Self-cleaning, antibacterial and anti-fog film

A self-cleaning anti-fog antimicrobial film

technical field

[0001] The invention belongs to the high - molecular material and nano photo-catalysis a composite film field, specifically relating to any one of self-cleaning anti-fog antimicrobial film.

background technology

[0002]Use of researching, quite the semiconductor photocatalyst majority belonging to η model of forbidden band semiconductor, for example, The ZnS, Sn02, Zno, Catio3, V2O5 and so on. And the semi-conductor The compound, CdS and ZnO photo-catalysis activity is quite rod, further PbS and other semiconductor containing heavy metal ions, CdS, ZnO and so on stable in the light emitting, easy without adopting, and generate Cd2+ and Zn2+, wherein the heavy metal ion is the environment-friendly effects of an inner. Ratio of the material 1102, with high activity and oxidizing of catalytically is strongly, and yellow light stability height and heat resistance and good, non-toxic, low-cost source and method of the advantages, the use of one of green promising environment-friendly catalyst. Natural, wherein the material of the criterion, wherein the surface of the centre can be added wherein medicine catalytically by using photochemical catalysis reaction rate, nanometre TiO2 according to relies wherein the cheap non-toxic, catalytically the high activity and oxidizing of a strong, wherein the aerobic and easy preparation of transparent film of the advantages, comprising the photo-catalysis antibacterial building material (antibacterial ceramic, glass and so on novel favorite. Wherein it adopts the light source the illumination, generate the following of the strengthening hydroxide radical, wherein the is harmful gas, pollutants bacteria and contacting, wherein the oxidation reduction reaction, and an and bacteria and removing each of harmful gas, harmful of such that the pollution-free water and carbon dioxide, wherein achiefs and purifying, action of the air discharge. A further aspect, nanometre TiO2 with a hydrophily under ultraviolet rays, wherein the water and surface, wherein a temperature of all, adopted by the water uniformly film, a powder and vertical in the inorganic material, the mixture at the ratio of the powder and soil according uniformly the action of gravity of the film and air, the self-cleaning. , And under ultraviolet light condition, since the water or the vapour in the coagulation, TiO2 film of the condensed water of forming a water, and is formed water uniformly film coated with all of the preceding therefore, the surface of a light scattering water. When there is a rain water to break a surface, adhesion's rain water to quickly side of the water uniformly film, comprising an alcohol with a water sight's, a will not the anti-fog a role.

[0003] The prior art mostly of the glass, ceramic and so on material base material surface through a nanometre TiO2 film, wherein the method is mainly comprising: The magnetron sputtering method of chemical vapour deposition (CVD) and gel solating method and so on, the preparing method of the device reques height of the film according criterion a control and is provided with a uniformly film forming and other; disadvantagesThe there is a nanometre TiO2 is any of the victory of self-cleaning and antibacterial bifunctional coating, and TiO2 in the solar utilization ratio and low the photo-catalysis performing the height, the photo-catalysis stability of very good and other disadvantages. The invention is ball-mill/ultrasonic/method of the high-speed stirring the nanometre TiO2 are uniformly alcohol in the substrate, and high - molecular material and is agent is a, drying to obtain masterbatch; The plastic masterbatch for preparing the self-cleaning anti-fog antimicrobial film is the novel synthesis blow-moulding, or a novel the left. 1102 Nanometre particle is capable of the formula is multiple, wherein for preparing the nanometre TiO2 nanometre particle slurry and organic high molecular material and addition agent, mixing with the photo-catalysis high activity, totally the miscibility is good, self-cleaning anti-fog antimicrobial film for preparing simple and convenient, operations of the advantages, the system under the nanometre TiO2 powder uniformly alcohol in plastic base material, having displaying function from inside to outside; the bactericidal coefficient reached as high as 99%. The method according self-cleaning anti-fog antimicrobial film has a height visible light transmissibility and self-cleaning effect, wherein the pressure-sensitive sealant and heat-sensitive said compounding, and structural glass, vehicle and steamboat according widow's the film.

The invention

[0004] A objective of the present invention is one of the preceding of system, comprising a purpose of any one of the aerobic visible light, transparency to any of the shielded ultraviolet ray, has self-cleaning, sterilizing degerming and anti-fog and a self-cleaning anti-fog antimicrobial film and preparation method and purpose.

[0005] The way of the invention is precipitated: A self-cleaning anti-fog antimicrobial film, which is composed of the following preparation method, preparing the following steps as follows:

[0006] the (I) preparing nanometre TiO2 衆 particle material, the following steps as follows:

[0007] (1 )Water: treatmentNanometre TiO2 powder particles in mass concentration of 68%_99% nitric acid or acetic acid, control and mixing liquid; pH=l-5The 30-60°C TiO2 at the water - state, the treatment water 1-10 hours, water in step 30-60°C drying standby;

[0008] The nanometre TiO2 powder particle has an average particle diameter of 15_30nm;

[0009] (2 )Comprising: solutionThe the first surface is active agent, and then adding the stabiliser, wherein the suspension liquid Ife, wherein the surface active agent and stabiliser and acid liquid mass ratio is (2-10): (2-10): The 0.005-0.015 stirring, a stirrer, 20-60 degrees centigrade in the isothermal water - bath heating for 0.5-2 hours, the same the solution is 2.5-2.8 to be applied;

[0010] The stabiliser is methylcellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyl ethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methylcellulose or powder or one or two;

[0011] Surface active agent is polymerization degree 2000 polyethylene glycol, terpinols, alkylphenol ethoxylates, acetylacetone or polyethylene glycol to different octyl ether mixture in one or two;

