt% of the zirconium oxide raw material, such as 1 wt%, 2 wt%, 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, or 20 wt%, or other values ​​within the range of 1 wt% to 20 wt%. In some preferred embodiments, the amount of dispersant used is 5 wt% to 10 wt% of the zirconium oxide raw material.

[0068] In this invention, the resin component is an optical resin. In some preferred embodiments, the resin component is a UV-curable acrylic resin, which may, by way of example but not limitation, include at least one of benzyl acrylate, benzyl methacrylate, phenyl acrylate, diphenyl acrylate, biphenyl acrylate, phenoxybenzyl acrylate, 3-phenoxybenzyl acrylate, phenyl methacrylate, biphenyl methacrylate, 4-nitrobenzene methacrylate, 4-nitrobenzene methacrylate, 2-chlorophenyl acrylate, 4-chlorophenyl acrylate, 2-chlorophenyl methacrylate, biphenylmethanol acrylate, 4-chlorophenyl methacrylate, o-phenylphenol ethyl acrylate, bisphenol diacrylate, hydroxyethyl acrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate.

[0069] In some embodiments, the amount of resin can be obtained by subtracting 100% of the total content of zirconium oxide raw material, surface modifier and dispersant in zirconium oxide dispersion.

[0070] In some embodiments, the zirconium oxide dispersion is at a shear rate of 50 s. -1 The viscosity value under certain conditions is below 6000 mPa·s, for example, it can be 196 mPa·s to 5756 mPa·s.

[0071] In some embodiments, the zirconium oxide dispersion is at a shear rate of 1000 s. -1 The viscosity value under certain conditions is below 4000 mPa·s, for example, it can be 154 mPa·s to 3350 mPa·s.

[0072] In some embodiments, the rheological properties of the zirconium oxide dispersion are 1.1 to 2.5, for example, 1.167 to 2.456.

[0073] In some embodiments, the transmittance of the zirconium oxide dispersion at a wavelength of 600 nm is not less than 50%, for example, it can be 51.4% to 65.2%.

[0074] In some embodiments, the refractive index of the zirconium oxide dispersion is >1.65, further >1.67, and even further >1.70.

[0075] Accordingly, the present invention also provides a method for preparing the above-mentioned zirconium oxide dispersion, which includes the following steps: mixing a mixed solution containing an organic solvent, a zirconium oxide component and a dispersant with a resin component, and then removing the organic solvent.

[0076] In some embodiments, the zirconium oxide raw material is first modified with a surface modifier to obtain a zirconium oxide component; the zirconium oxide component is mixed with a dispersant and an organic solvent to obtain a mixed solution; the mixed solution is mixed with a resin component, and the organic solvent is removed to obtain a zirconium oxide dispersion.

[0077] In some embodiments, the content of the zirconia raw material in the mixed solution can be 10 wt% to 80 wt%, such as 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, or 80 wt%, or other values ​​within the range of 10 wt% to 80 wt%. In some preferred embodiments, the content of the zirconia raw material in the mixed solution is 20 wt% to 50 wt%, and in some more preferred embodiments, the content of the zirconia raw material in the mixed solution is 20 wt% to 30 wt%.

[0078] In some embodiments, the amount of organic solvent can be obtained by subtracting 100% of the total content of zirconium oxide raw material, surface modifier, and dispersant in the mixed solution.

[0079] This invention does not specifically limit the organic solvent. In some embodiments, the organic solvent may include at least one selected from alcohols, ketones, ethers, esters, aliphatic hydrocarbons, cycloaliphatic hydrocarbons, and aromatics. In some preferred embodiments, the organic solvent may include at least one selected from propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, toluene, butanone, and butyl acetate.

[0080] The present invention does not particularly limit the method of removing organic solvents; a rotary evaporator or other vacuum distillation apparatus may be used for removal, but not limited to this invention.

[0081] In addition, the present invention also provides an optical path adjustment coating, the raw materials for which the optical path adjustment coating is prepared include the above-mentioned zirconium oxide dispersion.

[0082] Furthermore, the raw materials for preparing this optical path modulation coating also include an initiator.

[0083] In an optional embodiment, when the resin component is a UV-curable acrylic resin, the initiator is a photoinitiator.

