CN110713746A - High-refractive-index wear-resistant hardened coating composition and preparation method of hardened film thereof - Google Patents
High-refractive-index wear-resistant hardened coating composition and preparation method of hardened film thereof Download PDFInfo
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Abstract
The invention discloses a high-refractive-index wear-resistant hardened coating composition and a preparation method of a hardened film thereof. The composite material with the excellent performance of the organic and inorganic materials is obtained by compounding the zirconia nano particles with the photocuring resin, has stable property, high hardness, strong wear resistance, good water resistance and corrosion resistance and high refractive index, and can be applied to the fields of protection of electronic products and electronic components or coating of furniture and artware and the like.
Description
Technical Field
The invention relates to the technical field of hardened films, in particular to a hardened coating composition with high refractive index, high transparency and high wear resistance and a preparation method of a hardened film thereof.
Background
With the progress of electronic technology, transparent hardening films have been widely applied to various fields such as smart phones, computer liquid crystal screens, vehicle-mounted touch screens, industrial touch screens, household appliance control screens and the like, and the core effect of the transparent hardening films is to provide a scratch-resistant protective layer on the surface and prevent the screen or the panel from being damaged in the normal use process to influence the user experience. With the continuous improvement of user experience, the requirement for the hardened film is higher and higher. The hardening film is usually made of tempered glass. However, glass has poor flexibility, cannot be bent, has low production efficiency, and is a great obstacle in the production of electronic products. Therefore, an ultra-hard cured film using a thin film as a base material is urgently needed in the market.
The light-cured resin is a common adhesive material, and can be polymerized when being exposed to light, and a hardened film prepared by the light-cured resin can be used in the fields of surface coating of wooden products or stone products, screen protective films of electronic products and the like, wherein the aliphatic polyurethane acrylic resin has excellent mechanical property combination property, so that the aliphatic polyurethane acrylic resin is particularly suitable for the application fields with higher requirements on elasticity, flexibility, wear resistance and chemical corrosion resistance. Zirconia, also known as zirconium dioxide and zirconic anhydride, is a white solid which is insoluble in water and soluble in hot acid solution, has the physical properties of high melting point and high flash point, and compared with oxides of the same family elements, the zirconium dioxide has the advantages of high strength, stable property and easily available preparation raw materials. The nano material is a material which is at least one dimension of nano size in a three-dimensional space or is formed by taking the nano size as a basic unit, has a surface effect, a small-scale effect, a quantum size effect and a macroscopic quantum tunneling effect, is a nano material with good properties, and is also applied to the fields of chemical reaction catalysis, 3D printing and the like in recent years. Meanwhile, the zirconium dioxide has the excellent optical property of no photocatalysis, so that the nano zirconium dioxide particles have very wide application prospect in the photoelectric field, especially in the aspect of packaging of light-emitting elements. The nanometer zirconium dioxide is doped into the resin to be used as a screen coating or an LED (light-emitting diode) packaging agent, so that the refractive index of the material can be improved, the light loss is greatly reduced, and the aims of saving energy, protecting environment and effectively utilizing resources are fulfilled. However, the nano zirconium dioxide produced by the common preparation process has the defects of easy agglomeration and difficult dispersion in organic dispersoids, and if the nano zirconium dioxide is directly added into resin materials, small particles are easy to agglomerate into large particles, but the light transmittance of the composite material is reduced. Patent CN106277049B describes a method for preparing small-particle-size aqueous nano-zirconia dispersion, and patent CN201810836953.x describes surface modification of zirconia particles dispersed in an aqueous environment with hydrogen peroxide, but the photocurable resin is insoluble in water, and thus it is difficult to form a uniformly dispersed transparent nanocomposite with hydrophilic nano-zirconia. In order to solve the problem, a commonly adopted method is to modify the surface of the nano zirconium dioxide particles by utilizing the hydrophilicity and the hydrophobicity of certain special groups. Therefore, the key point of the technical field is that firstly, an organic zirconium dioxide dispersion which has small particle size and high dispersity and can be stably stored for a long time in an environment is required to be prepared, then the dispersion is uniformly mixed with the packaging adhesive, and the dispersion and the high refractive index of zirconium oxide are not changed after the dispersion is mixed, and the transparent property and the property of photocuring of the packaging adhesive are not changed.
