WO2017104853A1 - 複合タングステン酸化物超微粒子およびその分散液 - Google Patents
複合タングステン酸化物超微粒子およびその分散液 Download PDFInfo
- Publication number
- WO2017104853A1 WO2017104853A1 PCT/JP2016/087795 JP2016087795W WO2017104853A1 WO 2017104853 A1 WO2017104853 A1 WO 2017104853A1 JP 2016087795 W JP2016087795 W JP 2016087795W WO 2017104853 A1 WO2017104853 A1 WO 2017104853A1
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- WO
- WIPO (PCT)
- Prior art keywords
- tungsten oxide
- composite tungsten
- oxide ultrafine
- ultrafine particles
- dispersion
- Prior art date
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- 239000011882 ultra-fine particle Substances 0.000 title claims abstract description 417
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 380
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 380
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/22—Oxides; Hydroxides of metals
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- G—PHYSICS
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- G02B5/00—Optical elements other than lenses
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- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/00—Crystal-structural characteristics
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- C01P2002/54—Solid solutions containing elements as dopants one element only
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
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- C01P2004/00—Particle morphology
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Definitions
- the present invention is a versatile composite tungsten oxide ultrafine particle capable of producing a dispersion liquid with high productivity while having a property of shielding visible light in the near infrared region and a dispersion thereof. Regarding liquids.
- near-infrared shielding technology that has good visible light transmittance and lowers solar radiation transmittance while maintaining transparency.
- near infrared shielding technology using conductive fine particles that are inorganic is superior to other technologies in terms of near infrared shielding properties, low cost, radio wave transmission, and high weather resistance, etc. There are benefits.
- Patent Document 1 describes a technique that applies the near-infrared shielding characteristics of tin oxide fine powder, and includes a transparent resin containing tin oxide fine powder in a dispersed state and tin oxide fine powder contained in a dispersed state.
- a near-infrared shielding synthetic resin molded product obtained by laminating a transparent synthetic resin formed into a sheet or film on a transparent synthetic resin substrate has been proposed.
- Patent Document 2 includes metals such as Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, and Mo, and the metal Technology that applies the near-infrared shielding properties of oxides of the above, nitrides of the metals, sulfides of the metals, dopes of Sb and F to the metals, or mixtures thereof are described in the medium.
- a laminated glass in which a dispersed intermediate layer is sandwiched has been proposed.
- the applicant has proposed a technology applying the near-infrared shielding properties of titanium nitride fine particles and lanthanum boride fine particles, and at least one of these is dispersed in a solvent or a medium.
- a selectively permeable membrane coating solution and a selectively permeable membrane are disclosed.
- the near infrared shielding structures such as the near infrared shielding synthetic resin molded products disclosed in Patent Documents 1 to 3 are all near infrared rays when high visible light transmittance is required. There existed a problem that a shielding characteristic was not enough and the function as a near-infrared shielding structure was not enough.
- the visible light transmittance calculated based on JIS R 3106 (in the present invention, When the visible light transmittance is 70%, the solar transmittance calculated based on JIS R 3106 (in the present invention, it may be simply referred to as “sunlight transmittance”). Is over 50%).
- Patent Document 4 a general formula M x W y O z in Patent Document 4 (where M element is H, He, alkali 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, one or more elements, W is tungsten, O is oxygen, 0.
- M element is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe).
- a technique in which the composite tungsten oxide fine particles are applied as near-infrared shielding fine particles is proposed, and the composite tungsten oxide fine particles are produced.
- Method and the composite tungsten oxide is hexagonal, tetragonal
- a near-infrared shielding dispersion comprising at least one kind of composite tungsten oxide fine particles having a cubic crystal structure, wherein the near-infrared shielding material fine particles have a particle diameter of 1 nm to 800 nm. did.
- the near-infrared shielding fine particle dispersion containing the composite tungsten oxide fine particles represented by the general formula M x W y O z exhibits high near-infrared shielding properties and a visible light transmittance of 70.
- the solar transmittance was improved to less than 50%.
