CN113831569B - Nano anti-fingerprint anti-dazzle film and preparation process thereof - Google Patents
Nano anti-fingerprint anti-dazzle film and preparation process thereof Download PDFInfo
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses a nano anti-fingerprint anti-dazzle film and a preparation process thereof, wherein magnetic silica is selectively introduced, the magnetic silica is dispersed and improved through a dispersing agent to obtain a magnetic filler, the dispersing agent is Tween-20, the terminal hydroxyl of the Tween-20 can be bonded with the hydroxyl on the surface of the silica, and the dispersing performance of the magnetic silica is improved through hydrogen bond adsorption to obtain the magnetic filler with excellent dispersibility. The application discloses nanometer anti-fingerprint anti-dazzle membrane and preparation technology thereof, process design is reasonable, easy operation, and the anti-dazzle membrane that obtains of preparation not only has excellent anti-dazzle performance, and the surface is hydrophobic simultaneously, and antifouling anti-fingerprint performance is excellent, carries out directional arrangement through the magnetic filler that adopts different particle diameters, and the anti-dazzle membrane that obtains of preparation is excellent in wear resistance, and the practicality is higher.
Description
Technical Field
The invention relates to the technical field of anti-dazzle films, in particular to a nano anti-fingerprint anti-dazzle film and a preparation process thereof.
Background
An anti-glare film, abbreviated as an AG film, can reduce reflected light from a surface to be processed and reduce interference of light with vision. The whole film is in a foggy shape, but the transmittance is good, the viewing effect is not influenced, and the anti-dazzle film can be widely applied to the technical fields of mobile phone screen protection, electronic devices and the like.
In the prior art, a coating containing inorganic particles is generally selected to be coated on the surface of a transparent substrate, and the particles form a concave-convex structure on the surface of the coating to realize diffuse reflection, so that an anti-dazzle effect is realized; however, in actual practice, researchers found that the inorganic particles had poor dispersibility, and were not uniformly dispersed in the coating layer, and the unevenness on the substrate surface was also not uniformly distributed, and thus the antiglare effect was poor.
Aiming at the technical problem, a nano anti-fingerprint anti-dazzle film and a preparation process thereof are disclosed to solve the technical problem.
Disclosure of Invention
The invention aims to provide a nano anti-fingerprint anti-dazzle film and a preparation process thereof, which aim to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation process of a nano anti-fingerprint anti-dazzle film comprises the following steps:
(1) mixing and stirring magnetic silicon dioxide and a dispersing agent, transferring the mixture into a crusher to be crushed for 2-3min, baking the crushed mixture at the temperature of 140 ℃ and 150 ℃, washing the crushed mixture with absolute ethyl alcohol, and drying the washed mixture in vacuum to obtain a magnetic filler;
(2) taking ethyl orthosilicate, 1, 2-bis (triethoxysilyl) ethane and a fluoroalcohol solvent, adjusting the pH to 4-5 at 38-40 ℃, stirring, adding deionized water and perfluorooctyl triethoxysilane, reacting, distilling under reduced pressure to remove the solvent and residual water, and performing ultrasonic dispersion to obtain an anti-fingerprint agent;
(3) taking magnetic filler and butyl acetate, carrying out ultrasonic dispersion, adding urethane acrylate, dipentaerythritol pentaacrylate, polyperfluoropropylene oxide glycol, an anti-fingerprint agent, a photoinitiator and a leveling agent, and continuously stirring for 30-40min to obtain coating slurry;
(4) coating the surface of the base film with coating slurry, baking at 75-80 deg.C for 2-3min, and ultraviolet curing to obtain the final product.
The optimized scheme comprises the following steps:
(1) mixing and stirring magnetic silicon dioxide and a dispersing agent for 10-15min, transferring the mixture into a crusher for crushing for 2-3min, baking the crushed mixture for 2-2.5h at the temperature of 140-;
(2) taking ethyl orthosilicate, 1, 2-bis (triethoxysilyl) ethane and a fluoroalcohol solvent, regulating the pH to 4-5 with hydrochloric acid at 38-40 ℃, stirring for 10-15min, adding deionized water and perfluorooctyltriethoxysilane, reacting for 12-14h, carrying out reduced pressure distillation to remove the solvent and residual water, and carrying out ultrasonic dispersion to obtain the anti-fingerprint agent;
(3) taking magnetic filler and butyl acetate, carrying out ultrasonic dispersion for 10-20min, adding urethane acrylate, dipentaerythritol pentaacrylate, poly (perfluoropropylene oxide) glycol, an anti-fingerprint agent, a photoinitiator and a leveling agent, and continuously stirring for 30-40min at 50-60 ℃ to obtain coating slurry;
(4) coating the surface of the base film with coating slurry, baking at 75-80 deg.C for 2-3min, and ultraviolet curing to obtain the final product.
