CN103074002A - Intelligent temperature-control energy-saving composite coating film - Google Patents

Intelligent temperature-control energy-saving composite coating film Download PDF

Info

Publication number
CN103074002A
CN103074002A CN201210019446XA CN201210019446A CN103074002A CN 103074002 A CN103074002 A CN 103074002A CN 201210019446X A CN201210019446X A CN 201210019446XA CN 201210019446 A CN201210019446 A CN 201210019446A CN 103074002 A CN103074002 A CN 103074002A
Authority
CN
China
Prior art keywords
temperature control
intelligent temperature
coating
vanadium dioxide
energy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201210019446XA
Other languages
Chinese (zh)
Other versions
CN103074002B (en
Inventor
刘奕燎
蔡朝辉
林裕卫
吴耀根
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FSPG Hi Tech Co Ltd
Original Assignee
FSPG Hi Tech Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by FSPG Hi Tech Co Ltd filed Critical FSPG Hi Tech Co Ltd
Priority to CN201210019446.XA priority Critical patent/CN103074002B/en
Priority to PCT/CN2012/072024 priority patent/WO2013107082A1/en
Publication of CN103074002A publication Critical patent/CN103074002A/en
Application granted granted Critical
Publication of CN103074002B publication Critical patent/CN103074002B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/028—Pigments; Filters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The invention relates to an intelligent temperature-control energy-saving composite coating film comprising, from inside to outside, a release film layer, an installation adhesive coating layer, a vanadium dioxide intelligent temperature-control coating provided by the invention, a substrate, and a surface functional layer. The intelligent temperature-control coating is formed by coating a mixture of vanadium dioxide powder slurry, polymer emulsion, and a coating auxiliary agent on a substrate. The vanadium dioxide powder slurry comprises vanadium dioxide composite powder and a dispersing medium. The vanadium dioxide composite powder comprises vanadium dioxide nano-powder with a chemical structure of V1-xMxO2; organic modification long-chain molecules are grafted on the surface of the nano-powder, wherein M is a doping element, and x is no smaller than 0 and no greater than 5. The intelligent temperature-control energy-saving composite coating film provided by the invention has a multi-layer structure. The surface functional layer provides high-performance characteristics such as scratch resistance, wear resistance, stain resistance, fingerprint resistance, static resistance, and the like. With the film, wear resistance requirement of daily washing can be satisfied, and building can look as new after long time use.