- the near-infrared shielding fine particle dispersion using composite tungsten oxide fine particles having at least one selected from specific elements such as Cs, Rb, and Tl as the M element and having a hexagonal crystal structure is an excellent near-infrared ray.
- the visible light transmittance was 70%, the solar radiation transmittance was improved to be less than 37%. Obtaining this result, adding a hard coat process etc. to the said near-infrared shielding fine particle dispersion
- these applications require high transparency (low haze value) as well as near-infrared shielding properties, so that the particle size of the composite tungsten oxide fine particles is further refined for the purpose of reducing the haze value. Attempts were made to reduce the haze value by miniaturizing these fine particles.
- Patent Document 5 a slurry obtained by mixing the composite tungsten oxide powder, the solvent, and the dispersing agent manufactured by the same method as the manufacturing method disclosed in Patent Document 4 with yttria-stabilized zirconia beads.
- a near-infrared shielding fine particle dispersion, a near-infrared shielding dispersion, etc. in which the blue haze phenomenon is suppressed by putting into a medium stirring mill and carrying out pulverization and dispersion treatment until a predetermined particle size is disclosed.
- the particle diameter of the composite tungsten oxide produced in Patent Document 5 is as large as 1 to 5 ⁇ m. Therefore, in order to obtain a near-infrared shielding fine particle dispersion capable of suppressing the blue haze phenomenon, it has been necessary to pulverize the composite tungsten oxide for a long time using a medium stirring mill to refine the particles. This long pulverization process significantly lowered the productivity of the near-infrared shielding fine particle dispersion.
- Patent Document 6 composite tungsten oxide ultrafine particles having a particle size of 100 nm or less manufactured by using a plasma reaction.
- Patent Document 7 also describes a method for producing composite tungsten oxide ultrafine particles using a plasma reaction.
- the composite tungsten oxide ultrafine particles produced by the method disclosed in Patent Document 6 have a low crystallinity, so that it is close to the dispersion using the composite tungsten oxide ultrafine particles. Infrared shielding properties were not sufficient.
- the composite tungsten oxide fine particles produced by using the plasma reaction described in Patent Document 7 include binary tungsten oxide (that is, a phase consisting essentially of elements W and O) in addition to the composite tungsten oxide fine particles. .) And tungsten metal. For this reason, the near-infrared shielding property was not sufficient.
- the present invention has been made under the above-mentioned circumstances, and the problem to be solved is transparent in the visible light region and having excellent near-infrared shielding properties due to high crystallinity.
- An object is to provide a composite tungsten oxide ultrafine particle having versatility capable of producing a dispersion with high productivity, and a composite tungsten oxide ultrafine particle dispersion using the same.
- the inventors of the present invention have made extensive studies to achieve the above object. Then, in the X-ray diffraction pattern (may be described as “XRD” in the present invention) of the composite tungsten oxide ultrafine particles, the composite tungsten oxide ultrafine particles having a predetermined peak top intensity ratio value are obtained. I found out. Specifically, the value of the ratio of the XRD peak top intensity of the composite tungsten oxide ultrafine particles when the value of the XRD peak intensity relating to the (220) plane of the silicon powder standard sample (manufactured by NIST, 640c) is 1. Is a composite tungsten oxide ultrafine particle having a particle size of 0.13 or more.
- the composite tungsten oxide ultrafine particles are versatile composite tungsten oxide ultrafine particles that are transparent in the visible light region and have excellent near-infrared shielding properties, and can produce a dispersion with high productivity. It was. Furthermore, in the dispersion using the composite tungsten oxide ultrafine particles, the present inventors have also found that the blue haze phenomenon can be suppressed if the composite tungsten oxide ultrafine particles have a dispersed particle diameter of 200 nm or less.
- the first invention for solving the above-described problem is Composite tungsten oxide ultrafine particles having near infrared shielding properties
- the XRD peak intensity relating to the (220) plane of a silicon powder standard sample manufactured by NIST, 640c
- the ratio value of the XRD peak top intensity of the composite tungsten oxide ultrafine particles is 0.13 or more. This is a composite tungsten oxide ultrafine particle.
