CN100590154C - Infrared shielding material microparticle dispersion, infrared shield, process for producing infrared shielding material microparticle, and infrared shielding material microparticle - Google Patents
Infrared shielding material microparticle dispersion, infrared shield, process for producing infrared shielding material microparticle, and infrared shielding material microparticle Download PDFInfo
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- CN100590154C CN100590154C CN200480003236A CN200480003236A CN100590154C CN 100590154 C CN100590154 C CN 100590154C CN 200480003236 A CN200480003236 A CN 200480003236A CN 200480003236 A CN200480003236 A CN 200480003236A CN 100590154 C CN100590154 C CN 100590154C
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- infrared rays
- masking material
- powder
- particulate
- tungsten
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- 238000000034 method Methods 0.000 title claims abstract description 62
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- 239000000843 powder Substances 0.000 claims abstract description 131
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- 150000003658 tungsten compounds Chemical class 0.000 claims abstract description 19
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- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 146
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 78
- -1 compound tungsten oxide Chemical class 0.000 claims description 72
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 69
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- 239000010937 tungsten Substances 0.000 claims description 39
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 230000014509 gene expression Effects 0.000 claims description 34
- 238000004519 manufacturing process Methods 0.000 claims description 32
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 26
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- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
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- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
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- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
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- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
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- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
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- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 1
Images
Abstract
An infrared shield that satisfactorily transmits visible light, not having any half mirror appearance and does not need any large-scale production apparatus in the film formation on base material, andthat not requiring any high temperature heat treatment after film formation, efficiently blocks invisible near-infrared rays of 780 nm or above wavelength and is transparent and free from color tonechanges. An infrared shielding film of transmission profile shown was obtained by a process comprising providing a starting material resulting from weighing of given amount of tungsten compounds and mixing thereof; heating the starting material in a reducing atmosphere at 550 1/2 C for 1 hr, lowering the temperature to room temperature once and thereafter heating the material in an argon atmosphere for 1 hr to thereby obtain powder of W18O49; mixing the powder with a solvent and a dispersant and dispersing them into a dispersion liquid; mixing this dispersion liquid with an ultraviolet curableresin for hard coat to thereby obtain an infrared shielding material microparticle dispersion liquid; coating a PET resin film with this infrared shielding material microparticle dispersion liquid soas to effect film formation; and curing the coating film.
Description
Technical field
The present invention relates to will be transparent in the visible region, have infrared rays masking material microparticle dispersion that the microparticulate of the oxide material of absorptive function obtains near infrared range in medium, by the infrared shield of this infrared rays masking material microparticle dispersion manufacturing be used for the manufacture method of infrared material particulate of this infrared material microparticle dispersion and the infrared material particulate of making by the manufacture method of this infrared material particulate.Particularly, relate to contain the tungsten oxide particulate in medium or/and the infrared rays masking material microparticle dispersion that the infrared rays masking material microparticulate of compound tungsten oxide particulate obtains.
Background technology
As the light screening material that is used for window material, a kind of shading film that contains the black series pigments has been proposed in patent documentation 1, the pigment dyestuffs such as nigrosine etc. that this black series pigments contains mineral dyes such as the carbon black that has absorptive function from the visible region to the near infrared range, titanium be black and only has strong absorptive function in the visible region, patent documentation 2 has proposed the semitransparent reflector type light screening material with metals such as AM aluminum metallization.
In patent documentation 3, a kind of invisible heat blocking glass has been proposed, this invisible heat blocking glass is on transparent glass substrate, side from substrate, setting contains the IIIa family that is selected from the periodic table of elements, IV family, the compound tungsten oxide film of at least 1 metal ion species in VIb family of Vb family and the VIIb family is as the 1st layer, on above-mentioned the 1st layer, transparent dielectric material film is set as the 2nd layer, on above-mentioned the 2nd layer, setting contains the IIIa family that is selected from the periodic table of elements, IVa family, the compound tungsten oxide film of at least 1 metal ion species in VIb family of Vb family and the VIIb family is as the 3rd layer, and the specific refractory power of above-mentioned the 2nd layer transparent dielectric material film refractive index ratio above-mentioned the 1st layer and above-mentioned the 3rd layer compound tungsten oxide film is low, therefore goes for requiring the position of the high and good invisible heat blocking performance of visible light penetration coefficient.
In patent documentation 4, a kind of invisible heat blocking glass of using the method identical with patent documentation 3 to make has been proposed, this invisible heat blocking glass is on transparent glass substrate, side from substrate, the 1st dielectric material film is set as the 1st layer, the tungsten oxide film is set as the 2nd layer on this film, the 2nd dielectric material film is set on the 2nd layer as the 3rd layer.
In patent documentation 5, a kind of invisible heat blocking glass of using the method identical with patent documentation 3 to make has been proposed, this invisible heat blocking glass is on transparent glass substrate, side from substrate, setting contains the compound tungsten oxide film of same metallic element, transparent dielectric material film is set as the 2nd layer on above-mentioned the 1st layer.
In patent documentation 6, a kind of sunlight feed glass sheet has been proposed, this sunlight feed glass sheet is to contain the tungstic oxide (WO that hydrogen, lithium, sodium or potassium etc. add material with being selected from
3), molybdic oxide (MoO
3), Columbium pentoxide (Nb
2O
5), five thallium oxide (Ta
2O
5), vanadium pentoxide (V
2O
5) and vanadium dioxide (VO
2) in the metal oxide film more than a kind or a kind coat with CVD method or spray method, and under 250 ℃, carry out thermolysis and form have a sunlight feed glass sheet that sunlight covers characteristic.
The variable light modulation thermal insulation material of a kind of sunlight is proposed in patent documentation 7, this sunlight light modulation thermal insulation material, the tungsten oxide that use obtains the wolframic acid hydrolysis, in this tungsten oxide, by adding the organic polymer that Polyvinylpyrolidone (PVP) etc. has ad hoc structure, when solar radiation, ultraviolet ray in the light is absorbed by this tungsten oxide, produce excitation electron and hole,, be accompanied by colour response and accelerate because a spot of ultraviolet ray makes the generation of 5 valency tungsten significantly increase, depth of shade uprises, simultaneously, because blocking light, 5 valency tungsten are oxidized to 6 valency tungsten rapidly, the characteristic of using decoloring reaction to accelerate, can make for the painted and decoloring reaction of sunlight and accelerate, absorption peak occur near infrared region wavelength 1250nm place when painted, the near infrared ray in can blanch.
In addition, present inventor etc. have proposed in patent documentation 8, and tungsten hexachloride is dissolved in alcohol, directly with after solvent evaporation or the reflux with solvent evaporation, afterwards, by 100 ℃～500 ℃ heating down, obtain comprising the powder of tungstic oxide or its hydrate or the two mixture; Use this tungsten oxide particulate, obtain electricity and cause the colorful light-emitting element; When importing proton in constituting the film of multilayer laminate, the optical characteristics of this film changes etc.
In addition, in patent documentation 9, proposed ammonium metawolframate and water miscible various metal-salt as raw material, in about 300～700 ℃ of heating down, simultaneously supply with the hydrogen that has added reactive gas not (the about 50 volume % of addition or more than the 50 volume %) or water vapour (the about 15 volume % of addition or 15 volume % below), prepare and use M to the dry substance of this mixed aqueous solution
xWO
3The method of the various tungsten bronze(s)s of (M is basic metal, alkaline-earth metal, rare earth metal element etc., 0＜x＜1) expression.
Patent documentation 1: the spy opens the 2003-029314 communique
Patent documentation 2: the spy opens flat 9-107815 communique
Patent documentation 3: the spy opens flat 8-59300 communique
Patent documentation 4: the spy opens flat 8-12378 communique
Patent documentation 5: the spy opens flat 8-283044 communique
Patent documentation 6: the spy opens the 2000-119045 communique
Patent documentation 7: the spy opens flat 9-127559 communique
Patent documentation 8: the spy opens the 2003-121884 communique
Patent documentation 9: the spy opens flat 8-73223 communique
Summary of the invention
Invent problem to be solved
But therefore the black series pigments of record, can use these window material tone deepening owing to have big absorptive function in the visible region in patent documentation 1, and use-pattern is restricted.
In addition, record uses the outward appearances such as window material of metal evaporation film to be the semitransparent reflector shape in the patent documentation 2, when using out of doors, because reflection is strong, can have the problem on the view.
In addition, the invisible heat blocking material put down in writing of patent documentation 3～5 is mainly to use the method manufacturing of the drying process of being undertaken by sputtering method, vapour deposition method, ion plating method and chemical gas-phase method (CVD) equal vacuum thin film-forming method.Therefore, existence needs large-scale manufacturing installation and the high problem of manufacturing cost.In addition, the body material of invisible heat blocking material is exposed in the pyritous plasma body, or owing to need to heat after the film forming, when therefore being body material with resins such as films, is necessary other approach, equipment, filming condition are studied.In addition, when shown tungsten oxide film of these patent documentations or the conduct of compound tungsten oxide film formed multilayer film with other transparent dielectric material films, the performance function had a great difference with the present invention.
In addition, the control of the sunlight of record coats sheet glass in the patent documentation 6, by with raw material and CVD method or spray method and thermal decomposition method and be used in formation tunicle on glass, but from cost of material height as precursor, thermolysis at high temperature waits, when being body material, be necessary other approach, filming condition are studied with resins such as films.In addition, must have more than 2 layers or 2 layers to constitute, different with the present invention.
Have, because the variable light modulation thermal insulation material of sunlight of record is in the patent documentation 7～8, electricity causes the colorful light-emitting element again, changes the material of its tone by ultraviolet ray and potential difference, so the complex structure of film, is difficult to be applied in the purposes field of not wishing to change tone.
In addition, in the patent documentation 9, put down in writing the making method of tungsten bronze(s), but do not had to put down in writing particle diameter, the optical characteristics of the powder that obtains.Here,, can consider the electrode materials of electrolyzer or fuel cell and the catalystic material of organic synthesis,, can think not to be to cover purposes as solar ray as the present invention as the purposes of this tungsten bronze(s).