Description

The energy-conservation composite film-stuck of a kind of intelligent temperature control
Technical field
The present invention relates to the energy-conservation composite film-stuck of a kind of intelligent temperature control.The energy-conservation pad pasting of the intelligent temperature control of this invention can be realized cold and hot two-ways regulation, and it is warming to reach winter, summer cold insulation effect, thereby effective save energy is mainly used at building doors and windows vehicle glass or Industrial Metal container etc.
Background technology
The building energy consumption of China has accounted for 27.8% of social total energy consumption, and wherein the energy consumption of heating and air-conditioning accounts for 55% of building total energy consumption.In modern building, it is increasing that glass accounts for the area ratio of exterior wall, and the heat of being undertaken by glass port according to measuring and calculating is delivered in winter and summer and accounts for respectively 48% and 71%.If adopt air-conditioning to regulate room temp, refrigeration temperature improves 2 ℃, and cooling load reduces about 20%; Heat temperature and turn down 2 ℃, heating load reduce about 30%, by sticking thermal isolation film or the coating heat insulating coat can significantly reduce energy consumption on glass.
Present thermal isolation film or coating on the market is main still to intercept infrared property as main, can not change by response environment, they only have the function of reflects infrared light, and at low temperatures through ultrared effect, can not play the effect of intelligent surge chamber internal-external temperature difference, the needs searching is a kind of can intelligence regulate the material of solar heat, thereby realizes effect cool in summer and warm in winter.
The vanadium dioxide material has the first-order phase transition characteristic, but the induced environment temperature variation, and this variation of intelligent response realizes that the band selective to sunlight sees through or covers.Usually when envrionment temperature was lower than transformation temperature, the film or the coating that contain vanadium dioxide almost were fully penetrating to the visible light in the sunlight and mid-infrared light; When temperature surpassed the semi-conductor of vanadium dioxide-metal phase change temperature, vanadium dioxide underwent phase transition and is converted into the R phase, and this moment, material can to the blocking of mid-infrared light selectivity, reach the purpose of transparent (visible light sees through) thermal resistance.Semi-conductor-the metal phase change of vanadium dioxide is thermoinducible reversible change, and its temperature switch effect can be used to the ultrared break-make of centering and carries out intelligent control.Utilize vanadium dioxide low under the infrared light district high temperature see through and low temperature under high transmission, can prepare the Energy Saving Windows port system of complete intelligence.
Optical computing shows (S.-Y.Li, a_G.A.Niklasson, and C.G.Granqvist Nanothermochromics:Calculations for VO 2Nanoparticles in dielectric hosts show much improved luminous transmittance and solar energy transmittance modulation, JOURNAL OF APPLIED PHYSICS 108,0635252010) if vanadium dioxide nano powder can be scattered in other matrix, such as transparent polymer, can be on the basis that keeps vanadium dioxide optics performance of control, improve visible light transmissivity to realistic scale, can carry out reducing energy consumption to the outside surface of the transportation means such as in commission glass, metope and car and boat.By the vanadium dioxide material being accomplished nano-scale and can being prepared a kind of intelligent temperature control coating with organically-modified Material cladding, but because the nanoparticle specific surface area is little and surface free energy is high, be easy between the particle reunite, this specific character has determined direct the vanadium dioxide nano particle to be joined in the coating, be difficult to the performance of real performance nano material, and reunite easily, affect optical property and the outward appearance of coating, thereby limited the application of material on adhering film to glass and transparent glass.As having mentioned a kind of vanadium dioxide intelligent temperature control coating in the Chinese patent application numbers 200410051965, but its vanadium dioxide particle of mentioning belongs to unmodified vanadium dioxide particle, do not relate to the pre-treatment of particle, particularly the vanadium dioxide particle mentioned of the present invention carries out front dispersion treatment, and particularly organically-modified processing is for the raising of its dispersing property and chemical stability performance.
Chinese patent application number: 200610117027.4 mention a kind of preparation method of hypovanadic oxide suspensoid, the dispersion treatment that wherein relates to hypovanadic oxide powder, but what it adopted is inorganic modified method, prepare the vanadium dioxide composite particles from organically-modified scheme that the present invention takes the different of essence are arranged, and adopt acidity or alkaline condition in the invention, can destroy the structure of vanadium dioxide.
Chinese patent application number: mentioned the surface treatment of light modulation paint particles in 200980123044.0 thermo-color microparticals and dispersion liquid thereof and manufacture method and light modulation coating, light modulation film, the light modulation printing ink, but it does not propose concrete method of modifying, and this invention processing is that titanium dioxide has the different of essence with the related vanadium dioxide composite granule of vanadium dioxide composite particles and this patent summary of the invention.
Chinese patent application numbers 200810033032.6 has been mentioned a kind of intelligent heat-insulating film and preparation method thereof, but it is not to the VO2 particle, particularly the present invention mentions son and carries out organically-modified front dispersion treatment, the present invention with organically-modified hypovanadic oxide powder modification after, after particularly silane coupling agent is processed, powder dispersity is greatly improved, the performance of real performance nano material, result near Theoretical Calculation, prepared intelligent temperature control coating significantly improves the performance of control of infrared light, near the result of Theoretical Calculation; Should invention be single layer structure simultaneously, we then comprise 5 layers of structure, have increased wear-resisting, antifouling, the explosion-proof and installation capability of pad pasting.
Chinese patent application number: CN101265374A discloses a kind of vanadium dioxide solar heat intelligent temperature control polymer film, it prepares by vanadium dioxide is directly joined in the polymeric film, the present invention then prepares by coating, the coating transparency of simultaneously the present invention preparation is higher, mist degree is less, and performance is more excellent.
Summary of the invention
Use hypovanadic oxide powder and hypovanadic oxide powder and the compound preparation film of other materials, method is simple, is convenient to large-scale operation, not only can be used for the energy-saving transformation of original glass port, and can be coated on the different substrates, enlarges the applicability of vanadium dioxide.But hypovanadic oxide powder is prepared into the vanadium dioxide slurries, when forming film and coating, requires hypovanadic oxide powder to have excellent dispersing property and chemical stability.
At this, the invention provides a kind of vanadium dioxide composite granule, comprise that chemical constitution is V 1-xM xO 2Vanadium dioxide nano powder, the vanadium dioxide nano powder surface is connected to machine modification long chain molecule, wherein M is doped element, 0≤x≤0.5.
Vanadium dioxide composite granule of the present invention, organically-modified to the surface process of vanadium dioxide and Dope nano-power thereof.It is different from the hypovanadic oxide powder of general unmodified or inorganic parcel and modification, and the mode by organic modifiers makes the vanadium dioxide surface connect organically-modified long chain molecule, thereby greatly improves chemical stability and the dispersiveness of hypovanadic oxide powder.Use vanadium dioxide composite granule stability provided by the invention and good dispersity, can prolonged preservation use, can be used as intelligent heat insulation powder and be applied to prepare intelligent energy-saving coating or coating, also can be used for the heat insulation occasions such as glass and exterior wall.It is different from general lagging material, and it can significantly intercept infrared light when transformation temperature is above, can highly see through and be lower than the transformation temperature infrared rays, and this variation is reversible, can realize that the intelligence of solar heat is regulated.
Preferably, in the vanadium dioxide composite granule of the present invention, the content of organically-modified long chain molecule is 0.1～50%.More preferably, organically-modified long chain molecule content is 1～10%.Organically-modified long chain molecule content is too small, then can't realize the abundant parcel of powder surface; Organically-modified long chain molecule content is excessive, can cause mutually tangling between the organic molecule, affects on the contrary dispersion effect.
Preferably, organically-modified long chain molecule chain length is at 0.1nm～100nm.
The present invention relates to the organic surface modifying of vanadium dioxide nano particle, can effectively improve the dispersiveness of vanadium dioxide and Dope nano-power thereof and the chemical stability of powder.
Organically-modified long chain molecule is for comprising the functionalized organic long-chains such as chain alkyl, polyacrylic acid group, polyvinyl alcohol group, epoxide group, chain alkyl amine groups, halogenation chain alkyl, carboxylated chain alkyl.
Vanadium dioxide composite granule of the present invention, by the grafting of organically-modified properties-correcting agent on the hypovanadic oxide powder surface, be wrapped in the hypovanadic oxide powder surface, thereby can change the surface property of vanadium dioxide, difference according to selected group, can increase the dispersing property of vanadium dioxide composite particles in different solvents, expand the purposes of vanadium dioxide particle in intelligent temperature control coating or coating.
Preferably, the vanadium dioxide nano powder in the vanadium dioxide composite granule of the present invention is Rutile Type, and phase transition temperature is adjustable at-20～70 ℃.The shared ratio of rutile phase hypovanadic oxide can be up to 80%, even can reach 100%.This vanadium dioxide nano powder has the first-order phase transition characteristic, but the induced environment temperature variation, and this variation of intelligent response realizes that the band selective to sunlight sees through or covers.Usually when envrionment temperature was lower than transformation temperature, the film or the coating that contain vanadium dioxide almost were fully penetrating to the visible light in the sunlight and mid-infrared light; When temperature surpassed the semi-conductor of vanadium dioxide-metal phase change temperature, vanadium dioxide underwent phase transition and is converted into the R phase, and this moment, material can to the blocking of mid-infrared light selectivity, reach the purpose of transparent (visible light sees through) thermal resistance.Semi-conductor-the metal phase change of vanadium dioxide is thermoinducible reversible change, and its temperature switch effect can be used to the ultrared break-make of centering and carries out intelligent control.
The doped element M of regulation can be or arbitrary combination in the elements such as near 21～30 transition element the vanadium in the periodic table of elements, tin and near element thereof and tungsten, molybdenum, ruthenium, niobium in the present invention.Wherein, near 21～30 transition element in the periodic table of elements vanadium comprise scandium, titanium, chromium, manganese, iron, cobalt, nickel, copper and zinc, and described tin and near element thereof comprise indium, antimony, tin, gallium, germanium, lead and bismuth.Preferred doped element is tungsten, molybdenum, bismuth, tin, iron, zinc and titanium.