- the second invention is General formula MxWyOz (where M is H, He, alkali 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, One or more elements selected from Re, Be, Hf, Os, Bi, I, and Yb, W is tungsten, O is oxygen, 0.001 ⁇ x / y ⁇ 1, 2.0 ⁇ z / y ⁇ 3.0).
- the composite tungsten oxide ultrafine particles according to the first aspect of the invention is The composite tungsten oxide ultrafine particles according to the first or second invention, wherein a crystallite diameter of the composite tungsten oxide ultrafine particles is 1 nm or more.
- the fourth invention is: The composite tungsten oxide ultrafine particles according to any one of the first to third inventions, wherein the composite tungsten oxide ultrafine particles include a hexagonal crystal structure.
- the fifth invention is: The composite tungsten oxide ultrafine particles according to any one of the first to fourth inventions, wherein the composite tungsten oxide ultrafine particles have a volatile component content of 2.5% by mass or less.
- the sixth invention is: The composite tungsten oxide ultrafine particles according to any one of the first to fifth inventions are dispersed and contained in a liquid medium, and the liquid medium is water, an organic solvent, oil or fat, liquid A composite tungsten oxide ultrafine particle dispersion characterized by being one or more selected from a resin, a plasticizer for liquid plastics, and a polymer monomer.
- the seventh invention The composite tungsten oxide ultrafine particles according to the sixth invention, wherein the composite tungsten oxide ultrafine particles contained in the composite tungsten oxide ultrafine particle dispersion have a dispersed particle diameter of 1 nm to 200 nm. It is a dispersion.
- the eighth invention The composite tungsten oxide ultrafine particle dispersion contained in the composite tungsten oxide ultrafine particle dispersion has a content of 0.01 mass% or more and 80 mass% or less, according to the sixth or seventh invention. This is a composite tungsten oxide ultrafine particle dispersion.
- a transparent near-infrared shielding dispersion having transparency in the visible light region, excellent near-infrared shielding properties, and versatility can be produced with high productivity.
- FIG. 2 is an X-ray diffraction pattern of ultrafine particles according to Example 1.
- FIG. 4 is a transmittance profile of a cured film according to Example 2.
- the composite tungsten oxide ultrafine particles according to the present invention have a near-infrared shielding property, and the value of the XRD peak intensity related to the (220) plane of a silicon powder standard sample (manufactured by NIST, 640c).
- the value of the ratio of the XRD peak top intensity of the composite tungsten oxide ultrafine particles with respect to 1 is 0.13 or more.
- (1) XRD peak top intensity ratio, (2) composition, (3) crystal structure, (4) BET specific surface area, (5) dispersed particle diameter, ( 6) Volatile components and (7) Summary will be described in this order.
- Ratio of XRD peak top intensity The powder X-ray diffraction method is used for the measurement of the XRD peak top intensity of the composite tungsten oxide ultrafine particles described above. At this time, in order to provide objective quantitativeness to the measurement results between the samples of the composite tungsten oxide ultrafine particles, a standard sample is determined, the peak intensity of the standard sample is measured, and the peak intensity of the standard sample is measured. The XRD peak top intensity of each ultrafine particle sample is expressed as the value of the XRD peak top intensity ratio of the ultrafine particle sample.
- the standard sample is a silicon powder standard sample (manufactured by NIST, 640c) that is universal in the industry, and does not overlap with the XRD peak of the composite tungsten oxide ultrafine particles.
- the (220) plane was used as a reference.
- an ultrafine particle sample is filled into a sample holder having a depth of 1.0 mm by a known operation in X-ray diffraction measurement.
- an X-ray source an X-ray tube whose anode target material is Cu is used with an output setting of 45 kV / 40 mA, step scan mode (step size: 0.0165 ° (2 ⁇ ) and counting time: 0.022 msec.
- the X-ray tube expected lifetime of a commercially available X-ray apparatus is several thousand hours or more and the measurement time per sample is almost several hours or less, the X-ray can be obtained by performing the above-described desirable measurement method.
