CN102816402B - A kind of highly-transparent ultraviolet-resistant imitates ceramic flexible nano composite film material and preparation method thereof - Google Patents
A kind of highly-transparent ultraviolet-resistant imitates ceramic flexible nano composite film material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of highly-transparent ultraviolet-resistant and imitate ceramic flexible nano composite film material and preparation method thereof, belong to field of nanocomposite materials.Composite film material forms: core-shell nanoparticles 20 ~ 85wt%, polymeric 15 ~ 80wt%.The present invention prepares composite film material by in-situ polymerization, comprises phase transition and the mass polymerization of nanoparticle in polymer monomer two steps of nanoparticle.By the method for solution phase transition, nanoparticle is transferred in polymer monomer by initial dispersion, then prepare highly-transparent ultraviolet-resistant by the method for thermal-initiated polymerization or uv-light polymerization and imitate ceramic flexible nano composite film material.Prepared by the present invention, nano composite membrane material transparent degree is high, has good thermostability and strong ultraviolet screening ability, and has certain snappiness, may be used for structure high transparency optics, uvioresistant device, special light regulation and control device etc.
Description
Technical field
The present invention relates to a kind of highly-transparent ultraviolet-resistant and imitate ceramic flexible nano composite film material and preparation method thereof, belong to polymer organic-inorganic nano-particle compounding technology synthesis composite membrane field.
Background technology
Being called as " invisible killer " ultraviolet is a kind of hertzian wave in fact, and the effect that appropriate ultraviolet radiation has a sterilization can also promote the synthesis of vitamins D, is conducive to the healthy of people.But excessive uviolizing can work the mischief to the skin of human body, eyes and immunity system etc.Since the twenties in last century, because the whole world uses freonll-11 and carbon fluorine range of solvents in a large number, caused the ozonosphere havoc in earth atmosphere, the radiation quantity that the ultraviolet in sunlight arrives ground increases.So there is the product intercepting ultraviolet function will have very large application prospect.
Polymer organic-inorganic nanometer particle compesite has caused people to study interest widely due to the performance of its uniqueness, its part overcomes the defect in single-material and conventional composite materials performance, material is made both to have had the advantage of inorganic materials (as rigidity, high thermal stability and special photoelectromagnetism performance etc.) there is again the advantage of polymer materials (as elasticity, dielectricity, ductility and workability etc.), so this nano composite material is often at optics, electricity, calorifics, mechanics, the aspects such as acoustics have unique performance, all there is very wide application prospect in a lot of fields.As the nanoparticle of functional stuffing owing to having peculiar activity and large surface energy, energy plays pendulum, reunion (especially nanoparticle content higher in) is very easily produced in polymer organic-inorganic nano composite material preparation process, destroy ultra-fine property and the dispersing uniformity of nanoparticle, cause the transparency of material and optical homogeneity property to reduce, badly influence the performance and application of matrix material.Meanwhile, when the content of nanoparticle is higher, the mechanical mechanics property of matrix material is deteriorated, and generally becomes more crisp, and snappiness is inadequate, can not meet the needs of actual use.And in many field of optical applications, need nano composite material to have and also there is high refractive index while high-clarity very much, strong luminescence, the characteristics such as high rigidity and good mechanical property, this just requires that functional nanoparticles content in the composite wants high dispersiveness simultaneously to get well, therefore in the polymer organic-inorganic nano composite material process of the high nanoparticle content of preparation, reduce as far as possible and avoid further reunion of nanoparticle to keep the optical property that material is good, the good snappiness of material is kept just to seem particularly important, also be one of difficult point in the middle of current Nano-composite materials technology.Chinese patent 200810203599.3 discloses a kind of transparent fluorescent film and preparation method thereof and purposes, and the transparent fluorescent film visible light transmissivity of its invention is 85%, and ZnS:Mn nanometer crystal powder body burden is not high, is only 0.01%-1%.Chinese patent 200410013860.5 discloses composition of a kind of Nanometer Transparent Wear-resisting Compound Coating and preparation method thereof, the average transmittances of its coating invented in visible-range is more than 80%, for the rate of ultraviolet shield of 200-400nm more than 50%, and the content of aluminium sesquioxide nano-powder is less than 20%.Chinese patent 200610080966.6 discloses a kind of transparent epoxy nano composite material and preparation method thereof and purposes, when the addition of Nano filling in matrix material is 0.1%, the transmitance at 500nm place is 86%, when increasing Nano filling consumption to 30%, the transmitance at 500nm place is down to 60%, transparency declines obviously, illustrates that Nano filling has reunion to a certain degree in the composite.
