CN109337673A - A kind of hypovanadic oxide-based fluorescence composite material and its application - Google Patents
A kind of hypovanadic oxide-based fluorescence composite material and its application Download PDFInfo
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- CN109337673A CN109337673A CN201811339331.2A CN201811339331A CN109337673A CN 109337673 A CN109337673 A CN 109337673A CN 201811339331 A CN201811339331 A CN 201811339331A CN 109337673 A CN109337673 A CN 109337673A
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Abstract
The present invention relates to a kind of hypovanadic oxide-based fluorescence composite material and its applications, the hypovanadic oxide-based fluorescence composite material includes hypovanadic oxide-based thermochromic material and the fluorescent material for absorbing ultraviolet light transmitting blue light, the hypovanadic oxide-based thermochromic material and the mass ratio for absorbing the fluorescent material of ultraviolet light transmitting blue light are 1:(0.1~10), preferably 2:1~1:2.
Description
Technical field
The present invention relates to a kind of hypovanadic oxide-based fluorescence composite material and its application, in particular to hypovanadic oxide-based thermotropic change
Color material film light transmittance and color belong to film light transmittance and color adaptation technical field.
Background technique
Global energy shortage problem is got worse, and excessive carbon emission causes environment worsening, and energy-saving and emission-reduction, which have become, works as
The top priority of preceding various countries.It is estimated that building energy consumption accounts for 1/3 or more of social total energy consumption, therefore, promoting building energy conservation is energy conservation
One of emission reduction, the emphasis measure for realizing sustainable development.Significant portion is used for air-conditioning in building energy consumption, and windowpane is as building
With the extraneous main thoroughfare for carrying out heat exchange, become the main path of air conditioner energy source loss.Therefore, using various types of energy conservations
Window can be effectively reduced energy consumption, reach energy-saving and environment-friendly purpose.
Existing market Energy Saving Windows main product is Low emissivity (Low-E) glass and heat-reflecting glass etc., due to technology maturation,
Cheap, heat-proof quality is good, is widely used in building energy conservation.But above-mentioned Energy Saving Windows optical property cannot be because of seasonal variations
Change with artificial demand, it is difficult to which adapting to China's most of cold summers, thermally the energy saving requirement in area and people are comfortable to living environment
Degree increasingly higher demands.Then, the new energy-conserving product of referred to as " Intelligent energy-saving window " just comes into being, and will become after Low-
Energy-saving glass product of new generation after E.
The cause off-color material that Intelligent energy-saving window uses optical property can be changed, the transflection that various physical stimulations are generated using it
The variation such as performance is penetrated, the controllable adjustment purpose of indoor environment photo-thermal is reached.Obviously, Intelligent energy-saving window is suitable for most areas
With the demand of Different climate condition, also make indoor living environment more suitable to people.According to physical stimulation type and Discoloration mechanism,
There is electrochromism, gas-discoloration is photochromic, the Intelligent energy-saving window of multiple types such as thermochromism.In various types of intelligence
In Energy Saving Windows, the thermochromism Energy Saving Windows of the semiconductor-metal reversible transition principle development of vanadium dioxide near room temperature, tool are utilized
Have structure simple, material utilization amount is few, completely dispense with switch or artificial energy source's control can accord with one's environment temperature change and realize from
The remarkable advantages such as dynamic photo-thermal regulation, obtain in various countries and pay attention to and research and develop in succession.Wherein, using the temperature control intelligence of nano vanadium dioxide
Energy saving Filming Technology has taken the lead in being broken through in China, and the hypovanadic oxide-based temperature control intelligent power saving pad pasting prepared will launch city
?.But the main inventive person as above-mentioned technology, while noticing that above-mentioned vanadium dioxide temperature control Intelligent energy-saving window still remains
Several deficiencies below: (1) to the insolation infrared band amplitude of accommodation with higher, but to the visible light for accounting for insolation gross energy 50%
Wave band hardly has adjustment effect, and result reduces global solar radiation regulation rate；(2) obvious due to not having in visible light wave range
Adjustment effect, enough visible changes can not be generated using this adjustings, to be helpless to the strong tune of customer's progress
Effect demonstration is saved, conclusive adverse effect is caused to conducting promotion to for product；(3) have strongly to short-wave band visible light
Sink effect leads to film yellow coloration.Mature technology there is no fundamentally to solve above-mentioned some problem so far.