Patent CN109971413A describes that zirconium dioxide is surface-modified by using phosphoric acid-based organic acid modifier, and the modified zirconium dioxide is dispersed in organic solvent such as toluene, chloroform, etc., and this method has simple process and easily available raw materials, but phosphoric acid-based modifier has high stability and is difficult to remove excessive modifier. In patent CN201580047465.5, a silane coupling agent and 1, 2-hydroxystearic acid are used to modify the surface of zirconium dioxide, and the zirconium dioxide is dispersed in an organic solvent except methanol or ethanol, but the particle size distribution of the modified nanoparticles is 1-20 nm, the particle size is not uniform, and if a composite material is prepared by using the modified nanoparticles, the problem of non-uniform distribution is easily caused, which affects the strength and light transmittance of the composite material.
According to the invention, an organic acid surface modifier such as acrylic acid and methacrylic acid is used as a modifier for first-step modification, hydroxyl on the surface of zirconia reacts with carboxyl in organic acid, a hydrophobic long chain is grafted on the surface of zirconia, then a silane coupling agent is used as a modifier for second-step modification, the silane coupling agent has siloxy, alkoxy is hydrolyzed to generate silicon hydroxyl, and then dehydration is carried out to generate oligosiloxane, the silicon hydroxyl can be adsorbed to the surface of a base material through hydrogen bond action and is condensed with hydroxyl on the surface of an inorganic material in the heating and curing process to form covalent bond connection, organic groups in the coupling agent can form bonds with macromolecules in the organic base material, so that the interface of the organic and inorganic material is coupled, the performance of the composite material is improved, the bonding strength is increased, and the composite material with excellent performance is obtained.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a preparation method of a high-dispersity organic phase nano zirconium oxide particle dispersion. According to the preparation method, firstly, a hydrothermal method and the like are utilized to prepare the nano-zirconia, and then the surface of the zirconia is connected with hydrophobic groups through a double modification method of olefine acid, olefine acid ester and a silane coupling agent, so that the nano-zirconia is dispersed in an organic solvent, and the organic-phase nano-zirconia particle dispersoid with good dispersibility is obtained. The particle size of the zirconium oxide particles prepared by the method is approximately distributed between 3 and 5 nanometers.
The second technical problem to be solved by the invention is to provide a high-dispersity organic phase nano zirconium oxide particle dispersion. According to the principle of similar compatibility, the zirconia nanoparticles with the long chain grafted on the surface can be dispersed in organic solvents with similar polarity. The surface modified zirconia nano-particles prepared by the experiment can form transparent dispersoid after being subjected to ultrasonic treatment or long-time oscillation in an organic solvent, and the solid content can reach 40 wt%.
The third technical problem to be solved by the invention is to provide an application description of the organic phase nano zirconium oxide particle dispersion with high dispersity. The composite material with the excellent performance of the organic and inorganic materials is obtained by compounding the zirconia nano particles with the photocuring resin, has stable property, high hardness, strong wear resistance, good water resistance and corrosion resistance and high refractive index, and can be applied to the fields of protection of electronic products and electronic components or coating of furniture and artware and the like.