Summary of the invention
The object of the invention is to the shortcoming and defect overcoming prior art, a kind of high nanoparticle content, the composite film material simultaneously also keeping matrix material high transparent, good snappiness nanometer and good thermostability and preparation method thereof are provided.
A kind of highly-transparent ultraviolet-resistant provided by the present invention imitates ceramic flexible nano composite film material, and in mould material, each component and percentage composition thereof are: core-shell nanoparticles 20 ~ 85wt%, polymeric 15 ~ 80wt%.
Wherein, core-shell nanoparticles is the nucleocapsid structure of double shells, stratum nucleare comprises the one of zinc oxide, titanium oxide, silicon oxide, cerium oxide, Indium sesquioxide, stannic oxide, doping zinc-oxide, adulterated TiOx, doped indium oxide, doped stannum oxide, shell is made up of two-layer, and wherein inner shell is silicon dioxide layer, outer shell is Coated with Organic Matter layer containing carbon-carbon double bond.Described core-shell nanoparticles is selected from one or more than one mixture wherein.
The metal adulterated in described doping zinc-oxide is selected from one or more mixing in aluminium, calcium, gallium, cadmium, cerium, copper, iron, magnesium, tin, antimony, silver, titanium, and the mol ratio of doping metals and zinc in zinc oxide is 0.1-25: 100.
The metal adulterated in described adulterated TiOx is selected from one or more the mixture in zinc, tin, lanthanum, and in doping metals and titanium oxide, the mol ratio of titanium is 0.1-25: 100.
The metal adulterated in described doped indium oxide is selected from one or more the mixture in tin, antimony, titanium, tungsten, copper, iron, and in doping metals and Indium sesquioxide, the mol ratio of indium is 0.1-25: 100.
The metal adulterated in described doped stannum oxide is selected from one or more the mixture in indium, antimony, titanium, zinc, tungsten, fluorine, iron, silver, platinum, and in doping metals and stannic oxide, the mol ratio of tin is 0.1-25: 100.
The quantum size effect of zinc oxide nano-particle, makes it produce " blue-shifted phenomenon " and " broadening phenomenon " the absorption band of UV-light, causes it to ultraviolet absorption successful, have good ultraviolet screening ability.Cerium oxide, titanium oxide, adulterated TiOx, doping zinc-oxide, stannic oxide, doped stannum oxide, Indium sesquioxide, doped indium oxide nanoparticle and zinc oxide nano-particle are similar, all belong to metal oxide semiconductor particle, visible ray is not significantly absorbed, there is similar ultraviolet absorption effect.Meanwhile, also there is high index and good thermal stability, the performance that composite film material is new can be given.