[0012] The acid liquid is the concentration of 68%_99% acetic acid or 68-99% nitric acid;

[0013] ( 3) Comprising: slurryNanometre TiO2 powder particles in step (2) composed solution in step ( 1 ) of water, the nanometre TiO2 powder particles and mass ratio parts of 1-3: 4 to -13, wherein 20-50°C at the temperature of the isothermal and 0.5-2 hours, results in the slurry;

[0014] ( 4 ) As following: Wherein the 60_80°C under heating the step (3) obtain's slurries, the slurry the condense to the TiO2 in the mass ratio of 10%-25%, obtaining nanometre TiO2 particle, slurry

[0015] (2) Is nanometre Tio2 particle slurry in the step (I) complex according an organic polymer is agent, fully stirring and mixing; the vacuum oven remove volatile micromolecule solvent, RS, masterbatch

[0016] Wherein the masterbatch comprising 72.89 to 92.34wt% organic high polymer, 0.5 to 22.63wt% nanometre Tio2 particle and 3.36 to 23.45wt% be agent;

[0017] The organic polymer selected from polystyrene, polyethylene, polypropylene, polybutylene, polymethacrylate, copolycarbonates and polyvinyl acetate, polytetrafluoroethylene the one or more of polyethylene glycol terephthalate and polyvinyl-chloride, or a wherein the material is 2 to 3 of the average diluted and;

[0018] The suspension agent is the plasticizer, coupling agent and stabiliser one or more than one or mixture;

[0019] Said plasticizer selected from terephthalic acid) phthalate, dioctyl phthalate and terephthalic acid And the oct epoxy ester of oils one or more than one or mixture;

[0020] The coupling agent is wood that 3 - epihydric alcohol and oxygen-containing or dimethoxy silica, wherein the 3 - epihydric alcohol and oxygen-containing or _■ the buffer methoxy, wherein B is a dimethoxy silica is one or two of methyl II) oxy) and benzylaminoethylaminopropyl vinyl trimethoxy silane, diethylenetriamine tri-amino propyl trimethoxy silane,

[0021] Stabiliser is benzotriazole, 2 to 2 ' - (-) ' - ditertiary Butyl wherein the ' - methyl phenyl) - -5 benzotriazole chloride, 2 to 2 ' - Hydroxyl wherein the ' - methyl phenyl) benzotriazole, 2 - (- 4) oxy oct ether, N- (B )(methyl ether, 2 ' - - 4 UV-9 methoxy and 2,4 - dihydroxy UV-9), 2 - (- 4) oxy methoxy is phenyl) - N, - phenyl methyl ether, N- (ethoxyl is phenyl) - N, -) - N, - 5 sulfonate or UV-9 2, 2- (2 ' - (-) ' -Tertiary butyl _5' of methyl phenyl) - 5 g/l chloride, 1,1,3 - tri (2) is - 4 (- 5 (s) phenyls one of butane and triphenyl phosphate, two of three or more stabilisers' mixture;

[0022] Step (3) (2) obtain's masterbatch by passing through a threaded rod at 170 degrees centigrade the glue, 190 degrees centigrade A moulded by extruding, the rolling wheel of such from the cleaning anti-fog antimicrobial film.

[0023] The invention claims a height visible light transmissibility and antibacterial self-cleaning function anti-fog, wherein the light and controlling the action of the ultraviolet and far infrared ray; A, antistatic of electromagnetic radiation; performanceThe preparation without perfect vacuum, the heating device and simple and flowing and costs.

[0024] The visual light transmissibility of the invention (@550nm) (%) 67-85% bacteria, rate 95-99%, photo-catalysis wherein 88-93%, minimal contacting angle 0°-8°, pencil hard; 2-3HA a pressure-sensitive sealant and heat-sensitive said compounding, and structural glass, vehicle and steamboat according widow's film, linker of the self-cleaning anti-fog antibacterial effect; Glass and process according widow and which is provided with a modify and cell with a construct, is small of the rough, for anti-marine-climate, environment and base material and size limit.

brief description fo the drawings

[0025] With 1 of the nanometre TiO2 method for preparing a heating the invention,

[0026] Figure 2 is invention preparing a heating.

Specifically embodiment

[0027] Self-cleaning anti-fog antimicrobial film of the invention is composed of the following preparation method, for preparing specific steps (is represented by Figure as FORMULA (2):

[0028] the (I) preparing nanometre TiO2 衆 particle material, the specific steps (is represented by Figure as FORMULA (1):

[0029] (1) Water: treatmentRegulated pH=l_5 with acid in the nanometre TiO2 powder particles; The 30_60°C a water - state processing water, drying standby;

[0030] (2 )Comprising: solutionThe surface active agent to a surface, stabiliser, the acid liquid, stirring, wherein the isothermal heating the water - bath of 20-600C, the same the solution is 2.5-2.8 is to the first in turn;

[0031] ( 3 ) Comprising: slurryThe nanometre TiO2 powder particles in step (2 )composed solution in the step ( 1 ) of water, wherein 20-50°C at the temperature of the isothermal and 0.5-2 hours, results in the slurry;

[0032] (4) As following: Wherein the 60_80°C under heating the step (3) obtain's slurries, the slurry the condense to the TiO2 in the mass ratio of 10%-25%, obtaining nanometre TiO2 particle slurry.

[0033] Nanometre TiO2 particle is not modified nanometre TiO2 modified or nanometre TiO2, crystal form is type or anatase and rutile mixture, grain size 15_30nm.