In the optimized scheme, in the step (1), the preparation steps of the magnetic silica are as follows:
a: mixing and stirring oleic acid, octadecylene and ferric oleate for 15-20min, heating to 310-320 ℃ in a nitrogen environment, keeping the temperature for reaction for 30-40min at the heating rate of 3 ℃/min, naturally cooling, precipitating with ethanol, and performing centrifugal separation to obtain ferroferric oxide nanocrystal;
b: mixing and stirring cetyl trimethyl ammonium bromide, urea and deionized water for 20-30min to obtain a material A;
mixing and stirring the ferroferric oxide nanocrystal and cyclohexane for dissolving, adding tetraethoxysilane and n-amyl alcohol, continuing stirring for 10-15min, adding the material A, stirring for 30-35min, reacting for 3.8-4h at the temperature of 120-560 ℃, washing, drying, and roasting for 5-6h at the temperature of 550-560 ℃ to obtain the magnetic silicon dioxide.
In the optimized scheme, in the step (4), the base film is placed in an external uniform magnetic field, the modified silicon dioxide is directionally arranged, and the arrangement direction is controlled to be parallel to the plane direction of the base film.
In the optimized scheme, in the step (4), the magnetic field intensity of the external uniform magnetic field is 5-8T.
According to a more optimized scheme, in the step (1), the mass ratio of the magnetic silica to the dispersing agent is 1: 10, the dispersant is Tween-20.
According to an optimized scheme, in the step (3), the photoinitiator is cyclohexyl phenyl ketone, the magnetic filler comprises a magnetic filler with the particle size of 15-20nm and a magnetic filler with the particle size of 30-40nm, and the mass ratio of the magnetic filler to the magnetic filler is 1: 1.
in an optimized scheme, in the step (4), the coating thickness of the coating slurry is 5-7 um.
According to an optimized scheme, in the step (3), the raw materials of the components comprise, by weight, 7-9% of a magnetic filler, 15-20% of polyurethane acrylate, 10-12% of dipentaerythritol pentaacrylate, 2-3% of polyperfluoropropylene oxide glycol, 3-5% of an anti-fingerprint agent, 1-1.2% of a photoinitiator, 1-2% of a leveling agent and the balance of butyl acetate.
According to an optimized scheme, the anti-dazzle film is prepared by the preparation process of the nano anti-fingerprint anti-dazzle film.
Compared with the prior art, the invention has the following beneficial effects:
the application discloses a nano anti-fingerprint anti-dazzle film and a preparation process thereof, wherein the anti-dazzle film has a unique light scattering effect and is widely applied to the fields of liquid crystal displays and electronics; in the prior art, a coating containing inorganic particles is generally selected to be coated on the surface of a transparent substrate, and the particles form a concave-convex structure on the surface of the coating to realize diffuse reflection, so that an anti-dazzle effect is realized; however, in actual practice, researchers found that the dispersion of inorganic particles was poor, the inorganic particles were not uniformly dispersed in the coating layer, and the unevenness of the substrate surface was also not uniformly distributed, and thus the antiglare effect was poor; therefore, in the technical problem, the magnetic silica is selectively introduced, the magnetic silica is dispersed and improved through the dispersing agent to obtain the magnetic filler, the dispersing agent is tween-20, the terminal hydroxyl of the tween-20 can be bonded with the hydroxyl on the surface of the silica, and the dispersing performance of the magnetic silica is improved through hydrogen bond adsorption, so that the magnetic filler with excellent dispersibility is obtained.
Adding a magnetic filler into the coating, selecting a PET (polyethylene terephthalate) material as a base material, coating the coating on the surface of the PET base material, wherein the integral operation is in a uniform magnetic field environment, the magnetic filler is magnetic, so that the surface of the PET base material can be directionally arranged under the action of a magnetic field, the arrangement direction is consistent with the plane direction of the PET base material, and the inorganic particles can be uniformly dispersed on the surface of the base material; in addition, the particles with the particle diameters of 15-20nm and 30-40nm of the magnetic filler are limited in the application, and after the particles are directionally arranged, the concave-convex distribution condition of the particles on the surface is relatively uniform, so that the overall anti-dazzle effect is more excellent.
According to the magnetic silica, hexadecyl trimethyl ammonium bromide, urea, ferroferric oxide nanocrystals and tetraethoxysilane are used as raw materials to be processed, the ferroferric oxide nanocrystals are added when mesoporous silica is synthesized, and are directly assembled into the mesoporous silica, in the prior art, the magnetic ferroferric oxide is generally loaded by using the silica as a carrier, but the technological parameter requirement of the scheme is high, the situations of ferroferric oxide falling off, low loading capacity and the like can also occur during actual use, and the scheme overcomes the defects, is introduced into a coating material, and has more excellent integral dispersion effect; meanwhile, the silicon dioxide and ferroferric oxide nanocrystals have excellent mechanical properties, and the magnetic fillers with different particle sizes are matched with each other, so that the wear resistance of the anti-dazzle film can be effectively improved.
