CN102343698B - Hard film and preparation method thereof - Google Patents
Hard film and preparation method thereof Download PDFInfo
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- CN102343698B CN102343698B CN201010240299.XA CN201010240299A CN102343698B CN 102343698 B CN102343698 B CN 102343698B CN 201010240299 A CN201010240299 A CN 201010240299A CN 102343698 B CN102343698 B CN 102343698B
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Abstract
The invention provides a hard film which comprises a transparent substrate and a coating formed on the transparent substrate; the coating comprises a transparent resin adhesive, spherical nanoparticles with an average particle diameter of 100-800 nanometers, and asymmetric hat-shaped nanoparticles; in the coating, on a basis of 100 parts by mass of transparent resin adhesive, the contents of the spherical nanoparticles and the asymmetric hat-shaped nanoparticles are 1-30 parts by mass. The invention also provides a preparation method of the hard film. In the hard film provided by the invention, not only the spherical nanoparticles in the coating has good effect of improving coating hardness, but also the asymmetric hat-shaped nanoparticles have both the effect of improving coating hardness and the effect of extinction for polarized light incident from a certain angle; by adjusting the angle of the incident light, the peep-proof effect is realized, and the film exhibits unique physical optical performance.
Description
Technical field
The invention belongs to field of optical films, particularly relate to a kind of ganoine thin film and preparation method thereof.
Background technology
Display panels itself can't be luminous, and its brightness derives from backlight module, but is not that display panels does not affect the brightness of liquid crystal display and definition; Contrary, in order to reach better Image texture effect, liquid crystal display is in the process assembled, sell and use, and purity requirements is very high, and any dirty and cut can not appear in surface.Countermeasure main at present pastes layer protecting film on display panels surface, but the case hardness of diaphragm is not high at present, and generally between 2H-4H, hardness is few at the diaphragm of more than 4H, and this just makes the effect of diaphragm and function have a greatly reduced quality.
In addition, the brightness of backlight module and the angle of emergent light, directly have influence on brightness and the visual angle of liquid crystal display, flourish along with LCD TV and mobile phone industry, people propose harsh requirement to vision: on the one hand, in large-screen liquid crystal display television field, people require higher brightness, color contrast and wide in range angular field of view, so researcher always improves brightness and the angular field of view of display screen by every means, to meet the requirement of client, solution the most economic and easy is at present in backlight module, arrange various optical thin film, the utilization rate of effective raising light source, on the other hand, in mobile phone display screen field, people not only pursue wide in range angular field of view, and also require the information security that can ensure mobile phone in public places, this just brings a difficult problem to designer, and mobile phone peep-proof has become stubborn problem.But up to the present, mobile phone peep-proof does not all have a kind of simple and effective way.
Summary of the invention
The present invention be solve diaphragm hardness in prior art not high, cannot the technical problem of peep-proof, provide a kind of hardness higher, can the ganoine thin film and preparation method thereof of peep-proof.
The present invention is achieved through the following technical solutions:
A kind of ganoine thin film, this ganoine thin film comprises transparent substrate and is formed at the coating on transparent substrate, the nano spherical particle that described coating comprises adhesive transparent resin, average particulate diameter is 100-800 nanometer and asymmetrical hat nano particle, in described coating, with adhesive transparent resin 100 mass parts for benchmark, the content of nano spherical particle and asymmetrical hat nano particle is 1-30 mass parts.
The present invention also provides a kind of preparation method of ganoine thin film, and the method comprises the following steps:
A, prepare nano spherical particle template, the average particulate diameter of described nano spherical particle is 100-800 nanometer;
B, the nano spherical particle template obtained in A is fixed in coating machine, take metal as evaporation source, plated film is carried out to described nano spherical particle template, prepare asymmetrical hat nano particle;
C, the template after plated film is put into the container filling anhydrous organic solvent soak, nano spherical particle and the non-hat nano particle to symmetry is made to come off and peel off, then evaporate, obtain the mixed-powder of nano spherical particle and asymmetrical hat nano particle;
D, with adhesive transparent resin 100 mass parts for benchmark, the mixed-powder content of nano spherical particle and asymmetrical hat nano particle is 1-30 mass parts, the mixed-powder of nano spherical particle and asymmetrical hat nano particle and adhesive transparent resin are mixed to get coating, by coating formation on a surface of transparent substrate.
In ganoine thin film provided by the invention, nano spherical particle not only in described coating can play the effect well improving coating hardness, and described asymmetrical hat nano particle had both been improved the effect of coating hardness, had again the effect of the polarised light of a certain angle incidence being carried out to delustring.Learn by experiment, the hardness on described ganoine thin film surface up to more than 5H, can show excellent case hardness characteristic; Can carry out delustring to polarised light incident within 0-60 angle again, the angle of adjustment emergent light, reaches the effect of peep-proof, shows unique physical optics performance simultaneously.
Accompanying drawing explanation
Fig. 1 is ganoine thin film schematic side view provided by the invention.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Please refer to shown in Fig. 1, a kind of ganoine thin film, the coating that this ganoine thin film comprises transparent substrate 11 and is formed on transparent substrate, the nano spherical particle 13 that described coating comprises adhesive transparent resin 12, average particulate diameter is 100-800 nanometer and asymmetrical hat nano particle 14, in described coating, with adhesive transparent resin 100 mass parts for benchmark, the content of nano spherical particle and asymmetrical hat nano particle is 1-30 mass parts.If the content of nano spherical particle and asymmetrical hat nano particle is more than 30 mass parts, then the light transmission of coating reduces, and is difficult to utilize sufficient light quantity; On the other hand, if the content of nano spherical particle and asymmetrical hat nano particle is less than 1 mass parts, can be difficult to obtain higher case hardness and good Extinction Characteristic.Preferably, the content of described nano spherical particle and asymmetrical hat nano particle is 1-10 mass parts.Concrete in the present invention, cannot treat different things as the same with the use of amount of adhesive transparent resin and nano spherical particle and asymmetrical hat nano particle, can change according to the asymmetrical material of hat nano particle and the thickness of coating.