The present invention carries out for solving above-mentioned problem, purpose provides and can fully see through visible light, do not have semitransparent reflector shape outward appearance, on body material during film forming, do not need large-scale manufacturing installation, do not need high-temperature heat treatment during film forming yet, simultaneously, cover wavelength 780nm or 780nm above invisible near infrared ray, the manufacture method of the indeclinable infrared rays masking material of transparent and tone microparticle dispersion, infrared shield and infrared rays masking material particulate and the infrared material particulate that produces by this infrared material particulate manufacture method efficiently.
Solve the measure of problem
Usually, the known material that contains unbound electron demonstrates the reflection-absorption response by the plasma body vibration to the hertzian wave around the zone of the solar ray of wavelength 200nm～2600nm.Known powder with such material is as than the little particulate of light wavelength the time, and (how much scatterings of wavelength 380nm～780nm) obtain the transparency to the visible region can to reduce the visible region.In addition, the so-called transparency of Shi Yonging in this manual, refer to the light scatter of visible region little, the perviousness height.
On the other hand, known to using WO
3-xThe so-called tungsten bronze(s) that adds electropositive element such as Na in the tungsten oxide of expression or the tungstic oxide is conductive material and the material that has unbound electron.And, by mcl analysis, pointed out response to the unbound electron of the light of infrared spectral range to these materials.
Inventors etc. expect increasing contains the tungsten oxide particulate or/and the unbound electron amount that comprises in the infrared rays masking material of compound tungsten oxide particulate, and the particle diameter of particulate is carried out micronize, becomes 1nm～800nm, as infrared rays masking material particulate.Have again, with this infrared rays masking material microparticulate in suitable medium and the film of film that the film of making and the drying process that is become embrane method by sputtering method, vapour deposition method, ion plating method and chemical gas-phase method (CVD method) equal vacuum are made or CVD method, spray method making is compared, the interference of light effect can not be used in discovery, also can absorb the light of solar ray, particularly near infrared range efficiently, see through the light of visible region simultaneously, so finished the present invention.
That is, the 1st invention of the present invention provides a kind of infrared rays masking material microparticle dispersion, it is characterized in that,
This dispersion is the infrared rays masking material microparticle dispersion that infrared rays masking material microparticulate obtains in medium,
Above-mentioned infrared rays masking material particulate contains the tungsten oxide particulate or/and compound tungsten oxide particulate,
The particle diameter of above-mentioned infrared rays masking material particulate is 1nm～800nm.
The 2nd invention of the present invention provides the infrared rays masking material microparticle dispersion of the 1st invention record, it is characterized in that,
Above-mentioned tungsten oxide particulate is to use general formula W
yO
zThe particulate of the tungsten oxide of (here, W is a tungsten, and O is an oxygen, 2.2≤z/y≤2.999) expression.
The 3rd invention of the present invention provides the infrared rays masking material microparticle dispersion of the 1st invention record, it is characterized in that,
Above-mentioned compound tungsten oxide particulate is to use formula M
xW
yO
z(here, M is the element of selecting from H, He, basic metal, alkaline-earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I more than a kind or a kind, W is a tungsten, O is an oxygen, 0.001≤x/y≤1,2.2≤z/y≤3.0) Biao Shi compound tungsten oxide particulate.
The 4th invention of the present invention provides any infrared rays masking material microparticle dispersion of being put down in writing in the 1st～3rd invention, it is characterized in that,
Above-mentioned tungsten oxide particulate is used general formula W or/and above-mentioned compound tungsten oxide particulate comprises
yO
zMa Genaili (the マ グ ネ リ) phase of the ratio of components of (here, W is a tungsten, and O is an oxygen, 2.45≤z/y≤2.999) expression.
The infrared rays masking material microparticle dispersion that the 5th invention of the present invention provides the 3rd invention to be put down in writing is characterized in that,
With formula M
xW
yO
zThe above-mentioned compound tungsten oxide particulate of expression contains the crystalline texture with six reef knot crystallographic systems or tetragonal spheroidal or isometric system, perhaps have in the particulate of non-crystalline structure any one or more than one.
The infrared rays masking material microparticle dispersion that the 6th invention of the present invention provides the 3rd invention to be put down in writing is characterized in that,
With formula M
xW
yO
zThe above-mentioned compound tungsten oxide particulate of expression contains six side's crystalline crystalline textures, perhaps has complete six side's crystalline crystalline textures.
The 7th invention of the present invention provides the 5th or the 6th the infrared rays masking material microparticle dispersion that invention is put down in writing, it is characterized in that,
Above-mentioned M element is one or more among Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, the Sn.
The 8th invention of the present invention provides any infrared rays masking material microparticle dispersion of being put down in writing in the 1st～the 7th invention, it is characterized in that,
The surface of above-mentioned infrared rays masking material particulate is to coat with the oxide compound that contains any one or more than one the element among Si, Ti, Zr, the Al.
The 9th invention of the present invention provides any infrared rays masking material microparticle dispersion of being put down in writing in the 1st～the 8th invention, it is characterized in that,
Above-mentioned medium is resin or glass.
The infrared rays masking material microparticle dispersion that the 10th invention of the present invention provides the 9th invention to be put down in writing is characterized in that,
Above-mentioned resin be in polyvinyl resin, polyvinyl chloride (PVC) RESINS, poly-inclined to one side chlorine vinylidene resin, polyvinyl alcohol resin, polystyrene resin, acrylic resin, ethane-acetic acid ethyenyl ester interpolymer, vibrin, pet resin, fluoro-resin, polycarbonate resin, acrylic resin, the polyvinyl butyral resin any one or more than one.
The 11st invention of the present invention provides a kind of infrared shield, it is characterized in that,
The infrared rays masking material microparticle dispersion of any record in the 1st～the 10th invention forms tabular or laminar or film like.
The 12nd invention of the present invention provides the manufacture method of infrared rays masking material particulate, it is characterized in that,
This method is to contain useful general formula W
yO
zThe tungsten oxide particulate of (here, W is a tungsten, and O is an oxygen, 2.2≤z/y≤2.999) expression is or/and use formula M
xW
yO
z(here, M is from H, He, basic metal, alkaline-earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, the element of selecting among the I more than a kind or a kind, W is a tungsten, O is an oxygen, 0.001≤x/y≤1,2.2≤z/y≤3.0) the manufacture method of the infrared rays masking material particulate of Biao Shi compound tungsten oxide particulate
With the initial feed of above-mentioned infrared rays masking material particulate in the reducing gas environment or/and do not heat-treat in the active gas environment, make above-mentioned infrared rays masking material particulate.
The 13rd invention of the present invention provides the 12nd manufacture method of inventing the infrared rays masking material particulate of being put down in writing, it is characterized in that,
Above-mentioned thermal treatment be initial feed with above-mentioned infrared rays masking material particulate in the reducing gas environment, heat-treat under 100 ℃～850 ℃, then in active gas environment not, heat-treat under 650 ℃～1200 ℃.
The 14th invention of the present invention provides the 12nd or the 13rd manufacture method of inventing the infrared rays masking material particulate of being put down in writing, it is characterized in that,
With above-mentioned general formula W
yO
zThe initial feed of tungsten oxide particulate of expression be from
Tungsten trioxide powder,
The Tungsten oxide powder,
The hydrate powder of tungsten oxide,
The tungsten hexachloride powder,
The ammonium tungstate powder,
After tungsten hexachloride is dissolved in the alcohol, the hydrate powder of the tungsten oxide that drying obtains,
After tungsten hexachloride is dissolved in the alcohol, adds water and generate precipitation, the hydrate powder of the tungsten oxide that dry this precipitation obtains,
The tungsten compound powder that dry ammonium tungstate aqueous solution obtains,
Any one or more than one the powder of selecting in the tungsten powder.
The 15th invention of the present invention provides the 12nd or the 13rd manufacture method of inventing the infrared rays masking material particulate of being put down in writing, it is characterized in that,
Use above-mentioned formula M
xW
yO
zThe initial feed of compound tungsten oxide particulate of expression be from
Tungsten trioxide powder,
The Tungsten oxide powder,
The hydrate powder of tungsten oxide,
The tungsten hexachloride powder,
The ammonium tungstate powder,
After tungsten hexachloride is dissolved in the alcohol, the hydrate powder of the tungsten oxide that drying obtains,
After tungsten hexachloride is dissolved in the alcohol, adds water and generate precipitation, the hydrate powder of the tungsten oxide that dry this precipitation obtains,
The tungsten compound powder that dry ammonium tungstate aqueous solution obtains,
The powder that any one or more than one the powder of selecting in the tungsten powder and the powder mixes of simple substance that contains above-mentioned M element or compound form.
The 16th invention of the present invention provides the 12nd or the 13rd manufacture method of inventing the infrared rays masking material particulate of being put down in writing, it is characterized in that,
Can use above-mentioned formula M
xW
yO
zThe initial feed of compound tungsten oxide particulate of expression be with
The alcoholic solution of tungsten hexachloride or the aqueous solution of ammonium tungstate and contain the powder that the solution mixing after drying of the compound of above-mentioned M element obtains.
The 17th invention of the present invention provides the 12nd or the 13rd manufacture method of inventing the infrared rays masking material particulate of being put down in writing, it is characterized in that,
Use above-mentioned formula M
xW
yO
zThe initial feed of compound tungsten oxide particulate of expression be with
After tungsten hexachloride is dissolved in the alcohol, add the sedimentary dispersion liquid of water generates and
Contain the powder of the simple substance of above-mentioned M element or compound or contain the powder that the solution mixing after drying of the compound of above-mentioned M element obtains.
The 18th invention of the present invention provides a kind of infrared rays masking material particulate, it is characterized in that,
That this particulate contains is that the manufacture method of the infrared rays masking material particulate of being put down in writing by any invention in the 12nd～the 17th is made, use general formula W
yO
zThe tungsten oxide particulate of (here, W is a tungsten, and O is an oxygen, 2.2≤z/y≤2.999) expression or and use formula M
xW
yO
z(here, M is the element of selecting from H, He, basic metal, alkaline-earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I more than a kind or a kind, W is a tungsten, O is an oxygen, 0.001≤x/y≤1,2.2≤z/y≤3.0) Biao Shi compound tungsten oxide particulate.