- the influence on the ratio of the XRD peak top intensity by the tube usage time can be made small enough to be ignored.
- the X-ray diffraction pattern of the composite tungsten oxide ultrafine particles is an X-ray diffraction pattern of a large number of composite tungsten oxide ultrafine particles constituting the powder sample of the composite tungsten oxide. Moreover, in order to obtain a composite tungsten oxide ultrafine particle dispersion, it is an X-ray diffraction pattern of the composite tungsten oxide ultrafine particles after being crushed, pulverized or dispersed as described later.
- the X-ray diffraction pattern of the composite tungsten oxide ultrafine particles according to the present invention and the composite tungsten oxide ultrafine particles contained in the dispersion liquid is the same as the X-ray diffraction pattern of the composite tungsten oxide ultrafine particle dispersion according to the present invention. Is also maintained.
- the XRD peak top intensity is a peak intensity at 2 ⁇ having the highest peak count in the X-ray diffraction pattern.
- the peak count 2 ⁇ in the X-ray diffraction pattern appears in the range of 25 ° to 31 °.
- the XRD peak top intensity of the composite tungsten oxide ultrafine particles described above has a close relationship with the crystallinity of the ultrafine particles, and further has a close relationship with the free electron density in the ultrafine particles.
- the present inventors have found that the XRD peak top intensity greatly affects the near-infrared shielding properties of the composite tungsten oxide ultrafine particles. Specifically, it has been found that when the value of the XRD peak top intensity ratio is 0.13 or more, the free electron density in the ultrafine particles is secured, and a desired near-infrared shielding property can be obtained. .
- the value of the XRD peak top intensity ratio may be 0.13 or more, and preferably 0.7 or less.
- the XRD peak top intensity of the composite tungsten oxide ultrafine particles will also be described from different viewpoints.
- a value of the XRD peak top ratio of the composite tungsten oxide ultrafine particles of 0.13 or more indicates that composite tungsten oxide ultrafine particles having good crystallinity containing almost no heterogeneous phase are obtained. That is, it is considered that the obtained composite tungsten oxide ultrafine particles are not amorphous (amorphous).
- a liquid medium such as an organic solvent that transmits visible light or a solid medium such as a resin that transmits visible light
- heterophase refers to a phase of a compound other than the composite tungsten oxide. Further, by analyzing the X-ray diffraction pattern obtained when measuring the XRD peak top intensity, the crystal structure and crystallite diameter of the composite tungsten oxide fine particles can be obtained.
- the composite tungsten oxide ultrafine particles according to the present invention have a general formula MxWyOz (where M is H, He, alkali 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, One or more elements selected from S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, and Yb, W is tungsten, and O is oxygen , 0.001 ⁇ x / y ⁇ 1, 2.0 ⁇ z / y ⁇ 3.0), and preferably a composite tungsten oxide ultrafine particle.
- MxWyOz where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, M
- the composite tungsten oxide ultrafine particles represented by the general formula MxWyOz will be described.
- the element M, x, y, z in the general formula MxWyOz and the crystal structure thereof are closely related to the free electron density of the composite tungsten oxide ultrafine particles, and have a great influence on the near-infrared shielding characteristics.
- M element is H, He, alkali 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,
- M element is H, He, alkali 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
- free electrons are generated in the composite tungsten oxide, a shielding property derived from free electrons is expressed in the near infrared region, and the composite tungsten oxide is effective as a near infrared shielding material in the vicinity
- the element M has been found to be effective as a near-infrared shielding material having excellent weather resistance, and M elements include Cs, Rb, K, Tl, Ba, Cu, Al, Mn, and In.
- M elements include Cs, Rb, K, Tl, Ba, Cu, Al, Mn, and In.
- the composite tungsten oxide can easily have a hexagonal crystal structure, which transmits visible light and absorbs and blocks near infrared rays. It is also found that it is particularly preferable for the reason.