[0034] Modified nanometre TiO2 is the dope the rare earth metal ion, transition metal ion and non-metal ion nanometre TiO2 and weight in noble metal nanometre TiO2 and compounding the gas after The nanometre TiO2 or photoactivate.

[0035] Dope of rare earth metal ion, transition metal ion and non-metal ion nanometre TiO2, rare earth metal ion is Ce and La, Nd, one Eu ion or more; Transition metal ion is the V, Fe, Cu and Co, N1, Cr, Mo, Ru, W and one or more of Re ion or more; The non-metallic ion is N, and wherein the one or more of ion or more.

[0036] The weight of the noble metal nanometre TiO2, wherein the noble metal is chloride, one of Ag and Au or more.

[0037] The compounding gas nanometre TiO2, wherein the is one of W03, Sn02, V2O5, ZnS, CdS, Mo03 and SiO2 or more.

[0038] The nanometre TiO2 in photoactivate, wherein photoactivate agent is any chloride, and Rh, Au one of chloride or chlorophyllin dipyridyl, ruthenium, eosine, c, tetrazaporphin and hermosa pink or or more.

[0039] The anatase nanometre TiO2 preparation method of refers to claim CN03119113.4, a stirring and alkali liquor is a certain amount of titanium compound aqueous solution, and ph of the solution is 1.5-4, obtained metatitanic acid seed crystal; The form of an inorganic following titanium solution in preparing the seed crystal I; For heating the solution to 50-140°C boiling, a wherein the white sediment, filtering, washing and obtain white filter cake; The of the mixture of the filter cake room temperature drying, having a particle size anatase nanometre TiO2 powder.

[0040] Type TiO2 and rutile TiO2 the preparation method of the mixture of refers to claim CNlO 1643242A, specifically titanium metal complex precursor in the special organic solvent, forming solution II, the oxyful to solution II, wherein a water - boiling react and react, heating and curing by rutile or anatase compounding TiO2 powder. By regulating titanium's precursor and organic solvent with volume amount can control or/the grain size of the shape of anatase compounding TiO2 powder.

[0041] The dope rare earth metal ion, transition metal ion and non-metal ion the preparation method of nanometre TiO2 isReference claim CN03119113.4 and CN101643242A I, or the solution II adding a certain amount of said element ACCORDING to any of the solution is wherein one of dissolving the compound in the organic solvent, element M is the rare earth metal ion, transition metal ions to the non-metallic ion, wherein the post-treatment.

[0042] The weight of noble metal the preparation method of nanometre TiO2 is: The reference (claim 102240546 ACCLIMATION CHANNELS, wherein the suspension formed solution the nanometre TiO2 powder is ration's anhydrous ethanol, air or nitrogen gas, the ultraviolet rays for the fields of condition

l-20min, wherein the titanium dioxide the blue light to the depth blue, is performed following noble metal precursor is as follows: The chloroauric acid, and molybdenum acid or silver nitrate and is poured into the suspension liquid; the reducing Ti3+, wherein the metal ion comprises an elementary metal nano-particle deposition of titanium dioxide surface, wherein by weight in noble metal nanometre Tio2.

[0043] Compounding the method for preparing nanometre TiO2 is: Following nanometre semiconductor is 22-57 the nanometre powder 1102 in the water solution the stirring 0.5h-10h, after filtering step, wherein the drying h, being l_5h roasting;

[0044] Photoactivate the preparation method of nanometre TiO2 is: The nanometre TiO2 powder is concentration of the 0.001-lmol/l sensitizer ethanol solution, stirring 0.5-10h, after filtering, centigrade for 5h.

[0045] (2) Is nanometre Tio2 particle slurry in the step (I) complex according an organic polymer is agent, fully stirring and mixing; the vacuum oven remove volatile micromolecule solvent, RS, masterbatch

[0046] The organic polymer selected from polystyrene, polyethylene, polypropylene, polybutylene, polymethacrylate, copolycarbonates and polyvinyl acetate, polytetrafluoroethylene the one or more of polyethylene glycol terephthalate and polyvinyl-chloride, or a wherein the material is 2 to 3 of the average diluted and;

[0047] The suspension agent is the plasticizer, coupling agent and stabiliser one or more than one or mixture;

[0048] Said plasticizer selected from terephthalic acid) phthalate, dioctyl phthalate and terephthalic acid And the oct epoxy ester of oils one or more than one or mixture;

[0049] The coupling agent is wood that 3 - epihydric alcohol and oxygen-containing or dimethoxy silica, wherein the 3 - epihydric alcohol and oxygen-containing or _■ the buffer methoxy, wherein B is a dimethoxy silica is one or two of methyl II) oxy) and benzylaminoethylaminopropyl vinyl trimethoxy silane, diethylenetriamine tri-amino propyl trimethoxy silane,

[0050] Stabiliser is benzotriazole, 2 to 2 ' - (-) ' - ditertiary Butyl wherein the ' - methyl phenyl) - -5 benzotriazole chloride, 2 to 2 ' - Hydroxyl wherein the ' - methyl phenyl) benzotriazole, 2 - (- 4) oxy oct ether, N- (B )(methyl ether, 2 ' - - 4 UV-9 methoxy and 2,4 - dihydroxy UV-9), 2 - (- 4) oxy methoxy is phenyl) - N, - phenyl methyl ether, N- (ethoxyl is phenyl) - N, -) - N, - 5 sulfonate UV-9), 2 to 2 ' - (-) ' -Tertiary Butyl wherein the ' - methyl phenyl) - 5 g/l chloride, 1,1,3 - tri (2) methyl to 4 ppm _5 tertiary butyl )phenyl) of the raw and triphenyl phosphate, least two or three of stabilisers the mixture.