Further, in order to improve hardness and the extinction effect of ganoine thin film, in described nano spherical particle and asymmetrical hat nano particle, the content of nano spherical particle is 40-60 mass parts, and the content of asymmetrical hat nano particle is 60-40 mass parts.
In ganoine thin film provided by the invention, nano spherical particle not only in described coating can play the effect well improving coating hardness, and described asymmetrical hat nano particle had both been improved the effect of coating hardness, have again and delustring is carried out to the polarised light of a certain angle incidence, the angle of adjustment emergent light, reach the effect of peep-proof, show unique physical optics performance.
Described transparent substrate 11 can be the various plastic substrates that this area routine uses, such as: can be at least one in PETG, polystyrene ester, polyether ester, Merlon and polymethyl methacrylate.
Described adhesive transparent resin 12 can be selected from least one in acrylic resin, vinyl acetate resin, epoxy resin, amine resin, allyl resin, Merlon, polystyrene, polymethacrylates, PETG and polyether ester.
Described nano spherical particle 13 is spherical organic granular or spherical inorganic particle, further, in order to improve the performance of described ganoine thin film, the organic granular of described nano spherical particle is preferably polymethacrylates particle, granules of polystyrene, polysiloxane particle, polyvinyl chloride, polyacrylic acid granules etc.; Preferably, described organic granular is granules of polystyrene, polyacrylic acid granules.The inorganic particle of described nano spherical particle is preferably silica dioxide granule, titanium dioxide granule, Zinc oxide particles, granules of stannic oxide etc.; Preferably, described inorganic particle is silica dioxide granule.
The average particulate diameter of described nano spherical particle is in 100-800 nanometer, but in order to make described ganoine thin film obtain better case hardness and Extinction Characteristic, the average particulate diameter of described nano spherical particle is 200-400 nanometer.
The material of described asymmetrical hat nano particle 14 is metal, on the sphere of nano spherical particle template, form asymmetrical hat nano particle by thermal evaporation, and asymmetrical hat nano particle can be realized depart from from the spherical face of nano spherical particle template under ul-trasonic irradiation.Usually, described asymmetrical hat nano particle can be formed by least one material in metal; Particularly, described metal is selected from least one in gold, silver, copper, aluminium, chromium, platinum, tin, tungsten, germanium, niobium, vanadium, zirconium, zinc, nickel, gadolinium, tantalum, titanium and iridium.
Coating of the present invention can be formed at the surface of transparent substrate by the mode of coating, the thickness of described coating changes according to nano spherical particle and the asymmetrical mixed-powder of hat nano particle and the use amount of adhesive transparent resin, is generally 1-20 micron; Preferably, the thickness of described coating is 5-10 micron.
Further, in order to reach Painting effect better, described coating comprises diluent and curing agent further, with adhesive transparent resin 100 mass parts for benchmark, the content of described nano spherical particle and asymmetrical hat nano particle is 1-10 mass parts, the content of diluent is 5-30 mass parts, and the content of curing agent is 5-40 mass parts.Described diluent can be at least one in MEK, acetone, methyl iso-butyl ketone (MIBK), acetylacetone,2,4-pentanedione, ethyl acetate, methyl acetate, isopropyl acetate, butyl acetate, methyl alcohol, ethanol, isopropyl alcohol, butanols, isobutanol, DAA, toluene, dimethylbenzene etc.; Further, MEK, methyl iso-butyl ketone (MIBK), acetylacetone,2,4-pentanedione, ethyl acetate is preferably.
The selection of curing agent has no particular limits, can be isocyanate ester compound, as at least one in xylylene diisocyanate, toluene phenylene diisocyanate, LDI, hexylene glycol vulcabond, methylcyclohexane diisocyanate etc.
The present invention also provides a kind of preparation method of ganoine thin film, and the method comprises the following steps:
A, prepare nano spherical particle template, the average particulate diameter of described nano spherical particle is 100-800 nanometer;
B, the nano spherical particle template obtained in A is fixed in coating machine, take metal as evaporation source, plated film is carried out to described nano spherical particle template, prepare asymmetrical hat nano particle;
C, the template after plated film is put into the container filling anhydrous organic solvent soak, nano spherical particle and the non-hat nano particle to symmetry is made to come off and peel off, then evaporate, obtain the mixed-powder of nano spherical particle and asymmetrical hat nano particle;
D, with adhesive transparent resin 100 mass parts for benchmark, the mixed-powder content of nano spherical particle and asymmetrical hat nano particle is 1-30 mass parts, the mixed-powder of nano spherical particle and asymmetrical hat nano particle and adhesive transparent resin are mixed to get coating, by coating formation on a surface of transparent substrate.
In order to be described method of the present invention further, as a kind of concrete embodiment, in described steps A, adopt the method for self assembly film forming to prepare nano spherical particle template, the method for described self assembly film forming comprises:
A described nano spherical particle is made colloid by (), and make described colloid spread film forming;
B one thin slice is placed on the bottom of the container that water is housed by (), and transfer in described container by the film that described colloid is formed;
C () discharges the water described container gradually from the bottom of described container, make described film be attached on the surface of described thin slice, then carry out drying.