The present invention adopts nuclear shell structured nano-particle, and shell is made up of two-layer, and wherein inner shell is silicon dioxide layer, outer shell is Coated with Organic Matter layer containing carbon-carbon double bond.Silicon-dioxide in inner shell is directly coated on nano-ZnO, TiO
2on the surface of nanoparticle, nanoparticle can be prevented around organic photocatalytic degradation.Accompanying drawing 1 is that the nucleocapsid structure ZnO of coated silica, ZnO nanoparticle are to the catalytic performance comparison diagram of organism rhodamine B.As can be seen from the figure, when using the nucleocapsid structure ZnO nanoparticle of coated silica, 180 minutes organic degradation rates are less than 90%, and that organism is degradable when not having a ZnO nanoparticle 20 minutes of coated silica.Therefore, use the ZnO nanoparticle of the nucleocapsid structure of coated with silica can significantly reduce ZnO to organic photocatalytic degradation capability, increase the anti-light aging performance of matrix material, improve its work-ing life.Outer shell is the Coated with Organic Matter layer containing carbon-carbon double bond, not only can improve the consistency between nanoparticle and polymer monomer, make nanoparticle can better redispersion in polymer monomer, nanoparticle can also be realized by the active group carbon-carbon double bond in Coated with Organic Matter layer to be connected with covalent linkage with polymeric, improve the reactive force between nanoparticle and matrix, reduce and avoid nanoparticle to reunite further.
Wherein, polymeric is polymerized by corresponding polymer monomer to obtain, and polymer monomer is the one or more than one mixture in (methyl) esters of acrylic acid, acryloxy organo-siloxane class, vinyl organosilicon alkanes or vinyl acetate.
Described (methyl) acrylic polymer monomer comprises C
2~ C
18(methyl) alkyl acrylate, (methyl) phenyl acrylate, (methyl) crylic acid hydroxy ester, ethers (methyl) acrylate or (methyl) acrylate cross linked monomer.
Described acryloxy organo-siloxane base polymer monomer comprises 3-methacryloxypropyl trimethoxy silane, 3-methacryloyloxypropyl methyl dimethoxysilane or 3-methacryloxypropyl;
Described vinyl organosilicon alkanes polymer monomer comprises vinyltrimethoxy silane, vinyltriethoxysilane or vinyl three ('beta '-methoxy oxyethyl group) silane.
Wherein, the thickness of film is 100nm ~ 10mm.
The preparation method that a kind of highly-transparent ultraviolet-resistant provided by the present invention imitates ceramic flexible nano composite film material is that phase transition-situ aggregation method prepares composite film material, specifically comprises the following steps:
1) phase transition of nanoparticle: by core-shell nanoparticles by initial dispersion, namely the dispersion in solvent orange 2 A, be precipitated by adding anti-solvent B, nano-powder is obtained after centrifugation, washing, vacuum-drying, through magnetic agitation, ultrasonic disperse nano-powder redispersion in polymer monomer, obtain nanoparticle monomer dispersion.Nanoparticle massfraction is in dispersions 20 ~ 85%.
2) mass polymerization of nanoparticle in polymer monomer: to 1) the nanoparticle monomer dispersion that obtains of step adopts thermal initiation radical polymerization, use thermal initiator, be polymerized 2 ~ 12 hours at 60 ~ 90 DEG C, then be polymerized 12 ~ 36 hours at 40 ~ 70 DEG C, finally thermal treatment 1 ~ 3 hour, 1 ~ 3 hour at 90 ~ 110 DEG C, 110 ~ 160 DEG C respectively;
Or, to 1) the nanoparticle monomer dispersion that obtains of step adopts UV-light to cause radical polymerization, and use ultraviolet initiator, the high voltage mercury lamp adopting 1 ~ 3KW is ultraviolet light source, and set time is 1 ~ 50 minute.Finally thermal treatment 1 ~ 3 hour, 1 ~ 3 hour at 90 ~ 110 DEG C, 110 ~ 160 DEG C respectively.
Above-mentioned a kind of highly-transparent ultraviolet-resistant imitates the phase transition part of the nanoparticle in ceramic flexible nano compound film material preparation method for material, and solvent orange 2 A is selected from the one in water, ethanol, Virahol, acetone, methyl ethyl ketone, ethyl acetate, butylacetate, benzene,toluene,xylene, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO).