Meanwhile, in order to improve the anti-fingerprint performance of the anti-dazzle film, the anti-fingerprint agent is prepared from tetraethoxysilane, 1, 2-bis (triethoxysilyl) ethane-fluoroalcohol solvent, perfluorooctyl triethoxysilane and other components, and during reaction, tetraethoxysilane and 1, 2-bis (triethoxysilyl) ethane are hydrolyzed and condensed to form silica sol, and perfluorooctyl triethoxysilane and polyperfluoropropylene glycol are introduced to reduce the surface energy of the anti-fingerprint agent; the component has excellent hydrophobic and oleophobic properties, can effectively improve the surface wear resistance of the coating, further improves the comprehensive properties of the anti-dazzle film, and has excellent anti-fingerprint properties.
The application discloses nanometer anti-fingerprint anti-dazzle membrane and preparation technology thereof, process design is reasonable, easy operation, and the anti-dazzle membrane that obtains of preparation not only has excellent anti-dazzle performance, and the surface is hydrophobic simultaneously, and antifouling anti-fingerprint performance is excellent, carries out directional arrangement through the magnetic filler that adopts different particle diameters, and the anti-dazzle membrane that obtains of preparation is excellent in wear resistance, and the practicality is higher.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the substrate was a PET film, and other factors were not added except for the change of parameters in each example, to compare the effects.
Example 1:
a preparation process of a nano anti-fingerprint anti-dazzle film comprises the following steps:
(1) the preparation steps of the magnetic silicon dioxide are as follows:
a: mixing and stirring oleic acid, octadecene and iron oleate for 15min, heating to 310 ℃ in a nitrogen environment, keeping the temperature for 40min at the heating rate of 3 ℃/min, naturally cooling, precipitating with ethanol, and performing centrifugal separation to obtain ferroferric oxide nanocrystal;
b: mixing and stirring cetyl trimethyl ammonium bromide, urea and deionized water for 20min to obtain a material A;
mixing and stirring ferroferric oxide nanocrystal and cyclohexane for dissolving, adding tetraethoxysilane and n-amyl alcohol, continuously stirring for 10min, adding the material A, stirring for 30min, reacting for 4h at 120 ℃, washing and drying, and roasting at 550 ℃ for 6h to obtain the magnetic silicon dioxide.
Taking magnetic silicon dioxide and a dispersing agent, wherein the mass ratio of the magnetic silicon dioxide to the dispersing agent is 1: 10, mixing and stirring a dispersing agent Tween-20 for 10min, transferring to a grinder to grind for 2min, baking at 140 ℃ for 2.5h after grinding, washing with absolute ethyl alcohol, and drying in vacuum to obtain a magnetic filler;
(2) taking ethyl orthosilicate, 1, 2-bis (triethoxysilyl) ethane and a fluoroalcohol solvent, regulating the pH to 4 with hydrochloric acid at 38 ℃, stirring for 10min, adding deionized water and perfluorooctyltriethoxysilane, reacting for 12h, carrying out reduced pressure distillation to remove the solvent and residual water, and carrying out ultrasonic dispersion to obtain the anti-fingerprint agent; wherein the mol ratio of the perfluorooctyl triethoxysilane to the tetraethoxysilane is 4: 10;
(3) taking magnetic filler and butyl acetate, carrying out ultrasonic dispersion for 10min, adding polyurethane acrylate, dipentaerythritol pentaacrylate, polyperfluoropropylene oxide glycol, an anti-fingerprint agent, a photoinitiator and a leveling agent, and continuously stirring for 40min at 50 ℃ to obtain coating slurry; the photoinitiator is cyclohexyl phenyl ketone. The magnetic filler comprises a magnetic filler with the particle size of 20nm and a magnetic filler with the particle size of 30nm, and the mass ratio of the magnetic filler to the magnetic filler is 1: 1.
(4) taking a base film, placing the base film in an external uniform magnetic field, wherein the magnetic field intensity is 8T, coating slurry on the surface, the coating thickness of the coating slurry is 6um, placing the base film at 75 ℃ for baking for 3min, and then carrying out ultraviolet curing, wherein the modified silicon dioxide is controlled to be directionally arranged in the whole process, and the arrangement direction is parallel to the plane direction of the base film, so that a finished product is obtained.
In step (3) of this embodiment, the raw materials of each component include, by weight, 7% of a magnetic filler, 15% of urethane acrylate, 10% of dipentaerythritol pentaacrylate, 2% of polyperfluoropropylene oxide glycol, 3% of an anti-fingerprint agent, 1% of a photoinitiator, 1% of a leveling agent, and the balance butyl acetate.