In step (a), the method that described nano spherical particle makes colloid is comprised, nano spherical particle is added in anhydrous solvent, as absolute ethyl alcohol, methyl alcohol, propane diols, butanols etc., then ultrasonic disperse is carried out, thus described nano spherical particle is dispersed in described anhydrous solvent, and form colloid.The time of described ultrasonic disperse can be 15-60 minute, and the content of nano spherical particle described in described colloid is 5-15 % by weight.
Further, the method that described colloid spreads film forming is comprised, the colloid drops formed by described nano spherical particle is on the thin slice of surfacing, and then place 10-60 second, described colloid can form colloidal film on described thin slice.In the present invention, the thickness that described colloidal film is formed makes it can float on follow-up horizontal plane; Preferably, the thickness of described colloidal film is 0.1-0.8 micron.Also there is no particular limitation in this step for described thin slice, can be sheet glass, also can for the plastic tab be made of plastics.Preferably, before described thin slice carries out film forming, need to clean described thin slice, there is no particular limitation for the method for described cleaning, and the method for this area routine can be adopted to clean, such as, can be ultrasonic cleaning.
When adopting above-mentioned steps (a) to make described colloid spread film forming, in step (b), the method transferred to by the film that described colloid is formed in described container can comprise, the described thin slice being formed with colloidal film is on the surface equipped with in the container of water described in the immersion of certain inclination angle, under the surface tension of water and the hydrophobic effect of colloidal particle, colloidal film on described thin slice is transferred in the water in described container, and fully launches on the water surface.In this step, described inclination angle can be 15-75 degree; But can be evenly distributed on the described water surface after ensureing in the water that described colloidal film is transferred in described container further, described inclination angle is preferably 40-60 degree.
In the method that this step provides, before a described thin slice is placed on the bottom of the container that water is housed, preferably described thin slice is cleaned, thus improve the adhesiving effect of described nano spherical particle on described sheet surface, and the probalility of success of described spheroidal particle film forming on described sheet surface can be improved.Also there is no particular limitation in this step for described thin slice, can be sheet glass, also can for the plastic tab be made of plastics; Preferably, described thin slice is sheet glass, and the method for described sheet glass being carried out to cleaning treatment is well known to those skilled in the art, does not repeat them here.
In step (c), probalility of success on described thin slice is attached in order to improve described colloidal film further, and ensure that the colloidal film be attached on described thin slice is evenly distributed, therefore, be preferably from the speed of the bottom discharge of described container, make the decline 1-100 per minute of the water in described container millimeter, more preferably 5-20 millimeter.
Adopt the method for above-mentioned self assembly film forming, the nano spherical particle film that described thin slice is formed is the film formed by the nano spherical particle of individual layer, multilayer or Local Multilevel.Preferably, described particle membrane is individual layer, thus better can control the shape of the asymmetrical hat nano particle of follow-up making.
Certainly, except the method for above-mentioned self assembly film forming, those skilled in the art can also adopt other method well known in the art, such as mask method, electrostatic induction method, masterplate revulsion, sedimentation etc., and this is no longer going to repeat them.
According to preparation method provided by the invention, in stepb, there is no particular limitation to prepare the method for described asymmetrical hat nano particle, can adopt other methods such as thermal evaporation coating method, magnetron sputtering method, ion plating method.Preferably, the method preparing asymmetrical hat nano particle is thermal evaporation coating method.Particularly, described thermal evaporation coating method adopts with different thermal evaporation angles, at the hat nano particle that the sphere formation thickness of nano spherical particle template does not wait, this hat nano particle is thicker near the side cap layers of thermal evaporation sources, side cap layers back to thermal evaporation sources is thinner, namely forms so-called asymmetrical hat nano particle.Usually, under the prerequisite that other condition is all identical, thermal evaporation angle is larger, and thickness difference is larger, and the asymmetry of asymmetric hat nano particle is also larger.Particularly, described thermal evaporation sources and nano spherical particle template in the vertical direction angulation are 30-80 degree, those skilled in the art according to different delustring needs, can select different thermal evaporation angles, to prepare different asymmetrical hat nano particles.Particularly, the implementation method of described thermal evaporation coating method and condition, for those skilled in the art know, do not repeat them here.
According to preparation method provided by the invention, in step C, the nano spherical particle template after thermal evaporation plated film is put into the container filling anhydrous organic solvent and soaks, the time of immersion is 15-60 minute, is then placed in ultrasonic wave by whole container and shakes.It is wherein a kind of that described anhydrous organic solvent can be selected from absolute ethyl alcohol, methyl alcohol, propane diols, butanols, acetone, butanone, MEK etc.By soaking and shaking, on the one hand, nano spherical particle is departed from from nano spherical particle template; On the other hand, asymmetrical hat nano particle is made to be separated from nano spherical particle surface.The time of concussion is 0.5-1 hour, nano spherical particle template is taken out, evaporate, the mixed liquor of particle with evaporation of solvent after concussion.The temperature of evaporation is 40-60 degree, because asymmetrical hat nano particle (for metal) is unique, fusing point is lower, if the too high nano particle of evaporating temperature will melt, as easy as rolling off a log oxidation, has a strong impact on its optical property.After solvent volatilization, obtain the mixed-powder of nano spherical particle and asymmetrical hat nano particle.
Further, after step c, also comprise drying is carried out to the mixed-powder of described nano spherical particle and asymmetrical hat nano particle.Particularly, its mixed-powder can be put into vacuum drying chamber dry, dry condition is: temperature 40-65 degree, vacuum 0.1-10 handkerchief.