Adopt above-mentioned doped element, can controlled doping hypovanadic oxide powder size and pattern, used doped element equally also can be regulated and control the phase transition temperature of vanadium dioxide.
In the present invention, doped vanadium dioxide powder is preferably particulate state, and the length-to-diameter ratio of particle is 1: 1～10: 1, is preferably 1: 1～5: 1, more preferably 1: 1～2: 1.Particle size is not more than 1um at least one dimension, preferably is not more than 100nm at least one dimension, more preferably all is not more than 100nm on three dimensions, most preferably all is not more than 70nm on three dimensions.Described particulate state can be such as subsphaeroidal, oval, snowflake shape, cube, sheet shape etc.
Hypovanadic oxide powder dispersed better with above-mentioned size and pattern.Dispersiveness through the composite granule after the modification also will be further enhanced.
The application also provides a kind of preparation method of vanadium dioxide composite granule, comprises that operation (1) is scattered in vanadium dioxide nano powder in the dispersion medium, gets mixture A; (2) in described mixture A, add dispersing auxiliary and the organic modifiers that is used to form hypovanadic oxide powder surface organic modification long chain molecule, be stirred to and fully mix to get mixture B; (3) mixture B drying is made organically-modified vanadium dioxide composite granule.
Hypovanadic oxide powder can be rutile phase hypovanadic oxide nanoparticle or doped rutile phase hypovanadic oxide nanoparticle.Can be the method preparation that provides according to publication 2010PA011267CN, also can be rutile phase hypovanadic oxide nanoparticle or the doped rutile phase hypovanadic oxide nanoparticle of other known method preparations.The powder granule gravel size decision is below 200nm.The pattern of powder can be particle, nanometer rod and flakes particle.If preparation doped rutile phase hypovanadic oxide nanoparticle, before doped element, can adopt alkaline reagents to process presoma (the tetravalent vanadium ion aqueous solution), can obtain the controlled hypovanadic oxide powder size of size and pattern (being not more than 1um at least one dimension) and pattern (particulate state, length-to-diameter ratio is not more than 10: 1), the hypovanadic oxide powder grain-size of preparation is little, uniform particle diameter, and stable crystal form, it is at water, good dispersity in the dispersion agent (for example polyvinylpyrrolidone), be easy to be coated on the matrixes such as glass, be suitable for preparing film and the coating of hypovanadic oxide powder.
The preparation method of vanadium dioxide composite granule provided by the invention, the dispersing auxiliary that adds in the operation (2) can be polyvinyl alcohol, one or more in polyvinylpyrrolidone, organic modified polyorganosiloxane dipropylene glycol monomethyl ether solution, organic silicon surfactant or fluorochemical surfactant or the dispersing auxiliary known altogether in the industry.
The organic modifiers that adds among the preparation method of vanadium dioxide composite granule provided by the invention, operation (2) can be the organic modifiers such as stearic acid, polyacrylic acid, silane coupling agent, aluminate coupling agent or titanate coupling agent.Be preferably the silane coupling agent of pbz polymer long-chain.
Mode by coupling agent can make the vanadium dioxide surface connect the organic long-chain molecule, thereby greatly improves chemical stability and the dispersiveness of hypovanadic oxide powder.
Used dispersion medium can be ethanol among the preparation method of vanadium dioxide composite granule provided by the invention, one or more in the inert solvents such as Virahol, chloroform, dimethyl formamide, dimethyl sulfoxide (DMSO) ethylene dichloride or acetone.
In inert media, carry out organically-modifiedly, can prevent the sex change of vanadium dioxide, improve the chemical stability of powder.
The preparation method of vanadium dioxide composite granule provided by the invention, preparation technology's innovation, by the organic surface modifying process of organic modifiers, can effectively improve dispersiveness and the chemical stability of vanadium dioxide (vanadium dioxide) and Dope nano-power thereof.
In addition, the present invention also provides a kind of hypovanadic oxide powder slurry that comprises vanadium dioxide composite granule of the present invention.
Wherein, hypovanadic oxide powder slurry provided by the invention can possess, (1) vanadium dioxide composite granule, and it comprises that chemical constitution is V 1-xM xO 2Vanadium dioxide nano powder, and described powder surface is connected to machine modification long chain molecule, wherein M is doped element, 0≤x≤0.5; And (2) dispersion medium.
In the hypovanadic oxide powder slurry of the present invention, vanadium dioxide composite granule weight ratio can be 1: 1～1: 1000.Preferably, the weight ratio of vanadium dioxide composite granule and dispersion medium is 1: 10～1: 100.Vanadium dioxide composite granule by the present invention's preparation can effectively disperse in 0～50% scope.If from the application point of smart coat, the scope of 1%-10% more preferably.Too high levels can affect the transmittance of coating, crosses the low intelligent effect of heat insulation that then is difficult to bring into play coating.
Can select in deionized water, ethanol, propyl alcohol, Virahol, ethyl acetate, toluene, the butanone one or more as the dispersion medium in the hypovanadic oxide powder slurry of the present invention again.
In addition, vanadium dioxide composite granule slurry of the present invention can also comprise dispersing auxiliary, this dispersing auxiliary can be to be selected from polyacrylate, polyacrylamide, polyphosphoric acid salt, polyvinyl alcohol, polyvinylpyrrolidone, modified poly ester, one or more in modified polyurethane and the modified acroleic acid dispersion agent.
Again, the present invention further also provides a kind of vanadium dioxide intelligent temperature control coating, is coated on flexible substrates after this coating is mixed by hypovanadic oxide powder slurry of the present invention, polymer emulsion and coatings additive(s) and forms.
The solid content of vanadium dioxide composite granule is 0.1～50% in the vanadium dioxide intelligent temperature control coating provided by the invention.Be preferably 2%-20%.Similarly, effective film forming in the scope of the solid content 0.1～50% of vanadium dioxide composite granule in the vanadium dioxide intelligent temperature control coating.From application point, the too high transmittance that can affect coating of solid content is crossed the low intelligent effect of heat insulation that then is difficult to bring into play coating.
Vanadium dioxide intelligent temperature control coating dry film thickness provided by the invention is 0.05～50um.Be preferably 0.5～10um;The coating of thermal control coating can be adopted the modes such as spraying, blade coating, brushing, showering or roller coat, for the higher occasion of some precision requirement, the general mode that adopts roller coat, coating thickness can be adjusted according to the order number of coating roll and the solid content of coating fluid, and adopting advanced roller coating technology minimum can be 0.05um with build.
In addition, the present invention also provides a kind of intelligent temperature control energy-conservation composite film-stuck, comprises from inside to outside release film layer, gel coating, vanadium dioxide intelligent temperature control coating of the present invention, base material and surface functional layer are installed.
In each layer of composite film-stuck, the thickness of release film and base material can be identical, for example is 2～250um.The thickness that gel coating and surface functional layer are installed also can be identical, for example is 0.05～50um.Gel coating and surface functional layer are installed all can be prepared by coating process, coating method comprises the in the industry coating method in common knowledge such as spraying, blade coating, brushing, showering or roller coat.
In each layer of composite film-stuck, gel coating is installed is formed on the one side that base material contains the intelligent temperature control layer; Described release film is compound on the base material by gel coating is installed.Surface functional layer is formed on the base material one side relative with the intelligent temperature control layer.
Surface functional layer can be the high hard coating of UV light-cured polyurethane, the high hard coating of UV light-cured acrylic, the high hard coating of UV photocuring organosilicon, also comprise some heat curing epoxy hardening resins, the high hard coating of urethane, the high hard coating of vinylformic acid and the high hard coating of organosilicon etc., also comprise some antifouling waterproof paints, anti-fingerprint coating and Antistatic Paint etc.Can adopt the modes such as spraying, blade coating, brushing, showering or roller coat that surface functional layer is formed at base material.
Vanadium dioxide composite granule of the present invention and the hypovanadic oxide powder slurry that comprises this powder, can be applicable to prepare intelligent energy-saving coating or coating, the coating transparency of preparation is high, low, the ageing-resistant ability of mist degree is strong, be mainly used in film, the flexible materialss such as cloth also can be used for the heat insulation occasions such as glass and exterior wall.
The energy-conservation composite film-stuck of intelligent temperature control of the present invention is multilayered structure, and surface functional layer provides high performance anti scuffing, wear-resisting or anti-soil, anti-fingerprint, the characteristic such as antistatic, can satisfy the required wear-resisting requirement of daily cleaning, keeps buildings for a long time as new; The intelligent temperature control coating is coated on the base material, have by adding special construction that vanadium dioxide and the Dope nano-power thereof of phase changing function are realized solar heat intelligent temperature control performance at a certain temperature, automatic variation according to envrionment temperature, regulate the transmitance of sunlight, can utilize the solar control temperature variation; It is adhesion and the installation capability that product is provided convenience that gel coating and release film layer are installed, and explosion prevention function.If at building doors and windows, this film of surface label last layer of vehicle glass and Industrial Metal container can be realized cold and hot two-ways regulation, and it is warming to reach winter, summer cold insulation effect, can be effectively save energy.
Description of drawings
Fig. 1 is that the hypovanadic oxide powder surface is without the transmission electron microscope picture of organically-modified hypovanadic oxide powder;
Fig. 2 is that the hypovanadic oxide powder surface is through the transmission electron microscope picture of organically-modified vanadium dioxide composite granule;
Fig. 3 is the high low temperature graphic representation of vanadium dioxide intelligent temperature control coating in the example of the present invention; To have adopted vanadium dioxide composite granule of the present invention and slurry thereof and the high low temperature graphic representation of the intelligent temperature control coating for preparing;
Fig. 4 serves as reasons without the high low temperature graphic representation of the intelligent temperature control coating of organically-modified hypovanadic oxide powder preparation;
Fig. 5 is the structural representation of an energy-conservation composite film-stuck of example intelligent temperature control of the present invention.Its structure comprises release film 1 from inside to outside in this example, and gel coating 2, intelligent temperature control layer 3, base material 4 and surface functional layer 5 five-layer structures are installed.
Embodiment
Below, with reference to accompanying drawing, and further specify the present invention in conjunction with subordinate's embodiment.