Patent 1 (Chinese publication number CN106443854A) discloses a kind of quantum dot film comprising silicon dioxide layer, dioxy
Change vanadium layers and quantum dot layer, on the one hand which has the function of absorbing blue light, on the other hand by interelectric interaction
Have the function of reflecting blue light.Its quantum dot layer is prepared using the method for Electrostatic Absorption, and titanium dioxide vanadium layers are using vacuum evaporation
The membranous layer binding force of method preparation, Electrostatic Absorption preparation is weak, and vacuum evaporation is at high cost, and industrialized production is difficult.Moreover, used in it
Quantum dot is the visible light for absorbing blue emission and going out other colors, this can also generate screen view effect certain unfavorable shadow
It rings.
Summary of the invention
In view of the above-mentioned problems, the present invention uses fluorescent material and hypovanadic oxide-based thermochromic material to form composite wood for the first time
Material, and a kind of hypovanadic oxide-based composite fluorescent film and preparation method thereof is provided using it.
In a first aspect, the present invention provides a kind of hypovanadic oxide-based fluorescence composite material, including hypovanadic oxide-based thermotropic change
Color material and the fluorescent material for absorbing ultraviolet light transmitting blue light, the hypovanadic oxide-based thermochromic material and absorption ultraviolet light hair
The mass ratio for penetrating the fluorescent material of blue light is 1:(0.1~10), preferably 2:1~1:2.
The present invention issues blue light using the ultraviolet excitation fluorescent material in sunlight and (wherein, absorbs ultraviolet light and emit indigo plant
Light has carried out limitation explanation to its partial size), on the one hand supplement hypovanadic oxide-based thermochromic material in the absorption of blue light region,
The complementary color for realizing vanadium dioxide basement membrane improves its visible light transmittance, on the other hand obstructs (absorption) ultraviolet light, improves titanium dioxide
The uvioresistant performance of vanadium basement membrane.If hypovanadic oxide-based thermochromic material content is low, gained composite membrane is in infrared region energy tune
Section rate is too low, and inconvenience uses；If the fluorescent material content for absorbing ultraviolet light transmitting blue light is lower, illumination effect is unobvious, reaches
Effect less than complementary color and barrier ultraviolet light is unobvious.
Preferably, the hypovanadic oxide-based thermochromic material be vanadium dioxide, preferably rutile phase hypovanadic oxide or/
And monoclinic phase vanadium dioxide；The partial size of the hypovanadic oxide-based thermochromic material is 10nm~10 μm, preferably 20~80nm.
Preferably, the fluorescent material for absorbing ultraviolet light transmitting blue light is fluorescent whitening agent OB, quantum dot, has nucleocapsid
At least one of quantum dot of structure, preferably ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgTe, GaN, GaAs,
At least one of InP, InAs, CdSe@ZnS core shell quantum dot (CdSe coats the core-shell quanta dots that ZnS is formed).
Second aspect, the present invention provides a kind of hypovanadic oxide-based composite fluorescent film, the hypovanadic oxide-based fluorescence is compound
Film is the organic polymer composite membrane formed containing above-mentioned hypovanadic oxide-based fluorescence composite material.
Preferably, the mass ratio of the hypovanadic oxide-based thermochromic material and organic polymer is 1:(1~100), it is excellent
It is selected as 1:(3~50).
Preferably, the hypovanadic oxide-based composite fluorescent film with a thickness of 1~200 μm.
Preferably, the organic polymer is carbochain polymer, heterochain polymer, at least one in elemento-organic polymer
Kind, preferably plycrystalline diamond resin, organic siliconresin, polyacrylic resin, polyethyleneglycol resins, polyvinyl butyral resin and poly-
At least one of vinyl alcohol resin.