Above-mentioned a kind of highly-transparent ultraviolet-resistant imitates the phase transition part of the nanoparticle in ceramic flexible nano compound film material preparation method for material, and solvent B is selected from water, isopropyl ether, methyl ethyl ether, diethyl ether, methyl alcohol, dimethyl sulfoxide (DMSO), dimethyl formamide, chloroform, tetracol phenixin, C
4~ C
8alkanes, one in benzene,toluene,xylene.
Above-mentioned thermal initiator is Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN), azo-bis-iso-dimethyl (AIBME), dibenzoyl peroxide (BPO), N, accelerine (DMA), azo-bis-isobutyrate hydrochloride (V-50) or Potassium Persulphate (KPS), the consumption of thermal initiator is 0.05 ~ 1.0% of whole reaction system gross weight.
Ultraviolet initiator is benzoin dimethylether (light trigger 651), 1-hydroxycyclohexyl phenyl ketone (light trigger 184) or 2-hydroxy-2-methyl Propiophenone (light trigger 1173), and ultraviolet initiator consumption is 0.5 ~ 8% of whole reaction system gross weight.
Compared with prior art, the present invention has the following advantages:
1) nano composite membrane material visible-light transmitance provided by the invention is greater than 90%, and ultraviolet ray transmissivity is less than 1%;
2) metal oxide nanoparticles such as ZnO has the effect of photocatalytic degradation to organism, directly adopts the organic matter degradation that nano-ZnO etc. can make in composite membrane.The present invention is with nanoparticles such as ZnO for core, and silicon-dioxide is the nuclear shell structured nano-particle of inner shell, and nanoparticle surface has the protection of silicon-dioxide, and the organism in composite membrane would not catalyzedly be degraded;
3) metal oxide nanoparticles such as ZnO is core, Coated with Organic Matter layer containing carbon-carbon double bond is the reactive force that the nucleocapsid structure of outer shell can increase between nanoparticle and polymeric matrix, reduce and avoid the reunion of nanoparticle in polymeric, improving the optical homogeneity property of matrix material;
4) nano combined mould material provided by the invention has certain snappiness;
5) preparation method of nano combined mould material provided by the invention is simple, and simple process is easy, is expected to be applied to structure high transparency optics, uvioresistant device, special light regulation and control device etc.
Accompanying drawing explanation
Fig. 1. the nucleocapsid structure ZnO of coated with silica, ZnO nanoparticle are to organic catalytic performance comparison diagram.
Fig. 2. the AFM picture of nano combined mould material.
Fig. 3. nano combined mould material is at 200 ~ 800nm optical transmission spectra curve.
Below in conjunction with embodiment, the present invention is described further.
Embodiment
The ZnO nanoparticle initial dispersion of the nucleocapsid structure of double shells used in the present embodiment is provided by Singapore Nano-Material Science & Technology Co. Ltd., and the outer field organism containing carbon-carbon double bond is Rocryl 410.Solvent is the one (i.e. solvent orange 2 A) in ethanol, Virahol, ethyl acetate, butylacetate, benzene,toluene,xylene.
TiO used in the present embodiment
2nanoparticle initial dispersion obtains by after laboratory treatment, and the outer field organism containing carbon-carbon double bond is Methacrylamide.Solvent is the one (i.e. solvent orange 2 A) in ethanol, Virahol, acetone, ethyl acetate, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO).
Tin-doped indium oxide nanoparticle initial dispersion used in the present embodiment obtains by after laboratory treatment, and the outer field organism containing carbon-carbon double bond is oleic acid.Solvent is the one (i.e. solvent orange 2 A) in ethanol, butylacetate, Virahol, acetone, ethyl acetate, tetrahydrofuran (THF).
AIST-NTSmartSPM type atomic force microscope is adopted to characterize the surface topography of the membrane sample prepared by the present invention.
UV-2501 type ultraviolet-visible spectrophotometer is adopted to measure the optical property of the membrane sample prepared by the present invention.