The effect of invention
According to the present invention; to contain the tungsten oxide particulate or/and the particle diameter micronize of the infrared rays masking material particle of compound tungsten oxide particulate becomes 1nm～800nm; with this infrared rays masking material microparticulate in medium the time; even with by sputtering method; vapour deposition method; ion plating method and chemical gas-phase method (CVD method) equal vacuum becomes the film of drying process making such as embrane method or uses the CVD method; the film that spray method is made is compared; also can produce to have and to block solar ray efficiently; the light of near infrared range particularly, transmittance that keeps the visible region simultaneously etc. has the infrared rays masking material microparticle dispersion of excellent optical.In addition, when using this infrared rays masking material microparticle dispersion to make infrared shield, do not need to use large-scale plant such as vacuum unit just can make infrared shield at an easy rate, industrial be practical.
The preferred plan that carries out an invention
The infrared rays masking material microparticle dispersion that the present invention relates to is characterised in that; this dispersion be with as containing the tungsten oxide particulate or/and the infrared rays masking material particle of compound tungsten oxide particulate; the particle diameter of this infrared rays masking material particulate is that 1nm～800nm and this infrared rays masking material microparticulate form in suitable medium described later.
Below, be described in detail for this infrared rays masking material particulate and infrared rays masking material microparticle dispersion.
1. infrared rays masking material
Usually, because tungstic oxide (WO
3) in do not have effective unbound electron, so the absorption reflection characteristic of near infrared range is few, can not be effective as the infrared rays masking material.Here, because with respect to the tungsten in the tungstic oxide, the ratio of oxygen is less than 3, in this tungsten oxide, can generate unbound electron as can be known, but discoveries such as present inventor in the specific part of the tungsten in this tungsten oxide and the compositing range of oxygen, have as the effective especially scope of infrared rays masking material.
The compositing range of this tungsten and oxygen is with respect to tungsten, and the ratio of components of oxygen is more preferably at this tungsten oxide is recited as W below 3 or 3
yO
zThe time, 2.2≤z/y≤2.999.If because this z/y value more than 2.2 or 2.2, can be avoided as the WO outside this target tungsten oxide
2The appearance of crystallization phases, simultaneously, can obtain chemical stability as material, can use as effective infrared rays masking material.
On the other hand, if this z/y value below 2.999, can generate the unbound electron of necessary amount in this tungsten oxide, become infrared rays masking material efficiently.
In addition, this tungsten oxide is being carried out in the micronized tungsten oxide particulate, as general formula W
yO
zThe time, promptly so-called " マ グ ネ リ phase " with the ratio of components that can be expressed as 2.45≤z/y≤2.999 is chemically stable, and be also good in the absorption characteristic of near infrared range, therefore preferably as the infrared rays masking material.
Have again, in this tungsten oxide, add element M (here, M is from H, He, basic metal, alkaline-earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, when the element of selecting among the I more than a kind or a kind) making compound tungsten oxide, generate unbound electron in this compound tungsten oxide, show absorption characteristic near infrared range from unbound electron, as near the near-infrared-absorbing material wavelength 1000nm is effectively, therefore preferred.Here, viewpoint from the stability of this compound tungsten oxide of adding element M, element M is preferably from basic metal, alkaline-earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, the element of selecting among the I more than a kind or a kind, from improving optical characteristics as the infrared rays masking material, on the viewpoint of weathering resistance, in above-mentioned element M, more preferably belong to basic metal, the alkaline-earth metal element, the transition metal element, 4B family element, the element of 5B family element.
Here, for this compound tungsten oxide,, can obtain efficient good infrared rays masking material owing to carry out the control of above-mentioned oxygen amount simultaneously and generate the interpolation of the element of unbound electron.With the control of this oxygen amount and the general formula that generates the infrared rays masking material that the interpolation of the element of unbound electron carries out simultaneously be recited as M
xW
yO
zWhen (here, M is above-mentioned M element, and W is a tungsten, and O is an oxygen), being expected to is the infrared rays masking material that satisfies 0.001≤x/y≤1,2.2≤z/y≤3.0 relations.
At first, the x/y value of addition to the expression element M describes.If the x/y value is bigger than 0.001, can obtain with the unbound electron that generates abundant amount is the infrared rays screening effect of purpose.And the addition of element M is many more, and the feed rate of unbound electron can increase, and the infrared rays screening effect also can rise, but about x/y value to 1, this effect is saturated.In addition, if the x/y value less than 1, can avoid generating the impurity phase in this infrared rays masking material, therefore preferred.In addition, element M preferably from H, He, basic metal, alkaline-earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, select more than a kind or a kind.Here, the viewpoint of the stability in this MxWyOz that adds element M, element M is preferably from basic metal, alkaline-earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, the element of selecting among the Re more than a kind or a kind, from improving optical characteristics as the infrared rays masking material, on the viewpoint of weathering resistance, in above-mentioned element M, more preferably belong to basic metal, the alkaline-earth metal element, the transition metal element, 4B family element, 5B family element.
Below, the z/y value of expression being controlled the oxygen amount describes.About the value of z/y, using M
xW
yO
zIn the infrared rays masking material of expression, with the above-mentioned W that uses
yO
zThe infrared rays masking material of expression has same principle, and, in z/y=3.0, for producing because the supply of the unbound electron that the addition of above-mentioned element M causes, preferred 2.2≤z/y≤3.0.
Have, when above-mentioned compound tungsten oxide particulate had the hexagonal crystal structure, the transmitance of the visible region of this particulate improved again, and the absorption of near infrared region improves.Reference describes as Fig. 4 of the mode view of this hexagonal crystal structure.In Fig. 4, the WO that represents with symbol 1
68 bodies that the unit forms, 6 set form hexagonal space (tunnel), and in this space, the element M that configuration is represented with symbol 2 constitutes 1 unit, 1 so a plurality of set in unit, the crystalline texture of formation hexagonal system.
Seeing through of the visible region that the present invention relates to for being improved, and the effect that improves the absorption of near infrared region (are used WO as long as contain the modular construction of Fig. 4 explanation in compound tungsten oxide particulate
66 set of 8 bodies that the unit forms constitute hexagonal spaces, the structure of configuration element M in this space) just can, this compound tungsten oxide particulate can be crystalline material, also can be amorphous substance.
In this hexagonal space, add and when retaining the positively charged ion of element M, the absorption of near infrared range improves.Here, usually, when adding the big element M of ionic radius, form this hexagonal system, particularly, add among Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, the Sn more than a kind or a kind the time, be easy to form hexagonal system, therefore preferred.Certainly, the element beyond these is as long as using WO
6Exist in the sexangle space that the unit forms add element M just can, be not limited to above-mentioned element.
When the compound tungsten oxide particulate with hexagonal crystal structure has uniform crystal structure, add the addition of element M, promptly the x/y value preferred 0.2～0.5, more preferred 0.33.During z/y=3,, can think so, add element M and can dispose into whole sexangles space if the value of x/y is 0.33.
Equally, during z/y=3, in isometric system, each compound tungsten oxide compound of tetragonal spheroidal, also there is the upper limit of addition of the interpolation element M of self-structure, with respect to 1 mole of tungsten, the maximum addition that adds element M is that isometric system is 1 mole, tetragonal spheroidal is (kind according to the M element changes, and to be relatively easy to be about 0.5 mole but industry is made) about 0.5 mole.But these structures are difficult to stipulate simply that this scope is a special case of expression base region, and therefore, the present invention is not limited thereto.
In addition, above-mentioned compound tungsten oxide particulate when taking the structure of tungsten bronze(s) of tetragonal spheroidal, isometric system, also is effective as the infrared rays masking material except that above-mentioned hexagonal system.The crystalline texture of being taked according to this compound tungsten oxide particulate, the vicissitudinous tendency in absorption position of near infrared range, compared with isometric system, during tetragonal spheroidal, the absorption position of this near infrared range is to long wavelength's one side shifting, during hexagonal system, during than tetragonal spheroidal further to long wavelength's one side shifting.In addition, with this change that absorbs the position, hexagonal system is to the absorption minimum of visible region, and tetragonal spheroidal is taken second place, and isometric system is maximum among the three.Therefore, see through the light of more visible regions, cover in the purposes of light of more infrared spectral ranges, preferably use the tungsten bronze(s) of hexagonal system at needs.But the tendency of said optical characteristics is tendency roughly after all here, changes to some extent according to the difference of the kind of adding element, addition, oxygen amount, and therefore, the present invention is not limited thereto.
The present invention relates to contain the tungsten oxide particulate or/and the infrared rays masking material of compound tungsten oxide particulate because near the light a large amount of absorption near infrared ray zone, particularly the wavelength 1000nm, it is more for the blue material that is tied to green system that it sees through tone.In addition, the particle diameter of this infrared rays masking material particle can be selected respectively according to its application target.At first, be used in the situation that keeps the transparency, preferably having 800nm or the following particle diameter of 800nm.This is because the particle that particle diameter ratio 800nm is little can not cover light fully by scattering, keeps the visibility of visible region, keeps the transparency efficiently simultaneously.Particularly pay attention to the occasion of the transparency of visible region, the more preferred scattering of considering by particle.
When the reduction of the scattering of paying attention to being brought by this particle, particle diameter is at 200nm or below the 200nm, and preferred 100nm or 100nm are following for well.Reason is, if particle diameter is little, because the light scatter of the visible region of wavelength 400nm～780nm that how much scatterings or Mie scattering bring reduces, consequently can avoid the infrared rays shielding film to become similar mat glass and can not obtain the distinct transparency like that.That is, particle diameter is when 200nm or 200nm are following, and above-mentioned how much scatterings or Mie scattering reduce, and become the Rayleigh scattering zone.Because in the Rayleigh scattering zone, 6 powers of scattered light and particle diameter are reverse proportionality to be reduced, and follows the minimizing of particle diameter, scattering reduces, and the transparency improves.Have, particle diameter is when 100nm or 100nm are following again, and scattered light is considerably less, and is therefore preferred.From avoiding the viewpoint of light scatter, preferable particle size is little, if particle diameter, is easy to industry manufacturing at 1nm or more than the 1nm.
By above-mentioned particle diameter being chosen as 800nm or below the 800nm, the haze value of infrared rays masking material microparticle dispersion that has disperseed infrared rays masking material particulate in medium is at visible light transmissivity 85% or 85% when following, can set mist degree 30% or 30% when following.If mist degree is than 30% big value, can become and be similar to mat glass, can not get the distinct transparency.