In order to solve the first technical problem, the invention adopts a technical scheme that a preparation method of a high-dispersity organic phase nano zirconium oxide particle dispersion is provided, and the preparation method comprises the following steps:
step 1): dissolving appropriate amount of zirconium salt and excessive alkali in water for hydrothermal reaction, wherein the alkali amount is 3-5 times of zirconium salt amount, and the mass of added water is not less than the total mass of solids. Obtaining alkaline zirconium dioxide slurry after the reaction is completed, and washing the alkaline zirconium dioxide slurry to reduce the alkalinity;
step 2): mixing the slurry obtained in the step 1), water and an organic acid surface modifier, wherein the mass ratio of the slurry to the organic acid is controlled within the range of 2: 1-5, adding water with the total mass not less than the total mass of solids, placing the mixture in a stirring reactor, and heating and stirring the mixture for a proper time to perform a surface modification reaction;
step 3): centrifugally separating the mixture obtained in the step 2), washing and precipitating for 1-2 times, and drying the precipitate for later use;
step 4): dispersing the dried powder obtained in the step 3) in an organic solvent, adding a proper amount of silane coupling agent, stirring and reacting, and obtaining the high-dispersity organic phase nano zirconium oxide particle dispersoid after complete reaction;
step 5): and (3) dissolving a proper amount of light-cured resin in the high-dispersity organic phase nano zirconium oxide particle dispersoid, and removing the solvent after the photocuring resin is completely dissolved to obtain the final product, namely the high-fracture wear-resistant hardened film material.
Preferably, the zirconium salt in step 1) is selected from a mixture of one or more of the following: zirconium hydrogen phosphate, zirconium stearate, basic zirconium acetate, basic zirconium carbonate, zirconium sulfate, zirconyl sulfate, zirconium nitrate, zirconium oxychloride, potassium zirconium fluoride, ammonium zirconium fluoride, and sodium zirconium silicate.
Preferably, the organic acid surface modifier in step 2) is selected from a mixture of one or more of the following: acrylic acid, acrylic ester, methacrylic acid, methyl methacrylate, butyl methacrylate, trimethylolpropane trimethacrylate, ethacrylic acid ester, n-hexyl acrylate, 2-chloropropionate, 2-naphthyl acrylate, pentafluorophenyl acrylate, trifluoromethyl acrylate and ethylene glycol diacrylate; more preferably, one or more of acrylic acid, acrylate, methacrylic acid, methyl methacrylate and butyl methacrylate are selected.
Preferably, the silane coupling agent in step 4) is selected from one or a mixture of more of the following: one or more of gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, N-BETA- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, triethoxysilane and gamma-aminopropyltriethoxysilane.
Preferably, the organic solvent in step 4) is selected from a mixture of one or more of the following: benzene, toluene, phenol, aniline, diethyl ether, petroleum ether, furan phenol, furanone, tetrahydrofuran, benzofuran, dichloromethane, trichloromethane, carbon tetrachloride, methyl acetate, ethyl acetate, phenyl acetate, methyl benzoate, butyl acetate.
Preferably, the stirred reactors in step 2) and step 4) are used for fully mixing the substances participating in the chemical reaction, and a gas flow stirred reactor, a jet flow stirred reactor, a static pipeline stirred reactor, an electromagnetic stirred reactor and the like can be selected. The reaction speed can be selected to be 50-700 rpm, more preferably 100 rpm and 300 rpm, and most preferably 200 rpm; the reaction time may be selected from 2 hours to 72 hours, more preferably, the reaction time is 12 hours to 48 hours, and most preferably, the reaction time is 24 hours.
Preferably, in step 5), the photocurable resin is selected from one or more of the following substances: unsaturated polyester, epoxy acrylate, polyurethane acrylate, polyester acrylate, polyether acrylate, pure acrylic resin, epoxy resin and organic silicon oligomer.
In order to solve the second technical problem, the invention adopts the following technical scheme: a high-dispersity organic phase nano-zirconia particle dispersoid comprises an organic phase medium and nano-zirconia particles, wherein the nano-zirconia particles are obtained by a preparation method of the high-dispersity organic phase nano-zirconia particle dispersoid; the solids content of the dispersion is from 0.01 to 50% by weight; the one-dimensional size of the nano zirconia particles is 4 nanometers; the liquid phase medium is one or more of benzene, toluene, phenol, aniline, diethyl ether, petroleum ether, furan phenol, furanone, tetrahydrofuran, benzofuran, dichloromethane, trichloromethane, carbon tetrachloride, methyl acetate, ethyl acetate, phenyl acetate, methyl benzoate and butyl acetate.