Embodiment 1
Get ZnO nanoparticle alcoholic dispersion (initial dispersion, solvent orange 2 A is ethanol), drip a large amount of isopropyl ether (solvent B), obtain white ZnO to precipitate, centrifugation, then three times vacuum drying oven drying is placed on to washing of precipitate, obtain ZnO nano powder.Get 1.0g ZnO nano powder to be distributed in 1.7g butyl methacrylate under magnetic agitation and hyperacoustic effect, realize the phase transition of ZnO nanoparticle.Add the AIBN of dispersion total mass 0.2wt%, stir and after deaeration, liquid poured into mould, polymerization 6 hours at 78 DEG C in an oven, then be polymerized 16 hours at 65 DEG C, finally thermal treatment 1 hour and 1 hour at 95 DEG C, 115 DEG C respectively, obtains the nano combined mould material of transparent flexible after the demoulding.Film thickness is 4.0mm, and its optical performance test result is as shown in table 1.
| Visible light transmissivity (%) (550nm) | 48.6 |
| Rate of ultraviolet shield (%) (350nm) | 99.9 |
Table 1
Embodiment 2
The 1.0g ZnO nano powder that Example 1 obtains is distributed in 1.7g butyl methacrylate under magnetic agitation and hyperacoustic effect, realizes the phase transition of ZnO nanoparticle.Add the AIBN of dispersion total mass 0.5wt%, stir and after deaeration, liquid poured into mould, polymerization 6 hours at 78 DEG C in an oven, is then polymerized 16 hours at 65 DEG C, finally thermal treatment 1 hour at 95 DEG C, 115 DEG C respectively, obtains the nano combined mould material of transparent flexible after the demoulding.Film thickness is 4.0mm, and its optical performance test result is as shown in table 2.
| Visible light transmissivity (%) (550nm) | 60.7 |
| Rate of ultraviolet shield (%) (350nm) | 99.9 |
Table 2
Embodiment 3
The 1.0g ZnO nano powder that Example 1 obtains is distributed in 1.7g 3-methacryloxypropyl trimethoxy silane under magnetic agitation and hyperacoustic effect, realizes the phase transition of ZnO nanoparticle.Add the AIBN of dispersion total mass 0.5wt%, stir and after deaeration, liquid poured into mould, polymerization 6 hours at 78 DEG C in an oven, is then polymerized 16 hours at 65 DEG C, finally thermal treatment 1 hour at 95 DEG C, 115 DEG C respectively, obtains the nano combined mould material of transparent flexible after the demoulding.Film thickness is 0.070mm, and its optical performance test result is as shown in table 3.Nano combined mould material is shown in Fig. 3 at 200 ~ 800nm optical transmission spectra curve.
| Visible light transmissivity (%) (550nm) | 90.9 |
| Rate of ultraviolet shield (%) (350nm) | 99.9 |
Table 3
Embodiment 4
The 1.0g ZnO nano powder that Example 1 obtains is distributed in 0.6g 3-methacryloxypropyl trimethoxy silane under magnetic agitation and hyperacoustic effect, realizes the phase transition of ZnO nanoparticle.Add the AIBN of dispersion total mass 0.5wt%, stir and after deaeration, liquid poured into mould, polymerization 6 hours at 78 DEG C in an oven, is then polymerized 16 hours at 65 DEG C, finally thermal treatment 1 hour at 95 DEG C, 115 DEG C respectively, obtains the nano combined mould material of transparent flexible after the demoulding.Film thickness is 0.070mm, and its optical performance test result is as shown in table 4.Nano combined mould material is shown in Fig. 3 at 200 ~ 800nm optical transmission spectra curve.
| Visible light transmissivity (%) (550nm) | 90.3 |
| Rate of ultraviolet shield (%) (350nm) | 99.9 |
Table 4
Embodiment 5
The 1.0g ZnO nano powder that Example 1 obtains is distributed in 1.0g butyl acrylate under magnetic agitation and hyperacoustic effect, realizes the phase transition of ZnO nanoparticle.Add the ultraviolet initiator 651 of dispersion total mass 4wt%, stir and after deaeration, liquid poured into mould, under the high voltage mercury lamp of 2KW 20 minutes, finally thermal treatment 1 hour at 95 DEG C, 115 DEG C respectively, obtained the nano combined mould material of transparent flexible after the demoulding.Film thickness is 0.023mm, and its optical performance test result is as shown in table 5.