- the present inventors' knowledge about the value of x which shows the addition amount of M element is demonstrated. If the value of x / y is 0.001 or more, a sufficient amount of free electrons are generated, and the desired near-infrared shielding characteristics can be obtained. As the amount of M element added increases, the supply amount of free electrons increases and the near-infrared shielding characteristics also increase. However, when the value of x / y is about 1, the effect is saturated. Moreover, if the value of x / y is 1 or less, it is preferable since an impurity phase can be prevented from being generated in the composite tungsten ultrafine particles.
- the present inventors' knowledge about the value of z indicating the control of the oxygen amount will be described.
- the value of z / y is preferably 2.0 ⁇ z / y ⁇ 3.0, more preferably 2.2 ⁇ z / y ⁇ 3. 0.0, more preferably 2.6 ⁇ z / y ⁇ 3.0, and most preferably 2.7 ⁇ z / y ⁇ 3.0. If the value of z / y is 2.0 or more, it is possible to avoid the appearance of a WO 2 crystal phase other than the intended purpose in the composite tungsten oxide, and the chemical stability as a material.
- any structure is effective as a near-infrared shielding material.
- the shielding position in the near-infrared region tends to change depending on the crystal structure of the composite tungsten oxide fine superparticle. That is, the shielding position in the near-infrared region tends to move to the longer wavelength side when it is tetragonal than the cubic crystal, and to move toward the longer wavelength side when it is hexagonal than when it is tetragonal.
- the shielding in the visible light region is the least in the hexagonal crystal, followed by the tetragonal crystal, and the cubic crystal is the largest in this. From the above knowledge, it is most preferable to use hexagonal tungsten bronze for the purpose of transmitting light in the visible light region and shielding light in the near infrared region.
- hexagonal tungsten bronze for the purpose of transmitting light in the visible light region and shielding light in the near infrared region.
- the composite tungsten oxide if the value of the XRD peak top intensity ratio satisfies the above-mentioned predetermined value and is a hexagonal tungsten bronze, excellent optical characteristics are exhibited.
- the composite tungsten oxide ultrafine particles have an orthorhombic crystal structure, or when the composite tungsten oxide has a monoclinic crystal structure similar to WO 2.72, which is referred to as a magnetic phase, it also absorbs infrared rays. It is excellent and may be effective as a near-field shielding material.
- the composite tungsten oxide ultrafine particles are preferably single crystals having a volume ratio of 50% or more. In other words, they are single crystals having a volume ratio of the amorphous phase of less than 50%. preferable.
- the crystallite diameter can be reduced to 200 nm or less while maintaining the XRD peak top strength.
- the dispersed particle size can be set to 1 nm or more and 200 nm or less.
- the dispersed particle diameter is 1 nm or more and 200 nm or less
- the amorphous phase is present in a volume ratio of 50% or more, or in the case of polycrystal
- the XRD peak top of the composite tungsten ultrafine particles The value of the intensity ratio is less than 0.13, and as a result, the near-infrared absorption characteristics may be insufficient and the near-infrared shielding characteristics may be insufficiently expressed.
- the crystallite diameter of the composite tungsten oxide ultrafine particles is more preferably 200 nm or less and 10 nm or more.
- the crystallite diameter is in the range of 200 nm or less and 10 nm or more, the value of the XRD peak top intensity ratio exceeds 0.13, and further excellent infrared shielding properties are exhibited.
- the X-ray diffraction pattern of the composite tungsten oxide ultrafine particles in the composite tungsten oxide ultrafine particle dispersion after pulverization, pulverization or dispersion described later is shown in the composite tungsten oxide ultrafine particle dispersion according to the present invention.
- the X-ray diffraction pattern of the composite tungsten oxide ultrafine particles obtained by removing the volatile components of the composite tungsten oxide and the X-ray diffraction pattern of the composite tungsten oxide ultrafine particles contained in the dispersion obtained from the dispersion are also maintained.
- the XRD pattern, XRD peak top intensity, crystallite size, etc. of the composite tungsten oxide ultrafine particles in the composite tungsten oxide ultrafine particle dispersion and the composite tungsten ultrafine particle dispersion obtained from the dispersion have a crystalline state. If the composite tungsten oxide ultrafine particles that can be used in the present invention are in a crystalline state, the effect of the present invention is exhibited.