Example 2:
a preparation process of a nano anti-fingerprint anti-dazzle film comprises the following steps:
(1) the preparation steps of the magnetic silicon dioxide are as follows:
a: mixing and stirring oleic acid, octadecene and iron oleate for 18min, heating to 315 ℃ in a nitrogen environment, keeping the temperature for reaction for 35min, naturally cooling, precipitating with ethanol, and performing centrifugal separation to obtain ferroferric oxide nanocrystal;
b: mixing and stirring cetyl trimethyl ammonium bromide, urea and deionized water for 25min to obtain a material A;
mixing and stirring ferroferric oxide nanocrystal and cyclohexane for dissolving, adding tetraethoxysilane and n-amyl alcohol, continuously stirring for 12min, adding the material A, stirring for 32min, reacting for 4h at 122 ℃, washing and drying, and roasting at 555 ℃ for 5.5h to obtain the magnetic silicon dioxide.
Taking magnetic silicon dioxide and a dispersing agent, wherein the mass ratio of the magnetic silicon dioxide to the dispersing agent is 1: 10, mixing and stirring a dispersant Tween-20 for 14min, transferring to a pulverizer to pulverize for 2min, baking at 145 ℃ for 2.2h after pulverizing, washing with absolute ethyl alcohol, and drying in vacuum to obtain a magnetic filler;
(2) taking ethyl orthosilicate, 1, 2-bis (triethoxysilyl) ethane and a fluoroalcohol solvent, regulating the pH to 5 with hydrochloric acid at 38 ℃, stirring for 12min, adding deionized water and perfluorooctyltriethoxysilane, reacting for 13h, carrying out reduced pressure distillation to remove the solvent and residual water, and carrying out ultrasonic dispersion to obtain the anti-fingerprint agent; wherein the mol ratio of the perfluorooctyl triethoxysilane to the ethyl orthosilicate is 4: 10;
(3) taking magnetic filler and butyl acetate, carrying out ultrasonic dispersion for 15min, adding urethane acrylate, dipentaerythritol pentaacrylate, polyperfluoropropylene oxide glycol, an anti-fingerprint agent, a photoinitiator and a leveling agent, and continuously stirring for 35min at 55 ℃ to obtain coating slurry; the photoinitiator is cyclohexyl phenyl ketone. The magnetic filler comprises a magnetic filler with the particle size of 20nm and a magnetic filler with the particle size of 30nm, and the mass ratio of the magnetic filler to the magnetic filler is 1: 1.
(4) taking a base film, placing the base film in an external uniform magnetic field, wherein the magnetic field intensity is 8T, coating slurry on the surface, the coating thickness of the coating slurry is 6um, placing the base film at 78 ℃ for baking for 3min, and then carrying out ultraviolet curing, wherein the modified silicon dioxide is controlled to be directionally arranged in the whole process, and the arrangement direction is parallel to the plane direction of the base film, so that a finished product is obtained.
In step (3) of this embodiment, the raw materials of each component include, by weight, 8% of a magnetic filler, 18% of a polyurethane acrylate, 11% of dipentaerythritol pentaacrylate, 3% of polyperfluoropropylene oxide glycol, 4% of an anti-fingerprint agent, 1.2% of a photoinitiator, 1.5% of a leveling agent, and the balance butyl acetate.
Example 3:
a preparation process of a nano anti-fingerprint anti-dazzle film comprises the following steps:
(1) the preparation steps of the magnetic silicon dioxide are as follows:
a: mixing and stirring oleic acid, octadecene and iron oleate for 20min, heating to 320 ℃ in a nitrogen environment, keeping the temperature for reaction for 30min, naturally cooling, precipitating with ethanol, and performing centrifugal separation to obtain ferroferric oxide nanocrystal;
b: mixing and stirring cetyl trimethyl ammonium bromide, urea and deionized water for 30min to obtain a material A;
and (2) mixing and stirring the ferroferric oxide nanocrystal and cyclohexane for dissolving, adding tetraethoxysilane and n-amyl alcohol, continuously stirring for 15min, adding the material A, stirring for 35min, reacting for 3.8h at 125 ℃, washing, drying, and roasting for 5h at 560 ℃ to obtain the magnetic silicon dioxide.
Taking magnetic silicon dioxide and a dispersing agent, wherein the mass ratio of the magnetic silicon dioxide to the dispersing agent is 1: 10, mixing and stirring a dispersing agent Tween-20 for 15min, transferring to a grinder to grind for 3min, baking at 150 ℃ for 2h after grinding, washing with absolute ethyl alcohol, and drying in vacuum to obtain a magnetic filler;
(2) taking ethyl orthosilicate, 1, 2-bis (triethoxysilyl) ethane and a fluoroalcohol solvent, regulating the pH to 5 with hydrochloric acid at 40 ℃, stirring for 15min, adding deionized water and perfluorooctyltriethoxysilane, reacting for 14h, removing the solvent and residual water by reduced pressure distillation, and performing ultrasonic dispersion to obtain the anti-fingerprint agent; wherein the mol ratio of the perfluorooctyl triethoxysilane to the ethyl orthosilicate is 4: 10;
(3) taking magnetic filler and butyl acetate, carrying out ultrasonic dispersion for 20min, adding polyurethane acrylate, dipentaerythritol pentaacrylate, polyperfluoropropylene oxide glycol, an anti-fingerprint agent, a photoinitiator and a leveling agent, and continuously stirring for 30min at 60 ℃ to obtain coating slurry; the photoinitiator is cyclohexyl phenyl ketone. The magnetic filler comprises a magnetic filler with the particle size of 20nm and a magnetic filler with the particle size of 30nm, and the mass ratio of the magnetic filler to the magnetic filler is 1: 1.