The third technical problem to be solved by the invention is to provide an application of the organic phase nano zirconium oxide particle dispersion with high dispersity. The high-dispersity organic phase nano zirconium oxide particle dispersoid has the characteristics of uniformity, stability, high transparency, easiness in storage, no deterioration after long-time storage and easiness in preparation of the dispersoid with high solid content, can be uniformly compounded with light-cured resin, can be applied to industrial large-scale production, and has high refractive index of zirconium oxide nano particles, so that the refractive index, hardness and wear resistance of the dispersion can be improved on the premise of not changing the high transparency of the resin after the zirconium oxide nano particles are added. The prepared composite film can have excellent performance in the fields of packaging of LED chips, surface coating of wooden products or stone products, manufacturing of screen protection films of electronic products and the like.
The invention has the beneficial effects that:
1. the nano zirconia particles subjected to twice surface modification prepared by the invention have the characteristics of high dispersibility, high stability, high solid content and the like in an organic phase. Compared with the existing method of dispersing the nano zirconia particles by using the aqueous phase, the method has the advantages that the obtained zirconia nano particles are smaller in particle size and uniform in distribution, the one-dimensional size is 4 nanometers, the application range of the nano zirconia is widened, and the nano zirconia can be used for preparing screen protective films of electronic products, coating wooden products or stone products, packaging electronic components and the like.
2. The dispersant of the transparent organic phase nano zirconium oxide liquid phase dispersion body obtained by the invention selects various organic matters or mixtures thereof, so that the dispersant has higher selectivity in preparation, has better adaptability to various organic solvents in the dispersion process, and can be better applied to industrial production.
3. After the modified zirconia nano-particles obtained by the invention are added into commercial photo-curing resin, the hardness, the water corrosion resistance, the acid and alkali corrosion resistance, the wear resistance, the impact resistance and the refractive index of the product are obviously improved.
4. The preparation method has the advantages of simple preparation process, easily controlled conditions, pure and good quality of the obtained product, wide and easily obtained raw materials, capability of realizing industrial amplification and potential of large-scale industrial production.
Drawings
FIG. 1 is a transmission electron microscope particle size statistical chart of modified nano zirconia particles in example 1;
FIG. 2 is a graph of the dynamic light scattering laser particle size of the modified nano zirconia particles of example 1;
FIG. 3 is a graph of the dynamic light scattering laser particle size of the modified nano zirconia particles of example 2;
FIG. 4 is a transmission electron microscope image of modified nano-zirconia particles in example 1;
FIG. 5 is a transmission electron microscope image of modified nano-zirconia particles in example 2;
FIG. 6 is a transmission electron microscope image of modified nano-zirconia particles in example 3;
FIG. 7 is a transmission electron microscope image of modified nano-zirconia particles in example 4;
FIG. 8 is a schematic representation of a modified nano zirconia dispersion of example 1;
FIG. 9 shows the refractive index of the urethane acrylic resin to which the modified nano zirconia of example 1 was added;
FIG. 10 shows the refractive index of the epoxy resin to which the modified nano zirconia of example 1 was added;
Detailed Description
The present invention will be further described with reference to the drawings and examples, but the present invention is not limited to the following examples or other similar examples.
Example 1
1) Weighing 10 g of basic zirconium carbonate and excessive alkali, dissolving the basic zirconium carbonate and the excessive alkali in water, carrying out hydrothermal reaction, filtering after the reaction is finished, and washing a filter cake until the pH value is about 10;
2) adding 2 ml of methyl acrylate and 20 ml of water into all filter cakes, putting the filter cakes into a bottle, stirring the mixture at 60 ℃ for reaction for 12 hours, filtering the mixture after the reaction is finished, and washing the filter cakes twice;
3) drying the filter cake for 10 hours at 70 ℃ to obtain zirconia powder;
4) adding the powder into tetrahydrofuran to prepare a dispersion with the solid content of 10 wt%, adding 10 microliter of N-BETA- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane, adding magnetons at the bottom of a bottle, placing the bottle on a magnetic stirrer, and stirring and reacting for 4 hours at the speed of 100 revolutions per minute to obtain the high-dispersity organic phase nano zirconium oxide particle dispersion. Wherein the particle size of the nano particles under an electron microscope is 3-8 nanometers. Dynamic light scattering laser particle size analysis the average particle size of the nanoparticles was 5.72 nm.