[0084] This invention does not specifically limit photoinitiation. In some embodiments, the photoinitiator may include at least one cationic photoinitiator selected from diazonium salts, sulfonium salts, and imidazoles. In other embodiments, the photoinitiator may also include at least one free radical photoinitiator selected from phosphorus-based, triazine-based, benzophenone-based, benzoin-based, oxime-based, acetone-based, aminoketone-based, ketone-based, anthraquinone-based, and aromatic phosphine oxide compounds. In some preferred embodiments, the photoinitiator may include at least one of TPO, 1173, 184, and 907.

[0085] In some embodiments, the amount of photoinitiator can be 1 wt% to 5 wt% of the zirconium oxide dispersion, such as 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt%, or other values ​​within the range of 1 wt% to 5 wt%.

[0086] Accordingly, the present invention also provides a method for preparing the above-mentioned optical path adjustment coating, comprising the following steps: coating the raw materials for preparing the optical path adjustment coating onto the surface of a substrate and curing.

[0087] The coating method is not particularly limited, but can be roll coating, spray coating, curtain coating or spin coating, etc., by way of example but not limitation.

[0088] The coating substrate is not particularly limited, but a substrate with high transmittance is preferred. In some embodiments, the light transmittance of the substrate is not less than 89%, preferably not less than 90%. In some specific embodiments, the substrate may include polyethylene terephthalate, cellulose triacetate, polycarbonate, or polymethyl methacrylate, etc.

[0089] Curing methods are exemplary but not limited to the use of mercury lamps and LEDs.

[0090] The aforementioned optical path adjustment coating has high hardness.

[0091] Furthermore, the present invention also provides the application of the above-mentioned optical path adjustment coating, which can be used to adjust the optical path.

[0092] In some embodiments, the optical path conditioning coating can be used in optical communication technologies, photonic computers, display panels, lenses, optical films, optical waveguides, solar cells, or light-emitting diodes. Among these, the optical films include anti-reflective films.

[0093] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0094] Example 1

[0095] This invention provides an optical path adjustment coating, the preparation method of which includes:

[0096] Step 1: Use 5.1g of silane coupling agent 3-(methacryloyloxy)propyltrimethoxysilane to couple 51g of zirconium oxide raw material powder (D 30 For 16.85nm, D 80 It is 21.98nm and D 95After modification (to a density of 37.82 nm), modified zirconia was obtained. The modified zirconia was ball-milled and dispersed in propylene glycol methyl ether (propylene glycol methyl ether) using 2.55 g of dispersant BYK-111 to obtain a mixed solution. The content of the zirconia raw material powder in this mixed solution was 30 wt%.

[0097] Step 2: Take 41.35g of 3-phenylbenzyl acrylate as a resin component and add it to the above mixed solution. After removing propylene glycol methyl ether using a rotary evaporator, a zirconium oxide dispersion with a refractive index RI>1.65 is obtained.

[0098] Step 3: Add 2 wt% of photoinitiator TPO to the above zirconium oxide dispersion, and then coat it onto PET for photocuring to form a film, thereby obtaining a light path conditioning coating.

[0099] Example 2

[0100] This invention provides an optical path adjustment coating, the preparation method of which includes:

[0101] Step 1: Use 5.8g of silane coupling agent 3-(methacryloyloxy)propyltrimethoxysilane to couple 58g of zirconium oxide raw material powder (D 30 9.53nm, D 80 It is 15.28nm and D 95 After modification (to a density of 34.71 nm), modified zirconia was obtained. The modified zirconia was ball-milled and dispersed in propylene glycol methyl ether (propylene glycol methyl ether) using 2.9 g of dispersant BYK-111 to obtain a mixed solution. The content of the zirconia raw material powder in this mixed solution was 30 wt%.

[0102] Step 2: Take 33.3g of 3-phenylbenzyl acrylate as a resin component and add it to the above mixed solution. After removing propylene glycol methyl ether using a rotary evaporator, a zirconium oxide dispersion with a refractive index RI>1.67 is obtained.

[0103] Step 3: Add 2 wt% of photoinitiator TPO to the above zirconium oxide dispersion, and then coat it onto PET for photocuring to form a film, thereby obtaining a light path conditioning coating.

[0104] Example 3

[0105] This invention provides an optical path adjustment coating, the preparation method of which includes:

[0106] Step 1: Use 6.2g of silane coupling agent 3-(methacryloyloxy)propyltrimethoxysilane to couple 62g of zirconium oxide raw material powder (D 30 19.54nm, D 80 It is 28.98nm and D 95After modification (to a density of 39.22 nm), modified zirconia was obtained. The modified zirconia was ball-milled and dispersed in the organic solvent propylene glycol methyl ether using 3.1 g of dispersant BYK-111 to obtain a mixed solution. The content of the zirconia raw material powder in this mixed solution was 30 wt%.