(4) taking a base film, placing the base film in an external uniform magnetic field, wherein the magnetic field intensity is 8T, coating slurry on the surface, the coating thickness of the coating slurry is 6um, placing the base film at 80 ℃ for baking for 2min, and then carrying out ultraviolet curing, wherein the modified silicon dioxide is controlled to be directionally arranged in the whole process, and the arrangement direction is parallel to the plane direction of the base film, so that a finished product is obtained.
In step (3) of this embodiment, the raw materials of each component include, by weight, 9% of a magnetic filler, 20% of urethane acrylate, 12% of dipentaerythritol pentaacrylate, 3% of polyperfluoropropylene oxide glycol, 5% of an anti-fingerprint agent, 1.2% of a photoinitiator, 2% of a leveling agent, and the balance butyl acetate.
Comparative example 1:
a preparation process of a nano anti-fingerprint anti-dazzle film comprises the following steps:
(1) the preparation steps of the magnetic silicon dioxide are as follows:
a: mixing oleic acid, octadecene and ferric oleate, stirring for 18min, heating to 315 ℃ in a nitrogen environment at the heating rate of 3 ℃/min, keeping the temperature for reaction for 35min, naturally cooling, precipitating with ethanol, and centrifuging to obtain ferroferric oxide nanocrystal;
b: mixing and stirring cetyl trimethyl ammonium bromide, urea and deionized water for 25min to obtain a material A;
mixing and stirring ferroferric oxide nanocrystal and cyclohexane for dissolving, adding tetraethoxysilane and n-amyl alcohol, continuously stirring for 12min, adding the material A, stirring for 32min, reacting for 4h at 122 ℃, washing and drying, and roasting at 555 ℃ for 5.5h to obtain the magnetic silicon dioxide.
Taking magnetic silicon dioxide and a dispersing agent, wherein the mass ratio of the magnetic silicon dioxide to the dispersing agent is 1: 10, mixing and stirring a dispersant Tween-20 for 14min, transferring to a pulverizer to pulverize for 2min, baking at 145 ℃ for 2.2h after pulverizing, washing with absolute ethyl alcohol, and drying in vacuum to obtain a magnetic filler;
(2) taking ethyl orthosilicate, 1, 2-bis (triethoxysilyl) ethane and a fluoroalcohol solvent, regulating the pH to 5 with hydrochloric acid at 38 ℃, stirring for 12min, adding deionized water and perfluorooctyltriethoxysilane, reacting for 13h, carrying out reduced pressure distillation to remove the solvent and residual water, and carrying out ultrasonic dispersion to obtain the anti-fingerprint agent; wherein the mol ratio of the perfluorooctyl triethoxysilane to the tetraethoxysilane is 4: 10;
(3) taking magnetic filler and butyl acetate, carrying out ultrasonic dispersion for 15min, adding polyurethane acrylate, dipentaerythritol pentaacrylate, polyperfluoropropylene oxide glycol, an anti-fingerprint agent, a photoinitiator and a leveling agent, and continuously stirring for 35min at 55 ℃ to obtain coating slurry; the photoinitiator is cyclohexyl phenyl ketone. The magnetic filler comprises a magnetic filler with the particle size of 20nm and a magnetic filler with the particle size of 30nm, and the mass ratio of the magnetic filler to the magnetic filler is 1: 1.
(4) coating slurry on the surface of a base film, wherein the coating thickness of the coating slurry is 6 microns, baking the base film at 78 ℃ for 3min, and curing the base film by ultraviolet light to obtain a finished product.
In step (3) of this embodiment, the raw materials of each component include, by weight, 8% of a magnetic filler, 18% of a polyurethane acrylate, 11% of dipentaerythritol pentaacrylate, 3% of polyperfluoropropylene oxide glycol, 4% of an anti-fingerprint agent, 1.2% of a photoinitiator, 1.5% of a leveling agent, and the balance butyl acetate.
Comparative example 1 is a control of example 2, no external magnetic field was introduced in comparative example 1, and the remaining process parameters were identical to those of example 2.
Comparative example 2:
a preparation process of a nano anti-fingerprint anti-dazzle film comprises the following steps:
(1) the preparation steps of the magnetic silicon dioxide are as follows:
a: mixing and stirring oleic acid, octadecene and iron oleate for 18min, heating to 315 ℃ in a nitrogen environment, keeping the temperature for reaction for 35min, naturally cooling, precipitating with ethanol, and performing centrifugal separation to obtain ferroferric oxide nanocrystal;
b: mixing and stirring cetyl trimethyl ammonium bromide, urea and deionized water for 25min to obtain a material A;
and (2) mixing and stirring the ferroferric oxide nanocrystal and cyclohexane for dissolving, adding tetraethoxysilane and n-amyl alcohol, continuously stirring for 12min, adding the material A, stirring for 32min, reacting for 4h at 122 ℃, washing, drying, and roasting for 5.5h at 555 ℃ to obtain the magnetic silicon dioxide.