5) Mixing the transparent organic phase nano zirconia particle dispersion with a pure glue material, wherein the weight of the modified nano zirconia accounts for 20 wt% of the total solid weight (the part does not contain solvent), spin-coating the mixture to form a glue film, measuring the refractive index of the glue film to obtain a refractive index curve, obtaining that the refractive index of the glue film is 1.61 at 600 nanometers, and keeping the transmittance at 98 wt%. The hardness test of the thick film prepared by the film pushing method by using a pencil hardness tester shows that the hardness is 2H. The adhesion was tested by the hundred grid test method by cutting through the thick film, resulting in 1/100.
Example 2
1) Weighing 10 g of basic zirconium carbonate and excessive alkali, dissolving the basic zirconium carbonate and the excessive alkali in water, carrying out hydrothermal reaction, filtering after the reaction is finished, and washing a filter cake until the pH value is about 10;
2) adding 2 ml of methyl methacrylate and 30 ml of water into all filter cakes, putting the filter cakes into a bottle, stirring the mixture at the temperature of 60 ℃ for reaction for 24 hours, filtering the mixture after the reaction is finished, and washing the filter cakes twice;
3) drying the filter cake for 10 hours at 70 ℃ to obtain zirconia powder;
4) adding the powder into tetrahydrofuran to prepare a dispersion with the solid content of 10 wt%, adding 10 microliter of gamma-aminopropyl triethoxysilane, adding magnetons at the bottom of a bottle, placing the bottle on a magnetic stirrer, and stirring and reacting at the speed of 100 revolutions per minute for 1 hour to obtain the high-dispersion organic phase nano zirconium oxide particle dispersion. Wherein the particle size of the nano particles under an electron microscope is 2-9 nanometers. Dynamic light scattering laser particle size analysis the average particle size of the nanoparticles was 4.36 nm.
5) Mixing the transparent organic phase nano zirconia particle dispersion with a pure glue material, wherein the weight of the modified nano zirconia accounts for 20 wt% of the total solid weight (the part does not contain solvent), spin-coating the mixture to form a glue film, measuring the refractive index of the glue film to obtain a refractive index curve, obtaining that the refractive index of the glue film is 1.63 at 600 nanometers, and keeping the transmittance at 97 wt%. The hardness test of the thick film prepared by the film pushing method by using a pencil hardness tester shows that the result is H. The adhesion was tested by the hundred grid test method by cutting through the thick film, resulting in 0/100.
Example 3
1) Weighing 20 g of zirconium oxychloride hydrate and excessive alkali, dissolving in water, carrying out hydrothermal reaction, filtering after the reaction is finished, and washing a filter cake until the pH value is about 8;
2) adding 1 ml of methacrylic acid and 40 ml of water into all filter cakes, putting the filter cakes into a bottle, stirring the mixture at 70 ℃ for reaction for 4 hours, filtering the mixture after the reaction is finished, and washing the filter cakes twice;
3) drying the filter cake for 8 hours at the temperature of 80 ℃ to obtain zirconia powder;
4) adding the powder into toluene to prepare a dispersion with the solid content of 10 wt%, adding 10 microliter of N-BETA- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane, adding magnetons at the bottom of a bottle, placing the bottle on a magnetic stirrer, and stirring and reacting for 4 hours at the speed of 120 revolutions per minute to obtain the high-dispersity organic phase nano zirconium oxide particle dispersion. Wherein the particle size of the nano particles under an electron microscope is 2-5 nanometers. Dynamic light scattering laser particle size analysis the average particle size of the nanoparticles was 3.16 nm.