The third aspect, the present invention also provides a kind of hypovanadic oxide-based composite fluorescent films, including are sequentially formed at substrate table
The organic polymer films containing hypovanadic oxide-based thermochromic material in face and the phosphor for containing absorption ultraviolet light transmitting blue light
Expect the organic polymer films of (fluorescent material).
Layered structure in the present invention is the interface of organic polymer resin, vanadium dioxide material and phosphor on interface
Material will not generate interelectric interaction (or very faint) without good contact.And it is hypovanadic oxide-based thermotropic in the present invention
Off-color material and fluorescent material have the ability for absorbing ultraviolet light, and the two is competitive relation, and the sun can be made by forming two layers of composite membrane
Light first passes through fluorescent material, to be converted into blue light, the ultraviolet light of only minute quantity (< 1%) can reach vanadium dioxide film layer,
To which fluorescence complementary color effect and ultraviolet protection effect are more obvious, the light transmittance of film is greatly improved.
Preferably, the quality of the fluorescent material of the hypovanadic oxide-based thermochromic material and absorption ultraviolet light transmitting blue light
Than for 1:(0.1~10), preferably 2:1~1:2.
Preferably, vanadium oxide base thermochromism in the organic polymer films containing hypovanadic oxide-based thermochromic material
The mass ratio of material and organic polymer is 1:(1~100), preferably 1:(3~50)；It is described blue containing ultraviolet light transmitting is absorbed
The mass ratio of fluorescent material and organic polymer is 1:(1~100 in the organic polymer films of the fluorescent material of light), preferably 1:
(2~10).
Preferably, the organic polymer films containing hypovanadic oxide-based thermochromic material or containing absorb ultraviolet light hair
Penetrate the organic polymer films of the fluorescent material of blue light with a thickness of 1~100 μm.
Preferably, the organic polymer is carbochain polymer, heterochain polymer, at least one in elemento-organic polymer
Kind, preferably plycrystalline diamond resin, organic siliconresin, polyacrylic resin, polyethyleneglycol resins, polyvinyl butyral resin and poly-
At least one of vinyl alcohol resin.
Preferably, the hypovanadic oxide-based thermochromic material is vanadium dioxide；Preferably, the vanadium dioxide is golden red
Stone phase or/and monoclinic phase vanadium dioxide.
Preferably, the partial size of the hypovanadic oxide-based thermochromic material is 10nm~10 μm, preferably 20~80nm.
Preferably, the fluorescent material for absorbing ultraviolet light transmitting blue light is fluorescent whitening agent OB, quantum dot, has nucleocapsid
At least one of quantum dot of structure, preferably ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgTe, GaN, GaAs,
At least one of InP, InAs, CdSe@ZnS core shell quantum dot.
Preferably, the organic polymer is carbochain polymer, heterochain polymer, at least one in elemento-organic polymer
Kind, preferably plycrystalline diamond resin, organic siliconresin, polyacrylic resin, polyethyleneglycol resins, polyvinyl butyral resin and poly-
At least one of vinyl alcohol resin.
Fourth aspect, the present invention also provides a kind of according to above-mentioned hypovanadic oxide-based composite fluorescent film (single layer composite membrane)
Preparation method, comprising:
Above-mentioned hypovanadic oxide-based fluorescence composite material is dispersed in solvent, mixed dispersion liquid is obtained；
Organic polymer is added to gained mixed dispersion liquid, obtains slurry；
Gained slurry is coated in substrate surface, then cured, obtains the hypovanadic oxide-based composite fluorescent film.
Preferably, the solvent is at least one of toluene, dimethylbenzene, ethyl alcohol, acetone；The mixed dispersion liquid it is dense
Degree is 0.1~10wt%.
5th aspect, the present invention also provides it is a kind of according to above-mentioned hypovanadic oxide-based composite fluorescent film (layering it is compound
Film) preparation method, comprising:
The fluorescent material of hypovanadic oxide-based thermochromic material and absorption ultraviolet light transmitting blue light is dispersed in solvent respectively
In, obtain mixed dispersion liquid 1 and mixed dispersion liquid 2；
Organic polymer is added separately to gained mixed dispersion liquid 1 and mixed dispersion liquid 2, obtains slurry and slurry 2；
By gained slurry 1 be coated in substrate surface, then it is cured after, obtain hypovanadic oxide-based thermochromic material layer；
In the hypovanadic oxide-based thermochromic material layer surface coating slurry 2 of gained, then through secondary curing, obtain the vanadium dioxide
Base composite fluorescent film.