In step D, described coating formation in the method on transparent substrate surface, can by coating mode realize, the mode of described coating comprises scraper plate, cutter is scraped, roller coat, spraying, rod be coated with, curtain coating; Certainly, those skilled in the art can also adopt other method known, other methods such as such as intaglio plate coating, steel wire blade coating, slit spraying.The thickness of described coating changes according to nano spherical particle and the asymmetrical mixed-powder of hat nano particle and the use amount of adhesive transparent resin, is generally 1-20 micron; Preferably, the thickness of described coating is 5-10 micron.
Further, in order to improve hardness and the extinction effect of ganoine thin film, in the mixed-powder of described nano spherical particle and asymmetrical hat nano particle, the content of nano spherical particle is 40-60 mass parts, and the content of asymmetrical hat nano particle is 60-40 mass parts.
Further, in order to reach Painting effect better, described coating comprises diluent and curing agent further, with adhesive transparent resin 100 mass parts for benchmark, the mixed-powder content of described nano spherical particle and asymmetrical hat nano particle is 1-10 mass parts, the content of diluent is 5-30 mass parts, and the content of curing agent is 5-40 mass parts.Described diluent can be at least one in MEK, acetone, methyl iso-butyl ketone (MIBK), acetylacetone,2,4-pentanedione, ethyl acetate, methyl acetate, isopropyl acetate, butyl acetate, methyl alcohol, ethanol, isopropyl alcohol, butanols, isobutanol, DAA, toluene, dimethylbenzene etc.; Further, MEK, methyl iso-butyl ketone (MIBK), acetylacetone,2,4-pentanedione, ethyl acetate is preferably.
The selection of curing agent has no particular limits, can be isocyanate ester compound, as at least one in xylylene diisocyanate, toluene phenylene diisocyanate, LDI, hexylene glycol vulcabond, methylcyclohexane diisocyanate etc.
Below, will in conjunction with specific embodiments the preparation method of ganoine thin film of the present invention be described in detail.
Embodiment 1:
A, prepare nano spherical particle template:
A, glass plate cut into the substrate of two pieces 80 millimeters × 80 millimeters, ultrasonic cleaning, then at temperature 100 degree dry 30 minutes;
B, fill pure water with the beakers of 500 milliliters (bottom is provided with sluice gate), then the one piece of glass substrate cut in step a is immersed the bottom of beaker;
C, be that the spherical silica particle (uniform particle sizes degree is within 5%) of 300 nanometers is added in absolute ethyl alcohol by average particulate diameter, then ultrasonic disperse 30 minutes in ultrasonic cleaner, thus make colloid, wherein the content of silica is 10 % by weight;
D, by colloid drops obtained in step c on another block glass substrate after process in step a, after static 10 seconds, described colloid spreads film forming on a glass substrate;
E, the glass flake being covered with colloidal film in steps d slowly to be immersed in the water in described beaker with 45 jiaos, the colloidal film on described glass substrate is transferred in water, and on the water surface, forms uniform film;
F, open the gate of described beaker bottom, water is released with the speed of decline per minute 5 millimeters by the water surface in described beaker, makes the film on the water surface be attached to described glass substrate surface;
G, the glass substrate that will be attached with film take out dry, thus on the surface of described glass substrate, form the individual layer rete formed by spherical silica particle that thickness is 0.1 micron, i.e. nano spherical particle template.
B, prepare asymmetrical hat nano particle:
Be fixed in evaporation coating machine by the sheet material of the nano spherical particle template obtained in A, using argent as evaporation source material, evaporation source and nano spherical particle template have the angle of 45 degree in the vertical direction, are 6.0 × 10 in vacuum
-4handkerchief, temperature is under the condition of 30 degree, carries out coating film treatment to described nano spherical particle template, and thermal evaporation speed is 0.2 nm/sec, and the plated film time is 5 minutes, obtains asymmetrical hat nano particle.
C, prepare the mixed-powder of nano spherical particle and asymmetrical hat nano particle:
Nano spherical particle template after plated film is put into absolute ethyl alcohol, soak 30 minutes, 1 hour is shaken with ultrasonic echography, spheroidal particle is allowed to come off from nano spherical particle template, asymmetrical hat nano particle is got off from nano spherical particle sur-face peeling, again glass substrate is taken out, be the condition evaporate to dryness of 50 degree in temperature by the mixed liquor of nano particle, obtain the mixed-powder of nano spherical particle and asymmetrical hat nano particle, again mixed-powder is put into vacuum drying chamber dry, temperature 65 degree, vacuum 0.1 handkerchief.
The preparation of D, ganoine thin film:
Prepare mixed-powder 10 mass parts of acrylic resin 100 mass parts, nano spherical particle and asymmetrical hat nano particle; In the mixed-powder of wherein said nano spherical particle and asymmetrical hat nano particle, the content of nano spherical particle is 50 mass parts, and the content of asymmetric hat nano particle is 50 mass parts.In above-mentioned material, first by acrylic resin with dispersator fully after, then add remaining material, stir with mixer, fully obtain coating fluid after mixing.
Thickness is used to be that the polyethylene terephthalate film of 38 microns is as substrate, by above-mentioned coating solution on a face of base material, carry out heated-air drying again, after dry, thickness is 1 micron, obtain ganoine thin film, in order to make the further sclerous reaction of sample, then thermostatic chamber sample being put into 40 degree is preserved 48 hours.