In addition, constitute the surface of the particulate of infrared rays masking material of the present invention, on the viewpoint of the weathering resistance that improves this infrared rays masking material, preferably coat with one or more the oxide compound that contains Si, Ti, Zr, Al.
2. the manufacturing of infrared rays masking material particulate
Contain with above-mentioned general formula W
yO
zThe tungsten oxide particulate of (here, W is a tungsten, and O is an oxygen, 2.2≤z/y≤2.999) expression is or/and use M
xW
yO
z(here, M is from H, He, basic metal, alkaline-earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, the element of selecting among the I more than a kind or a kind, W is a tungsten, O is an oxygen, 0.001≤x/y≤1,2.2≤z/y≤3.0) the infrared rays masking material particulate of Biao Shi compound tungsten oxide particulate, can be with tungsten compound as the initial feed of this tungsten oxide particulate and/or compound tungsten oxide particulate, in not active gas environment or reducing gas environment, heat-treat and make.The tungsten oxide particulate, the compound tungsten oxide particulate that obtain through this thermal treatment have sufficient near-infrared absorbing ability, have the preferred property that covers particulate as infrared rays.
As the tungsten compound of initial feed preferably after the hydrate of tungsten trioxide powder, Tungsten oxide powder or tungsten oxide or tungsten hexachloride powder or ammonium tungstate powder or tungsten hexachloride are dissolved in the alcohol, after the hydrate powder of the tungsten oxide that drying obtains or tungsten hexachloride are dissolved in the alcohol, add water and generate precipitation, select in the hydrate powder of the tungsten oxide that dry this precipitation obtains or tungsten compound powder that dry ammonium tungstate aqueous solution obtains or the tungsten powder any one or more than one.
Here, from when making the tungsten oxide particulate, manufacturing process is easy to viewpoint, be more preferably the tungsten compound powder that the hydrate powder, tungstic oxide or the dry ammonium tungstate aqueous solution that use tungsten oxide obtains, when making compound tungsten oxide particulate, if initial feed is a solution, can easy mixed uniformly viewpoint from each element, more preferably use ammonium tungstate aqueous solution, tungsten hexachloride solution.Use these raw materials, it is not being heat-treated in active gas environment or the reducing gas environment, can make and contain above-mentioned tungsten oxide particulate or/and the infrared rays masking material particulate of compound tungsten oxide particulate.
In addition, the formula M of using that contains above-mentioned element M
xW
yO
zThe initial feed of infrared rays masking material particulate of the compound tungsten oxide particulate of expression and contains with above-mentioned general formula W
yO
zThe initial feed of the infrared rays masking material particulate of the tungsten oxide particulate of expression is same tungsten compound, still, can also will contain the tungsten compound of element M as initial feed with element simple substance or compound form.Here, for producing tungsten compound as each composition mixed uniformly initial feed on molecular level, preferred each raw material mixes with solution state, the tungsten compound that contains element M preferably can be dissolved in the tungsten compound in water or the organic solvent equal solvent, can enumerate, for example contain tungstate, chloride salt, nitrate, vitriol, oxalate, oxide compound, carbonate, oxyhydroxide of element M etc., but be not limited to this, so long as solution state is preferably.
About making the raw material of above-mentioned tungsten oxide particulate, compound tungsten oxide particulate, below, be elaborated again.
As obtaining using general formula W
yO
zThe tungsten compound of initial feed of the tungsten oxide particulate of expression, preferably can use the hydrate of tungsten trioxide powder, Tungsten oxide powder or tungsten oxide or tungsten hexachloride powder or ammonium tungstate powder or tungsten hexachloride to be dissolved in to add after the hydrate powder of the tungsten oxide that after drying obtains in the alcohol or tungsten hexachloride are dissolved in the alcohol water to generate to select in the hydrate powder of the tungsten oxide that dry this precipitation of precipitation obtains or tungsten compound powder that dry ammonium tungstate aqueous solution obtains or the tungsten powder any one or more than one.But be easy to viewpoint from manufacturing process, be more preferably the tungsten compound powder that the hydrate powder, tungsten trioxide powder or the dry ammonium tungstate aqueous solution that use tungsten oxide obtains.
Can use formula M for what obtain containing element M
xW
yO
zThe initial feed that the compound tungsten oxide particulate of expression is used can be used will be from tungsten trioxide powder, the Tungsten oxide powder, or the hydrate of tungsten oxide, or tungsten hexachloride powder, or ammonium tungstate powder, or tungsten hexachloride is dissolved in the hydrate powder of the tungsten oxide that after drying obtains in the alcohol, or, tungsten hexachloride is dissolved in the hydrate powder of the tungsten oxide that alcohol back aqueous precipitation and dry this precipitation obtain, or the tungsten compound powder that obtains of dry ammonium tungstate aqueous solution, or the powder that obtains after the powder mixes of any one or more than one the powder of selecting in the tungsten powder and simple substance that contains above-mentioned M element or compound.
Moreover as in order to obtain the tungsten compound of the initial feed that this compound tungsten oxide particulate uses, if solution or dispersion liquid, each element is uniform mixing easily just.
From this viewpoint, the initial feed of compound tungsten oxide particulate is more preferably with the alcoholic solution of tungsten hexachloride or ammonium tungstate aqueous solution and contain the powder that obtains behind the solution combination drying of compound of above-mentioned element M.
Equally, after the preferred tungsten hexachloride of the initial feed of the particulate of compound tungsten oxide is dissolved in the alcohol, add water and generate sedimentary dispersion liquid, with monomer that contains above-mentioned element M or compound powder or contain the powder that obtains behind the solution combination drying of compound of above-mentioned element M.
As the compound that contains above-mentioned M element, can enumerate tungstate, chloride salt, nitrate, vitriol, oxalate, oxide compound, carbonate, oxyhydroxide of M element etc., but be not limited to this, so long as solution state gets final product.Have again, when this compound tungsten oxide particulate of industrial manufacturing,, can not produce obnoxious flavour etc. in the stages such as thermal treatments, so be preferred manufacture method if when using the carbonate of the hydrate powder of tungsten oxide or tungstic oxide and M element or oxyhydroxide.
Here, as the condition that tungsten oxide particulate and compound tungsten oxide particulate are heat-treated in active gas environment not, preferred more than 650 ℃ or 650 ℃.Have sufficient near-infrared absorbing ability in the initial feed of heat-treating more than 650 ℃ or 650 ℃, cover particulate, the efficient height as infrared rays.Can use Ar, N as reactive gas not
2Deng reactive gas not.In addition,, at first, initial feed is heat-treated under 100 ℃～850 ℃ in the reducing gas environment, then, under 650 ℃～1200 ℃ temperature, do not heat-treating in the active gas environment to good as the treatment condition in the reducing gas environment.There is no particular limitation for the reducing gas of this moment, but preferred H
2In addition, use H as reducing gas
2The time, as the composition of reducing gas environment, preferred H
2Volume ratio more than 0.1% or 0.1%, more than more preferred 2% or 2%.If H
2Volume ratio more than 0.1% or 0.1%, can promote effectively the reduction.
Tungsten oxide particulate with hydrogen reduction contains the Ma Genaili phase, shows good infrared rays and covers characteristic, under this state, can be used as infrared rays and covers the particulate use.But, owing to the hydrogen instability that remains in the tungsten oxide, so aspect weathering resistance, application may be restricted.Therefore, the tungsten oxide that will contain this hydrogen is not being heat-treated more than 650 ℃ or 650 ℃ in the reactive gas, can obtain more stable infrared rays and cover particulate.This 650 ℃ or 650 ℃ with thermal treatment the time environmental gas there is no particular limitation, but from the viewpoint of industry, preferred N
2, Ar.By this thermal treatment more than 650 ℃ or 650 ℃, cover at infrared rays and to exist Ma Genaili mutually and improve weathering resistance in the particulate.
The surface of the infrared rays masking material particulate that obtains in above-mentioned operation will use one or more the oxide compound of metal that contains Si, Ti, Zr, Al to coat, and is preferred in view of the viewpoint that improves weathering resistance then.There is no particular limitation for the method that coats, but can coat the surface of infrared rays masking material particulate by add the alkoxide of above-mentioned metal in the solution that has disperseed this infrared rays masking material particulate.
3. infrared rays masking material microparticle dispersion
Using method as the infrared rays masking material particulate that the present invention relates to has above-mentioned microparticulate in suitable medium, is formed on the method on the substrate material surface of expectation.This method, can with in advance through the infrared rays masking material microparticulate of high-temperature firing in body material, perhaps be bonded in substrate material surface by tackiness agent, therefore the low body materials of heat resisting temperature such as resin material be can be applied to, large-scale plant and advantages of being cheap do not needed when having formation.
In addition, the infrared rays masking material that the present invention relates to, has probably to absorb reflection and the electric wave of obstruction mobile telephone etc. when therefore using as the successive film because of being conductive material.But the infrared rays masking material as microparticulate in matrix the time, because particle scatter with isolated state one by one, has been given play to the perviousness of electric wave, therefore had widely-used property.
(a) with microparticulate in medium, the method that on substrate material surface, forms
For example; the infrared rays masking material that will the present invention relates to is carried out micronized infrared rays masking material microparticulate in appropriate solvent; obtain the dispersion liquid of infrared rays masking material particulate; perhaps this infrared rays masking material is mixed with appropriate solvent; this mixture is carried out case of wet attrition, obtain the dispersion liquid of infrared rays masking material particulate.After in the dispersion liquid of the infrared rays masking material particulate that obtains, adding dielectric resin, be coated on substrate material surface, evaporating solvent, the method cured resin with regulation just can form the film of this infrared rays masking material microparticulate in medium.As long as it is just passable that the method that coats can apply the resin that contains infrared rays masking material particulate equably at matrix surface, there is no particular limitation, can enumerate excellent cladding process, intaglio plate cladding process, spray application method, immersion coating method etc.In addition, the infrared rays masking material directly is scattered in method in the adhesive resin, after the substrate material surface coating, does not need evaporating solvent, on environment and industrial all be preferred.
Above-mentioned medium can be selected for example UV cured resin, heat reactive resin, electron(beam)curing resin, cold setting resin, thermoplastic resin etc. according to purpose.Particularly, can enumerate polyvinyl resin, polyvinyl chloride (PVC) RESINS, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, acrylic resin, ethylene-vinyl acetate copolymer, vibrin, pet resin, fluoro-resin, polycarbonate resin, acrylic resin, polyvinyl butyral resin.These resins can be used alone, but also also mix together.In addition, also can utilize the tackiness agent that has used metal alkoxide.As above-mentioned metal alkoxide, be representative with the metal alkoxide of Si, Ti, Al, Zr etc.Use the tackiness agent of these metal alkoxides to form oxide film by hydrolytie polycondensations such as heating.