- the composite tungsten oxide ultrafine particles are single crystals because, in an electron microscope image such as a transmission electron microscope, crystal grain boundaries are not observed inside each fine particle, and only uniform lattice fringes are observed. Can be confirmed. Also, in the composite tungsten oxide ultrafine particles, the volume ratio of the amorphous phase is less than 50%. Similarly, in the transmission electron microscope image, uniform lattice fringes are observed throughout the particles, and there are almost no places where the lattice fringes are unclear. This can be confirmed from the fact that it is not observed. Since the amorphous phase often exists in the outer periphery of the particle, the volume ratio of the amorphous phase can often be calculated by paying attention to the outer periphery of the particle.
- the composite tungsten oxide ultrafine particle when an amorphous phase with unclear lattice fringes is present in a layered manner on the outer periphery of the particle, the composite tungsten oxide has a thickness of 20% or less of the particle diameter.
- the volume ratio of the amorphous phase in the ultrafine particles is less than 50%.
- the composite tungsten oxide ultrafine particles are a coating film constituting the composite tungsten oxide ultrafine particle dispersion, a film obtained by applying a predetermined operation to the coating film and curing the resin of the coating film (in the present invention, “cured film”).
- the difference value obtained by subtracting the crystallite size from the average particle size of the dispersed composite tungsten oxide ultrafine particles is the average particle size. If the diameter is 20% or less, it can be said that the composite tungsten oxide ultrafine particles are single crystals having an amorphous phase volume ratio of less than 50%.
- the average particle diameter of the composite tungsten oxide ultrafine particles was determined by measuring the particle diameter of 100 composite tungsten oxide ultrafine particles using an image processing apparatus from a transmission electron microscope image of the composite tungsten oxide ultrafine particle dispersion. The average value can be calculated.
- the synthesis process of the composite tungsten oxide ultrafine particles so that the difference between the average particle diameter and the crystallite diameter of the composite tungsten oxide ultrafine particles dispersed in the composite tungsten oxide ultrafine particle dispersion is 20% or less, What is necessary is just to adjust a grinding
- the BET specific surface area of the composite tungsten oxide ultrafine particles described above is closely related to the particle size distribution of the ultrafine particles. This greatly affects the productivity, the near-infrared shielding properties of the ultrafine particles themselves, and the light resistance that suppresses light coloring.
- the small BET specific surface area of the ultrafine particles indicates that the crystallite size of the ultrafine particles is large. Therefore, if the ultrafine particles have a BET specific surface area of a predetermined value or more, a medium stirring mill is used to produce a near-infrared shielding dispersion that is transparent in the visible light region and can suppress the above-described blue haze phenomenon. It is not necessary to pulverize and refine the ultrafine particles for a long time, and the productivity of the near-infrared shielding dispersion can be improved.
- the BET specific surface area of the ultrafine particles is a predetermined value or less, for example, 200 m 2 / g or less, indicates that the BET particle size is 2 nm or more when the particle shape is assumed to be a true sphere, This means that there are almost no ultrafine particles having a crystallite diameter of 1 nm or less that do not contribute to the near-infrared shielding property. Therefore, when the BET specific surface area of the ultrafine particles is a predetermined value or less, the near-infrared shielding characteristics and light resistance of the ultrafine particles are ensured.
- the crystallite diameter of 1 nm or less that does not contribute to the near-infrared shielding property when the above-mentioned XRD peak top intensity value is a predetermined value or more. Since there are almost no ultrafine particles and there are ultrafine particles with good crystallinity, it is considered that the near-infrared shielding property and light resistance of the ultrafine particles are ensured.
- Nitrogen gas, argon gas, krypton gas, xenon gas, or the like is used as a gas used for adsorption in the measurement of the BET specific surface area of the composite tungsten oxide ultrafine particles described above.
- the specific surface area is 0.1 m 2 / g or more, as in the case of the composite tungsten oxide ultrafine particles according to the present invention, relatively easy handling and low-cost nitrogen gas is used. It is desirable to do.