[0051] Step (3) (2) obtain's masterbatch by passing through a threaded rod at 170 degrees centigrade the glue, 190 degrees centigrade A moulded by extruding, the rolling wheel, the inner surface is 165 160-175 degrees centigrade, the calender and speed of 45 to 70m/min, the preparation of such a cleaning anti-fog antimicrobial film. Self-cleaning anti-fog antimicrobial film for 23 μ m-120 the μ.

[0052] The relates to detail invention is specifically the embodiment:

[0053] embodiment 1:

[0054] the (I) preparing nanometre TiO2 衆 particle material, the following steps as follows: First according to any type nanometre TiO2 preparation method of nanometre sio2 anatase nanometre TiO2 powder particles,

[0055] (1 )Water: treatmentThe anatase nanometre TiO2 powder particles in mass concentration of 68% acetic acid, control and mixing liquid; PH=IThe centigrade under the condition that includes in the acidization H, treatment of TiO2 the water degrees centigrade in oven drying standby;

[0056] (2 )Comprising: solutionFirst is acetylacetone solvent in the same, and then adding methylcellulose, the mixture at the mass concentration of 68% acetic acid, acetylacetone the solvent, methylcellulose and acid liquid mass ratio of 5:10: 0.007, and a stirrer, wherein the mixture of the isothermal the heating is water - 0.5 hours, the same the solution is 2.5-2.8 to be applied;

[0057] Firstly adding acetylacetone solvent in the beaker, then adding methylcellulose, the mixture at the mass concentration of 68% acetic acid, composed of the solvent, according to the solvent in mass ratio: Acetic acid: acetylacetone: Methylcellulose: =0.0075: 10th,

[0058] (3 )Composed 衆: materialA g of nanometre TiO2 powder particles in step (2 )of preparing solution in the step ( 1 ) of water, centigrade at the temperature of the isothermal 0.5h, a wherein the stirring uniformly good dispersibility slurry;

[0059] (4 )As following: The degrees centigrade under heating the step (3 )obtain's slurries, the slurry the condense to the TiO2 in the mass ratio of 10%; the anatase nanometre TiO2 a slurry.

[0060] (2) To by weight percentage as follows, 0.5 type nanometre TiO2 slurries particles according to the discharging, the ratio of the polyvinyl-chloride 76.05, 1.51 vinyltrimethoxysilanes 19.01 and dioctyl phthalates, 1.11

2 To 2 ' - Hydroxyl group consisting of methyl phenyl) benzotriazole, 0.91 or 1,1,3 and 2 (-) - 4 (- 5 (s) phenyls butane 0.91 of triphenyl phosphate stirrings fully and mixings, and washing With U-SHAPED to remove volatile micromolecule in a vacuum drying oven, wherein the masterbatch.

[0061] (3) The masterbatch is a threaded rod in the viscosity and centigrade, A moulded by extruding, the rolling wheel, the inner surface are temperature, wherein calender and speed is 60m/min, wherein the thickness of 120 μ the film. Film performance test result to Table 1, wherein the resulting film can with the compounding glass.

[0062]The I

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[0064] embodiment 2: An embodiment 1, wherein in the step (2), the quantity of by weight percentage as follows, discharging the preparation

0.5 Type nanometre TiO2 particles, the slurry added 76.05 polycarbonates, 1.51 of glycidyl ether or oxygen-containing dimethoxy silane and 19.01 terephthalic acid And the Process Of 3, 1.11 2 to 2 ' - Hydroxyl group consisting of methyl phenyl) benzotriazole, 0.91 or 1,1,3 and 2 (-) - 4 (- 5 (s) phenyls butane 0.91 of triphenyl phosphate stirrings fully and mixings, and vacuum drying oven remove volatile micromolecule solvent, obtain masterbatch.

[0065] embodiment 3:

[0066] the (I) preparing nanometre TiO2 衆 particle material, the following steps as follows: First according to any type TiO2 and rutile TiO2 the preparation method for grain diameter 25nm rutile or anatase compounding nanometre TiO2 powder particles,

[0067] ( 1 ) Water: treatmentRutile or anatase compounding nanometre TiO2 powder particles in mass concentration of 68% nitric acid, control and mixing liquid; pH=5The centigrade under the condition that includes in the acidization 1-10 treatment, TiO2 in the water is in an oven drying standby;

[0068] (2) Comprising: solutionThe terpinol added in the beaker, the adding the alkylphenol ethoxylates, then adding water solution, the mixture at the mass concentration of 68% nitric acid, ethyl cellulose: alkylphenol ethoxylates: terpinol: Nitric acid: preferably 2: 3: 0.007, Wherein a stirrer, wherein the mixture to isothermal heating the water - bath, 2h the same the solution is 2.5-2.8 to be applied;

[0069] ( 3 ) Composed 衆: materialThe Mixture of rutile-type step( 1) of water/the compounding anatase nanometre TiO2 powder particles in step (2 )composed g, the temperature at the temperature of the isothermal 2h, a wherein the stirring uniformly good dispersibility slurry;

[0070] ( 4 ) As following: The degrees centigrade under heating the step( 3) obtain's slurries, the slurry the condense to the TiO2 in the mass ratio of 25%, by rutile or anatase compounding nanometre TiO2 a slurry.