Preferably, the solvent is at least one of toluene, dimethylbenzene, ethyl alcohol, acetone；1 He of mixed dispersion liquid
The concentration of mixed dispersion liquid 2 is 0.1~10wt%.
Beneficial effects of the present invention:
(1) present invention supplements hypovanadic oxide-based thermochromic material in indigo plant using the fluorescent material for absorbing ultraviolet light and emitting blue light
The absorption in light area increases the light transmittance of film；
(2) it since ultraviolet light induced off-color material can absorb ultraviolet light, reduces and even avoids hypovanadic oxide-based thermochromism absorption
To its unfavorable ultraviolet light, promote its uvioresistant irradiation stability；
(3) preparation method of the present invention is simple, is easy to produce in enormous quantities, may be used at building and automobile-used thermochromism intelligent power saving
Pad pasting, Intelligent energy-saving window etc. realize the tremendous breakthrough for hypovanadic oxide-based thermochromism Energy Saving Windows application technology.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the composite membrane of the multilayered structure prepared in embodiment 1；
Fig. 2 is the structural schematic diagram of hypovanadic oxide-based composite fluorescent film prepared by embodiment 2；
Fig. 3 is fluorescence spectrum of the OB fluorescent whitening agent under 365nm excitation；
Fig. 4 be in embodiment 1 the hypovanadic oxide-based composite fluorescent film for preparing at room temperature penetrate spectrum；
Fig. 5 be in comparative example 1 the hypovanadic oxide-based thermochromic film for preparing at room temperature penetrate spectrum；
Fig. 6 be comparative example 2 in prepare containing absorb ultraviolet light emit blue light fluorescent material film at room temperature penetrate light
Spectrum.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
In the disclosure, purple using hypovanadic oxide-based thermochromic material (for example, vanadium dioxide nano particle) and absorption
(wherein, the hypovanadic oxide-based thermochromism of hypovanadic oxide-based fluorescence composite material is prepared in the fluorescent material of outside line transmitting blue light
Material and the mass ratio for absorbing the fluorescent material of ultraviolet light transmitting blue light are 1:(0.1~10), preferably 2:1~1:2), it is used in combination
In hypovanadic oxide-based composite fluorescent film film is prepared.Wherein, hypovanadic oxide-based thermochromism is supplemented in indigo plant by fluorescent material
The absorption in light area realizes the complementary color of vanadium dioxide basement membrane, to reach demand of the consumer to film color.And fluorescent material can also mention
It rises the light transmittance of hypovanadic oxide-based thermochromic film and adjusts its color.
In one embodiment of the present invention, hypovanadic oxide-based composite fluorescent film is to contain hypovanadic oxide-based thermochromism material
Material and absorb ultraviolet light transmitting blue light fluorescent material formed organic polymer composite membrane, thermochromism near 40 DEG C
Reversible progress.The color of hypovanadic oxide-based composite fluorescent film realizes complementary color by the fluorescent material that absorption ultraviolet light emission goes out blue light.
In alternative embodiments, the mass ratio of hypovanadic oxide-based thermochromic material and organic polymer can be 1:
100~1:1, preferably 1:50~1:3.
In another embodiment of the present invention, the present invention is by the organic polymer containing vanadium dioxide solid phase nano particle
Dispersed system and containing absorb ultraviolet emission blue light fluorescent material organic polymer formed composite membrane, thermochromism
In 40 DEG C of reversible progress nearby.The color of hypovanadic oxide-based composite fluorescent film is gone out the fluorescent material of blue light by absorption ultraviolet light emission
Realize complementary color.