Taking magnetic silicon dioxide and a dispersing agent, wherein the mass ratio of the magnetic silicon dioxide to the dispersing agent is 1: 10, mixing and stirring a dispersant Tween-20 for 14min, transferring to a pulverizer to pulverize for 2min, baking at 145 ℃ for 2.2h after pulverizing, washing with absolute ethyl alcohol, and drying in vacuum to obtain a magnetic filler;
(2) taking ethyl orthosilicate, 1, 2-bis (triethoxysilyl) ethane and a fluoroalcohol solvent, regulating the pH to 5 with hydrochloric acid at 38 ℃, stirring for 12min, adding deionized water and perfluorooctyltriethoxysilane, reacting for 13h, carrying out reduced pressure distillation to remove the solvent and residual water, and carrying out ultrasonic dispersion to obtain the anti-fingerprint agent; wherein the mol ratio of the perfluorooctyl triethoxysilane to the ethyl orthosilicate is 4: 10;
(3) taking magnetic filler and butyl acetate, carrying out ultrasonic dispersion for 15min, adding polyurethane acrylate, dipentaerythritol pentaacrylate, polyperfluoropropylene oxide glycol, an anti-fingerprint agent, a photoinitiator and a leveling agent, and continuously stirring for 35min at 55 ℃ to obtain coating slurry; the photoinitiator is cyclohexyl phenyl ketone. The magnetic filler is a magnetic filler with the particle size of 30 nm.
(4) Taking a base film, placing the base film in an external uniform magnetic field with the magnetic field intensity of 8T, coating slurry on the surface, wherein the coating thickness of the coating slurry is 6 mu m, placing the base film at 78 ℃ for baking for 3min, and then carrying out ultraviolet curing, wherein the directional arrangement of the modified silicon dioxide is controlled in the whole process, and the arrangement direction is parallel to the plane direction of the base film, so that a finished product is obtained.
In step (3) of this embodiment, the raw materials of each component include, by weight, 8% of a magnetic filler, 18% of a polyurethane acrylate, 11% of dipentaerythritol pentaacrylate, 3% of polyperfluoropropylene oxide glycol, 4% of an anti-fingerprint agent, 1.2% of a photoinitiator, 1.5% of a leveling agent, and the balance butyl acetate.
Comparative example 2 is a control of example 2, the particle sizes of the magnetic fillers of comparative example 2 are all 30nm, and the rest of the process parameters are completely consistent with those of example 2.
Comparative example 3:
a preparation process of a nano anti-fingerprint anti-dazzle film comprises the following steps:
(1) the preparation steps of the magnetic silicon dioxide are as follows:
a: mixing and stirring oleic acid, octadecene and iron oleate for 18min, heating to 315 ℃ in a nitrogen environment, keeping the temperature for reaction for 35min, naturally cooling, precipitating with ethanol, and performing centrifugal separation to obtain ferroferric oxide nanocrystal;
b: mixing and stirring cetyl trimethyl ammonium bromide, urea and deionized water for 25min to obtain a material A;
and (2) mixing and stirring the ferroferric oxide nanocrystal and cyclohexane for dissolving, adding tetraethoxysilane and n-amyl alcohol, continuously stirring for 12min, adding the material A, stirring for 32min, reacting for 4h at 122 ℃, washing, drying, and roasting for 5.5h at 555 ℃ to obtain the magnetic silicon dioxide.
Taking magnetic silicon dioxide and a dispersing agent, wherein the mass ratio of the magnetic silicon dioxide to the dispersing agent is 1: 10, mixing and stirring a dispersant Tween-20 for 14min, transferring to a pulverizer to pulverize for 2min, baking at 145 ℃ for 2.2h after pulverizing, washing with absolute ethyl alcohol, and drying in vacuum to obtain a magnetic filler;
(2) taking magnetic filler and butyl acetate, carrying out ultrasonic dispersion for 15min, adding urethane acrylate, dipentaerythritol pentaacrylate, polyperfluoropropylene oxide glycol, a photoinitiator and a leveling agent, and continuously stirring for 35min at 55 ℃ to obtain coating slurry; the photoinitiator is cyclohexyl phenyl ketone. The magnetic filler comprises a magnetic filler with the particle size of 20nm and a magnetic filler with the particle size of 30nm, and the mass ratio of the magnetic filler to the magnetic filler is 1: 1.
(3) taking a base film, placing the base film in an external uniform magnetic field, wherein the magnetic field intensity is 8T, coating slurry on the surface, the coating thickness of the coating slurry is 6um, placing the base film at 78 ℃ for baking for 3min, and then carrying out ultraviolet curing, wherein the modified silicon dioxide is controlled to be directionally arranged in the whole process, and the arrangement direction is parallel to the plane direction of the base film, so that a finished product is obtained.