[0071] (2) To by weight percentage as follows, 22.34 of rutiles according to the discharging and/or compounding anatase nanometre TiO2 powder particles, the slurry added 72.89, polyvinyl-chloride 1.47 (II) oxy silane and 1.09 terephthalic acid butyl, phthalates 1.11 2 to 2 ' - (-) ' - ditertiary butyl _5' of methyl phenyl) - 5 g/l chloride, 0.74 or 1,1,3 and 2 (-) - 4 (- 5 (s) phenyls butane 0.36 of triphenyl phosphate stirrings fully and mixings, and vacuum drying oven remove volatile micromolecule solvent, obtain masterbatch.

[0072] (3) The masterbatch is a threaded the viscosity of the glue, 1900C A moulded by extruding, the roller, and cylinder surface 1700C temperature, wherein calender and speed is 70m/min, wherein the thickness of 100 μ the film. Film performance test result to Table 2, wherein the resulting film can with the compounding glass.

[0073]The 2

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[0075] embodiment 4:

[0076] the (I) preparing nanometre TiO2 particle slurry, the following steps as follows: The method according to dope non-metal ion type nanometre TiO2 powder particles preparation method for grain diameter of said deposited up of anatase nanometre TiO2 powder particles.

[0077] ( 1 ) Water: treatmentThe of said compounding anatase nanometre TiO2 powder particles in mass concentration of 99% acetic acid, control and mixing liquid, hydrochloricThe centigrade under the condition that includes the additive processing water, TiO2 in the water is centigrade in oven drying standby;

[0078] (2) Comprising: solutionThe the first acetylacetone in the beaker, then adding polyethylene glycol (polymerization degree 2000), then adding hydroxypropyl methylcellulose and methylcellulose, the mixture at the mass concentration of 90% nitric acid, hydroxypropyl methylcellulose: A cellulosic: polyethylene glycol (polymerization degree 2000): acetylacetone: nitric acid =3: 6:3:3:0.005. A a stirrer, wherein the mixture of isothermal for heating the water - bath, 0.5-1 the same the solution is 2.5-2.8 to be applied;

[0079] ( 3 ) Comprising: slurryThe 3g dope of anatase nanometre TiO2 powder particles in step (2) composed ml of solution in the step ( 1 ) of water, centigrade at a temperature isothermal 0.5-1 stirring, a wherein the stirring uniformly good dispersibility slurry;

[0080] (4 )As following: The degrees centigrade under heating the step (3) obtain's slurries, the slurry the condense to the TiO2 in the mass ratio of 15%; the dope of anatase nanometre TiO2 a slurry.

[0081] (2) To by weight percentage as follows, 3.45 of sulphur said compounding anatase nanometre TiO2 powder particles slurries for the discharging preparation, adding 91.52, polybutylene 1.83 benzylaminoethylaminopropyl vinyl trimethoxy silane, diethylenetriamine tri-amino propyl trimethoxy silane, 1.83 g/l, 1.37 of epoxy soy oil stirrings fully and mixings, and vacuum drying oven remove volatile micromolecule solvent, obtain masterbatch.

[0082] (3) The masterbatch is a threaded rod in the viscosity and centigrade, A moulded by extruding, the roller, and cylinder surface 1750C temperature, wherein calender and speed is 60m/min, wherein the thickness of 23 μ the film. Film performance test result to Table 3, wherein the resulting film can with the compounding glass.

[0083] The 3

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[0085] embodiment 5: An embodiment 4, wherein the compound is preparing the grain diameter of said deposited up and anatase nanometre TiO2 powder particles.

[0086] embodiment 6: An embodiment 4, wherein the compound is preparing the grain diameter of said deposited up preparing anatase nanometre TiO2 powder particles.

[0087] embodiment 7:

[0088] the (I) preparing nanometre TiO2 particle slurry, the following steps as follows: The method according to dope transition metal ion rutile or anatase nanometre TiO2 powder particles preparation method for grain diameter 25nm iron said rutile or anatase nanometre TiO2 powder particles.

[0089] ( 1 ) Water: treatmentThe doped iron's oxide and compounding anatase nanometre TiO2 powder particles in mass concentration of 90% acetic acid, control and mixing liquid; pH=2Temperature of 1102 under the condition that includes the additive processing water, water in step 501: A drying oven drying standby;

[0090] (2) Comprising: solutionThe the first polyethylene glycol in the beaker to the different octyl ether mixture, the adding the alkylphenol ethoxylates, then adding hydroxymethyl cellulose and cellulosic powder, the mixture at the mass concentration of 90% nitric acid, A hydroxyl or: Or: powderalkylphenol ethoxylates: Polyethylene glycol to different octyl mixture of: Nitric acid: in 6: 3:

5: 0.015. A a stirrer, wherein the mixture temperature isothermal heating the water - bath, 2h the same the solution is 2.5-2.8 to be applied;

[0091] (3) Comprising: slurryMixture of dope iron oxide and of anatase nanometre TiO2 powder particles in step (2) composed 13g the step (1) of water, and degrees centigrade at the temperature of the isothermal 1.5h, a wherein the stirring uniformly good dispersibility slurry;

[0092] ( 4 ) As following: The degrees centigrade under heating the step (3) obtain's slurries, the slurry the condense to the TiO2 in the mass ratio of 13%; the dope nigrin/anatase nanometre TiO2 a slurry.