Among the preparation method of vanadium dioxide composite granule of the present invention, comprise, vanadium dioxide nano powder is scattered in the dispersion medium, get the operation of mixture A; In described mixture A, add dispersing auxiliary and be used to form the organic modifiers of hypovanadic oxide powder surface organic modification long chain molecule, be stirred to and fully mix to get the operation of mixture B; Mixture B drying is made the operation of organically-modified vanadium dioxide composite granule.
The preparation method of above-mentioned vanadium dioxide composite granule, particularly, dispersion medium elder generation's high-speed stirring dispersing and mixing and the ultra-sonic dispersion that can be with weight percent content 1～50% hypovanadic oxide powder and 50～99% get mixture, in mixture, add again afterwards dispersing auxiliary and organic modifiers, 0～200 ℃ of lower stirring of constant temperature, disperse by modes such as ultrasonic, sand milling or ball millings, again centrifugation, vacuum-drying obtains organically-modified vanadium dioxide composite granule under the certain temperature.
Wherein, with in vanadium dioxide nano powder and the operation that dispersion medium mixes, the weight ratio of vanadium dioxide nano powder and dispersion medium can be 1: 1～1: 20.Preferably, the weight ratio of vanadium dioxide nano powder and dispersion medium is 1: 1～1: 10.It more preferably is 1: 2～1: 5.When weight ratio was too small, then hypovanadic oxide powder was low with the organic modifiers contact probability, needed long jitter time and larger properties-correcting agent consumption; Weight ratio is excessive, then is unfavorable for the abundant dispersion of powder in dispersion medium and wetting, affects the modified effect in later stage.
In the above-mentioned vanadium dioxide nano powder surface organic modification, organic modifiers can be the organic modifiers such as stearic acid, polyacrylic acid, silane coupling agent, aluminate coupling agent or titanate coupling agent, is preferably the silane coupling agent of pbz polymer long-chain.The amount that organic modifiers adds in the mixture can be 0.05～5 % by weight; Be preferably 0.1～2 % by weight.Organically-modified long chain molecule content is too small, then can't realize the abundant parcel of powder surface; Organically-modified long chain molecule content is excessive, can cause mutually tangling between the organic molecule, affects on the contrary dispersion effect.Mode by coupling agent can make the vanadium dioxide surface connect the organic long-chain molecule, thereby greatly improves chemical stability and the dispersiveness of hypovanadic oxide powder.In addition, used dispersing auxiliary can be polyvinyl alcohol, one or more in polyvinylpyrrolidone, organic modified polyorganosiloxane dipropylene glycol monomethyl ether solution, organic silicon surfactant or fluorochemical surfactant or the dispersing auxiliary known altogether in the industry.Dispersing auxiliary is mainly used in reducing the surface tension of solution, and the raising solvent is wetting powder surface, thereby improves dispersion effect.The amount that dispersing auxiliary adds in the mixture can be 0.02～2 % by weight; Be preferably 0.05～1 % by weight.Few add-on can reach needed dispersion effect.Add the surface organic modification process that too much can affect on the contrary powder.
The preparation method of hypovanadic oxide powder slurry provided by the invention, particularly, can be with weight percent content 0.1～50% hypovanadic oxide powder add 40～99% the middle and high speed of dispersion medium stir carry out pre-dispersed, in mixture, add again afterwards dispersing auxiliary, the hypovanadic oxide powder slurry that high-speed stirring must mix.Can described slurry be mixed by dispersion methods such as ultrasonic, ball milling and/or sand millings in addition.
Among the present invention, no matter be in the preparation process of vanadium dioxide composite granule or in the preparation process of composite granule slurry, the rotating speed of high-speed stirring can be 1000～3000rad/min.Ultrasonic power can be 50～5000W, and frequency is 21KHz.In addition, drum's speed of rotation can be chosen as 10～2000rad/min.Again, the rotating speed of sand mill can be 10～2000rad/min.Grinding medium can be selected zirconia balls, and particle diameter is preferably the grinding medium of small particle size at 0.02mm～50mm.
Be coated on flexible substrates after intelligent temperature control coating of the present invention is mixed by hypovanadic oxide powder slurry of the present invention, polymer emulsion and coatings additive(s) and form.Particularly, desirable hypovanadic oxide powder slurry 10～60 % by weight of the present invention, the polymer emulsion that adds therein 20～80 % by weight, and then adding amounts to the coatings additive(s) of 0.01～5 % by weight, for example wetting aid, film coalescence aid, flow agent, defoamer and/or thickening material, high-speed stirring stirs appropriate time, must be used for forming the mixed solution (coating) of coating.When being coated flexible substrates, the coating that makes to select the modes such as spraying, blade coating, brushing, showering or roller coat.Described base material can be the plastics film of the materials such as polypropylene (PP), polyethylene (PE), polymeric amide (PA), polyvinyl chloride (PVC), polyethylene terephthalate (PET) and polymethylmethacrylate (PMMA), the fiber or the woven bag that are perhaps prepared by these materials.
Film coalescence aid in the coatings additive(s) can be in ethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol methyl ether ether ester, propylene glycol monobutyl ether, glycol propyl ether, the dipropyl ether one or more.
Wetting aid in the coatings additive(s) can be in dodecyl sulfate, dodecane sulfonate, polyvinyl alcohol, polyvinylpyrrolidone, silicoorganic compound and the organofluorine compound one or more.
Defoamer in the coatings additive(s) can be in dimethyl silicone oil, ether ester compound, modified mineral oil, polyoxy ethyl glyceryl ether, small molecules metallorganics and the silicon modified organic polymer one or more.
Flow agent in the coatings additive(s) can be in butyl glycol ether, cellaburate, polyacrylate(s), silicone oil and the modified organic silicon compound one or more.
Thickening material in the coatings additive(s) can be cellulose thickener, polyethylene wax, aerosil, agent for polyacrylic acid thickening, or association type polyurethanes thickening material.
In addition, can also in coating, add 0.2～2% UV light absorber, use such as the UV light absorber that benzophenone and derivative, o-hydroxy-phenyl benzotriazole and derivative thereof, aromatic ester compound or hydroxy phenyl s-triazine and derivative thereof etc. all can be used as in the coating of the present invention.
Below, by embodiment the present invention is described in more details.
Should be understood that the above-mentioned embodiment that the present invention describes in detail, and following examples only are used for explanation the present invention and are not used in and limit the scope of the invention.The raw material that adopts, reagent can marketable material or traditional chemical transform mode are synthetic to be made by buying.Unless otherwise defined or explanation, same meanings of being familiar with of all specialties used herein and scientific words and those skilled in the art.Any method and material similar to described content or that be equal to all can be applicable in the inventive method in addition.Other aspects of the present invention are because the disclosure of this paper is that appearance is intelligible to those skilled in the art.
Fig. 1 is that the hypovanadic oxide powder surface is without the transmission electron microscope picture of organically-modified hypovanadic oxide powder; Referring to Fig. 1 as can be known, without the pattern of organically-modified vanadium dioxide nano powder particle, diameter of particle 10～100nm does not wait, and is that agglomerating particles exists but comparatively loose between the particle.
Fig. 2 is that the hypovanadic oxide powder surface is through the transmission electron microscope picture of organically-modified vanadium dioxide composite granule; Referring to Fig. 2 as can be known, the pattern of the vanadium dioxide composite granule of process organic surface modifying, diameter of particle 10～100nm does not wait, and powder is because be coated with the machine group, and the more not organically-modified particle of particle diameter increases slightly, but presents dispersion state between the powder.
Fig. 3 is the high low temperature graphic representation of vanadium dioxide intelligent temperature control coating in the example of the present invention (embodiment 1); To have adopted hypovanadic oxide powder of the present invention and slurry thereof and the high low temperature graphic representation of the intelligent temperature control coating for preparing; Referring to Fig. 3 as can be known, the visual transmitance low temperature 53.3% of this embodiment floating coat, high temperature 51.8%, sun power transmitance low temperature 57%, high temperature 43.6%, 40 ℃ of the transformation temperatures of coating, high low-temperature solar energy is regulated efficient can reach 13.4%, the infrared integral adjustment rate 24.2% of high low temperature, high low temperature infrared light 1500nm transmitance difference can reach 36.8%.
Fig. 4 is the high low temperature curve (comparison example 6) that does not adopt the intelligent temperature control coating of modification vanadium dioxide preparation, its difference with the coating (Fig. 3) that adopts organically-modified vanadium dioxide preparation is, owing to do not adopt the modification hypovanadic oxide powder, its dispersiveness is bad, cause high temperature curve (red line) will be lower than low temperature curve (black line) at visible light part, and adopt the coating high-temp curve (red line) of modification hypovanadic oxide powder preparation will be higher than low temperature curve (black line) at visible light part.And visible light transmissivity, infrared performance of control will be lower than the coating (Fig. 3) that adopts the preparation of modification hypovanadic oxide powder.
Embodiment 1
(1) surface organic modification of vanadium dioxide nano powder:
It is as follows to get each constituent mass:
Vanadium dioxide nano powder (Doped Tungsten, particle diameter 20～100nm), 20g
Ethanol (dispersion medium), 80g
Silane coupling agent (containing the polyvinyl alcohol group, organic modifiers), 1g
Polyvinylpyrrolidone (dispersing auxiliary), 0.05g;
High-speed stirring under 1500rad/min is disperseed 30min with vanadium dioxide nano powder and dispersion medium first, and ultra-sonic dispersion 30min, again dispersing auxiliary and silane coupling agent are added wherein, 70 ℃ of lower 2h that stir of constant temperature on homogenizer, again centrifugation, 60 ℃ of lower vacuum-dryings obtain the vanadium dioxide composite granule of organo-silicon coupling agent modification;
(2) preparation of vanadium dioxide composite granule slurry:
It is as follows to get each constituent mass:
The vanadium dioxide composite granule that makes in the present embodiment (1), 4g
Deionized water, 95.5g
The modified acroleic acid dispersion agent, 0.5g
The organic modified nano powder is added the pre-dispersed 5min of deionized water high-speed stirring, add dispersion agent ultra-sonic dispersion 60min again, stir process 2h on homogenizer obtains vanadium dioxide composite granule slurry;
The salient features of resulting vanadium dioxide composite granule and slurry thereof sees Table 1 in the present embodiment;
(3) preparation vanadium dioxide intelligent temperature control coating
Each raw material accounts for mass percent:
Polymer emulsion (polyaminoester emulsion): 40%
The hypovanadic oxide powder slurry that makes in the present embodiment (2) (solid content 4%): 30%
Deionized water: 28%
Film coalescence aid (propylene glycol monobutyl ether): 0.5%
Wetting aid (polyvinyl alcohol): 0.2%
Flow agent (polyacrylate(s)): 0.25%
Defoamer (modified organic silicon compound): 0.25%
Thickening material (cellulose thickener): 0.4%
UV light absorber (hydroxy phenyl s-triazine derivative): 0.5%