[0107] Step 2: Take 28.7g of 3-phenylbenzyl acrylate as a resin component and add it to the above mixed solution. After removing propylene glycol methyl ether using a rotary evaporator, a zirconium oxide dispersion with a refractive index RI>1.70 is obtained.

[0108] Step 3: Add 2 wt% of photoinitiator TPO to the above zirconium oxide dispersion, and then coat it onto PET for photocuring to form a film, thereby obtaining a light path conditioning coating.

[0109] Example 4

[0110] The difference between this embodiment and Embodiment 1 is that the D of the zirconium oxide raw material powder... 30 13.48nm, D 80 It is 17.20nm and D 95 The wavelength is 35.51 nm; the dispersant is BYK-180.

[0111] The refractive index RI of the zirconium oxide dispersion in this embodiment is >1.65.

[0112] Example 5

[0113] The difference between this embodiment and Embodiment 2 is that the D of the zirconium oxide raw material powder 30 7.63nm, D 80 It is 10.28nm and D 95 The wavelength is 33.46 nm; the dispersant is BYK-180.

[0114] The refractive index RI of the zirconium oxide dispersion in this embodiment is >1.67.

[0115] Example 6

[0116] The difference between this embodiment and Embodiment 3 is that the D of the zirconium oxide raw material powder... 30 3.87nm, D 80 It is 6.46nm and D 95 The wavelength is 30.05 nm; the dispersant is BYK-180.

[0117] The refractive index RI of the zirconium oxide dispersion in this embodiment is >1.70.

[0118] Example 7

[0119] The difference between this embodiment and Embodiment 1 is that the D of the zirconium oxide raw material powder... 30 17.45nm, D80 It is 27.58nm and D 95 The wavelength is 38.36 nm; the silane coupling agent is (2-methylallyloxy)trimethylsilane; the dispersant is BYK-9010.

[0120] The refractive index RI of the zirconium oxide dispersion in this embodiment is >1.65.

[0121] Example 8

[0122] The difference between this embodiment and Embodiment 2 is that the D of the zirconium oxide raw material powder 30 18.37nm, D 80 It is 29.55nm and D 95 The wavelength is 95.05 nm; the silane coupling agent is (2-methylallyloxy)trimethylsilane; the dispersant is BYK-9010.

[0123] The refractive index RI of the zirconium oxide dispersion in this embodiment is >1.67.

[0124] Example 9

[0125] The difference between this embodiment and Embodiment 3 is that the D of the zirconium oxide raw material powder... 30 19.87nm, D 80 It is 28.46nm and D 95 The wavelength is 80.39 nm; the silane coupling agent is (2-methylallyloxy)trimethylsilane; the dispersant is BYK-9010.

[0126] The refractive index RI of the zirconium oxide dispersion in this embodiment is >1.70.

[0127] Comparative Example 1

[0128] The difference between this comparative example and Example 1 is that the D of the zirconium oxide raw material powder is... 30 22.77nm, D 80 It is 33.96nm and D 95 It is 108.25nm.

[0129] Comparative Example 2

[0130] The difference between this comparative example and Example 2 is that the D of the zirconium oxide raw material powder is... 30 22.77nm, D 80 It is 33.96nm and D 95 It is 112.52nm.

[0131] Comparative Example 3

[0132] The difference between this comparative example and Example 3 is that the D of the zirconium oxide raw material powder is... 30 22.77nm, D80 It is 33.96nm and D 95 It is 123.56nm.

[0133] Comparative Example 4

[0134] The difference between this comparative example and Example 4 is that the D of the zirconium oxide raw material powder... 30 28.32nm, D 80 It is 37.13m and D 95 It is 128.46nm.

[0135] Comparative Example 5

[0136] The difference between this comparative example and Example 5 is that the D of the zirconium oxide raw material powder is... 30 28.32nm, D 80 It is 37.13nm and D 95 It is 135.46nm.

[0137] Comparative Example 6

[0138] The difference between this comparative example and Example 6 is that the D of the zirconium oxide raw material powder... 30 28.32nm, D 80 It is 37.13nm and D 95 It is 141.46nm.

[0139] Comparative Example 7

[0140] The difference between this comparative example and Example 7 is that the D of the zirconium oxide raw material powder is... 30 32.92nm, D 80 It is 40.56nm and D 95 It is 146.23nm.