- BET specific surface area of the composite tungsten oxide nanoparticles may have to the 30.0 m 2 / g or more 120.0m 2 / g or less, more preferably, 30.0 m 2 / g or more 90.0m 2 / g or less , more preferably it is better to less 35.0 m 2 / g or more 70.0m 2 / g.
- the BET specific surface area of the composite tungsten oxide ultrafine particles is desirably the above-mentioned value even before and after pulverization and dispersion when obtaining the composite tungsten oxide ultrafine particle dispersion.
- the dispersion particle diameter of the composite tungsten oxide ultrafine particles is preferably 200 nm or less, and more preferably, the dispersion particle diameter is 200 nm or less and 10 nm or more.
- the composite tungsten oxide ultrafine particles in the composite tungsten oxide ultrafine particle dispersion in which the dispersed particle diameter of the composite tungsten oxide ultrafine particles is preferably 200 nm or less. This is because the crystallite diameter of the composite tungsten oxide ultrafine particles is preferably 200 nm or less at the maximum.
- the crystal grain size is preferably 1 nm or more, and more preferably 10 nm or more.
- the above-described composite tungsten oxide ultrafine particles may contain a component that volatilizes by heating (may be referred to as “volatile component” in the present invention).
- the volatile component is a component that is adsorbed when the composite tungsten oxide ultrafine particles are exposed to a storage atmosphere or air or during the synthesis process.
- specific examples of the volatile component include water and a dispersion solvent described later.
- the volatile component is volatilized from the composite tungsten oxide ultrafine particles by heating at 150 ° C. or lower. It is an ingredient to do.
- the volatile component in the composite tungsten oxide ultrafine particles and the content thereof are related to the amount of water adsorbed when the ultrafine particles are exposed to the atmosphere or the like, and the residual solvent amount in the drying step of the ultrafine particles. And the said volatile component and its content rate may have big influence on the dispersibility at the time of disperse
- the composite tungsten oxide ultrafine particles are detached from the near-infrared absorbing dispersion, Peeling may occur. That is, the deterioration of the compatibility between the ultrafine particles and the resin causes the deterioration of the near-infrared absorbing dispersion produced.
- the composite tungsten oxide ultrafine particles containing a large amount of volatile components may be influenced by whether the dispersion of the ultrafine particles is good or not depending on the compatibility with the dispersion medium used in the dispersion system. Means that. Therefore, if the volatile component content in the composite tungsten oxide ultrafine particles according to the present invention is not more than a predetermined amount, wide versatility is exhibited.
- the ultrafine particles if the content of the volatile component is 2.5% by mass or less, the ultrafine particles are used in the dispersion medium used in most dispersion systems. It was found that the composite tungsten oxide ultrafine particles can be dispersed and have versatility. On the other hand, it was also found that there is no particular limitation on the lower limit of the content of the volatile component. As a result, if the ultrafine particles having a volatile component content of 2.5% by mass or less are not excessively aggregated, such as tumbler, nauter mixer, Henschel mixer, super mixer, planetary mixer, etc.
- the ultrafine particles can be dispersed in a resin or the like using a mixer and a method of uniformly mixing (including melt mixing) with a kneader such as a Banbury mixer, kneader, roll, single-screw extruder, or twin-screw extruder. .
- a kneader such as a Banbury mixer, kneader, roll, single-screw extruder, or twin-screw extruder.
- the content of volatile components in the composite tungsten oxide ultrafine particles can be measured by thermal analysis. Specifically, the weight loss may be measured by holding the composite tungsten oxide ultrafine particle sample at a temperature lower than the temperature at which the composite tungsten oxide ultrafine particles are thermally decomposed and higher than the volatile component is volatilized. . Moreover, what is necessary is just to use gas mass spectrometry together, when specifying a volatile component.
- the XRD peak top intensity value and BET specific surface area of the composite tungsten oxide ultrafine particles described in detail above can be controlled by predetermined manufacturing conditions.