In the disclosure, hypovanadic oxide-based thermochromic material has with what the fluorescent material for absorbing ultraviolet emission blue light was formed
The single layer composite membrane or multilayer film that machine composite membrane of polymer complex form both either directly mixes be compound or titanium dioxide
Vanadium base fluorescence composite material, secondly the mass ratio of vanadium oxide particle and fluorescent powder can be 1:0.1~1:10, preferably 2:1~
1:2。
In the disclosure, vanadium dioxide particle is doping and/or undoped Rutile Type (space group P42/ mnm) and/
Or monoclinic phase (space group P21/ c) vanadium dioxide, and whether there is or not the vanadium dioxide particles of clad.Wherein, vanadium dioxide
The particle size range of grain can be 10nm~10 μm, preferably 20~80nm.
In alternative embodiments, the fluorescent material of hypovanadic oxide-based thermochromic material and absorption ultraviolet emission blue light
Thickness can be 1~200 μm after film layer solidification when the two directly mixes.Hypovanadic oxide-based thermochromic material and absorption ultraviolet emission
Thickness can be 1~100 μm after the fluorescent material of blue light prepares each film layer solidification of film layer compound tense respectively.
In alternative embodiments, absorb ultraviolet emission blue light fluorescent material be fluorescent whitening agent (
OB), quantum dot (for example, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgTe, GaN, GaAs, InP, InAs etc.), tool
It is preferably glimmering by one or more in the quantum dot (any at least two core-shell structure formed in above-mentioned quantum dot) of core-shell structure
Optical brightener OB (OB fluorescent whitening agent, molecular formula C26H26N2O2) or CdSe@ZnS core shell quantum dot S.Organic polymer material
There is certain bond strength with certain film forming and after solidifying, in carbochain polymer, heterochain polymer, elemento-organic polymer
At least one.
In the present invention, the fluorescent material (fluorescent material) for absorbing ultraviolet emission blue light, which is can absorb, vanadium dioxide basement membrane
Harmful ultraviolet light, can reinforcing material photochemical stability, and the method prepare it is at low cost, simple and reliable, it is easy to accomplish big rule
Mould production.Illustrate to following exemplary the preparation method of hypovanadic oxide-based composite fluorescent film.
Hypovanadic oxide-based thermochromic material and fluorescent material are homogeneously dispersed in organic polymer and form stable slurry.
Then slurry obtained is coated in substrate (for example, the transparent objects such as glass, PET, PMMA polyester) surface, is formed after its solidification purple
Emit the organic polymer composite membrane of blue light under outer illumination.Wherein, further include solvent in slurry, solvent can for toluene, dimethylbenzene,
At least one of ethyl alcohol, acetone.
It is formed alternatively, hypovanadic oxide-based thermochromic material is homogeneously dispersed in organic polymer with fluorescent material respectively
Stable slurry 1 and slurry 2.Then slurry 1 obtained is coated in substrate surface, slurry 2 is coated with after its solidification, through secondary solid
Change, ultimately forms the organic polymer composite membrane for emitting blue light under ultraviolet lighting.It wherein, further include molten in slurry 1 and slurry 2
Agent, solvent can be at least one of toluene, dimethylbenzene, ethyl alcohol, acetone.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.In following embodiments unless otherwise specified, titanium dioxide
The partial size of vanadium particle is 30~60nm；OB fluorescent whitening agent is fluorescent whitening agentOB。
Embodiment 1
The dispersion liquid that 0.1g vanadium dioxide particle ultrasonic disperse forms 5wt% in 2g ethyl alcohol is weighed, 4g is then added thereto
Silicone resin forms uniform slurry by magnetic agitation, (glass etc.) is applied on substrate by the way of blade coating, at room temperature
It places 2h and waits for its solidification (heating in baking oven can also be put into and accelerate its solidification), obtain hypovanadic oxide-based thermochromic film, with a thickness of
80 μm, yellow is presented.
OB fluorescent whitening agent is dissolved in the solution for forming 5wt% in toluene, the 2g dispersion liquid is taken and is added thereto
2.5g plycrystalline diamond resin and 1g silicone resin, magnetic agitation form uniform slurry, and are scratched previously prepared vanadium dioxide
In base thermochromic film, it can reach solar irradiation after its solidification and penetrate lower film (overall thickness is 200 μm) sending blue light.