[0141] Comparative Example 8

[0142] The difference between this comparative example and Example 8 is that the D of the zirconium oxide raw material powder is... 30 32.92nm, D 80 It is 40.56nm and D 95 It is 147.23nm.

[0143] Comparative Example 9

[0144] The difference between this comparative example and Example 9 is that the D of the zirconium oxide raw material powder is... 30 32.92nm, D 80 It is 40.56nm and D 95 It is 156.23nm.

[0145] Comparative Example 10

[0146] The difference between this comparative example and Example 1 is that the D of the zirconium oxide raw material powder is... 30 18.11nm, D 80 It is 32.54nm and D 95 It is 108.29nm.

[0147] Comparative Example 11

[0148] The difference between this comparative example and Example 1 is that the D of the zirconium oxide raw material powder is... 30 23.62nm, D 80 It is 28.74nm and D 95 It is 105.36nm.

[0149] Comparative Example 12

[0150] The difference between this comparative example and Example 1 is that the D of the zirconium oxide raw material powder is... 30 27.52nm, D 80 It is 36.88nm and D 95 It is 96.49nm.

[0151] Comparative Example 13

[0152] The difference between this comparative example and Example 1 is that the D of the zirconium oxide raw material powder is... 30 17.44nm, D 80 It is 27.62nm and D 95 It is 107.41nm.

[0153] Comparative Example 14

[0154] The difference between this comparative example and Example 1 is that the D of the zirconium oxide raw material powder is... 30 For 18.36nm, D 80 It is 32.59nm and D 95 It is 93.72nm.

[0155] Comparative Example 15

[0156] The difference between this comparative example and Example 1 is that the D of the zirconium oxide raw material powder is... 30 22.92nm, D 80 It is 28.98nm and D 95 It is 96.66nm.

[0157] Comparative Example 16

[0158] The difference between this comparative example and Example 1 is that the pore volume of the zirconium oxide raw material powder is 0.0372 cm³. 3 / g, pore size 0.8645nm, average particle size 10nm, D 30 18.22nm, D80 It is 36.54nm and D 95 It is 110.32nm.

[0159] Test case

[0160] ① The zirconium oxide dispersions prepared in Examples 1-9 and Comparative Examples 1-16 were subjected to the following tests:

[0161] A. At a shear rate of 50s -1 The viscosity value was measured under the specified conditions, and the unit is mPa·s.

[0162] B. At a shear rate of 1000 s -1 The viscosity value was measured under the specified conditions, and the unit is mPa·s.

[0163] C. Measure the rheological properties; the rheological value equals the shear rate at 50 s⁻¹. -1 The viscosity / shear rate obtained under the conditions was 1000 s. -1 The viscosity value was measured under the specified conditions;

[0164] D. Measure the transmittance at a wavelength of 600 nm, in units of %.

[0165] ② The optical path adjustment coatings prepared in Examples 1 to 9 and Comparative Examples 1 to 16 were subjected to the following tests: the hardness was tested according to the "GBT6739-1996 Pencil Hardness Test Method for Coatings".

[0166] The test results are shown in Tables 1 to 3.

[0167] Table 1 Test Results

[0168]

[0169] Table 2 Test Results

[0170]

[0171] Table 3 Test Results

[0172]

[0173] As can be seen from Tables 1 to 3, the zirconia dispersions prepared in Examples 1 to 9 exhibit better rheological properties and light transmittance, and higher refractive index compared to Comparative Examples 1 to 16. Furthermore, the optical path adjustment coatings prepared in Examples 1 to 9 have higher hardness than those prepared in Comparative Examples 1 to 16, which is beneficial for maintaining the stability and functionality of the product.

[0174] In summary, this invention limits the D of nano-zirconia in the zirconia dispersion system. 30 ≤20nm and D80 A particle size ≤30nm ensures relatively uniform particle size and narrow particle size distribution in the zirconia dispersion system, thereby achieving a zirconia dispersion with excellent rheological properties. Furthermore, satisfying the above-mentioned D... 30 and D 80 The presence of nano-zirconia within a certain range allows for a more uniform and dense arrangement of nanoparticles in the zirconia dispersion system during curing, thereby improving the hardness of the resulting coating. Through the aforementioned D... 30 and D 80 On the basis of this, the D of nano-zirconia is further limited. 95 This method effectively controls the content of large particles in the entire zirconia dispersion system, preventing them from affecting the light transmittance of the dispersion and thus improving its light transmittance. The resulting zirconia dispersion exhibits good rheological properties and light transmittance, with a high refractive index. The optical path adjustment coating further prepared from this zirconia dispersion has higher hardness, which is beneficial for maintaining the stability and functionality of the product.