In step (3) of this embodiment, the raw materials of each component include, by weight, 8% of a magnetic filler, 18% of urethane acrylate, 11% of dipentaerythritol pentaacrylate, 3% of polyperfluoropropylene oxide glycol, 1.2% of a photoinitiator, 1.5% of a leveling agent, and the balance butyl acetate.
Comparative example 3 is a control of example 2, and comparative example 3 does not incorporate an anti-fingerprint agent, and the remaining process parameters are identical to those of example 2.
Detection experiment:
1. the samples prepared in examples 1 to 3 and comparative examples 1 to 3 were measured by an NDH-5000 light transmittance haze meter according to ASTM D1003, respectively, and the total light transmittance and haze value errors at 4 points at different positions of each sample were controlled to be within 5%, and the average value was determined.
2. Samples prepared in examples 1-3 and comparative examples 1-3 were taken, the hydrophobic and oleophobic properties of the coating were tested by using a JC-2000C1 type contact angle measuring instrument, ultrapure water/edible oil was used as a probe liquid, the dropping amount was 5. mu.L, and the average value was obtained by measuring 5 times at different positions of the sample.
3. The hardness of the coating film was measured by the GB/T6739-.
The samples prepared in examples 1-3 and comparative examples 1-3 were tested for adhesion rating according to GB/T1720-. The coating was scored 10X 10 small squares of 1mm X1 mm during the test. And (5) flattening the transparent adhesive tape on the grid. And (3) taking off the adhesive sticker at a right angle in the opposite direction, observing the falling condition of the coating and classifying according to the grades: grade 0 (no shedding), grade 1 (less than 5% shedding), grade 2 (5% -15% shedding).
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Total light transmittance% | 92.4 | 92.1 | 92.2 | 94.4 | 93.2 | 93.9 |
| Haze%) | 11.4 | 12.9 | 11.8 | 6.2 | 7.1 | 6.8 |
| Hardness of | 5H | 5H | 5H | 4H | 4H | 3H |
| Adhesion force | Level 1 | Level 1 | Level 1 | / | / | / |
| Hydrophobicity | 123.4° | 124.2° | 123.8° | / | / | / |
| Oil repellency | 102.3° | 104.1 | 103.5° | / | / | / |
And (4) conclusion: the application discloses nanometer anti-fingerprint anti-dazzle membrane and preparation technology thereof, process design is reasonable, easy operation, and the anti-dazzle membrane that obtains of preparation not only has excellent anti-dazzle performance, and the surface is hydrophobic simultaneously, and antifouling anti-fingerprint performance is excellent, carries out directional arrangement through the magnetic filler that adopts different particle diameters, and the anti-dazzle membrane that obtains of preparation is excellent in wear resistance, and the practicality is higher.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A preparation process of a nanometer anti-fingerprint anti-dazzle film is characterized by comprising the following steps: the method comprises the following steps:
(1) the preparation steps of the magnetic silicon dioxide are as follows:
a: mixing and stirring oleic acid, octadecylene and ferric oleate for 15-20min, heating to 310-320 ℃ in a nitrogen environment, keeping the temperature for reaction for 30-40min at the heating rate of 3 ℃/min, naturally cooling, precipitating with ethanol, and performing centrifugal separation to obtain ferroferric oxide nanocrystal;
b: mixing and stirring cetyl trimethyl ammonium bromide, urea and deionized water for 20-30min to obtain a material A;
mixing and stirring ferroferric oxide nanocrystal and cyclohexane for dissolving, adding tetraethoxysilane and n-amyl alcohol, continuing stirring for 10-15min, adding the material A, stirring for 30-35min, reacting at the temperature of 120-560 ℃, washing, drying, and roasting at the temperature of 550-560 ℃ for 5-6h to obtain magnetic silicon dioxide;
mixing and stirring magnetic silicon dioxide and a dispersing agent, transferring the mixture into a crusher to be crushed for 2-3min, baking the crushed mixture at the temperature of 140 ℃ and 150 ℃, washing the crushed mixture with absolute ethyl alcohol, and drying the washed mixture in vacuum to obtain a magnetic filler; the mass ratio of the magnetic silica to the dispersant is 1: 10, the dispersant is tween-20;
(2) taking ethyl orthosilicate, 1, 2-bis (triethoxysilyl) ethane and a fluoroalcohol solvent, adjusting the pH to 4-5 at 38-40 ℃, stirring, adding deionized water and perfluorooctyl triethoxysilane, reacting, distilling under reduced pressure to remove the solvent and residual water, and performing ultrasonic dispersion to obtain an anti-fingerprint agent;
(3) taking magnetic filler and butyl acetate, carrying out ultrasonic dispersion, adding urethane acrylate, dipentaerythritol pentaacrylate, polyperfluoropropylene oxide glycol, an anti-fingerprint agent, a photoinitiator and a leveling agent, and continuously stirring for 30-40min to obtain coating slurry;
(4) coating the surface of a base film with coating slurry, baking at 75-80 ℃ for 2-3min, and curing by ultraviolet light to obtain a finished product; in the step (4), the base film is placed in an external uniform magnetic field, the modified silicon dioxide is directionally arranged, and the arrangement direction is controlled to be parallel to the plane direction of the base film.