[0093] (2) To by weight percentage as follows, wherein said 2.97 rutile or anatase for compounding nanometre TiO2 powder particles method of the discharging preparation, adding 91.84 polymethacrylate or 1.84 3-glycidyl ether oxy-propyl trimethoxy silane, 1.83 2 to 2 ' - (-) ' - ditertiary butyl _5' of methyl phenyl) - 5 g/l chloride, 1.52 of epoxy soy oil stirrings fully and mixings, and vacuum drying oven remove volatile micromolecule solvent, obtain masterbatch.

[0094] (3) The masterbatch is a threaded rod 175°C of the glue, 1950C A moulded by extruding, the roller, and cylinder surface 1650C temperature, wherein calender and speed is 50m/min, wherein the thickness of 75 μ the film. Film performance test result to Table 4, wherein the resulting film can with the compounding glass.

[0095]The 4

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[0097] embodiment 8: An embodiment 7, wherein the compound is preparing the grain size 25nm doped vanadium oxide and anatase nanometre TiO2 powder particles.

[0098] embodiment 9: An embodiment 7, wherein the compound is one of the preparing method of said 25nm copper oxide and anatase nanometre TiO2 powder particles.

[0099] embodiment 10: An embodiment 7, wherein the compound is one of the preparing method of said 25nm cobalt oxide and anatase nanometre TiO2 powder particles.

[0100] embodiment 11: An embodiment 7, wherein the compound is preparing the grain size 25nm nickle said oxide and anatase nanometre TiO2 powder particles.

[0101] embodiment 12: An embodiment 7, wherein the compound is preparing the grain size 25nm and said oxide and anatase nanometre TiO2 powder particles.

[0102] embodiment 13: An embodiment 7, wherein the compound is preparing the grain size 25nm s said oxide and anatase nanometre TiO2 powder particles.

[0103] embodiment 14: An embodiment 7, wherein the compound is one of the preparing method of said 25nm tungsten oxide and anatase nanometre TiO2 powder particles.

[0104] embodiment 15:

[0105] the (I) preparing nanometre TiO2 particle slurry, the following steps as follows: The method according to dope rare earth metal ion type nanometre TiO2 powder particles preparation method for grain diameter 15nm lanthanum said anatase nanometre TiO2 powder particles.

[0106] (1) Water: treatmentThe anatase nanometre TiO2 powder particles in mass concentration of lanthanum said of 83% nitric acid, control and mixing liquid; pH=2Degrees centigrade under the condition that includes in the acidization 1-10 treatment, TiO2 in the water is used in oven drying standby;

[0107] ( 2 ) Comprising: solutionThe the first polyethylene glycol (polymerization degree 2000) in the beaker, the adding terpinol, then adding hydroxypropyl methylcellulose, the methylcellulose, the mixture at the mass concentration of 83% nitric acid, composed of the solvent, according to the solvent in mass ratio: hydroxy propyl methylcellulose: methylcellulose: terpinol: polyethylene glycol (polymerization degree 2000): Nitric acid: in6:2:3: 0.007. A a stirrer, wherein the mixture to isothermal the heating is water - 3, the same the solution is 2.5-2.8 to be applied;

[0108] (3) Comprising: slurryA Mixture of lanthanum dope anatase nanometre TiO2 powder particles in step (2) composed Sg solution in the step (1) of water, degrees centigrade at the temperature of the isothermal and 1.6, adding the stirring uniformly good dispersibility slurry;

[0109] (4 )As following: The degrees centigrade under heating the step (3) obtain's slurries, the slurry the condense to the TiO2 in the mass ratio of 23%; the dope lanthanum anatase nanometre TiO2 a slurry.

[0110] (2) To by weight percentage as follows, 5.08 of lanthanum said anatase nanometre TiO2 powder particles slurries for the discharging preparation, adding 60.98 polyvinyl-chloride and 30.48 polystyrenes, 1.73 of (B )(methyl ether, 2 ' - - 4 - benzophenone methoxy 1.73 and 2 to 2 ' - Hydroxyl wherein the ' - methyl phenyl) benzotriazole fully stirring and mixing, and vacuum drying oven remove volatile micromolecule solvent, obtain masterbatch.

[0111] (3) The masterbatch is a threaded rod is the glue, centigrade A moulded by extruding, the roller, and cylinder surface 1700C temperature, wherein calender and speed is 70m/min, wherein the thickness of 36 μ the film. Film performance test result to Table 5, wherein the resulting film can with the compounding glass.

[0112]The 5

<img id="idf0005" file="CN103396634AD00121.tif" img-content="drawing" img-format="tif" />

[0114] embodiment 16: An embodiment 15, wherein the compound is preparing the grain size 15nm wherein said anatase nanometre TiO2 powder particles.

[0115] embodiment 17: An embodiment 15, wherein the compound is preparing the grain size 15nm neodymium said anatase nanometre TiO2 powder particles.

[0116] embodiment 18: An embodiment 15, wherein the compound is preparing the grain size 15nm terbium said anatase nanometre TiO2 powder particles.

[0117] embodiment 19:

[0118] the (I) preparing nanometre TiO2 衆 particle material, the following steps as follows: The noble metal nanometre TiO2 powder particles preparation method for grain diameter 25nm weight of the molybdenum nanometre TiO2 powder particle according to any of the first.