Embodiment 2:
A, prepare nano spherical particle template:
A, glass plate cut into the substrate of two pieces 80 millimeters × 80 millimeters, ultrasonic cleaning, then at temperature 100 degree dry 30 minutes;
B, fill pure water with the beakers of 500 milliliters (bottom is provided with sluice gate), then the one piece of glass substrate cut in step a is immersed the bottom of beaker;
C, be that the spherical silica particle (uniform particle sizes degree is within 5%) of 100 nanometers is added in absolute ethyl alcohol by average particulate diameter, then ultrasonic disperse 30 minutes in ultrasonic cleaner, thus make colloid, wherein the content of silica is 10 % by weight;
D, by colloid drops obtained in step c on another block glass substrate after process in step a, after static 10 seconds, described colloid spreads film forming on a glass substrate;
E, the glass flake being covered with colloidal film in steps d slowly to be immersed in the water in described beaker with 45 jiaos, the colloidal film on described glass substrate is transferred in water, and on the water surface, forms uniform film;
F, open the gate of described beaker bottom, water is released with the speed of decline per minute 5 millimeters by the water surface in described beaker, makes the film on the water surface be attached to described glass substrate surface;
G, the glass substrate that will be attached with film take out dry, thus on the surface of described glass substrate, form the individual layer rete formed by spherical silica particle that thickness is 0.1 micron, i.e. nano spherical particle template.
B, prepare asymmetrical hat nano particle:
Be fixed in evaporation coating machine by the sheet material of the nano spherical particle template obtained in A, using argent as evaporation source material, evaporation source and nano spherical particle template have the angle of 30 degree in the vertical direction, are 6.0 × 10 in vacuum
-4handkerchief, temperature is under the condition of 30 degree, carries out coating film treatment to described nano spherical particle template, and thermal evaporation speed is 0.2 nm/sec, and the plated film time is 5 minutes, obtains asymmetrical hat nano particle.
C, prepare the mixed-powder of nano spherical particle and asymmetrical hat nano particle:
Nano spherical particle template after plated film is put into absolute ethyl alcohol, soak 30 minutes, 1 hour is shaken with ultrasonic echography, spheroidal particle is allowed to come off from nano spherical particle template, asymmetrical hat nano particle is got off from nano spherical particle sur-face peeling, again glass substrate is taken out, be the condition evaporate to dryness of 40 degree in temperature by the mixed liquor of nano particle, obtain the mixed-powder of nano spherical particle and asymmetrical hat nano particle, again mixed-powder is put into vacuum drying chamber dry, temperature 65 degree, vacuum 0.1 handkerchief.
The preparation of D, ganoine thin film:
Prepare mixed-powder 1 mass parts, MEK 5 mass parts of acrylic resin 100 mass parts, isocyanates 5 mass parts, nano spherical particle and asymmetrical hat nano particle; In the mixed-powder of wherein said nano spherical particle and asymmetrical hat nano particle, the content of nano spherical particle is 50 mass parts, and the content of asymmetric hat nano particle is 50 mass parts.In above-mentioned material, first by acrylic resin and MEK with dispersator fully after, then add remaining material, stir with mixer, fully obtain coating fluid after mixing.
Thickness is used to be that the polyethylene terephthalate film of 38 microns is as substrate, by above-mentioned coating solution on a face of base material, carry out heated-air drying again, after dry, thickness is 1 micron, obtain ganoine thin film, in order to make the further sclerous reaction of sample, then thermostatic chamber sample being put into 40 degree is preserved 48 hours.
Embodiment 3:
A, prepare nano spherical particle template:
A, glass plate cut into the substrate of two pieces 80 millimeters × 80 millimeters, ultrasonic cleaning, then at temperature 100 degree dry 30 minutes;
B, fill pure water with the beakers of 500 milliliters (bottom is provided with sluice gate), then the one piece of glass substrate cut in step a is immersed the bottom of beaker;
C, be that the spherical silica particle (uniform particle sizes degree is within 5%) of 200 nanometers is added in absolute ethyl alcohol by average particulate diameter, then ultrasonic disperse 30 minutes in ultrasonic cleaner, thus make colloid, wherein the content of silica is 10 % by weight;
D, by colloid drops obtained in step c on another block glass substrate after process in step a, after static 30 seconds, described colloid spreads film forming on a glass substrate;
E, the glass flake being covered with colloidal film in steps d slowly to be immersed in the water in described beaker with 45 jiaos, the colloidal film on described glass substrate is transferred in water, and on the water surface, forms uniform film;
F, open the gate of described beaker bottom, water is released with the speed of decline per minute 5 millimeters by the water surface in described beaker, makes the film on the water surface be attached to described glass substrate surface;
G, the glass substrate that will be attached with film take out dry, thus on the surface of described glass substrate, form the individual layer rete formed by spherical silica particle that thickness is 0.2 micron, i.e. nano spherical particle template.
B, prepare asymmetrical hat nano particle:
Be fixed in evaporation coating machine by the sheet material of the nano spherical particle template obtained in A, using metallic gold as evaporation source material, evaporation source and nano spherical particle template have the angle of 45 degree in the vertical direction, are 6.0 × 10 in vacuum
-4handkerchief, temperature is under the condition of 30 degree, carries out coating film treatment to described nano spherical particle template, and thermal evaporation speed is 0.2 nm/sec, and the plated film time is 5 minutes, obtains asymmetrical hat nano particle.