5) Mixing the transparent organic phase nano zirconia particle dispersoid with a pure glue material, wherein the weight of the modified nano zirconia accounts for 30 wt% of the total solid weight (the part does not contain solvent), spin-coating the mixture to form a glue film, measuring the refractive index of the glue film to obtain a refractive index curve, obtaining the refractive index of the glue film to be 1.63 at 600 nanometers, and keeping the transmittance to be 98 wt%. The hardness test of the thick film prepared by the film pushing method by using a pencil hardness tester shows that the hardness is 2H. The adhesion was tested by the hundred grid test method by cutting through the thick film, resulting in 2/100.
Example 4
1) Weighing 10 g of zirconium hydrogen phosphate and excessive alkali, dissolving in water for hydrothermal reaction, filtering after the reaction is finished, and washing a filter cake until the pH value is about 9;
2) adding 3 ml of butyl methacrylate and 20 ml of water into all filter cakes, putting the filter cakes into a bottle, stirring the mixture at 80 ℃ for reaction for 48 hours, filtering the mixture after the reaction is finished, and washing the filter cakes twice;
3) drying the filter cake for 10 hours at 70 ℃ to obtain zirconia powder;
4) adding the powder into trichloromethane to prepare a dispersion with the solid content of 10 wt%, adding 10 microliter of gamma-methacryloxypropyl trimethoxy silane, adding magnetons at the bottom of a bottle, placing the bottle on a magnetic stirrer, and stirring and reacting at the speed of 500 revolutions per minute for 2 hours to obtain the high-dispersity organic phase nano zirconium oxide particle dispersion. Wherein the particle size of the nano particles under an electron microscope is 3-6 nanometers. Dynamic light scattering laser particle size analysis the average particle size of the nanoparticles was 4.28 nm.
5) Mixing the transparent organic phase nano zirconia particle dispersion with a pure glue material, wherein the weight of the modified nano zirconia accounts for 50 wt% of the total solid weight (the part does not contain solvent), spin-coating the mixture to form a glue film, measuring the refractive index of the glue film to obtain a refractive index curve, obtaining that the refractive index of the glue film is 1.64 at 600 nanometers, and keeping the transmittance at 97 wt%. The hardness test of the thick film prepared by the film pushing method by using a pencil hardness tester shows that the thickness is 3H. The adhesion was tested by the hundred grid test method by cutting through the thick film, resulting in 0/100.
Example 5
1) Weighing 10 g of basic zirconium carbonate and excessive alkali, dissolving the basic zirconium carbonate and the excessive alkali in water, carrying out hydrothermal reaction, filtering after the reaction is finished, and washing a filter cake until the pH value is about 10;
2) adding 1 ml of acrylate and 40 ml of water into all filter cakes, putting the filter cakes into a bottle, stirring the mixture at 60 ℃ for reaction for 48 hours, filtering the mixture after the reaction is finished, and washing the filter cakes twice;
3) drying the filter cake for 10 hours at 70 ℃ to obtain zirconia powder;
4) adding the powder into tetrahydrofuran to prepare a dispersion with the solid content of 10 wt%, adding 10 microliters of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, adding magnetons at the bottom of a bottle, placing the bottle on a magnetic stirrer, and stirring and reacting at the speed of 50 revolutions per minute for 48 hours to obtain the product high-dispersity organic phase nano zirconium oxide particle dispersion. Wherein the particle size of the nano particles under an electron microscope is 2-7 nanometers. Dynamic light scattering laser particle size analysis the average particle size of the nanoparticles was 3.67 nm.
5) Mixing the transparent organic phase nano zirconia particle dispersion with a pure glue material, wherein the weight of the modified nano zirconia accounts for 50 wt% of the total solid weight (the part does not contain solvent), spin-coating the mixture to form a glue film, measuring the refractive index of the glue film to obtain a refractive index curve, obtaining that the refractive index of the glue film is 1.66 at 600 nanometers, and keeping the transmittance at 96 wt%. The hardness test of the thick film prepared by the film pushing method by using a pencil hardness tester shows that the hardness is 2H. The adhesion was tested by the hundred grid test method by cutting through the thick film, resulting in 1/100.