In the hypovanadic oxide powder slurry, add ACRYLIC EMULSION and deionized water, add again wetting aid, film coalescence aid, flow agent, defoamer, UV light absorber and thickening material high-speed stirring under 1500rad/min stirs 1h, obtains water-based vanadium dioxide intelligent temperature control coating.Resulting vanadium dioxide intelligent temperature control coating is applied on the PET with the mode of roller coat, and coat-thickness is controlled at 3.5 microns, and the intelligent temperature control coating fundamental property that obtains sees Table 2.
Embodiment 2
(1) surface organic modification of vanadium dioxide nano powder:
It is as follows to get each constituent mass:
Vanadium dioxide nano powder (undopes particle diameter 20～100nm), 10g
Ethanol (dispersion medium), 90g
Silane coupling agent (containing the chain alkyl amine groups, organic modifiers), 1g
Polyvinyl alcohol (dispersing auxiliary), 0.05g
High-speed stirring under 1500rad/min is disperseed 30min with vanadium dioxide nano powder and dispersion medium first, and ultra-sonic dispersion 30min, again dispersing auxiliary and stearic acid are added wherein, 60 ℃ of lower 2h that stir of constant temperature on homogenizer, again centrifugation, 60 ℃ of lower vacuum-dryings obtain the vanadium dioxide nano composite granule of chain alkyl amine groups modification;
(2) preparation of vanadium dioxide composite granule slurry:
It is as follows to get each constituent mass:
The vanadium dioxide composite granule that makes in the present embodiment (1), 5g
Deionized water, 94.5g
The polyacrylic acid dipersant, 0.05g
The organic modified nano powder is added the pre-dispersed 10min of deionized water high-speed stirring, add dispersion agent ultra-sonic dispersion 30min again, stir process 1h on homogenizer obtains vanadium dioxide composite granule slurry;
The salient features of resulting vanadium dioxide composite granule and slurry thereof sees Table 1 in the present embodiment;
(3) preparation vanadium dioxide intelligent temperature control coating
Each raw material accounts for mass percent:
Polymer emulsion (polyaminoester emulsion): 60%
The hypovanadic oxide powder slurry that makes in the present embodiment (2) (solid content 5%): 30%
Deionized water: 8.5%
Film coalescence aid (propylene glycol monobutyl ether): 0.25%
Wetting aid (polyvinyl alcohol): 0.1%
Flow agent (polyacrylate(s)): 0.15%
Defoamer (modified organic silicon compound): 0.25%
Thickening material (association type polyurethanes thickening material): 0.35%
UV light absorber (o-hydroxy-phenyl benzotriazole derivatives): 0.4%
Add ACRYLIC EMULSION and deionized water in the hypovanadic oxide powder slurry, add wetting aid again, film coalescence aid, flow agent, defoamer, UV light absorber and thickening material high-speed stirring under 1500rad/min stirs 1h, obtains vanadium dioxide intelligent temperature control coating.Resulting vanadium dioxide intelligent temperature control coating is applied on the PET with the mode of roller coat, and coat-thickness is controlled at 2.5 microns, and the intelligent temperature control coating fundamental property that obtains sees Table 2.
Embodiment 3
(1) surface organic modification of vanadium dioxide nano powder:
It is as follows to get each constituent mass:
Vanadium dioxide nano powder (Doped Tungsten, particle diameter 20～100nm), 15g
Virahol (dispersion medium), 85g
Silane coupling agent (containing epoxy functionalized group, organic modifiers), 1g
Organic modified polyorganosiloxane dipropylene glycol monomethyl ether solution (dispersing auxiliary), 0.08g
High-speed stirring under 1000rad/min is disperseed 20min with vanadium dioxide nano powder and dispersion medium first, and ultra-sonic dispersion 60min, again dispersing auxiliary and silane coupling agent are added wherein, 80 ℃ of lower 2h that stir of constant temperature on homogenizer, again centrifugation, 60 ℃ of lower vacuum-dryings obtain the vanadium dioxide nano composite granule that the surface is connected to chain alkyl;
(2) preparation of vanadium dioxide composite granule slurry:
It is as follows to get each constituent mass:
The vanadium dioxide composite granule that makes in the present embodiment (1), 1.5g
Deionized water, 98g
The modified poly ester dispersion agent, 0.5g
The organic modified nano powder is added the pre-dispersed 5min of deionized water high-speed stirring, add dispersion agent ultra-sonic dispersion 20min again, stir process 1h on homogenizer obtains vanadium dioxide composite granule slurry;
The salient features of resulting vanadium dioxide composite granule and slurry thereof sees Table 1 in the present embodiment;
(3) preparation vanadium dioxide intelligent temperature control coating
Each raw material accounts for mass percent:
Polymer emulsion (ACRYLIC EMULSION): 45%
The hypovanadic oxide powder slurry that makes in the present embodiment (2) (solid content 1.5%): 45%
Deionized water: 5%
Film coalescence aid (phenyl ether): 0.5%
Wetting aid (silicoorganic compound): 0.2%
Flow agent (modified organic silicon compound): 0.25%
Defoamer (small molecules metallorganics): 0.25%
Thickening material (association type polyurethanes thickening material): 0.8%
UV light absorber (o-hydroxy-phenyl benzotriazole derivatives): 0.5%
Add ACRYLIC EMULSION and deionized water in the hypovanadic oxide powder slurry, add wetting aid again, film coalescence aid, flow agent, defoamer, UV light absorber and thickening material high-speed stirring under 2500rad/min stirs 3h, obtains vanadium dioxide intelligent temperature control coating.Resulting vanadium dioxide intelligent temperature control coating is applied on the PET with the mode of spraying, and coat-thickness is controlled at 6.5 microns, and the intelligent temperature control coating fundamental property that obtains sees Table 2.
Embodiment 4
(1) surface organic modification of vanadium dioxide nano powder:
It is as follows to get each constituent mass:
Vanadium dioxide nano powder (doping molybdenum, particle diameter 20～100nm), 25g
Virahol (dispersion medium), 75g
Titanate coupling agent (containing epoxide group, organic modifiers), 1g
Polyvinyl alcohol (dispersing auxiliary), 0.15g
High-speed stirring under 1500rad/min is disperseed 20min with vanadium dioxide nano powder and dispersion medium first, and ultra-sonic dispersion 60min, again dispersing auxiliary and titanate coupling agent are added wherein, 80 ℃ of lower 2h that stir of constant temperature on homogenizer, again centrifugation, 70 ℃ of lower vacuum-dryings obtain the vanadium dioxide nano composite granule that the surface is connected to epoxide group;
(2) preparation of vanadium dioxide composite granule slurry:
It is as follows to get each constituent mass:
The vanadium dioxide composite granule that makes in the present embodiment (1), 3g
Deionized water, 96.95g
The modified acroleic acid dispersion agent, 0.05g
The organic modified nano powder is added the pre-dispersed 5min of deionized water high-speed stirring, add dispersion agent ultra-sonic dispersion 30min again, stir process 1h on homogenizer obtains vanadium dioxide and Dope nano-power slurry thereof;
The salient features of resulting vanadium dioxide composite granule and slurry thereof sees Table 1 in the present embodiment;
(3) preparation vanadium dioxide intelligent temperature control coating
Each raw material accounts for mass percent:
Polymer emulsion (ACRYLIC EMULSION): 50%
The hypovanadic oxide powder slurry that makes in the present embodiment (2) (solid content 3%): 30%
Deionized water: 18.5%
Film coalescence aid (ethylene glycol monobutyl ether): 0.2
Wetting aid (silicoorganic compound): 0.05%
Flow agent (cellaburate): 0.2%
Defoamer (modified mineral oil): 0.35%
Thickening material (agent for polyacrylic acid thickening): 0.2%
UV light absorber (benzophenone derivates): 0.5%
Add ACRYLIC EMULSION and deionized water in the hypovanadic oxide powder slurry, add wetting aid again, film coalescence aid, flow agent, defoamer, UV light absorber and thickening material high-speed stirring under 2500rad/min stirs 2h, obtains vanadium dioxide intelligent temperature control coating; Resulting vanadium dioxide intelligent temperature control coating is applied on the PET with the mode of roller coat, and coat-thickness is controlled at 2.5 microns, and the intelligent temperature control coating fundamental property that obtains sees Table 2.
Embodiment 5
(1) surface organic modification of vanadium dioxide nano powder:
It is as follows to get each constituent mass:
Vanadium dioxide nano powder (Doped Tungsten, particle diameter 20～100nm), 5g
Virahol (dispersion medium), 95g
Aluminate coupling agent (containing chain alkyl, organic modifiers), 0.7g
Polyvinylpyrrolidone (dispersing auxiliary), 0.04g
High-speed stirring under 1500rad/min is disperseed 20min with vanadium dioxide nano powder and dispersion medium first, and ultra-sonic dispersion 60min, again dispersing auxiliary and aluminate coupling agent are added wherein, 80 ℃ of lower 2h that stir of constant temperature on homogenizer, again centrifugation, 60 ℃ of lower vacuum-dryings obtain the vanadium dioxide nano powder that the surface is connected to chain alkyl;
(2) preparation of vanadium dioxide composite granule slurry:
It is as follows to get each constituent mass:
The vanadium dioxide composite granule that makes in the present embodiment (1), 4g
Ethyl acetate, 95.5g
The modified polyurethane dispersion agent, 0.5g
The organic modified nano powder is added the pre-dispersed 5min of deionized water high-speed stirring, add dispersion agent ultra-sonic dispersion 60min again, stir process 2h on homogenizer obtains vanadium dioxide composite granule slurry;
The salient features of resulting vanadium dioxide composite granule and slurry thereof sees Table 1 in the present embodiment;
(3) preparation vanadium dioxide intelligent temperature control coating
Each raw material accounts for mass percent:
Polymer emulsion (polyaminoester emulsion): 70%
The hypovanadic oxide powder slurry that makes in the present embodiment (2) (solid content 4%): 20%
Deionized water: 8.5%
Film coalescence aid (propylene glycol monobutyl ether): 0.5%
Wetting aid (polyvinyl alcohol): 0.2%
Flow agent (polyacrylate(s)): 0.25%
Defoamer (modified organic silicon compound): 0.25%
Thickening material (cellulose thickener): 0.4%
In the hypovanadic oxide powder slurry, add ACRYLIC EMULSION and deionized water, add again wetting aid, film coalescence aid, flow agent, defoamer, UV light absorber and thickening material high-speed stirring under 1500rad/min stirs 1h, obtains water-based vanadium dioxide intelligent temperature control coating.Resulting vanadium dioxide intelligent temperature control coating is applied on the PET with the mode of blade coating, and coat-thickness is controlled at 5.5 microns, and the intelligent temperature control coating fundamental property that obtains sees Table 2.
Comparative example 6
(1) gets the vanadium dioxide nano powder of the non-modified of using in above-described embodiment 1 (1), 4g
Deionized water, 95.5g
The modified acroleic acid dispersion agent, 0.5g
The organic modified nano powder is added the pre-dispersed 5min of deionized water high-speed stirring, add dispersion agent ultra-sonic dispersion 60min again, stir process 2h on homogenizer obtains vanadium dioxide composite granule slurry;
The salient features of resulting vanadium dioxide composite granule and slurry thereof sees Table 1 in the present embodiment;
(2) get in this comparative example the slurry that makes in above-mentioned (1), each raw material is by following mass percent preparation:
Each raw material accounts for mass percent:
Polymer emulsion (polyaminoester emulsion): 40%
The hypovanadic oxide powder slurry that makes in the present embodiment (2) (solid content 4%): 30%
Deionized water: 28%
Film coalescence aid (propylene glycol monobutyl ether): 0.5%
Wetting aid (polyvinyl alcohol): 0.2%
Flow agent (polyacrylate(s)): 0.25%
Defoamer (modified organic silicon compound): 0.25%
Thickening material (cellulose thickener): 0.4%
UV light absorber (hydroxy phenyl s-triazine derivative): 0.5%
In the hypovanadic oxide powder slurry, add ACRYLIC EMULSION and deionized water, add again wetting aid, film coalescence aid, flow agent, defoamer, UV light absorber and thickening material high-speed stirring under 1500rad/min stirs 1h, obtains water-based vanadium dioxide intelligent temperature control coating.Resulting vanadium dioxide intelligent temperature control coating is applied on the PET with the mode of roller coat, and coat-thickness is controlled at 5.5 microns, and the intelligent temperature control coating fundamental property that obtains sees Table 2.