C, prepare the mixed-powder of nano spherical particle and asymmetrical hat nano particle:
Nano spherical particle template after plated film is put into absolute ethyl alcohol, soak 30 minutes, 1 hour is shaken with ultrasonic echography, spheroidal particle is allowed to come off from nano spherical particle template, asymmetrical hat nano particle is got off from nano spherical particle sur-face peeling, again glass substrate is taken out, be the condition evaporate to dryness of 50 degree in temperature by the mixed liquor of nano particle, obtain the mixed-powder of nano spherical particle and asymmetrical hat nano particle, again mixed-powder is put into vacuum drying chamber dry, temperature 65 degree, vacuum 0.1 handkerchief.
The preparation of D, ganoine thin film:
Prepare mixed-powder 5 mass parts, MEK 15 mass parts of acrylic resin 100 mass parts, isocyanates 15 mass parts, nano spherical particle and asymmetrical hat nano particle; In the mixed-powder of wherein said nano spherical particle and asymmetrical hat nano particle, the content of nano spherical particle is 40 mass parts, and the content of asymmetric hat nano particle is 60 mass parts.In above-mentioned material, first by acrylic resin and MEK with dispersator fully after, then add remaining material, stir with mixer, fully obtain coating fluid after mixing.
Thickness is used to be that the polyethylene terephthalate film of 38 microns is as substrate, by above-mentioned coating solution on a face of base material, carry out heated-air drying again, after dry, thickness is 5 microns, obtain ganoine thin film, in order to make the further sclerous reaction of sample, then thermostatic chamber sample being put into 40 degree is preserved 48 hours.
Embodiment 4:
A, prepare nano spherical particle template:
A, glass plate cut into the substrate of two pieces 80 millimeters × 80 millimeters, ultrasonic cleaning, then at temperature 100 degree dry 30 minutes;
B, fill pure water with the beakers of 500 milliliters (bottom is provided with sluice gate), then the one piece of glass substrate cut in step a is immersed the bottom of beaker;
C, be that the spherical silica particle (uniform particle sizes degree is within 5%) of 400 nanometers is added in absolute ethyl alcohol by average particulate diameter, then ultrasonic disperse 45 minutes in ultrasonic cleaner, thus make colloid, wherein the content of silica is 10 % by weight;
D, by colloid drops obtained in step c on another block glass substrate after process in step a, after static 45 seconds, described colloid spreads film forming on a glass substrate;
E, the glass flake being covered with colloidal film in steps d slowly to be immersed in the water in described beaker with 45 jiaos, the colloidal film on described glass substrate is transferred in water, and on the water surface, forms uniform film;
F, open the gate of described beaker bottom, water is released with the speed of decline per minute 5 millimeters by the water surface in described beaker, makes the film on the water surface be attached to described glass substrate surface;
G, the glass substrate that will be attached with film take out dry, thus on the surface of described glass substrate, form the individual layer rete formed by spherical silica particle that thickness is 0.5 micron, i.e. nano spherical particle template.
B, prepare asymmetrical hat nano particle:
Be fixed in evaporation coating machine by the sheet material of the nano spherical particle template obtained in A, using metallic copper as evaporation source material, evaporation source and nano spherical particle template have the angle of 60 degree in the vertical direction, are 6.0 × 10 in vacuum
-4handkerchief, temperature is under the condition of 30 degree, carries out coating film treatment to described nano spherical particle template, and thermal evaporation speed is 0.2 nm/sec, and the plated film time is 5 minutes, obtains asymmetrical hat nano particle.
C, prepare the mixed-powder of nano spherical particle and asymmetrical hat nano particle:
Nano spherical particle template after plated film is put into absolute ethyl alcohol, soak 30 minutes, 1 hour is shaken with ultrasonic echography, spheroidal particle is allowed to come off from nano spherical particle template, asymmetrical hat nano particle is got off from nano spherical particle sur-face peeling, again glass substrate is taken out, be the condition evaporate to dryness of 50 degree in temperature by the mixed liquor of nano particle, obtain the mixed-powder of nano spherical particle and asymmetrical hat nano particle, again mixed-powder is put into vacuum drying chamber dry, temperature 65 degree, vacuum 3.0 × 10
-2mPa.
The preparation of D, ganoine thin film:
Prepare mixed-powder 8 mass parts, MEK 20 mass parts of acrylic resin 100 mass parts, isocyanates 30 mass parts, nano spherical particle and asymmetrical hat nano particle; In the mixed-powder of wherein said nano spherical particle and asymmetrical hat nano particle, the content of nano spherical particle is 60 mass parts, and the content of asymmetric hat nano particle is 40 mass parts.In above-mentioned material, first by acrylic resin and MEK with dispersator fully after, then add remaining material, stir with mixer, fully obtain coating fluid after mixing.
Thickness is used to be that the polyethylene terephthalate film of 38 microns is as substrate, by above-mentioned coating solution on a face of base material, carry out heated-air drying again, after dry, thickness is 5 microns, obtain ganoine thin film, in order to make the further sclerous reaction of sample, then thermostatic chamber sample being put into 40 degree is preserved 48 hours.
Embodiment 5:
A, prepare nano spherical particle template:
A, glass plate cut into the substrate of two pieces 80 millimeters × 80 millimeters, ultrasonic cleaning, then at temperature 100 degree dry 30 minutes;
B, fill pure water with the beakers of 500 milliliters (bottom is provided with sluice gate), then the one piece of glass substrate cut in step a is immersed the bottom of beaker;
C, be that the spherical silica particle (uniform particle sizes degree is within 5%) of 800 nanometers is added in absolute ethyl alcohol by average particulate diameter, then ultrasonic disperse 60 minutes in ultrasonic cleaner, thus make colloid, wherein the content of silica is 15 % by weight;
D, by colloid drops obtained in step c on another block glass substrate after process in step a, after static 60 seconds, described colloid spreads film forming on a glass substrate;
E, the glass flake being covered with colloidal film in steps d slowly to be immersed in the water in described beaker with 45 jiaos, the colloidal film on described glass substrate is transferred in water, and on the water surface, forms uniform film;
F, open the gate of described beaker bottom, water is released with the speed of decline per minute 5 millimeters by the water surface in described beaker, makes the film on the water surface be attached to described glass substrate surface;
G, the glass substrate that will be attached with film take out dry, thus on the surface of described glass substrate, form the individual layer rete formed by spherical silica particle that thickness is 0.8 micron, i.e. nano spherical particle template.