Claims (10)
1. A preparation method of a high-dispersity organic phase nano zirconium oxide particle dispersoid is characterized by comprising the following steps of: the preparation method comprises the following steps:
step 1): dissolving a proper amount of zirconium salt and excessive alkali in water for hydrothermal reaction, wherein the alkali amount is 3-5 times of the zirconium salt amount, and the mass of the added water is not less than the total mass of the solid; obtaining alkaline zirconium dioxide slurry after the reaction is completed, and washing the alkaline zirconium dioxide slurry to reduce the alkalinity;
step 2): mixing the slurry obtained in the step 1), water and an organic acid surface modifier, wherein the mass ratio of the slurry to the organic acid is controlled within the range of 2: 1-5, adding water with the total mass not less than the total mass of solids, placing the mixture in a stirring reactor, and heating and stirring the mixture for a proper time to perform a surface modification reaction;
step 3): centrifugally separating the mixture obtained in the step 2), washing and precipitating for 1-2 times, and drying the precipitate for later use;
step 4): dispersing the dried powder obtained in the step 3) in an organic solvent, adding a proper amount of silane coupling agent, stirring and reacting, and obtaining the high-dispersity organic phase nano zirconium oxide particle dispersoid after complete reaction;
step 5): and (3) dissolving a proper amount of light-cured resin in the high-dispersity organic phase nano zirconium oxide particle dispersoid, and removing the solvent after the photocuring resin is completely dissolved to obtain the final product, namely the high-fracture wear-resistant hardened film material.
2. The method for preparing the organic phase nano zirconium oxide particle dispersion with high dispersity, according to claim 1, is characterized in that: the zirconium salt in step 1) is selected from one or a mixture of more of the following: zirconium hydrogen phosphate, zirconium stearate, basic zirconium acetate, basic zirconium carbonate, zirconium sulfate, zirconyl sulfate, zirconium nitrate, zirconium oxychloride, potassium zirconium fluoride, ammonium zirconium fluoride, and sodium zirconium silicate.
3. The method for preparing the organic phase nano zirconium oxide particle dispersion with high dispersity, according to claim 1, is characterized in that: the organic acid surface modifier in the step 2) is selected from one or a mixture of more of the following substances: acrylic acid, acrylic ester, methacrylic acid, methyl methacrylate, butyl methacrylate, trimethylolpropane trimethacrylate, ethacrylic acid ester, n-hexyl acrylate, 2-chloropropionate, 2-naphthyl acrylate, pentafluorophenyl acrylate, trifluoromethyl acrylate and ethylene glycol diacrylate; more preferably, one or more of acrylic acid, acrylate, methacrylic acid, methyl methacrylate and butyl methacrylate are selected.
4. The method for preparing the organic phase nano zirconium oxide particle dispersion with high dispersity, according to claim 1, is characterized in that: the silane coupling agent in the step 4) is selected from one or more of the following substances: one or more of gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, N-BETA- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, triethoxysilane and gamma-aminopropyltriethoxysilane.
5. The method for preparing the organic phase nano zirconium oxide particle dispersion with high dispersity, according to claim 1, is characterized in that: the organic solvent in the step 4) is selected from one or more of the following mixtures: benzene, toluene, phenol, aniline, diethyl ether, petroleum ether, furan phenol, furanone, tetrahydrofuran, benzofuran, dichloromethane, trichloromethane, carbon tetrachloride, methyl acetate, ethyl acetate, phenyl acetate, methyl benzoate, butyl acetate.
6. The method for preparing the organic phase nano zirconium oxide particle dispersion with high dispersity, according to claim 1, is characterized in that: the stirring reactors in the steps 2) and 4) are used for fully mixing substances participating in chemical reaction, and an airflow stirring reactor, a jet stirring reactor, a static pipeline stirring reactor, an electromagnetic stirring reactor and the like are selected; the reaction speed can be selected to be 50-700 rpm, more preferably 100 rpm and 300 rpm, and most preferably 200 rpm; the reaction time may be selected from 2 hours to 72 hours.