Referring to following table 1, from this table organically-modified vanadium dioxide composite granule and the slurry thereof that method provided by the invention obtains can be described, its particle diameter is significantly less than unmodified powder, and the BET specific surface area is greater than unmodified powder, and Stability of Slurry also will be significantly better than unmodified powdery pulp.Can find out by the surface organic modification process by 300 ℃ of weightless data, can connect at nano powder surface 5～10% organic long-chain, thereby greatly improve chemical stability and the dispersiveness of hypovanadic oxide powder.
Table 1:
Figure BDA0000132601480000151
Figure BDA0000132601480000161
Referring to following table 2, coating of the present invention has higher visible light transmissivity, complete shielding ultraviolet rays almost simultaneously, can carry out intelligence to the higher infrared rays of energy in the sunlight simultaneously and regulate (seeing through difference from high low temperature infrared rays can find out), the transparent light of appearance of coat (the coating mist degree is low) is ageing-resistant simultaneously, waterproof, sticking power is good, and abrasion resistance is strong; And not organically-modified VO2 slurry (contrast application example 6) is compared together, and the coating intelligent control rate that present method obtains is better, and visible light transmissivity is low, and mist degree is less.
Table 2 (coating property test):
Figure BDA0000132601480000162
Figure BDA0000132601480000171
Below, by embodiment energy-conservation composite film-stuck of intelligent temperature control of the present invention and preparation method thereof is described in detail.Should understand, below also can omit or use other alternative steps that can reach with texts about in the energy-conservation composite film-stuck preparation method of the intelligent temperature control of the present invention step certain, and each feature in each step neither be necessary or replaceable regularly and not, and just example ground explanation.
Embodiment 7
(1) chooses the PET release film, thickness 50um;
The preparation of (2) intelligent temperature control coating.The coating (being made by above-described embodiment 4) that will contain organically-modified vanadium dioxide composite granule is applied on the PET base material by the mode of roller coat, base material thickness 50um, surface covered 35m/min, the rolling of process oven drying obtains containing the PET temperature control film of intelligent temperature control coating again, 90～120 ℃ of oven temperatures, dry film coating thickness 2.5um;
(3) preparation of surface functional layer.To contain the mode of light-cured acrylic cured coating by roller coat is applied on another surface of PET temperature control film that step (2) contains the intelligent temperature control coating, surface covered 30m/min, after passing through again the baking oven preheating and drying, solidify through the UV lamp, rolling obtains that one side contains the intelligent temperature control coating, one side contains the PET temperature control film of surface functional layer, 80～100 ℃ of oven temperatures, UV lamp power 80～150W/cm, dry film coating thickness 1.5um;
(4) the energy-conservation composite film-stuck of intelligent temperature control is compound.The mode of acrylate pressure sensitive adhesive by roller coat is applied on the one side that contains the intelligent temperature control coating of PET temperature control laminated film of step (3) preparation, surface covered 30m/min, pass through oven drying again after, dry film coating thickness 5um.The one side that directly will be coated with acrylate pressure sensitive adhesive after the drying is compound by pressure roller with the release film of step (1) preparation, 50～60 ℃ of roller temperatures, 90～110 ℃ of oven temperatures.
Embodiment 8
(1) chooses the PET release film, thickness 25um;
The preparation of (2) intelligent temperature control coating.The coating (being made by above-described embodiment 1) that will contain organically-modified vanadium dioxide composite granule is applied on the PET base material by the mode of roller coat, base material thickness 100um, surface covered 35m/min, the rolling of process oven drying obtains containing the PET temperature control film of intelligent temperature control coating again, 90～120 ℃ of oven temperatures, dry film coating thickness 3.5um;
(3) preparation of the preparation release film of surface functional layer is similar with embodiment 7;
(4) preparation of the compound release film of the energy-conservation composite film-stuck of intelligent temperature control is similar with embodiment 7.
Embodiment 9
(1) chooses the PET release film, thickness 20um;
The preparation of (2) intelligent temperature control coating.The coating (being made by above-described embodiment 3) that will contain organically-modified vanadium dioxide composite granule is applied on the PET base material by the mode of roller coat, base material thickness 25um, surface covered 35m/min, the rolling of process oven drying obtains containing the PET temperature control film of intelligent temperature control coating again, 90～120 ℃ of oven temperatures, dry film coating thickness 4.5um;
(3) surface functional layer is selected antistatic coating, and the preparation of the preparation release film of coating is similar with embodiment 7;
(4) preparation of the compound release film of the energy-conservation composite film-stuck of intelligent temperature control is similar with embodiment 7.
Embodiment 10
(1) chooses the PP release film, thickness 20um;
The preparation of (2) intelligent temperature control coating.The coating (being made by above-described embodiment 1) that will contain organically-modified vanadium dioxide composite granule is applied on the PP base material by the mode that sprays, base material thickness 50um, surface covered 35m/min, the rolling of process oven drying obtains containing the PP temperature control film of intelligent temperature control coating again, 90～120 ℃ of oven temperatures, dry film coating thickness 3.5um;
(3) preparation of surface functional layer.To contain the mode of photocuring organosilicon cured coating by spraying is applied on another surface of PP temperature control film that step (2) contains the intelligent temperature control coating, surface covered 30m/min, after passing through again the baking oven preheating and drying, solidify through the UV lamp, rolling obtains that one side contains the intelligent temperature control coating, one side contains the PET temperature control film of surface functional layer, 90～120 ℃ of oven temperatures, UV lamp power 80～150W/cm, dry film coating thickness 2um;
(4) the energy-conservation composite film-stuck of intelligent temperature control is compound.The mode of organic silica gel by spraying is applied on the one side that contains the intelligent temperature control coating of PET temperature control laminated film of step (3) preparation, surface covered 30m/min, pass through oven drying again after, roller dry film coating thickness 10um.The one side that will be coated with afterwards acrylate pressure sensitive adhesive is compound by pressure roller with the release film of step (1) preparation, 50～60 ℃ of roller temperatures, 90～110 ℃ of oven temperatures.
Embodiment 11
(1) chooses the PVC release film, thickness 15um;
The preparation of (2) intelligent temperature control coating.The slurry (being made by above-described embodiment 1) that will contain organically-modified vanadium dioxide composite granule is applied on the PVC base material by the mode of blade coating, base material thickness 80um, surface covered 35m/min, the rolling of process oven drying obtains containing the PVC temperature control film of intelligent temperature control coating again, 90～120 ℃ of oven temperatures, dry film coating thickness 3.5um;
(3) preparation of surface functional layer.To contain the mode of thermofixation vinylformic acid cured coating by blade coating is applied on another surface of PVC temperature control film that step (2) contains the intelligent temperature control coating, surface covered 30m/min, after passing through again the baking oven preheating and drying, solidify through the UV lamp, rolling obtains that one side contains the intelligent temperature control coating, one side contains the PET temperature control film of surface functional layer, 90～120 ℃ of oven temperatures, UV lamp power 80～150W/cm, dry film coating thickness 2um;
(4) the energy-conservation composite film-stuck of intelligent temperature control is compound.The mode of organic silica gel by blade coating is applied on the one side that contains the intelligent temperature control coating of PET temperature control laminated film of step (3) preparation, surface covered 30m/min, pass through oven drying again after, roller dry film coating thickness 10um.The one side that directly will be coated with acrylate pressure sensitive adhesive after the drying is compound by pressure roller with the release film of step (1) preparation, 50～60 ℃ of roller temperatures, 90～110 ℃ of oven temperatures.
Embodiment 12
(1) chooses the PET release film, thickness 25um;
The preparation of (2) intelligent temperature control coating.The slurry (being made by above-described embodiment 1) that will contain 3% organically-modified vanadium dioxide composite granule is applied on the PET base material by the mode of roller coat, base material thickness 80um, surface covered 35m/min, the rolling of process oven drying obtains containing the PET temperature control film of intelligent temperature control coating again, 90～120 ℃ of oven temperatures, dry film coating thickness 3.5um;
(3) preparation of surface functional layer is similar with embodiment 10;
(4) the energy-conservation composite film-stuck of intelligent temperature control is compound.The mode of acrylate pressure sensitive adhesive by roller coat is applied on the one side that contains the intelligent temperature control coating of PET temperature control laminated film of step (3) preparation, surface covered 30m/min, pass through oven drying again after, dry film coating thickness 5um.The one side that will be coated with afterwards acrylate pressure sensitive adhesive is compound by pressure roller with the release film of step (1) preparation, 50～60 ℃ of roller temperatures, 90～110 ℃ of oven temperatures.
Following table 3 is salient features and the performance test of the prepared intelligent temperature control composite film-stuck of embodiment 7-12:
Figure BDA0000132601480000201
Figure BDA0000132601480000211
Table 3 explanation, the energy-conservation composite film-stuck of intelligent temperature control of the present invention has higher visible light transmissivity, complete shielding ultraviolet rays almost simultaneously, can carry out intelligence to the higher infrared rays of energy in the sunlight simultaneously and regulate (seeing through difference from high low temperature infrared rays can find out), the transparent light of appearance of coat (the coating mist degree is low) is ageing-resistant simultaneously, waterproof, sticking power is good, and abrasion resistance is strong.
Industrial applicability: the preparation method of vanadium dioxide composite granule provided by the invention, preparation technology's innovation, by the organic surface modifying process of organic modifiers, can effectively improve dispersiveness and the chemical stability of vanadium dioxide (vanadium dioxide) and Dope nano-power thereof.Vanadium dioxide composite granule of the present invention can be applicable to prepare the energy-conservation composite film-stuck of intelligent power saving coating, coating or intelligent temperature control, the coating of preparation or pad pasting transparency are high, low, the ageing-resistant ability of mist degree is strong, be mainly used in film, the flexible materialss such as cloth also can be used for the heat insulation occasions such as glass and exterior wall.Also can be widely used in energy-saving and emission-reduction equipment, for example energy-conservation film, energy-saving coatings, sun power temperature control unit; Or energy information equipment, for example, micro photo electric switch device, thermistor, battery material and optical information storage spare.