B, prepare asymmetrical hat nano particle:
Be fixed in evaporation coating machine by the sheet material of the nano spherical particle template obtained in A, using metallic aluminium as evaporation source material, evaporation source and nano spherical particle template have the angle of 80 degree in the vertical direction, are 6.0 × 10 in vacuum
-4handkerchief, temperature is under the condition of 30 degree, carries out coating film treatment to described nano spherical particle template, and thermal evaporation speed is 0.2 nm/sec, and the plated film time is 20 minutes, obtains asymmetrical hat nano particle.
C, prepare the mixed-powder of nano spherical particle and asymmetrical hat nano particle:
Nano spherical particle template after plated film is put into absolute ethyl alcohol, soak 30 minutes, 1 hour is shaken with ultrasonic echography, spheroidal particle is allowed to come off from nano spherical particle template, asymmetrical hat nano particle is got off from nano spherical particle sur-face peeling, again glass substrate is taken out, be the condition evaporate to dryness of 60 degree in temperature by the mixed liquor of nano particle, obtain the mixed-powder of nano spherical particle and asymmetrical hat nano particle, again mixed-powder is put into vacuum drying chamber dry, temperature 65 degree, vacuum 0.1 handkerchief.
The preparation of D, ganoine thin film:
Prepare mixed-powder 10 mass parts, MEK 30 mass parts of acrylic resin 100 mass parts, isocyanates 40 mass parts, nano spherical particle and asymmetrical hat nano particle; In the mixed-powder of wherein said nano spherical particle and asymmetrical hat nano particle, the content of nano spherical particle is 50 mass parts, and the content of asymmetric hat nano particle is 50 mass parts.In above-mentioned material, first by acrylic resin and MEK with dispersator fully after, then add remaining material, stir with mixer, fully obtain coating fluid after mixing.
Thickness is used to be that the polyethylene terephthalate film of 38 microns is as substrate, by above-mentioned coating solution on a face of base material, carry out heated-air drying again, after dry, thickness is 5 microns, obtain ganoine thin film, in order to make the further sclerous reaction of sample, then thermostatic chamber sample being put into 40 degree is preserved 48 hours.
In introduction according to previous embodiment 1-5 preparation method, those skilled in the art should know, and in aforementioned embodiment, choosing of certain material only lists wherein one, and object is for the ease of comparative illustration.Further, the materials such as adhesive transparent resin, diluent, curing agent, evaporation source, nano spherical particle and choosing of various parameter can also make some substituting or change, and can produce more embodiment thus, this is no longer going to repeat them.
Ganoine thin film performance evaluation:
1, the evaluation of case hardness:
Use the ganoine thin film case hardness of pencil hardness test machine to embodiment 1-4 to test, test loading is 500 grams, and rule against product with the angle of 45 degree, line speed is 2 mm/second, marking lengths 6 millimeters, and test result is as shown in table 1 below:
| Parameter type | Spheroidal particle | Asymmetric hat particle thermal evaporation angle | Adhesive transparent resin | Case hardness |
| Embodiment 1 | Silica | 45° | Acrylic resin | 5H |
| Embodiment 2 | Silica | 30° | Acrylic resin | 5H |
| Embodiment 3 | Silica | 45° | Acrylic resin | 5H |
| Embodiment 4 | Silica | 60° | Acrylic resin | 5H |
| Embodiment 5 | Silica | 80° | Acrylic resin | 5H |
Chart 1 shows, the ganoine thin film case hardness prepared by method provided by the invention is higher, reaches 5H, illustrates that ganoine thin film has very strong damage resistant ability; Meanwhile, the data in table 1 show that the case hardness of the thermal evaporation angle and coating preparing asymmetrical hat nano particle has nothing to do.
2, the evaluation of optical property:
FPDM-102 visual angel measuring device is adopted to measure the visual angle of display screen, measuring method is: point centered by display screen central luminescence pixel, with the brightness value of its normal direction for reference, be designated as BF, from the brightness of display screen left and right sides detection display screen, when both sides brightness value drops to BF/2, between two lines of observation, form horizontal view angle; Equally from the brightness of display screen upper and lower both sides detection display screen, when the brightness value of upper and lower both sides drops to BF/2, two lines of observation form vertical angle of view.The visual angle of the mobile phone display screen measured in this approach, its horizontal view angle is 150 °, and vertical angle of view is 150 °.On aforementioned display screen after the prepared ganoine thin film of laminating, the test result at its visual angle is as shown in table 2 below:
Chart 2 shows, the polarised light of the ganoine thin film prepared by method provided by the invention to a certain angle incidence has photoextinction, the angular range of its delustring is relevant with the thermal evaporation angle of the asymmetrical hat nano particle of preparation, hot steaming method angle is larger, the scope of delustring is larger, angular field of view is narrower, and the optical characteristics of this uniqueness has wide application space in fields such as mobile phone and display screen peep-proofs.Further, embodiment 3 is compared with embodiment 1, and its difference is only that the outward appearance of embodiment 3 is better than embodiment 1.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (15)
1. a ganoine thin film, it is characterized in that, this ganoine thin film comprises transparent substrate and is formed at the coating on transparent substrate, described coating comprises adhesive transparent resin, average particulate diameter is the nano spherical particle of 100-800 nanometer and asymmetrical hat nano particle, in described coating, with adhesive transparent resin 100 mass parts for benchmark, the content of described nano spherical particle and asymmetrical hat nano particle is 1-30 mass parts, wherein, in described nano spherical particle and asymmetrical hat nano particle, the content of nano spherical particle is 40-60 mass parts, the content of asymmetrical hat nano particle is 60-40 mass parts.