[0175] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A zirconium oxide dispersion, characterized in that, The zirconium oxide dispersion comprises zirconium oxide components, a dispersant, and a resin component; The zirconium oxide raw material used in the zirconium oxide composition has a D30 of 3nm~20nm, a D80 of 6nm~30nm, and a D95 of 30nm~100nm. The content of the zirconium oxide raw material in the zirconium oxide dispersion is 50wt%~75wt%; The dispersant includes at least one of polyether acid compounds, polyether amine compounds, polyether acid / amine mixtures, ester compounds with phosphate groups, and polyether compounds including phosphate groups; The zirconium oxide dispersion was subjected to a shear rate of 50 s. -1 The viscosity value under the specified conditions is less than 6000 mPa·s; The zirconium oxide dispersion was subjected to a shear rate of 1000 s. -1 The viscosity value under the specified conditions is less than 4000 mPa·s; The rheological properties of the zirconium oxide dispersion are 1.1 to 2.

5.

2. The zirconium oxide dispersion according to claim 1, characterized in that, The zirconium oxide component is obtained by modifying the zirconium oxide raw material with a surface modifier.

3. The zirconium oxide dispersion according to claim 2, characterized in that, The amount of the surface modifier is 1 wt% to 30 wt% of the zirconium oxide raw material.

4. The zirconium oxide dispersion according to claim 2 or 3, characterized in that, The surface modifier includes at least one of organic acid compounds, phosphonic acid compounds, coupling agents, and chelating agents.

5. The zirconium oxide dispersion according to claim 1, characterized in that, The amount of the dispersant is 1 wt% to 20 wt% of the zirconium oxide raw material; Alternatively, the resin component may be an optical resin.

6. The zirconium oxide dispersion according to claim 1, characterized in that, The zirconium oxide dispersion has at least one of the following characteristics: Feature 4: The transmittance of the zirconium oxide dispersion at a wavelength of 600 nm is not less than 50%; Feature 5: The refractive index of the zirconium oxide dispersion is >1.

65.

7. A method for preparing a zirconium oxide dispersion as described in any one of claims 1 to 6, characterized in that, Includes the following steps: A mixed solution containing an organic solvent, zirconium oxide, and a dispersant is mixed with a resin component, and then the organic solvent is removed.

8. The method for preparing the zirconium oxide dispersion according to claim 7, characterized in that, The zirconium oxide content in the mixed solution is 10wt%~80wt%.

9. The method for preparing the zirconium oxide dispersion according to claim 7, characterized in that, The organic solvent includes at least one of alcohols, ketones, ethers, esters, aliphatic hydrocarbons, cycloaliphatic hydrocarbons, and aromatics.

10. A light path adjustment coating, characterized in that, The raw materials for preparing the optical path adjustment coating include the zirconia dispersion according to any one of claims 1 to 6 or the zirconia dispersion obtained by the preparation method according to any one of claims 7 to 9.

11. The optical path adjustment coating according to claim 10, characterized in that, The raw materials for preparing the optical path adjustment coating also include an initiator.

12. The optical path adjustment coating according to claim 11, characterized in that, The amount of the initiator is 1 wt% to 5 wt% of the zirconium oxide dispersion.

13. The optical path adjustment coating according to claim 10, characterized in that, The hardness of the optical path adjustment coating is 2B.

14. A method for preparing an optical path adjustment coating as described in any one of claims 10-13, characterized in that, Includes the following steps: The raw materials for preparing the optical path adjustment coating are coated onto the surface of the substrate and then cured.

15. The method for preparing the optical path adjustment coating according to claim 14, characterized in that, The light transmittance of the substrate is not less than 89%.

16. The method for preparing the optical path adjustment coating according to claim 14, characterized in that, The substrate includes polyethylene terephthalate, cellulose triacetate, polycarbonate, or polymethyl methacrylate.

17. An application of the optical path adjustment coating as described in any one of claims 10-13, characterized in that, The optical path adjustment coating is used to adjust the optical path.

18. An application of the optical path adjustment coating as described in claim 17, characterized in that, The optical path adjustment coating is used in optical communication technology, photonic computers, display panels, lenses, optical films, optical waveguides, solar cells, or light-emitting diodes.

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