Claims (22)

1. the energy-conservation composite film-stuck of intelligent temperature control comprises from inside to outside release film layer, gel coating, vanadium dioxide intelligent temperature control coating, base material and surface functional layer is installed, it is characterized in that,
Be coated on after described vanadium dioxide intelligent temperature control coating is mixed by hypovanadic oxide powder slurry, polymer emulsion and coatings additive(s) on the base material and form; And
Described hypovanadic oxide powder slurry comprises vanadium dioxide composite granule and dispersion medium, and described vanadium dioxide composite granule comprises that chemical constitution is V 1-xM xO 2Vanadium dioxide nano powder, and described nano powder surface is connected to machine modification long chain molecule, wherein M is doped element, 0≤x≤0.5.
2. the energy-conservation composite film-stuck of intelligent temperature control according to claim 1 is characterized in that, described organically-modified long chain molecule content is 0.1～50%.
3. the energy-conservation composite film-stuck of intelligent temperature control according to claim 2 is characterized in that, described organically-modified long chain molecule content is 1～10%.
4. the energy-conservation composite film-stuck of intelligent temperature control according to claim 1 is characterized in that, described organically-modified long chain molecule chain length is at 0.1nm～100nm.
5. the energy-conservation composite film-stuck of each described intelligent temperature control is characterized in that according to claim 1-4, and described organically-modified long chain molecule is functionalized organic long-chain.
6. the energy-conservation composite film-stuck of each described intelligent temperature control according to claim 1-4, it is characterized in that described functionalized organic long-chain is chain alkyl, polyacrylic acid group, polyvinyl alcohol group, epoxide group, chain alkyl amine groups, halogenation chain alkyl and/or carboxylated chain alkyl.
7. the energy-conservation composite film-stuck of each described intelligent temperature control is characterized in that according to claim 1～4, and described vanadium dioxide nano powder is Rutile Type, and transformation temperature is adjustable at-20～70 ℃.
8. the energy-conservation composite film-stuck of intelligent temperature control according to claim 7 is characterized in that, described doped element M is or arbitrary combination near 21～30 transition element the vanadium in the periodic table of elements, tin and near element thereof and tungsten, molybdenum, ruthenium, the niobium.
9. the energy-conservation composite film-stuck of intelligent temperature control according to claim 8, it is characterized in that, near 21～30 transition element in the periodic table of elements vanadium comprise scandium, titanium, chromium, manganese, iron, cobalt, nickel, copper and zinc, and described tin and near element thereof comprise indium, antimony, tin, gallium, germanium, lead and bismuth.
10. the energy-conservation composite film-stuck of each described intelligent temperature control is characterized in that the particle size of described vanadium dioxide composite granule is below 200nm according to claim 1～4.
11. the energy-conservation composite film-stuck of each described intelligent temperature control is characterized in that in the claim 1～4, the solid content of vanadium dioxide composite granule is 0.1%-50% in the described intelligent temperature control coating.
12. the energy-conservation composite film-stuck of intelligent temperature control according to claim 11 is characterized in that, the solid content of vanadium dioxide composite granule is 2%-20% in the described intelligent temperature control coating.
13. the energy-conservation composite film-stuck of each described intelligent temperature control is characterized in that according to claim 1～4, described intelligent temperature control coating dry film thickness is 0.05～50um.
14. the energy-conservation composite film-stuck of each described intelligent temperature control is characterized in that according to claim 1～4, described base material is the plastics film of PP, PE, PA, PVC, PET or PMMA, the fiber or the woven bag that are perhaps prepared by described material; Described release film is PP, PE, PA, PVC, PET or PMMA film.
15. the energy-conservation composite film-stuck of each described intelligent temperature control is characterized in that according to claim 1～4, described release film thickness is 2～250um; Described base material thickness is 2～250um.
16. the energy-conservation composite film-stuck of each described intelligent temperature control is characterized in that according to claim 1～4, described installation gel coating is formed on the one side that base material contains the intelligent temperature control layer; Described release film is compound on the base material by gel coating is installed.
17. the energy-conservation composite film-stuck of each described intelligent temperature control according to claim 1～4, it is characterized in that described installation glue is painted with unsaturated polyester resin glue, Phenol aldehyde resin, polyvinyl chloride glue, epoxy glue, polyurethane adhesive, organosilicon glue or acrylate pressure sensitive adhesive.
18. the energy-conservation composite film-stuck of intelligent temperature control according to claim 17 is characterized in that, the thickness of described installation gel coating is 0.05～50um.
19. the energy-conservation composite film-stuck of each described intelligent temperature control is characterized in that according to claim 1～4, described surface functional layer is formed on the base material one side relative with the intelligent temperature control layer.
20. the energy-conservation composite film-stuck of intelligent temperature control according to claim 19, it is characterized in that described surface functional layer is the high hard coating of UV light-cured polyurethane, the high hard coating of UV light-cured acrylic, the high hard coating of UV photocuring organosilicon, heat curing epoxy hardening resin, the high hard coating of urethane, the high hard coating of vinylformic acid and the high hard coating of organosilicon, antifouling waterproof paint, anti-fingerprint coating or Antistatic Paint.
21. the energy-conservation composite film-stuck of intelligent temperature control according to claim 20 is characterized in that, described function of surface layer thickness is 0.05～50um.
22. the energy-conservation composite film-stuck of each described intelligent temperature control according to claim 1～4, it is characterized in that described installation gel coating, vanadium dioxide intelligent temperature control coating and surface functional layer all are by comprising the coating process preparation of spraying, blade coating, brushing, showering or roller coat.
CN201210019446.XA 2012-01-19 2012-01-19 Intelligent temperature-control energy-saving composite coating film Expired - Fee Related CN103074002B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201210019446.XA CN103074002B (en) 2012-01-19 2012-01-19 Intelligent temperature-control energy-saving composite coating film
PCT/CN2012/072024 WO2013107082A1 (en) 2012-01-19 2012-03-07 Intelligent, temperature-controlling, and energy-saving composite film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210019446.XA CN103074002B (en) 2012-01-19 2012-01-19 Intelligent temperature-control energy-saving composite coating film