As above-mentioned body material, can be that film can be a plate also according to expectation, shape is unqualified.As the transparent base material, can use PET, acrylic resin, urethane, polycarbonate, polyethylene, ethene-vinyl acetate interpolymer, polyvinyl chloride, fluoro-resin etc. according to various purposes.In addition, except that resin, can also use glass.
(b) method of disperse particles in body material
In addition, as the additive method that the infrared rays masking material that will the present invention relates to is used as particulate, also can be in body material with microparticulate.For with microparticulate in body material, can soak into from substrate material surface, also temperature can be risen to the melt temperature of body material or more than it, make it fusion after, with particulate and mixed with resin.The resin that the contains particulate method according to the rules that obtains like this forms film or tabular, can be used as the infrared rays masking material and uses.
For example, as method, at first PET resin and particle dispersion liquid are mixed to PET resin dispersion particulate, behind the evaporation dispersion solvent, be heated to about 300 ℃ of the melt temperatures of PET, fusion PET resin, by mixing and cooling off, can prepare the PET resin that has disperseed particulate.
There is no particular limitation for the method for the above-mentioned infrared rays masking material of grinding dispersion particulate, but can use for example ultrasonic irradiation, granulated glass sphere runner milling, sand mill etc.In addition, for obtaining uniform dispersion, also can add various additives or dispersion agent or adjust the pH value.Dispersion agent can be selected according to purposes, for example, high score subclass dispersion agent or silicane coupler, titanate ester coupler, aluminium class coupler etc. is arranged, but be not limited to these.
4. the optical characteristics of infrared rays masking material microparticle dispersion
Based on architectural glazings with film JIS A 5759 (1998) (light source: A light) optical characteristics of the infrared rays masking material microparticle dispersion that the present invention relates to is measured, calculated visible light transmissivity, sunshine transmitance.But it is on glass that the sample of measuring usefulness is not that card is attached to, and be to use sample film itself.Haze value is measured based on JISK 7105.The average mark shot directly is by using the determinator (ELS-800 (Otsuka Electronics Co., Ltd. system) of dynamic light scattering method) mean value measured.
As the example of measurement result, with W
18O
49The curve (プ ロ イ Off ア イ Le) that sees through of microparticulate film be shown in Fig. 1.Fig. 1 is that transverse axis is the wavelength of the light that sees through, and the longitudinal axis is the graphic representation of the transmitance (%) of light.Can judge the W that the present invention relates to significantly from Fig. 1
18O
49The microparticulate film, can be through the light (for example: the transmitance of the visible light of wavelength 500nm is 60%) that as wavelength of visible light is 380～780, can optionally to absorb wavelength as sightless invisible heat be near the 1000nm and above infrared rays (for example: the ultrared transmitance of wavelength 1000nm is 18%, the infrared rays transmitance of wavelength 1250nm is 15%), given play to perviousness for the light of visible region, and the light of infrared spectral range is had absorptivity, can confirm to have excellent infrared rays and cover characteristic.
Below, with the dispersion membrane of the compound tungsten oxide particulate that contains hexagonal system to see through curve be example, with Cs
0.33WO
3The curve that sees through be shown in Fig. 2.It is that transverse axis is the wavelength of the light that sees through, and the longitudinal axis is the graphic representation of the transmitance (%) of light.Can judge the Cs that the present invention relates to significantly from Fig. 2
0.33WO
3The microparticulate film, can be through the light (for example: the transmitance of the visible light of wavelength 500nm is 79.5%) that as wavelength of visible light is 380～780, as the wavelength of sightless invisible heat is near the 1000nm and above infrared rays can absorb optionally that (for example: the ultrared transmitance of wavelength 1000nm is 19.0%, the infrared rays transmitance of wavelength 1250nm is 12.9%), given play to perviousness for the light of visible region, and the light of infrared spectral range is had absorptivity, have excellent infrared rays and cover characteristic.
Below, as the different examples that see through curve of the dispersion membrane that contains the compound tungsten oxide particulate of hexagonal system, with Rb
0.33WO
3The curve that sees through be shown in Fig. 3.It is that transverse axis is the wavelength of the light that sees through, and the longitudinal axis is the graphic representation of the transmitance (%) of light.Can judge the Rb that the present invention relates to significantly from Fig. 3
0.33WO
3The microparticulate film, can be through the light (for example: the transmitance of the visible light of wavelength 500nm is 80%) that as wavelength of visible light is 380～780, as the wavelength of sightless invisible heat is near the 1000nm and above infrared rays can absorb optionally that (for example: the ultrared transmitance of wavelength 1000nm is 14.32%, the infrared rays transmitance of wavelength 1250nm is 8.0%), given play to perviousness for the light of visible region, and the light of infrared spectral range is had absorptivity, have excellent infrared rays and cover characteristic.
Below, for embodiment the present invention is described in more detail, but the present invention is not limited thereto.Optical detecting in embodiment and comparative example is based on architectural glazings with film JIS A 5759 (1998) (light source: A light) measure, calculate visible light transmissivity, sunshine transmitance.But it is on glass that the sample of measuring usefulness is not that card is attached to, and be to use sample film itself.Haze value is measured based on JISK 7105.The average mark shot directly is by using the determinator (ELS-800 (Otsuka Electronics Co., Ltd. system) of dynamic light scattering method) mean value measured.
The optical characteristics of the body material PET film that uses in an embodiment in addition, (HPE-50 Supreme Being people system) is visible light transmissivity 89%, sunshine transmitance 89%, haze value 0.8%.
Is that 1 to 0.2 ratio weighs up specified amount with tungsten hexachloride and cuprous chloride according to the mol ratio of W and Cu, is dissolved in slightly in the ethanol at every turn, obtains mixing solutions.This mixing solutions is dry under 130 ℃, as pulverous initial feed.This initial feed was heated 1 hour under 550 ℃ in reducing gas environment (argon/hydrogen=95/5 volume ratio).And, after once turning back to room temperature, in 800 ℃, ar gas environment, heated 1 hour preparation Cu
0.2WO
2.72Powder.The qualification result of the crystallization phases of measuring by X-ray diffraction is observed W
18O
49Crystallization phases, this Cu
0.2WO
2.72Specific surface area be 30m
2/ g.
With this Cu
0.2WO
2.72 Powder 20 weight parts, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix, carry out dispersion treatment, as the dispersion liquid (A liquid) of average mark shot footpath 80nm.These A liquid 10 weight parts and hard coat are mixed with ultraviolet curable resin (solids component 100%) 100 weight parts, make infrared rays masking material particle dispersion liquid.This infrared rays masking material particle dispersion liquid is coated with machine with rod is coated on the PET resin film (HPE-50), and film forming.At 60 ℃ down behind dry 30 seconds and the evaporating solvent, hardening with high pressure mercury vapour lamp obtains the infrared rays shielding film with the film of this formation.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 61%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 45%, covers the direct incident light of about 55% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.9%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
Here, above-mentioned visible light transmissivity, sunshine, transmitance changed to some extent according to the amount difference of unit surface dispersive infrared rays masking material, so visible light transmissivity, sunshine, transmitance all increased and decreased with the amount of infrared rays masking material relatedly.In addition, the summary of the creating conditions of infrared rays masking material of record, powder feature and optical characteristics is recorded in table look-up shown in Figure 5 in this embodiment.
Following examples are also identical.
Tungsten hexachloride is dissolved in the ethanol at every turn slightly, obtains mixing solutions.This solution is dry under 130 ℃, as pulverous initial feed.This initial feed was heated 1 hour under 550 ℃ in reducing gas environment (argon/hydrogen=95/5 volume ratio).And, after once turning back to room temperature, in 800 ℃, ar gas environment, heated 1 hour preparation W
18O
49(WO
2.72) powder.
The qualification result of the crystallization phases by X-ray diffraction is observed W
18O
49Crystallization phases, this WO
2.72Specific surface area be 30m
2/ g.
With this WO
2.72 Powder 20 weight parts, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix, and carry out dispersion treatment, as the dispersion liquid (B liquid) of average mark shot footpath 80nm.These B liquid 10 weight parts and hard coat are mixed with ultraviolet curable resin (solids component 100%) 100 weight parts, as infrared rays masking material particle dispersion liquid.This infrared rays masking material particle dispersion liquid is coated with machine with rod is coated on the PET resin film (HPE-50), and film forming.At 60 ℃ down behind dry 30 seconds and the evaporating solvent, hardening with high pressure mercury vapour lamp obtains the infrared rays shielding film with the film of this formation.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 57%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 42%, covers the direct incident light of about 58% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.9%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
Is that 1 to 0.2 ratio weighs up specified amount with tungsten hexachloride and cuprous chloride according to the mol ratio of W and Cu, is dissolved in slightly in the ethanol at every turn, obtains mixing solutions.In atmosphere, 350 ℃ dry down, as pulverous initial feed with this mixing solutions.This initial feed was heated 15 hours under 980 ℃ in ar gas environment.Preparation Cu
0.2WO
2.72Powder.This Cu
0.2WO
2.72The specific surface area of powder be 31m
2/ g.
With this Cu
0.2WO
2.72 Powder 20 weight parts, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix, carry out dispersion treatment, as the dispersion liquid (C liquid) of average mark shot footpath 80nm.These C liquid 10 weight parts and hard coat are mixed with ultraviolet curable resin (solids component 100%) 100 weight parts, as infrared rays masking material particle dispersion liquid.This infrared rays masking material particle dispersion liquid is coated with machine with rod is coated on the PET resin film (HPE-50), and film forming.At 60 ℃ down behind dry 30 seconds and the evaporating solvent, hardening with high pressure mercury vapour lamp obtains the infrared rays shielding film with the film of this formation.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 58%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 43%, covers the direct incident light of about 57% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.9%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
Is that 1 to 0.1 ratio weighs up specified amount with tungsten hexachloride and aluminum nitrate according to the mol ratio of W and Al, is dissolved in slightly in the ethanol at every turn, obtains mixing solutions.This mixing solutions is dry under 130 ℃, as pulverous initial feed.This initial feed was heated 1 hour under 550 ℃ in reducing gas environment (argon/hydrogen=95/5 volume ratio).And, after once turning back to room temperature, in 800 ℃, ar gas environment, heated 1 hour preparation Al
0.1WO
2.72Powder.The qualification result of the crystallization phases of measuring by X-ray diffraction is observed W
18O
49Crystallization phases, this Al
0.1WO
2.72Specific surface area be 28m
2/ g.