2. ganoine thin film according to claim 1, it is characterized in that, described adhesive transparent resin is selected from least one in acrylic resin, vinyl acetate resin, epoxy resin, amine resin, allyl resin, Merlon, polystyrene, polymethacrylates, PETG and polyether ester.
3. ganoine thin film according to claim 1, is characterized in that, described nano spherical particle is spherical organic granular or spherical inorganic particle.
4. ganoine thin film according to claim 3, is characterized in that, described spherical organic granular is selected from least one in polymethacrylates particle, granules of polystyrene, polysiloxane particle, polyvinyl chloride, polyacrylic acid granules.
5. ganoine thin film according to claim 3, is characterized in that, described spherical inorganic particle is selected from least one in silica dioxide granule, titanium dioxide granule, Zinc oxide particles, granules of stannic oxide.
6. ganoine thin film according to claim 1, is characterized in that, the average particulate diameter of described nano spherical particle is 200-400 nanometer.
7. ganoine thin film according to claim 1, is characterized in that, the material of described asymmetrical hat nano particle is metal.
8. ganoine thin film according to claim 7, is characterized in that, described metal is selected from least one in gold, silver, copper, aluminium, chromium, platinum, tin, tungsten, germanium, niobium, vanadium, zirconium, zinc, nickel, gadolinium, tantalum, titanium and iridium.
9. ganoine thin film according to claim 1, it is characterized in that, described coating comprises diluent and curing agent further, with adhesive transparent resin 100 mass parts for benchmark, the content of described nano spherical particle and asymmetrical hat nano particle is 1-10 mass parts, the content of diluent is 5-30 mass parts, and the content of curing agent is 5-40 mass parts.
10. a preparation method for ganoine thin film, is characterized in that, the method comprises the following steps:
A, prepare nano spherical particle template, the average particulate diameter of described nano spherical particle is 100-800 nanometer;
B, the nano spherical particle template obtained in A is fixed in coating machine, take metal as evaporation source, plated film is carried out to described nano spherical particle template, prepare asymmetrical hat nano particle;
C, the template after plated film is put into the container filling anhydrous organic solvent soak, nano spherical particle and the non-hat nano particle to symmetry is made to come off and peel off, then evaporate, obtain the mixed-powder of nano spherical particle and asymmetrical hat nano particle, in described mixed-powder, the content of nano spherical particle is 40-60 mass parts, and the content of asymmetrical hat nano particle is 60-40 mass parts;
D, with adhesive transparent resin 100 mass parts for benchmark, the mixed-powder content of nano spherical particle and asymmetrical hat nano particle is 1-30 mass parts, the mixed-powder of nano spherical particle and asymmetrical hat nano particle and adhesive transparent resin are mixed to get coating, by coating formation on a surface of transparent substrate.
The preparation method of 11. ganoine thin films according to claim 10, is characterized in that, in step, adopt the method for self assembly film forming to prepare nano spherical particle template, the method for described self assembly film forming comprises:
A described nano spherical particle is made colloid by (), and make described colloid spread film forming;
B one thin slice is placed on the bottom of the container that water is housed by (), and transfer in described container by the film that described colloid is formed;
C () discharges the water described container gradually from the bottom of described container, make described film be attached on the surface of described thin slice, then carry out drying.
The preparation method of 12. ganoine thin films according to claim 10, is characterized in that, in stepb, described thermal evaporation sources and nano spherical particle template in the vertical direction angulation are 30-80 degree.
The preparation method of 13. ganoine thin films according to claim 10, is characterized in that, in step C, the temperature of described evaporation is 40-60 degree.
The preparation method of 14. ganoine thin films according to claim 10, is characterized in that, after step C, comprises further and carries out drying to the mixed-powder of described nano spherical particle and asymmetrical hat nano particle.
The preparation method of 15. ganoine thin films according to claim 10, it is characterized in that, described coating comprises diluent and curing agent further, with adhesive transparent resin 100 mass parts for benchmark, the mixed-powder content of described nano spherical particle and asymmetrical hat nano particle is 1-10 mass parts, the content of diluent is 5-30 mass parts, and the content of curing agent is 5-40 mass parts.
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| US9349630B2 (en) | 2013-03-15 | 2016-05-24 | Applied Materials, Inc. | Methods and apparatus for electrostatic chuck repair and refurbishment |
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| CN101100000A (en) * | 2007-06-05 | 2008-01-09 | 暨南大学 | Core-shell structure composite nanometer material and preparation method thereof |
| CN101779146A (en) * | 2008-06-09 | 2010-07-14 | 索尼公司 | Blooming and manufacture method thereof, antiglare film, polaroid and display device with optical layers |
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| CN101779146A (en) * | 2008-06-09 | 2010-07-14 | 索尼公司 | Blooming and manufacture method thereof, antiglare film, polaroid and display device with optical layers |
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