2. The preparation process of the nano anti-fingerprint anti-glare film according to claim 1, characterized in that: the method comprises the following steps:
(1) mixing and stirring magnetic silicon dioxide and a dispersing agent for 10-15min, transferring the mixture to a crusher for crushing for 2-3min, baking the crushed mixture for 2-2.5h at the temperature of 140 ℃ and 150 ℃, washing the crushed mixture with absolute ethyl alcohol, and drying the washed mixture in vacuum to obtain a magnetic filler;
(2) taking ethyl orthosilicate, 1, 2-bis (triethoxysilyl) ethane and a fluoroalcohol solvent, regulating the pH to 4-5 with hydrochloric acid at 38-40 ℃, stirring for 10-15min, adding deionized water and perfluorooctyltriethoxysilane, reacting for 12-14h, carrying out reduced pressure distillation to remove the solvent and residual water, and carrying out ultrasonic dispersion to obtain the anti-fingerprint agent;
(3) taking magnetic filler and butyl acetate, carrying out ultrasonic dispersion for 10-20min, adding urethane acrylate, dipentaerythritol pentaacrylate, poly (perfluoropropylene oxide) glycol, an anti-fingerprint agent, a photoinitiator and a leveling agent, and continuously stirring for 30-40min at 50-60 ℃ to obtain coating slurry; the photoinitiator is cyclohexyl phenyl ketone, the magnetic filler comprises a magnetic filler with the particle size of 15-20nm and a magnetic filler with the particle size of 30-40nm, and the mass ratio of the magnetic filler to the magnetic filler is 1: 1;
(4) coating the surface of the base film with coating slurry, baking at 75-80 deg.C for 2-3min, and ultraviolet curing to obtain the final product.
3. The preparation process of the nano anti-fingerprint anti-glare film according to claim 2, characterized in that: in the step (4), the intensity of the external uniform magnetic field is 5-8T.
4. The preparation process of the nano anti-fingerprint anti-glare film according to claim 2, characterized in that: in the step (4), the coating thickness of the coating slurry is 5-7 um.
5. The preparation process of the nano anti-fingerprint anti-glare film according to claim 2, characterized in that: in the step (3), the raw materials of the components comprise, by weight, 7-9% of a magnetic filler, 15-20% of polyurethane acrylate, 10-12% of dipentaerythritol pentaacrylate, 2-3% of polyperfluoropropylene oxide glycol, 3-5% of an anti-fingerprint agent, 1-1.2% of a photoinitiator, 1-2% of a leveling agent and the balance butyl acetate.
6. The anti-glare film prepared by the preparation process of the nano anti-fingerprint anti-glare film according to any one of claims 1 to 5.
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| CN101783217A (en) * | 2009-12-25 | 2010-07-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing silicon dioxide-coated magnetic microspheres |
| CN105907287A (en) * | 2016-05-16 | 2016-08-31 | 四川龙华光电薄膜股份有限公司 | Anti-ultraviolet anti-glare anti-fingerprint hardness-increasing coating liquid composition, coating and preparation method of coating |
| CN110511673A (en) * | 2019-09-27 | 2019-11-29 | 深圳市信濠光电科技股份有限公司 | A kind of anti-fingerprint masking liquid and preparation method thereof |
| CN111423880A (en) * | 2020-04-25 | 2020-07-17 | 华中科技大学 | Magnetic fluorescent mesoporous silica composite nano material and preparation method thereof |
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| JP5049542B2 (en) * | 2005-09-26 | 2012-10-17 | 富士フイルム株式会社 | Antireflection film, polarizing plate, and image display device using the same |
| KR101501682B1 (en) * | 2011-07-18 | 2015-03-11 | 주식회사 엘지화학 | Anti-Glare Coating Composition Having Improved Anti-Fingerprinting and Anti-Glare Coating Film Prepared Therefrom |
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| CN101783217A (en) * | 2009-12-25 | 2010-07-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing silicon dioxide-coated magnetic microspheres |
| CN105907287A (en) * | 2016-05-16 | 2016-08-31 | 四川龙华光电薄膜股份有限公司 | Anti-ultraviolet anti-glare anti-fingerprint hardness-increasing coating liquid composition, coating and preparation method of coating |
| CN110511673A (en) * | 2019-09-27 | 2019-11-29 | 深圳市信濠光电科技股份有限公司 | A kind of anti-fingerprint masking liquid and preparation method thereof |
| CN111423880A (en) * | 2020-04-25 | 2020-07-17 | 华中科技大学 | Magnetic fluorescent mesoporous silica composite nano material and preparation method thereof |
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