With this Al
0.1WO
2.72 Powder 20 weight parts, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix, carry out dispersion treatment, as the dispersion liquid (D liquid) of average mark shot footpath 80nm.These D liquid 10 weight parts and hard coat are mixed with ultraviolet curable resin (solids component 100%) 100 weight parts, as infrared rays masking material particle dispersion liquid.This infrared rays masking material particle dispersion liquid is coated with machine with rod is coated on the PET resin film (HPE-50), and film forming.At 60 ℃ down behind dry 30 seconds and the evaporating solvent, hardening with high pressure mercury vapour lamp obtains the infrared rays shielding film with the film of this formation.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 61%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 45%, covers the direct incident light of about 55% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.9%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
Is that 1 to 0.1 ratio weighs up specified amount with tungsten hexachloride and manganous nitrate according to the mol ratio of W and Mn, is dissolved in slightly in the ethanol at every turn, obtains mixing solutions.This mixing solutions is dry under 130 ℃, as pulverous initial feed.This initial feed was heated 1 hour under 550 ℃ in reducing gas environment (argon/hydrogen=95/5 volume ratio).And, after once turning back to room temperature, in 800 ℃, ar gas environment, heated 1 hour preparation Mn
0.1WO
2.72Powder.The qualification result of the crystallization phases of measuring by X-ray diffraction is observed W
18O
49Crystallization phases, this Mn
0.1WO
2.72Specific surface area be 30m
2/ g.
With this Mn
0.1WO
2.72 Powder 20 weight parts, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix, carry out dispersion treatment, as the dispersion liquid (E liquid) of average mark shot footpath 80nm.These E liquid 10 weight parts and hard coat are mixed with ultraviolet curable resin (solids component 100%) 100 weight parts, as infrared rays masking material particle dispersion liquid.This infrared rays masking material particle dispersion liquid is coated with machine with rod is coated on the PET resin film (HPE-50), and film forming.At 60 ℃ down behind dry 30 seconds and the evaporating solvent, hardening with high pressure mercury vapour lamp obtains the infrared rays shielding film with the film of this formation.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 60%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 49%, covers the direct incident light of about 51% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.9%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
Embodiment 6
As initial feed, 550 ℃ were heated 1 hour down in reducing gas environment (argon/hydrogen=95/5 volume ratio) with tungsten trioxide powder.And, after once turning back to room temperature, further in 800 ℃, ar gas environment, heated 1 hour preparation WO
2.72Powder.The qualification result of the crystallization phases of measuring by X-ray diffraction is observed W
18O
49Crystallization phases, this WO
2.72Specific surface area be 35m
2/ g.
With this WO
2.72 Powder 20 weight parts, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix, carry out dispersion treatment, as the dispersion liquid (F liquid) of average mark shot footpath 80nm.These F liquid 2 weight parts and hard coat are mixed with ultraviolet curable resin (solids component 100%) 100 weight parts, as infrared rays masking material particle dispersion liquid.This infrared rays masking material particle dispersion liquid is coated with machine with rod is coated on the PET resin film (HPE-50), and film forming.At 60 ℃ down behind dry 30 seconds and the evaporating solvent, hardening with high pressure mercury vapour lamp obtains the infrared rays shielding film with the film of this formation.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 65%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 50%, covers the direct incident light of about 50% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.9%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
Embodiment 7
Is that 1 to 0.3 ratio weighs up specified amount with tungsten hexachloride and indium nitrate according to the mol ratio of W and In, is dissolved in slightly in the ethanol at every turn, obtains mixing solutions.This mixing solutions is dry under 130 ℃, as pulverous initial feed.This initial feed was heated 1 hour under 500 ℃ in reducing gas environment (argon/hydrogen=95/5 volume ratio).And, after once turning back to room temperature, in 800 ℃, ar gas environment, heated 1 hour preparation In
0.3WO
3Powder.The qualification result of the crystallization phases of measuring by X-ray diffraction, the crystallization phases of observing hexagonal system tungsten bronze(s) (compound tungsten oxide particulate), this In
0.3WO
3Specific surface area be 30m
2/ g.
With this In
0.3WO
3 Powder 20 weight parts, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix, carry out dispersion treatment, as the dispersion liquid (H liquid) of average mark shot footpath 80nm.These H liquid 10 weight parts and hard coat are mixed with ultraviolet curable resin (solids component 100%) 100 weight parts, as infrared rays masking material particle dispersion liquid.This infrared rays masking material particle dispersion liquid is coated with machine with rod is coated on the PET resin film (HPE-50), and film forming.At 60 ℃ down behind dry 30 seconds and the evaporating solvent, hardening with high pressure mercury vapour lamp obtains the infrared rays shielding film with the film of this formation.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 65%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 44%, covers the direct incident light of about 56% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.9%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
WO with embodiment 2 preparations
2.72Powder 20 weight parts, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix, carry out dispersion treatment, as the dispersion liquid (I liquid) of average mark shot footpath 80nm.This I liquid under 50 ℃, is removed solvent composition with Vacuumdrier, become powder (I powder).This I powder 0.01kg and PET resin 8.7kg are carried out after dry type mixes with V-Mixer, near the melt temperature of resin, carry out abundant airtight mixing, become mixture, this mixture is melt extruded, be configured as the film of the about 50 μ m of thickness, become the infrared rays shielding film.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 58%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 42%, covers the direct incident light of about 58% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.7%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
Tungsten hexachloride is dissolved in the ethanol at every turn slightly, obtains solution.This solution is dry under 130 ℃, as pulverous initial feed.This initial feed was heated 1 hour under 350 ℃ in reducing gas environment (argon/hydrogen=95/5 volume ratio).And, after once turning back to room temperature, in 800 ℃, ar gas environment, heated 1 hour preparation WO
2.83And WO
2.92Mixed powder.The qualification result of the crystallization phases of measuring by X-ray diffraction is observed W
24O
68And W
25O
73Crystallization phases, this WO
2.83And WO
2.92Specific surface area be 30m
2/ g.
With this WO
2.83Powder and WO
2.92 Mixture 20 weight parts of powder, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix, and carry out dispersion treatment, as the dispersion liquid (J liquid) of average mark shot footpath 80nm.These J liquid 10 weight parts and hard coat are mixed with ultraviolet curable resin (solids component 100%) 100 weight parts, as infrared rays masking material particle dispersion liquid.This infrared rays masking material particle dispersion liquid is coated with machine with rod is coated on the PET resin film (HPE-50), and film forming.At 60 ℃ down behind dry 30 seconds and the evaporating solvent, hardening with high pressure mercury vapour lamp obtains the infrared rays shielding film with the film of this formation.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 61%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 42%, covers the direct incident light of about 58% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.9%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
Tungsten hexachloride is dissolved in the ethanol at every turn slightly, obtains solution.This solution is dry under 130 ℃, as pulverous initial feed.This initial feed in 800 ℃, ar gas environment, was heated 1 hour preparation WO
2.83And WO
2.92Mixed powder.The qualification result of the crystallization phases of measuring by X-ray diffraction is observed W
24O
68And W
25O
73Crystallization phases, this WO
2.83And WO
2.92The blended specific surface area be 30m
2/ g.
With this WO
2.83Powder and WO
2.92 Mixture 20 weight parts of powder, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix, and carry out dispersion treatment, as the dispersion liquid (K liquid) of average mark shot footpath 80nm.These K liquid 10 weight parts and hard coat are mixed with ultraviolet curable resin (solids component 100%) 100 weight parts, as infrared rays masking material particle dispersion liquid.This infrared rays masking material particle dispersion liquid is coated with machine with rod is coated on the PET resin film (HPE-50), and film forming.At 60 ℃ down behind dry 30 seconds and the evaporating solvent, hardening with high pressure mercury vapour lamp obtains the infrared rays shielding film with the film of this formation.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 67%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 49%, covers the direct incident light of about 51% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.9%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
Is that 1 to 0.21 ratio weighs up specified amount with 3 hydrates of tungsten hexachloride and barium perchlorate according to the mol ratio of W and Ba, is dissolved in slightly in the ethanol respectively at every turn, mixes two liquid and obtains mixing solutions.This mixing solutions is dry under 130 ℃, as pulverous initial feed.This initial feed was heated 1 hour under 550 ℃ in reducing gas environment (argon/hydrogen=95/5 volume ratio).And, after once turning back to room temperature, in 800 ℃, ar gas environment, heated 1 hour preparation Ba
0.21WO
3Powder.This Ba
0.21WO
3Specific surface area be 30m
2/ g.
With this Ba
0.21WO
3 Powder 20 weight parts, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix, carry out dispersion treatment, as the dispersion liquid (L liquid) of average mark shot footpath 80nm.These L liquid 10 weight parts and hard coat are mixed with ultraviolet curable resin (solids component 100%) 100 weight parts, as infrared rays masking material particle dispersion liquid.This infrared rays masking material particle dispersion liquid is coated with machine with rod is coated on the PET resin film (HPE-50), and film forming.At 60 ℃ down behind dry 30 seconds and the evaporating solvent, hardening with high pressure mercury vapour lamp obtains the infrared rays shielding film with the film of this formation.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 59%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 35%, covers the direct incident light of about 65% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.9%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
With ammonium tungstate aqueous solution (with WO
3Conversion 50wt%) and the cesium chloride aqueous solution be that 1 to 0.33 ratio weighs up specified amount according to the mol ratio of W and Cs, mix two liquid and obtain mixing solutions.This mixing solutions is dry under 130 ℃, as pulverous initial feed.This initial feed was heated 1 hour under 550 ℃ in reducing gas environment (argon/hydrogen=95/5 volume ratio).And, after once turning back to room temperature, in 800 ℃, ar gas environment, heated 1 hour preparation Cs
0.33WO
3Powder.The specific surface area of being somebody's turn to do is 20m
2/ g.In addition, the qualification result of the crystallization phases that obtains by X ray, the crystallization phases of observing hexagonal system tungsten bronze(s) (compound tungsten oxide particulate).