[0119] (1) Water: treatmentThe nanometre TiO2 powder particles in mass concentration of the molybdenum weight of 99% nitric acid, control and mixing liquid; pH=5The centigrade under the condition that includes in the acidization 3h treatment, TiO2 in the water is used in oven drying standby;

[0120] ( 2 ) Comprising: solutionThe terpinol added in the beaker, pressing the acetylacetone, then adding methylcellulose and ethyl cellulose, the mixture at the mass concentration of 99% nitric acid, composed of the solvent, according to the solvent in mass ratio: methylcellulose: Water solution: terpinol: acetylacetone: nitric acid =5: 5:1:1: 0.015. A a stirrer, wherein isothermal centigrade heating the water - 1.5h, the same the solution is 2.5-2.8 to be applied;

[0121] ( 3 ) Comprising: slurryThe Mixture in the step ( 1 ) of the water to be of molybdenum nanometre TiO2 powder particles in step (2) composed Sg solution, centigrade at the temperature of the isothermal 1.5h, a wherein the stirring uniformly good dispersibility slurry;

[0122] ( 4 ) And condense slurry centigrade under the condition to the TiO2 mass in the slurry the mass ratio of 25%; by weight of a platinum the preparation method of nanometre TiO2.

[0123] (2) To by weight percentage as follows, wherein to 22.63 for the preparation of molybdenum is nanometre TiO2 slurries, 73.16 parts of polyvinyl acetate and hydroxyls 2.81 - 2 - 4 methoxy oxygen-containing is phenyl) - N, - phenyl methyl ether, N- (ethoxyl is phenyl) - N, -) - N, - 5 sulfonate or UV-9 1.4 and mixings benzotriazole, and vacuum drying oven remove volatile micromolecule solvent, obtain masterbatch.

[0124] (3) The masterbatch is a threaded the viscosity of the glue, 1900C A moulded by extruding, the roller, and cylinder surface 1750C temperature, wherein calender and speed is 45m/min, wherein the thickness of 100 μ the film. Film performance test result to Table 6, wherein the resulting film can with the compounding glass.

[0125]The 6

<img id="idf0006" file="CN103396634AD00131.tif" img-content="drawing" img-format="tif" />

[0127] embodiment 20: An embodiment 19, wherein the compound is preparing the grain size 25nm weight in preparing nanometre TiO2 powder particles.

[0128] embodiment 21: An embodiment 19, wherein the compound is preparing the grain size 25nm weight in the gold nanometre TiO2 powder particles.

[0129] embodiment 22:

[0130] the (I) preparing nanometre TiO2 衆 particle material, the following steps as follows: First according to any type nanometre TiO2 or anatase TiO2 and rutile TiO2 mixture preparation method for grain diameter 15nm type TiO2 rutile or anatase and/or compounding nanometre TiO2 powder particles, and to the compounding gas nanometre TiO2 preparation method for grain diameter 15nm the resulting from WO3 anatase nanometre TiO2 powder particles or the resulting from WO3 rutile or anatase compounding nanometre TiO2 powder particles.

[0131] (1) Water: treatmentThe resulting from WO3 the nanometre TiO2 powder particles in mass concentration of 96% acetic acid, control and mixing liquid; PH=ITemperature under the condition that includes in the acidization 3h treatment, TiO2 of the water temperature of oven drying standby;

[0132] ( 2 ) Is the same solution, firstly adding acetylacetone in beaker, the adding polyethylene glycol to the different octyl ether mixture, and then adding the hydroxymethyl cellulose and hydroxypropyl cellulose, the mixture at the mass concentration of 70% nitric acid, comprising forming solution; according to the solvent in mass ratio: A process of: hydroxy propyl cellulose: Polyethylene glycol to different octyl mixture of: acetylacetone: Nitric acid: in5:5:5: 0.015, Wherein a stirrer, wherein isothermal for heating the water - bath, 2h the same the solution is 2.5-2.8 to be applied;

[0133] (3 )And the water to of the 3g TiO2 powder g in step (2) composed solution, the centigrade at the temperature of the isothermal 1.5h, a dispersing uniformly mixed alcohol and 衆 material;

[0134] ( 4 ) And condense slurry centigrade under the condition to the TiO2 mass in the slurry the mass ratio of 15%, or the resulting from WO3 nanometre TiO2 slurry.

[0135] (2) To by weight percentage as follows, 7.84 of compoundings for the preparation of the left WO3 nanometre TiO2 slurries, 72, 16.8 wt% and 1.68 2,4 of ethanol or UV-9 1.68 and 2 to 2 ' - Hydroxyl wherein the ' - methyl phenyl) benzotriazole fully stirring and mixing, and vacuum drying oven remove volatile micromolecule solvent, obtain masterbatch.

[0136] (3) The masterbatch is a threaded the viscosity of the glue, 1900C A moulded by extruding, the roller, and cylinder surface 1750C temperature, wherein calender and speed is 45/min, wherein the thickness of 75 μ the film. Film performance test result to Table 7, wherein the resulting film can with the compounding glass.

<img id="idf0007" file="CN103396634AD00141.tif" img-content="drawing" img-format="tif" />

[0139] embodiment 23: An embodiment 22, wherein the compound is preparing the grain size 15nm compounding the Of anatase nanometre TiO2 powder particles or the compounding Of rutile or anatase compounding nanometre TiO2 powder particles.

[0140] embodiment 24: An embodiment 22, wherein the compound is preparing the grain size 15nm compounding the V2O5 anatase nanometre TiO2 powder particles or the compounding oxide V2O5 and/or compounding anatase nanometre TiO2 powder particles.

[0141] embodiment 25: An embodiment 22, wherein the compound is preparing the grain size 15nm compounding the ZnS anatase nanometre TiO2 powder particles or the compounding ZnS rutile or anatase compounding nanometre TiO2 powder particles.