Publications (2)

Publication Number Publication Date
CN103074002A true CN103074002A (en) 2013-05-01
CN103074002B CN103074002B (en) 2014-02-19

Family

ID=48150705

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210019446.XA Expired - Fee Related CN103074002B (en) 2012-01-19 2012-01-19 Intelligent temperature-control energy-saving composite coating film

Country Status (2)

Country Link
CN (1) CN103074002B (en)
WO (1) WO2013107082A1 (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104530872A (en) * 2014-12-30 2015-04-22 佛山金智节能膜有限公司 Intelligent temperature controlling coating with oriented structure and preparation method thereof
CN104746160A (en) * 2013-12-27 2015-07-01 中国科学院上海硅酸盐研究所 Infrared transmittance/reflectivity variable nano composite fiber and preparation method thereof
CN105218846A (en) * 2015-09-10 2016-01-06 昆山博益鑫成高分子材料有限公司 A kind of microballoon intelligence thermal-insulation window film and preparation method thereof
CN105348964A (en) * 2015-12-09 2016-02-24 夏百庆 Intelligent paint
CN105365288A (en) * 2015-11-13 2016-03-02 北汽福田汽车股份有限公司 Temperature regulating film, temperature regulating glass and automotive
CN105522770A (en) * 2016-01-20 2016-04-27 浙江农业商贸职业学院 Graphene temperature-resistant heat conduction film
CN106183271A (en) * 2016-08-30 2016-12-07 常州山由帝杉防护材料制造有限公司 Nana intelligent thermal-insulation window film
CN106543910A (en) * 2015-09-23 2017-03-29 上海沪正纳米科技有限公司 A kind of intelligent temperature control PVB glued membranes and preparation method thereof
CN106800379A (en) * 2015-11-26 2017-06-06 法国圣戈班玻璃公司 Laminated glass and its manufacture method, vehicle window
CN107922260A (en) * 2015-08-21 2018-04-17 柯尼卡美能达株式会社 Thermo-color film and thermo-color complex
CN109401656A (en) * 2018-09-30 2019-03-01 东莞市卓华高分子材料有限公司 Antistatic protective film with firmoviscosity
CN110467230A (en) * 2019-09-09 2019-11-19 湖北大学 The adjustable Ru of phase transition temperaturexV1-xO2Alloy semiconductor film material, preparation method and its application in smart window
CN113583540A (en) * 2018-11-01 2021-11-02 中山科邦化工材料技术有限公司 Multilayer light and thin composite insulation board and preparation method thereof

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014107494A1 (en) 2013-01-04 2014-07-10 DePuy Synthes Products, LLC Method for designing and manufacturing a bone implant
CN104445987A (en) * 2014-10-30 2015-03-25 中国建材国际工程集团有限公司 Method for preparing thermochromism intelligent membrane glass
CN107160799A (en) * 2017-04-24 2017-09-15 天津创新晶彩科技有限公司 A kind of adhering film to glass for avoiding condensation vapor
CN110156340A (en) * 2019-05-24 2019-08-23 武汉大学 A kind of temperature sensitive type VO2The preparation method of photocuring flexible membrane
CN114250024B (en) * 2021-12-07 2022-07-19 湖南航天三丰科工有限公司 Temperature-sensitive reflective coating and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101265374A (en) * 2008-01-24 2008-09-17 复旦大学 Intelligent heat-insulating film and its preparing process
EP1615238B1 (en) * 2004-07-10 2009-09-09 Coroplast Fritz Müller GmbH & Co. KG Thermically insulting technical adhesive tape and cable bundle having high temperature resistance
CN101618780A (en) * 2009-07-23 2010-01-06 武汉大学 Temperature-controlled polyvinyl alcohol packing film as well as preparation method and application thereof
US20100266801A1 (en) * 2009-04-15 2010-10-21 Optimum Coating Technologies, S.A. de C.V. Low-emissivity window film and process for producing such a film

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101993657A (en) * 2009-08-14 2011-03-30 北京建筑技术发展有限责任公司 Intelligent nano transparent insulating glass coating
KR101963525B1 (en) * 2010-03-01 2019-03-28 시피필름스 인코포레이션 Low emissivity and emi shielding window films
CN201863451U (en) * 2010-11-17 2011-06-15 苏州奥美材料科技有限公司 Intelligent temperature-control anti-aging transparent polycarbonate plate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1615238B1 (en) * 2004-07-10 2009-09-09 Coroplast Fritz Müller GmbH & Co. KG Thermically insulting technical adhesive tape and cable bundle having high temperature resistance
CN101265374A (en) * 2008-01-24 2008-09-17 复旦大学 Intelligent heat-insulating film and its preparing process
US20100266801A1 (en) * 2009-04-15 2010-10-21 Optimum Coating Technologies, S.A. de C.V. Low-emissivity window film and process for producing such a film
CN101618780A (en) * 2009-07-23 2010-01-06 武汉大学 Temperature-controlled polyvinyl alcohol packing film as well as preparation method and application thereof

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104746160A (en) * 2013-12-27 2015-07-01 中国科学院上海硅酸盐研究所 Infrared transmittance/reflectivity variable nano composite fiber and preparation method thereof
CN104530872A (en) * 2014-12-30 2015-04-22 佛山金智节能膜有限公司 Intelligent temperature controlling coating with oriented structure and preparation method thereof
CN107922260A (en) * 2015-08-21 2018-04-17 柯尼卡美能达株式会社 Thermo-color film and thermo-color complex
CN105218846A (en) * 2015-09-10 2016-01-06 昆山博益鑫成高分子材料有限公司 A kind of microballoon intelligence thermal-insulation window film and preparation method thereof
CN106543910A (en) * 2015-09-23 2017-03-29 上海沪正纳米科技有限公司 A kind of intelligent temperature control PVB glued membranes and preparation method thereof
CN105365288B (en) * 2015-11-13 2018-08-07 北汽福田汽车股份有限公司 Temperature adjustment film, temperature-regulating glass and automobile
CN105365288A (en) * 2015-11-13 2016-03-02 北汽福田汽车股份有限公司 Temperature regulating film, temperature regulating glass and automotive
CN106800379A (en) * 2015-11-26 2017-06-06 法国圣戈班玻璃公司 Laminated glass and its manufacture method, vehicle window
CN106800379B (en) * 2015-11-26 2020-11-10 法国圣戈班玻璃公司 Laminated glass, manufacturing method thereof and vehicle window
CN105348964A (en) * 2015-12-09 2016-02-24 夏百庆 Intelligent paint
CN105522770A (en) * 2016-01-20 2016-04-27 浙江农业商贸职业学院 Graphene temperature-resistant heat conduction film
CN106183271A (en) * 2016-08-30 2016-12-07 常州山由帝杉防护材料制造有限公司 Nana intelligent thermal-insulation window film
CN106183271B (en) * 2016-08-30 2019-03-01 常州山由帝杉防护材料制造有限公司 Nana intelligent thermal-insulation window film
CN109401656A (en) * 2018-09-30 2019-03-01 东莞市卓华高分子材料有限公司 Antistatic protective film with firmoviscosity
CN113583540A (en) * 2018-11-01 2021-11-02 中山科邦化工材料技术有限公司 Multilayer light and thin composite insulation board and preparation method thereof
CN113583540B (en) * 2018-11-01 2022-02-08 中山科邦化工材料技术有限公司 Multilayer light and thin composite insulation board and preparation method thereof
CN110467230A (en) * 2019-09-09 2019-11-19 湖北大学 The adjustable Ru of phase transition temperaturexV1-xO2Alloy semiconductor film material, preparation method and its application in smart window

Also Published As

Publication number Publication date
CN103074002B (en) 2014-02-19
WO2013107082A1 (en) 2013-07-25

Similar Documents

Publication Publication Date Title
CN103074002B (en) Intelligent temperature-control energy-saving composite coating film
CN103073943B (en) Vanadium dioxide intelligent temperature control coating
CN103073942B (en) Vanadium dioxide composite powder and preparation method thereof
CN103073941B (en) Vanadium dioxide powder slurry and preparation method thereof
CN104530872A (en) Intelligent temperature controlling coating with oriented structure and preparation method thereof
CN103387787B (en) A kind of transparent heat-insulated coating material of hybrid, preparation method and applications
WO2015055115A1 (en) Transparent flame-retardant thermal-insulating uv-blocking polymer composite film, preparation method and uses thereof
CN101538444B (en) Water-based nano heat insulating coating used for glass and preparation method thereof
CN101870842A (en) Aqueous cold pigment double-coat multifunctional thermal-insulation external wall paint and preparation method thereof
CN101899249A (en) Transparent thermal insulation anti-ultraviolet coating and preparation method thereof
CN103102791A (en) Preparation method of nano TiO2 self-cleaning transparent coating
CN102749666A (en) Preparation method for reflection-deducting coating
CN111690331A (en) Transparent heat-insulating anti-ultraviolet film based on photonic quasicrystal material and preparation method thereof
CN106084962A (en) Adiabatic compositions of additives and purposes
CN101885937A (en) Colored and transparent heat-insulating energy-saving protecting function coating and preparation method thereof
CN108795191A (en) A kind of aqueous reflective heat-insulation paint
CN106634349A (en) Color reflection heat insulation and temperature reduction paint and preparation method thereof
CN102911591A (en) Transparent thermal insulation coating with nano porous auxiliary and preparation method thereof
CN105131764A (en) Reflective heat-insulation texture coating and preparation method thereof
CN106752193A (en) A kind of preparation of UV curing chromatics nano transparent insulating coating
CN107083101A (en) A kind of tungstenic metal oxide nanoparticles dispersion and preparation method thereof
CN103923543A (en) Compound intelligent temperature control coating and preparation method thereof
AU2014100870A4 (en) Transparent, heat-insulting, UV-blocking coatings
CN113214740B (en) Light-reflecting transparent heat-insulating coating, preparation method thereof and light-reflecting heat-insulating top coat
CN107916066A (en) Vanadium dioxide composite powder of graphene-containing and preparation method and application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20130501

Assignee: FOSHAN K-SMART ENERGY SAVING FILM CO., LTD.

Assignor: FSPG Hi-Tech Co., Ltd.

Contract record no.: 2015990000841

Denomination of invention: Intelligent temperature-control energy-saving composite coating film

Granted publication date: 20140219

License type: Exclusive License

Record date: 20151014

LICC Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20140219

Termination date: 20190119

CF01 Termination of patent right due to non-payment of annual fee