With this Cs
0.33WO
3 Powder 20 weight parts, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix, carry out dispersion treatment, as the dispersion liquid (M liquid) of average mark shot footpath 80nm.These M liquid 10 weight parts and hard coat are mixed with ultraviolet curable resin (solids component 100%) 100 weight parts, as infrared rays masking material particle dispersion liquid.This infrared rays masking material particle dispersion liquid is coated with machine with rod is coated on the PET resin film (HPE-50), and film forming.At 60 ℃ down behind dry 30 seconds and the evaporating solvent, hardening with high pressure mercury vapour lamp obtains the infrared rays shielding film with this film.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 72%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 39%, covers the direct incident light of about 61% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.9%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
With ammonium tungstate aqueous solution (with WO
3Conversion 50wt%) and the formic acid thallium aqueous solution be that 1 to 0.33 ratio weighs up specified amount according to the mol ratio of W and Tl, mix two liquid and obtain mixing solutions.This mixing solutions is dry under 130 ℃, as pulverous initial feed.This initial feed was heated 1 hour under 550 ℃ in reducing gas environment (argon/hydrogen=95/5 volume ratio).And, after once turning back to room temperature, in 800 ℃, ar gas environment, heated 1 hour preparation Tl
0.33WO
3Powder.The specific surface area of being somebody's turn to do is 20m
2/ g.In addition, the qualification result of the crystallization phases that obtains by X-ray diffraction, the crystallization phases of observing hexagonal system tungsten bronze(s) (compound tungsten oxide particulate).
With this Tl
0.33WO
3 Powder 20 weight parts, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix, carry out dispersion treatment, as the dispersion liquid (N liquid) of average mark shot footpath 80nm.These N liquid 10 weight parts and hard coat are mixed with ultraviolet curable resin (solids component 100%) 100 weight parts, as infrared rays masking material particle dispersion liquid.This infrared rays masking material particle dispersion liquid is coated with machine with rod is coated on the PET resin film (HPE-50), and film forming.At 60 ℃ down behind dry 30 seconds and the evaporating solvent, hardening with high pressure mercury vapour lamp obtains the infrared rays shielding film with the film of this formation.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 71%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 42%, covers the direct incident light of about 58% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.9%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
With ammonium tungstate aqueous solution (with WO
3Conversion 50wt%) and the rubidium chloride aqueous solution be that 1 to 0.33 ratio weighs up specified amount according to the mol ratio of W and Rb, mix two liquid and obtain mixing solutions.This mixing solutions is dry under 130 ℃, as pulverous initial feed.This initial feed was heated 1 hour under 550 ℃ in reducing gas environment (argon/hydrogen=95/5 volume ratio).And, after once turning back to room temperature, in 800 ℃, ar gas environment, heated 1 hour preparation Rb
0.33WO
3Powder.The specific surface area of being somebody's turn to do is 20m
2/ g.In addition, the qualification result of the crystallization phases that obtains by X-ray diffraction, the crystallization phases of observing hexagonal system tungsten bronze(s) (compound tungsten oxide particulate).
With this Rb
0.33WO
3 Powder 20 weight parts, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix, carry out dispersion treatment, as the dispersion liquid (O liquid) of average mark shot footpath 80nm.These O liquid 10 weight parts and hard coat are mixed with ultraviolet curable resin (solids component 100%) 100 weight parts, as infrared rays masking material particle dispersion liquid.This infrared rays masking material particle dispersion liquid is coated with machine with rod is coated on the PET resin film (HPE-50), and film forming.At 60 ℃ down behind dry 30 seconds and the evaporating solvent, hardening with high pressure mercury vapour lamp obtains the infrared rays shielding film with this film.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 76%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 47%, covers the direct incident light of about 53% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.9%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
With ammonium tungstate aqueous solution (with WO
3Conversion 50wt%) and potassium chloride solution be that 1 to 0.33 ratio weighs up specified amount according to the mol ratio of W and K, mix two liquid and obtain mixing solutions.This mixing solutions is dry under 130 ℃, as pulverous initial feed.This initial feed was heated 1 hour under 550 ℃ in reducing gas environment (argon/hydrogen=95/5 volume ratio).And, after once turning back to room temperature, in 800 ℃, ar gas environment, heated 1 hour preparation K
0.33WO
3Powder.The specific surface area of being somebody's turn to do is 20m
2/ g.In addition, the qualification result of the crystallization phases that obtains by X-ray diffraction, the crystallization phases of observing hexagonal system tungsten bronze(s) (compound tungsten oxide particulate).
With this K
0.33WO
3 Powder 20 weight parts, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix, carry out dispersion treatment, as the dispersion liquid (P liquid) of average mark shot footpath 80nm.These P liquid 10 weight parts and hard coat are mixed with ultraviolet curable resin (solids component 100%) 100 weight parts, as infrared rays masking material particle dispersion liquid.This infrared rays masking material particle dispersion liquid is coated with machine with rod is coated on the PET resin film (HPE-50), and film forming.At 60 ℃ down behind dry 30 seconds and the evaporating solvent, hardening with high pressure mercury vapour lamp obtains the infrared rays shielding film with the film of this formation.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 68%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 43%, covers the direct incident light of about 57% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.9%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
With ammonium tungstate aqueous solution (with WO
3Conversion 50wt%) and the hydrated barta eight hydrate aqueous solution be that 1 to 0.33 ratio weighs up specified amount according to the mol ratio of W and Ba, mix two liquid and obtain mixing solutions.This mixing solutions is dry under 130 ℃, as pulverous initial feed.This initial feed was heated 1 hour under 450 ℃ in reducing gas environment (argon/hydrogen=95/5 volume ratio).And, after once turning back to room temperature, in 700 ℃, ar gas environment, heated 1 hour preparation Ba
0.33WO
3Powder.The specific surface area of being somebody's turn to do is 20m
2/ g.In addition, the qualification result of the crystallization phases that obtains by X-ray diffraction, the crystallization phases of observing hexagonal crystal tungsten system's bronze (compound tungsten oxide particulate).
With this Ba
0.33WO
3 Powder 20 weight parts, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix, carry out dispersion treatment, as the dispersion liquid (Q liquid) of average mark shot footpath 80nm.These Q liquid 10 weight parts and hard coat are mixed with ultraviolet curable resin (solids component 100%) 100 weight parts, as infrared rays masking material particle dispersion liquid.This infrared rays masking material particle dispersion liquid is coated with machine with rod is coated on the PET resin film (HPE-50), and film forming.At 60 ℃ down behind dry 30 seconds and the evaporating solvent, hardening with high pressure mercury vapour lamp obtains the infrared rays shielding film with the film of this formation.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 75%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 54%, covers the direct incident light of about 46% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.9%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
Will be with WO
3H
2The hydrate powder of the tungsten oxide of O record and cesium carbonate powder are that 1 to 0.33 ratio weighs up specified amount according to the mol ratio of W and Cs, mix two powder.With this mixed powder as initial feed.This initial feed was heated 1 hour under 600 ℃ in reducing gas environment (argon/hydrogen=97/3 volume ratio).After becoming ar gas environment, under 800 ℃, heated 1 hour preparation Cs
0.33WO
3Powder.The specific surface area of being somebody's turn to do is 20m
2/ g.In addition, the qualification result of the crystallization phases that obtains by X-ray diffraction, the crystallization phases of observing hexagonal crystal tungsten system's bronze (compound tungsten oxide particulate).
With this Cs
0.33WO
3 Powder 20 weight parts, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix, carry out dispersion treatment, as the dispersion liquid (R liquid) of average mark shot footpath 80nm.These R liquid 10 weight parts and hard coat are mixed with ultraviolet curable resin (solids component 100%) 100 weight parts, as infrared rays masking material particle dispersion liquid.This infrared rays masking material particle dispersion liquid is coated with machine with rod is coated on the PET resin film (HPE-50), and film forming.At 60 ℃ down behind dry 30 seconds and the evaporating solvent, hardening with high pressure mercury vapour lamp obtains the infrared rays shielding film with the film of this formation.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 70%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 36%, covers the direct incident light of about 64% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.9%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
Will be with WO
3H
2The hydrate powder of the tungsten oxide of O record and potassium carbonate powder are that 1 to 0.55 ratio weighs up specified amount according to the mol ratio of W and K, mix two powder.With this mixed powder as initial feed.This initial feed was heated 1 hour under 600 ℃ in reducing gas environment (argon/hydrogen=97/3 volume ratio).After becoming ar gas environment, in 800 ℃, ar gas environment, heated 1 hour preparation K
0.55WO
3Powder.The specific surface area of being somebody's turn to do is 30m
2/ g.In addition, the qualification result of the crystallization phases that obtains by X-ray diffraction, the crystallization phases of observing hexagonal system tungsten bronze(s) (compound tungsten oxide particulate).
With this K
0.55WO
3 Powder 20 weight parts, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix after, carry out dispersion treatment, as the dispersion liquid (S liquid) of average mark shot footpath 80nm.These S liquid 10 weight parts and hard coat are mixed with ultraviolet curable resin (solids component 100%) 100 weight parts, as infrared rays masking material particle dispersion liquid.This infrared rays masking material particle dispersion liquid is coated with machine with rod is coated on the PET resin film (HPE-50), and film forming.At 60 ℃ down behind dry 30 seconds and the evaporating solvent, hardening with high pressure mercury vapour lamp obtains the infrared rays shielding film with this film.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 69%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 40%, covers the direct incident light of about 60% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.9%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
Will be with WO
3H
2The hydrate powder of the tungsten oxide of O record and powdered sodium carbonate are that 1 to 0.50 ratio weighs up specified amount according to the mol ratio of W and Na, mix two powder.With this mixed powder as initial feed.This initial feed was heated 1 hour under 600 ℃ in reducing gas environment (argon/hydrogen=97/3 volume ratio).After becoming ar gas environment, under 800 ℃, heated 1 hour preparation Na
0.5WO
3Powder.The specific surface area of being somebody's turn to do is 20m
2/ g.In addition, the qualification result of the crystallization phases that obtains by X-ray diffraction, the crystallization phases of observing hexagonal system tungsten bronze(s) (compound tungsten oxide particulate).