Embodiment 2
In mass ratio be vanadium dioxide particle: Quantum dots CdS e@ZnS=1:1 is added in ball mill, is equipped with toluene as solvent suitable
Work as dispersing agent, obtain the mixed dispersion liquid of vanadium dioxide particle and photosensitive powder, concentration 5wt% then takes 2g dispersion liquid
And 4g silicone resin is added thereto, uniform slurry is formed by magnetic agitation, is applied on substrate by the way of blade coating,
To its solidification, the hypovanadic oxide-based composite fluorescent film with a thickness of 120 μm is obtained.
Embodiment 3
Hypovanadic oxide-based thermochromic film is prepared by embodiment 1, with a thickness of 80 μm；
Quantum dot powder CdSe@ZnS toluene is made into the dispersion liquid that solvent forms by ball milling 5wt%, take 0.5 respectively, 1,3,
4g dispersion liquid, and 2.5g plycrystalline diamond resin and 1g silicone resin are added thereto, magnetic agitation forms uniform slurry, and is scratched
Onto previously prepared hypovanadic oxide-based thermochromic film, obtain the adjustable film of light emission luminance (overall thickness is 200 μm).
Embodiment 4
Hypovanadic oxide-based thermochromic film is prepared by embodiment 1, with a thickness of 80 μm；
OB fluorescent whitening agent is dissolved in the solution for forming 5wt% in toluene, takes 0.5,1,3,4g dispersion liquid respectively, and thereto
2.5g plycrystalline diamond resin is added and 1g silicone resin, magnetic agitation form uniform slurry, and is scratched previously prepared dioxy
Change in vanadium base thermochromic film, obtain the adjustable film of light emission luminance (overall thickness is 200 μm).
Embodiment 5
In mass ratio be vanadium dioxide particle: OB fluorescent whitening agent=1:1 is added in ball mill, is equipped with suitably with toluene as solvent
Dispersing agent, obtains the mixed dispersion liquid for containing hypovanadic oxide-based fluorescence composite material, and concentration 5wt% then takes 2g to disperse
Simultaneously 4g silicone resin is added in liquid thereto, forms uniform slurry by magnetic agitation, substrate is applied to by the way of blade coating
On, to its solidification, obtain the hypovanadic oxide-based composite fluorescent film with a thickness of 120 μm.
Comparative example 1
Hypovanadic oxide-based thermochromic film is prepared by embodiment 1, it is seen that light transmission rate is 74.4% (referring to Fig. 5), with a thickness of 80 μ
m。
Comparative example 2
OB fluorescent whitening agent is dissolved in the solution for forming 5wt% in toluene, take the 2g dispersion liquid and 2.5g is added thereto is poly-
Brilliant resin and 1g silicone resin, magnetic agitation forms uniform slurry, and is scratched on substrate, obtains containing absorption ultraviolet light
Emit blue light fluorescent material film, absorb ultraviolet light emission blue light, correspond to spectrum middle-ultraviolet lamp area's transmitance close to
0, blue light region transmitance is greater than 100%, as shown in Figure 6.
Fig. 3 is fluorescence spectrum of the OB fluorescent whitening agent under 365nm excitation, its fluorescence generation peak is located at as can be seen from Figure
Between 400-600nm, highest peak is located at 440nm, just at blue light region；
Fig. 4 be in embodiment 1 the hypovanadic oxide-based composite fluorescent film for preparing at room temperature penetrate spectrum, as can be seen from Figure two
One layer of its visible light transmittance rate of OB fluorescent whitening agent film is covered in vanadium oxide base thermochromic film to improve from 74.4% to 80.8%.
Above embodiments are served only for that invention is further explained, should not be understood as the limit to the scope of the present invention
System, some nonessential modifications and adaptations that those skilled in the art's above content according to the present invention is made belong to this hair
Bright protection scope.
Claims (13)
1. a kind of hypovanadic oxide-based fluorescence composite material, which is characterized in that including hypovanadic oxide-based thermochromic material and absorption
Ultraviolet light emits the fluorescent material of blue light, the hypovanadic oxide-based thermochromic material and the fluorescence for absorbing ultraviolet light transmitting blue light
The mass ratio of material is 1:(0.1~10), preferably 2:1~1:2.