[0142] embodiment 26: An embodiment 22, wherein the compound is preparing the grain size 15nm resulting from the CdS anatase nanometre TiO2 powder particles or resulting from the CdS rutile or anatase compounding nanometre TiO2 powder particles.

[0143] embodiment 27: An embodiment 22, wherein the compound is preparing the grain size 15nm compounding the MoO3 anatase nanometre TiO2 powder particles or the compounding MoO3 rutile or anatase compounding nanometre TiO2 powder particles.

[0144] embodiment 28: An embodiment 22, wherein the compound is preparing the grain size 15nm compounding the SiO2 anatase nanometre TiO2 powder particles or compounding the SiO2 rutile or anatase compounding nanometre TiO2 powder particles.

[0145] embodiment 29:

[0146] the (I) preparing nanometre TiO2 衆 particle material, the following steps as follows: First according to any type nanometre TiO2 or anatase TiO2 and TiO2 or mixture preparation method of nanometre sio2 anatase nanometre TiO2 powder or or/compounding's anatase nanometre TiO2 powder particles, and to any photoactivate the preparation method of nanometre TiO2 to use of the sensitizer preparation method of sio2 photoactivate (rutile or anatase nanometre TiO2 powder or photoactivate/compounding anatase nanometre TiO2 powder.

[0147] (1) Water: treatmentThe inkjet photoactivate's nanometre TiO2 powder particles in mass concentration of 99% acetic acid, control and mixing liquid; pH=2The centigrade under the condition that includes in the acidization 2h treatment, TiO2 in the water is in an oven drying standby;

[0148] ( 2 ) Is the same solution, firstly adding acetylacetone in beaker, the adding polyethylene glycol to the different octyl ether mixture, and then adding cellulose process, the hydroxyethylcellulose, wherein the height is 99% acetic acid, composed of the solvent, according to the solvent in mass ratio: A process of: hydroxy ethyl cellulose: Polyethylene glycol to different octyl mixture of: acetylacetone: Acetate is: 1:5:5: 0.015, Wherein a stirrer, wherein isothermal for heating the water - h, the aerobic active solution is 2.5-2.8 to be applied;

[0149] (3 )And the water to of the 3g TiO2 powder in step (2) composed g of solution, centigrade at the temperature of the isothermal 1.5h, a dispersing uniformly mixed alcohol and 衆 material;

[0150] (4 )And condense slurry and under the condition to the TiO2 mass in the slurry the mass ratio of 15%; the nanometre TiO2 slurry is obtained photoactivate.

[0151] (2) To by weight percentage as follows, 1.97 of c photoactivates nanometre TiO2 slurries 92.34, poly polyethylene glycol terephthalates and hydroxyls 1.89 to 2 for the preparation of discharging - 4 oct oxygen-containing ether, 3.71 2 to 2 ' - Hydroxyl wherein the ' - methyl phenyl) benzotriazole, 0.09 to 1,1,3 and (2) methyl to 4 ppm _5 tertiary butyl )phenyl) butane fully stirring and mixing, and vacuum drying oven remove volatile micromolecule solvent, obtain masterbatch.

[0152] (3) The masterbatch is a threaded rod is the glue, centigrade A moulded by extruding, the roller, and cylinder surface 1700C temperature, wherein calender and speed is 50m/min, wherein the thickness of 36 μ the film. Film performance test result to Table 8, wherein the resulting film can with the compounding glass.

[0153]The 8

<img id="idf0008" file="CN103396634AD00151.tif" img-content="drawing" img-format="tif" />

[0155] embodiment 30: An embodiment 29, wherein the compound is preparing the grain size dipyridyl sio2 ruthenium photoactivate anatase nanometre TiO2 powder or dipyridyl ruthenium oxide photoactivate/compounding anatase nanometre TiO2 powder.

[0156] embodiment 31: An embodiment 29, wherein the compound is preparing the grain size eosine nm photoactivate anatase nanometre TiO2 powder or eosine photoactivate rutile or anatase the compounding nanometre TiO2 powder.

[0157] embodiment 32: An embodiment 29, wherein the compound is the systemPreparing the grain size tetrazaporphin nm photoactivate anatase nanometre TiO2 powder or tetrazaporphin photoactivate rutile or anatase the compounding nanometre TiO2 powder.

[0158] embodiment 33: An embodiment 29, wherein the compound is preparing the grain size of sio2 pink colour photoactivate anatase nanometre TiO2 powder or hermosa pink photoactivate colour rutile or anatase the compounding nanometre TiO2 powder.

[0159] embodiment 34: An embodiment 29, wherein the compound is preparing the grain size Ru's sio2 chloride photoactivate anatase nanometre TiO2 powder or Ru's chloride photoactivate rutile or anatase the compounding nanometre TiO2 powder.

[0160] embodiment 35: An embodiment 29, wherein the compound is preparing the grain size of sio2 chloride photoactivate anatase nanometre TiO2 powder or photoactivate chloride or and chloride/compounding anatase nanometre TiO2 powder.

[0161] embodiment 36: An embodiment 29, wherein the compound is preparing the grain size chlorophyllin nm photoactivate anatase nanometre TiO2 powder or chlorophyllin photoactivate or Rh consisting of/compounding anatase nanometre TiO2 powder.

[0162] embodiment 37: An embodiment 29, wherein the compound is preparing the grain size of Au nm chlorophyllin photoactivate anatase nanometre TiO2 powder or Au chlorophyllin photoactivate rutile or anatase the compounding nanometre TiO2 powder.