With this Na
0.5WO
3 Powder 20 weight parts, toluene 75 weight parts, polyacrylate(s) dispersion agent 5 weight parts mix, carry out dispersion treatment, as the dispersion liquid (T liquid) of average mark shot footpath 80nm.These T liquid 10 weight parts and hard coat are mixed with ultraviolet curable resin (solids component 100%) 100 weight parts, as infrared rays masking material particle dispersion liquid.This infrared rays masking material particle dispersion liquid is coated with machine with rod is coated on the PET resin film (HPE-50), and film forming.At 60 ℃ down behind dry 30 seconds and the evaporating solvent, hardening with high pressure mercury vapour lamp obtains the infrared rays shielding film with the film of this formation.
When measuring the optical characteristics of this infrared rays shielding film, its visible light transmissivity is 75%, fully see through the light of visible region as can be known, moreover sunshine, transmitance is 53%, covers the direct incident light of about 47% solar ray as can be known, and insulation effect is good.In addition, haze value is 0.9%, and the transparency is high, and inner situation also can clearly be confirmed from the outside.See through tone and present blueness attractive in appearance.
(comparative example 1)
Measure the optical characteristics of embodiment 1～10 as the PET resin film (HPE-50) of body material use itself.So, as mentioned above, can judge, visible light transmissivity is 88%, fully see through the light of visible region, but sunshine, transmitance is 88%, only covers direct incident light about 12% of solar ray, insulation effect is poor.
(reference example 1)
Remove and use WO
3(tungstic oxide) powder replaces W
18O
49Beyond the powder, use the method identical to prepare the microparticle dispersion film with embodiment 2.When measuring the optical characteristics of this microparticulate film, can judge, visible light transmissivity is 83.44%, sunshine transmitance be 81.76%, cover about 17.24% of the direct incident light of solar ray.
Industrial practicality
The present invention can be the window material that is used in building field, transportation field of machines etc. etc. and electronics When the ideals such as machinery are given the infrared ray screening effect, use ideally.
The simple declaration of accompanying drawing
[Fig. 1] is the W that the present invention relates to
18O
49The example that sees through the curve determination result of microparticulate film.
[Fig. 2] is the hexagonal system Cs that the present invention relates to
0.33WO
3The example that sees through the curve determination result of compound tungsten oxide microparticulate film.
[Fig. 3] is the hexagonal system Rb that the present invention relates to
0.33WO
3The example that sees through the curve determination result of compound tungsten oxide microparticulate film.
[Fig. 4] is the mode chart of crystalline texture with compound tungsten oxide of the hexagonal system that the present invention relates to.
[Fig. 5] is the creating conditions of the infrared rays masking material that relates to of the embodiment of the invention, powder feature and optical characteristics table look-up.
Nomenclature
1.WO6 unit
2. element M
3. the crystalline texture of hexagonal system
Claims (18)
1. infrared rays masking material microparticle dispersion, this dispersion be infrared rays masking material microparticulate in medium and the infrared rays masking material microparticle dispersion that forms is characterized in that,
Above-mentioned infrared rays masking material particulate contains to be selected from uses general formula W
yO
z, here, W is a tungsten, O is an oxygen, the tungsten oxide particulate of 2.72≤z/y≤2.999 expression and/or use M
xW
yO
z, here, M is any element among Cu, Al, Mn, In, Ba, Cs, Tl, Rb, K and the Na, and W is a tungsten, and O is an oxygen, the infrared rays masking material particulate of the compound tungsten oxide particulate of 0.1≤x/y≤0.55,2.72≤z/y≤3.0 expressions; The particle diameter of above-mentioned infrared rays masking material particulate is 1nm～200nm.
2. the infrared rays masking material microparticle dispersion of putting down in writing according to claim 1 is characterized in that,
General formula W
yO
zIn, 2.72≤z/y≤2.92.
3. the infrared rays masking material microparticle dispersion of putting down in writing according to claim 1 is characterized in that, above-mentioned tungsten oxide particulate and/or above-mentioned compound tungsten oxide particulate comprise the Ma Genaili phase.
4. the infrared rays masking material microparticle dispersion of putting down in writing according to claim 1 is characterized in that, with formula M
xW
yO
zThe above-mentioned compound tungsten oxide particulate of expression comprise in the particulate of crystalline texture with hexagonal system or tetragonal spheroidal or isometric system any one or more than one.
5. the infrared rays masking material microparticle dispersion of putting down in writing according to claim 1 is characterized in that, with formula M
xW
yO
zThe above-mentioned compound tungsten oxide particulate of expression contains the crystalline texture of hexagonal system, and perhaps having all is the crystalline texture of hexagonal system.
6. the infrared rays masking material microparticle dispersion of putting down in writing according to claim 1 is characterized in that, the surface of above-mentioned infrared rays masking material particulate is to coat with the oxide compound that contains any one or more than one the element among Si, Ti, Zr, the Al.
7. the infrared rays masking material microparticle dispersion of putting down in writing according to claim 1 is characterized in that, above-mentioned medium is resin or glass.
8. the infrared rays masking material microparticle dispersion of putting down in writing according to claim 7, it is characterized in that, above-mentioned resin be in polyvinyl resin, polyvinyl chloride (PVC) RESINS, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, acrylic resin, ethylene-vinyl acetate copolymer, vibrin, pet resin, fluoro-resin, polycarbonate resin, acrylic resin, the polyvinyl butyral resin any one or more than one.
9. an infrared shield is characterized in that, the infrared rays masking material microparticle dispersion of record is the dispersion that forms tabular or laminar or film like in the claim 1.
10. the manufacture method of an infrared rays masking material particulate, this method be,
Be selected from and contain useful general formula W
yO
z, here, W is a tungsten, O is an oxygen, the tungsten oxide particulate of 2.72≤z/y≤2.999 expression and/or use formula M
xW
yO
zHere, M is any element among Cu, Al, Mn, In, Ba, Cs, Tl, Rb, K and the Na, W is a tungsten, and O is an oxygen, 0.1≤x/y≤0.55,2.72 the compound tungsten oxide particulate of≤z/y≤3.0 expressions, diameter of particle is the manufacture method of the infrared rays masking material particulate of 1nm～200nm, it is characterized in that
The initial feed of above-mentioned infrared rays masking material particulate is heat-treated in being selected from reducing gas environment, non-active gas environment and in the atmosphere surrounding in the mixed-gas environment of these gases, make above-mentioned infrared rays masking material particulate.
11. the manufacture method of the infrared rays masking material particulate of putting down in writing according to claim 10 is characterized in that,
General formula W
yO
zIn, 2.72≤z/y≤2.92.
12. the manufacture method of the infrared rays masking material particulate of putting down in writing according to claim 10, it is characterized in that, above-mentioned thermal treatment is that initial feed with above-mentioned infrared rays masking material particulate is in the reducing gas environment, heat-treat under 100 ℃～850 ℃, then in active gas environment not, heat-treat under 650 ℃～1200 ℃ the temperature.
13. the manufacture method of the infrared rays masking material particulate of putting down in writing according to claim 10 is characterized in that,
With above-mentioned general formula W
yO
zThe initial feed of tungsten oxide particulate of expression be from
Tungsten trioxide powder,
The Tungsten oxide powder,
The hydrate powder of tungsten oxide,
The tungsten hexachloride powder,
The ammonium tungstate powder,
After tungsten hexachloride is dissolved in the alcohol, the hydrate powder of the tungsten oxide that drying obtains,
After tungsten hexachloride is dissolved in the alcohol, adds water and generate precipitation, the hydrate powder of the tungsten oxide that dry this precipitation obtains,
The tungsten compound powder that dry ammonium tungstate aqueous solution obtains,
Any one or more than one the powder of selecting in the tungsten powder.
14. the manufacture method of the infrared rays masking material particulate of putting down in writing according to claim 10 is characterized in that,
Use above-mentioned formula M
xW
yO
zThe initial feed of compound tungsten oxide particulate of expression be with from
Tungsten trioxide powder,
The Tungsten oxide powder,
The hydrate powder of tungsten oxide,
The tungsten hexachloride powder,
The ammonium tungstate powder,
After tungsten hexachloride is dissolved in the alcohol, the hydrate powder of the tungsten oxide that drying obtains,
After tungsten hexachloride is dissolved in the alcohol, adds water and generate precipitation, the hydrate powder of the tungsten oxide that dry this precipitation obtains,
The tungsten compound powder that dry ammonium tungstate aqueous solution obtains,
The powder that any one or more than one the powder of selecting in the tungsten powder and the powder mixes of simple substance that contains above-mentioned M element or compound form.
15. the manufacture method of the infrared rays masking material particulate of putting down in writing according to claim 10 is characterized in that,
Use above-mentioned formula M
xW
yO
zThe initial feed of compound tungsten oxide particulate of expression be with
The alcoholic solution of tungsten hexachloride or the aqueous solution of ammonium tungstate and contain the powder that the solution mixing after drying of the compound of above-mentioned M element obtains.
16. the manufacture method of the infrared rays masking material particulate of putting down in writing according to claim 10 is characterized in that,
Use above-mentioned formula M
xW
yO
zThe initial feed of compound tungsten oxide particulate of expression be with
After tungsten hexachloride is dissolved in the alcohol, add the sedimentary dispersion liquid of water generates and
Contain the simple substance of above-mentioned M element or the powder of compound, or contain the powder that the solution mixing after drying of the compound of above-mentioned M element obtains.
17. an infrared rays masking material particulate is characterized in that this particulate contains
That the manufacture method of the infrared rays masking material particulate of putting down in writing by claim 10 is made, use general formula W
yO
z, here, W is a tungsten, and O is an oxygen, and the tungsten oxide particulate of 2.72≤z/y≤2.999 expressions is or/and use formula M
xW
yO
z, here, M is any element among Cu, Al, Mn, In, Ba, Cs, Tl, Rb, K and the Na, and W is a tungsten, and O is an oxygen, the compound tungsten oxide particulate of 0.1≤x/y≤0.55,2.72≤z/y≤3.0 expressions.
18. infrared rays masking material particulate according to claim 17 is characterized in that general formula W
yO
zIn, 2.72≤z/y≤2.92.
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| JP026901/2004 | 2004-02-03 |
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