| Visible light transmissivity (%) (550nm) | 91.0 |
| Rate of ultraviolet shield (%) (350nm) | 99.9 |
Table 5
Embodiment 6
Get the TiO obtained according to treatment process similar in embodiment 1
2nano-powder 1.0g, is distributed in 1.0g vinyl acetate, realizes TiO under magnetic agitation and hyperacoustic effect
2the phase transition of nanoparticle.Add the ultraviolet initiator 651 of dispersion total mass 4wt%, stir and after deaeration, liquid poured into mould, under the high voltage mercury lamp of 2KW 20 minutes, finally thermal treatment 1 hour at 95 DEG C, 115 DEG C respectively, obtained the nano combined mould material of transparent flexible after the demoulding.Film thickness is 0.023mm, and its optical performance test result is as shown in table 6.
| Visible light transmissivity (%) (550nm) | 90.2 |
| Rate of ultraviolet shield (%) (350nm) | 99.1 |
Table 6
Embodiment 7
Get the tin-doped indium oxide nano-powder 0.4g and ZnO nano powder 0.6g that obtain according to treatment process similar in embodiment 1, be distributed in 3.0g Hydroxyethyl acrylate under magnetic agitation and hyperacoustic effect, realize the phase transition of tin-doped indium oxide and ZnO nanoparticle.Add the AIBN of dispersion total mass 0.5wt%, stir and after deaeration, liquid poured into mould, polymerization 6 hours at 78 DEG C in an oven, is then polymerized 16 hours at 65 DEG C, finally thermal treatment 1 hour at 95 DEG C, 115 DEG C respectively, obtains the nano combined mould material of transparent flexible after the demoulding.Film thickness is 0.023mm, and its optical performance test result is as shown in table 7.
| Visible light transmissivity (%) (550nm) | 90.0 |
| Rate of ultraviolet shield (%) (350nm) | 99.5 |
Table 7
Claims (9)
1. highly-transparent ultraviolet-resistant imitates a preparation method for ceramic flexible nano composite film material, and in mould material, each component and percentage composition thereof are: core-shell nanoparticles 20 ~ 85wt%, polymeric 15 ~ 80wt%;
Wherein, core-shell nanoparticles is the nucleocapsid structure of double shells, stratum nucleare comprises the one of zinc oxide, titanium oxide, silicon oxide, cerium oxide, Indium sesquioxide, stannic oxide, doping zinc-oxide, adulterated TiOx, doped indium oxide, doped stannum oxide, shell is made up of two-layer, wherein inner shell is silicon dioxide layer, outer shell is Coated with Organic Matter layer containing carbon-carbon double bond, described core-shell nanoparticles is selected from one or more than one mixture wherein, it is characterized in that, for phase transition-situ aggregation method prepares composite film material, specifically comprise the following steps:
1) phase transition of nanoparticle: by core-shell nanoparticles by initial dispersion, namely the dispersion in solvent orange 2 A, be precipitated by adding anti-solvent B, nano-powder is obtained after centrifugation, washing, vacuum-drying, through magnetic agitation, ultrasonic disperse nano-powder redispersion in the monomer of polymeric, obtain nanoparticle monomer dispersion, nanoparticle massfraction is in dispersions 20 ~ 85%;
2) mass polymerization of nanoparticle in polymer monomer: to 1) the nanoparticle monomer dispersion that obtains of step adopts thermal initiation radical polymerization, use thermal initiator, be polymerized 2 ~ 12 hours at 60 ~ 90 DEG C, then be polymerized 12 ~ 36 hours at 40 ~ 70 DEG C, finally thermal treatment 1 ~ 3 hour, 1 ~ 3 hour at 90 ~ 110 DEG C, 110 ~ 160 DEG C respectively;
Or, to 1) the nanoparticle monomer dispersion that obtains of step adopts UV-light to cause radical polymerization, use ultraviolet initiator, the high voltage mercury lamp adopting 1 ~ 3KW is ultraviolet light source, set time is 1 ~ 50 minute, finally thermal treatment 1 ~ 3 hour, 1 ~ 3 hour at 90 ~ 110 DEG C, 110 ~ 160 DEG C respectively.