2. hypovanadic oxide-based fluorescence composite material according to claim 1, which is characterized in that described hypovanadic oxide-based thermotropic
Off-color material is vanadium dioxide, preferably rutile phase hypovanadic oxide or/and monoclinic phase vanadium dioxide；The hypovanadic oxide-based heat
The partial size for causing off-color material is 10nm~10 μm, preferably 20~80nm.
3. hypovanadic oxide-based fluorescence composite material according to claim 1 or 2, which is characterized in that the absorption ultraviolet light
Emit the fluorescent material of blue light at least one of fluorescent whitening agent OB, quantum dot, the quantum dot with core-shell structure, preferably
For in ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgTe, GaN, GaAs, InP, InAs, CdSe@ZnS core shell quantum dot
At least one.
4. a kind of hypovanadic oxide-based composite fluorescent film, which is characterized in that the hypovanadic oxide-based composite fluorescent film is containing having the right
It is required that the organic polymer composite membrane that hypovanadic oxide-based fluorescence composite material is formed described in any one of 1-3.
5. hypovanadic oxide-based composite fluorescent film according to claim 4, which is characterized in that the hypovanadic oxide-based thermotropic change
The mass ratio of color material and organic polymer is 1:(1~100), preferably 1:(3~50).
6. hypovanadic oxide-based composite fluorescent film according to claim 4 or 5, which is characterized in that described hypovanadic oxide-based glimmering
Photoreactivation film with a thickness of 1~200 μm.
7. a kind of hypovanadic oxide-based composite fluorescent film, which is characterized in that contain titanium dioxide including be sequentially formed at substrate surface
The organic polymer of the organic polymer films of vanadium base thermochromic material and the fluorescent material containing absorption ultraviolet light transmitting blue light
Film.
8. hypovanadic oxide-based composite fluorescent film according to claim 7, which is characterized in that described to contain hypovanadic oxide-based heat
Cause off-color material organic polymer films in the mass ratio of hypovanadic oxide-based thermochromic material and organic polymer be 1:(1~
100), preferably 1:(3~50)；Fluorescence in the organic polymer films containing the fluorescent material for absorbing ultraviolet light transmitting blue light
The mass ratio of material and organic polymer is 1:(1~100), preferably 1:(2~10).
9. hypovanadic oxide-based composite fluorescent film according to claim 7 or 8, which is characterized in that described to contain vanadium dioxide
The organic polymer films of the organic polymer films of base thermochromic material or the fluorescent material containing absorption ultraviolet light transmitting blue light
With a thickness of 1~100 μm.
10. the hypovanadic oxide-based composite fluorescent film according to any one of claim 7-9, which is characterized in that the dioxy
Change vanadium base thermochromic material is vanadium dioxide, preferably rutile phase hypovanadic oxide or/and monoclinic phase vanadium dioxide；Described two
The partial size of vanadium oxide base thermochromic material is 10nm~10 μm, preferably 20~80nm.
11. the hypovanadic oxide-based composite fluorescent film according to any one of claim 7-10, which is characterized in that the absorption
Ultraviolet light emits the fluorescent material of blue light as at least one in fluorescent whitening agent OB, quantum dot, the quantum dot with core-shell structure
Kind, preferably ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgTe, GaN, GaAs, InP, InAs, CdSe@ZnS core shell
At least one of quantum dot.
12. the hypovanadic oxide-based composite fluorescent film stated according to any one of claim 7-11, which is characterized in that the titanium dioxide
Vanadium base thermochromic material and the mass ratio for absorbing the fluorescent material of ultraviolet light transmitting blue light are 1:(0.1~10), preferably 2:1
~1:2.
13. the hypovanadic oxide-based composite fluorescent film according to any one of claim 4-12, which is characterized in that described organic
Polymer is at least one of carbochain polymer, heterochain polymer, elemento-organic polymer, preferably plycrystalline diamond resin, organic
At least one in silicone resin, polyacrylic resin, polyethyleneglycol resins, polyvinyl butyral resin and polyvinyl alcohol resin
Kind.
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