7. The method for preparing the organic phase nano zirconium oxide particle dispersion with high dispersity, according to claim 1, is characterized in that: in the step 5), the light-cured resin is selected from one or more of the following substances: unsaturated polyester, epoxy acrylate, polyurethane acrylate, polyester acrylate, polyether acrylate, pure acrylic resin, epoxy resin and organic silicon oligomer.
8. A high-dispersity organic phase nano zirconium oxide particle dispersoid is characterized in that: the organic phase medium and the nano zirconia particles are included, and the nano zirconia particles are obtained by the preparation method of the organic phase nano zirconia particle dispersoid with high dispersity; the solids content of the dispersion is from 0.01 to 50% by weight; the liquid phase medium is one or more of benzene, toluene, phenol, aniline, diethyl ether, petroleum ether, furan phenol, furanone, tetrahydrofuran, benzofuran, dichloromethane, trichloromethane, carbon tetrachloride, methyl acetate, ethyl acetate, phenyl acetate, methyl benzoate and butyl acetate.
9. The organic phase nano zirconia particle dispersion with high dispersity according to claim 8, wherein: the high-dispersity organic phase nano zirconium oxide particle dispersoid has the advantages of uniformity, stability, high transparency, uniform composition with light-cured resin and high refractive index of zirconium oxide nano particles contained in the dispersoid.
10. The organic phase nano zirconia particle dispersion with high dispersity according to claim 8, wherein: the particle size of the zirconium oxide particles prepared by the method is approximately distributed between 3 and 5 nanometers.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111744747A (en) * | 2020-07-06 | 2020-10-09 | 深圳市中暨复合材料有限公司 | Manufacturing method of novel high-hardness micro-ceramic metal coating plate |
| CN113773691A (en) * | 2021-09-13 | 2021-12-10 | 山东国瓷功能材料股份有限公司 | Nano zirconium oxide dispersion liquid, preparation method thereof, monomer dispersion liquid and optical film |
| CN113912792A (en) * | 2021-11-08 | 2022-01-11 | 东莞市光志光电有限公司 | Preparation method and application of high-refractive-index nano-zirconia composite resin |
| CN114230864A (en) * | 2021-12-14 | 2022-03-25 | 南京大学 | Modified zirconia nanoparticle alcohol dispersion system, preparation method and application thereof, and ultraviolet-curable resin material |
| CN114773879A (en) * | 2022-02-24 | 2022-07-22 | 山东国瓷功能材料股份有限公司 | Nano zirconium oxide dispersion liquid, preparation method thereof, modified zirconium oxide powder and application |
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| CN115044250A (en) * | 2022-06-15 | 2022-09-13 | 深圳市华星光电半导体显示技术有限公司 | Zirconium dioxide monomer dispersion liquid, preparation method thereof and high-refraction ink |
| CN115894795A (en) * | 2023-01-05 | 2023-04-04 | 璞璘科技(杭州)有限公司 | Preparation method and application of zirconium-containing nano organosol |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108529674A (en) * | 2018-07-01 | 2018-09-14 | 北京化工大学 | A kind of preparation method of high dispersion nanometer oxide zirconium particle and its transparent dispersion |
-
2019
- 2019-11-20 CN CN201911152104.3A patent/CN110713746A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108529674A (en) * | 2018-07-01 | 2018-09-14 | 北京化工大学 | A kind of preparation method of high dispersion nanometer oxide zirconium particle and its transparent dispersion |
Non-Patent Citations (2)
| Title |
|---|
| 国家食品药品监督管理总局执业药师资格认证中心: "《中药学专业知识（一）》", 31 January 2017, 中国医药科技出版社 * |
| 杨成德: "《涂料开发与试验》", 28 February 2015, 科学技术文献出版社 * |
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