2. according to the method for claim 1, it is characterized in that, solvent orange 2 A is selected from the one in water, ethanol, Virahol, acetone, methyl ethyl ketone, ethyl acetate, butylacetate, benzene,toluene,xylene, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO).
3. according to the method for claim 1, it is characterized in that, solvent B is selected from water, isopropyl ether, methyl ethyl ether, diethyl ether, methyl alcohol, dimethyl sulfoxide (DMSO), dimethyl formamide, chloroform, tetracol phenixin, C
4~ C
8alkanes, one in benzene,toluene,xylene.
4. according to the method for claim 1, it is characterized in that, thermal initiator is Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN), azo-bis-iso-dimethyl (AIBME), dibenzoyl peroxide (BPO), N, accelerine (DMA), azo-bis-isobutyrate hydrochloride (V-50) or Potassium Persulphate (KPS), the consumption of thermal initiator is 0.05 ~ 1.0% of whole reaction system gross weight.
5. according to the method for claim 1, it is characterized in that, ultraviolet initiator is light trigger 651,1-hydroxycyclohexyl phenyl ketone (light trigger 184) or 2-hydroxy-2-methyl Propiophenone (light trigger 1173), and ultraviolet initiator consumption is 0.5 ~ 8% of whole reaction system gross weight.
6. according to the method for claim 1, it is characterized in that, the metal adulterated in described doping zinc-oxide is selected from one or more mixing in aluminium, calcium, gallium, cadmium, cerium, copper, iron, magnesium, tin, antimony, silver, titanium, and the mol ratio of doping metals and zinc in zinc oxide is 0.1-25:100;
The metal adulterated in described adulterated TiOx is selected from one or more the mixture in zinc, tin, lanthanum, and in doping metals and titanium oxide, the mol ratio of titanium is 0.1-25:100;
The metal adulterated in described doped indium oxide is selected from one or more the mixture in tin, antimony, titanium, tungsten, copper, iron, and in doping metals and Indium sesquioxide, the mol ratio of indium is 0.1-25:100;
The element adulterated in described doped stannum oxide is selected from one or more the mixture in indium, antimony, titanium, zinc, tungsten, fluorine, iron, silver, platinum, and in doped element and stannic oxide, the mol ratio of tin is 0.1-25:100.
7. according to the method for claim 1, it is characterized in that, described polymeric is polymerized by corresponding polymer monomer to obtain, and polymer monomer is the one or more than one mixture in (methyl) esters of acrylic acid, acryloxy organo-siloxane class, vinyl organosilicon alkanes or vinyl acetate.
8. according to the method for claim 7, it is characterized in that, described (methyl) acrylic polymer monomer comprises C
2~ C
18(methyl) alkyl acrylate, (methyl) phenyl acrylate, (methyl) crylic acid hydroxy ester, ethers (methyl) acrylate or (methyl) acrylate cross linked monomer;
Described acryloxy organo-siloxane base polymer monomer comprises 3-methacryloxypropyl trimethoxy silane, 3-methacryloyloxypropyl methyl dimethoxysilane or 3-methacryloxypropyl;
Described vinyl organosilicon alkanes polymer monomer comprises vinyltrimethoxy silane, vinyltriethoxysilane or vinyl three ('beta '-methoxy oxyethyl group) silane.
9. according to the method for claim 1, it is characterized in that, it is characterized in that, the thickness of film is 100nm ~ 10mm.
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