- the temperature at which the ultrafine particles are produced by a thermal plasma method or a solid phase reaction method (firing temperature), a production time (firing time), a production atmosphere (firing atmosphere), a precursor raw material form
- the content of the volatile component of the composite tungsten oxide ultrafine particles is determined depending on the production conditions such as the storage method and storage atmosphere of the ultrafine particles, the temperature when drying the ultrafine particle dispersion, the drying time, and the drying method.
- the content rate of the volatile component of the composite tungsten oxide ultrafine particles does not depend on the crystal structure of the composite tungsten oxide ultrafine particles or a synthesis method such as a thermal plasma method or a solid phase reaction described later.
- Thermal Plasma Method The thermal plasma method will be described in the order of (i) raw materials used in the thermal plasma method and (ii) the thermal plasma method and its conditions.
- tungsten oxide ultrafine particles according to the present invention are synthesized by the thermal plasma method
- a mixed powder of a tungsten compound and an M element compound can be used as a raw material.
- the tungsten compound tungsten hydrate obtained by adding water to tungstic acid (H 2 WO 4 ), ammonium tungstate, tungsten hexachloride, tungsten hexachloride dissolved in alcohol and hydrolyzing it, and then evaporating the solvent, It is preferable that it is 1 or more types chosen from.
- M element compound it is preferable to use one or more selected from M element oxides, hydroxides, nitrates, sulfates, chlorides, and carbonates.
- An aqueous solution containing the above-described tungsten compound and the above-described M element compound has a ratio of M element to W element of MxWyOz (where M is the M element, W is tungsten, O is oxygen, 0.001 ⁇ x / Wet mixing is performed so that the ratio of the M element to the W element satisfies y ⁇ 1.0 and 2.0 ⁇ z / y ⁇ 3.0).
- the mixed powder of M element compound and a tungsten compound is obtained by drying the obtained liquid mixture, and the said mixed powder can be used as the raw material of a thermal plasma method.
- the mixed powder is obtained by using a composite tungsten oxide obtained by firing in the first stage in an inert gas alone or in a mixed gas atmosphere of an inert gas and a reducing gas as a raw material for the thermal plasma method.
- a composite tungsten oxide obtained by firing in the first stage in an inert gas alone or in a mixed gas atmosphere of an inert gas and a reducing gas as a raw material for the thermal plasma method.
- it is fired in a mixed gas atmosphere of an inert gas and a reducing gas in the first stage, and the fired product in the first stage is fired in an inert gas atmosphere in the second stage.
- the composite tungsten oxide obtained by the stage firing can also be used as a raw material for the thermal plasma method.
- thermal plasma method for example, one of DC arc plasma, high frequency plasma, microwave plasma, low frequency AC plasma, or a superposition of these plasmas, or Plasma generated by an electric method in which a magnetic field is applied to DC plasma, plasma generated by irradiation with a high-power laser, plasma generated by a high-power electron beam or ion beam can be applied.
- thermal plasma is a thermal plasma having a high temperature part of 10,000 to 15000 K, and particularly preferably a plasma capable of controlling the generation time of ultrafine particles.
- the raw material supplied into the thermal plasma having the high temperature part instantly evaporates in the high temperature part.
- the evaporated raw material is condensed in the process of reaching the plasma tail flame part, and rapidly solidified outside the plasma flame to produce composite tungsten oxide ultrafine particles.
- the synthesis method will be described with reference to FIG. 1, taking the case of using a high-frequency plasma reactor as an example.
- the inside of the reaction system constituted by the water-cooled quartz double tube and the reaction vessel 6 is evacuated to about 0.1 Pa (about 0.001 Torr) by a vacuum exhaust device.
- the inside of the reaction system is filled with argon gas, and an argon gas circulation system of 1 atm is formed. Thereafter, any gas selected from argon gas, a mixed gas of argon and helium (Ar—He mixed gas), or a mixed gas of argon and nitrogen (Ar—N 2 mixed gas) as a plasma gas in the reaction vessel At a flow rate of 30 to 45 L / min.
- an Ar—He mixed gas is introduced at a flow rate of 60 to 70 L / min as a sheath gas that flows just outside the plasma region. Then, an alternating current is applied to the high frequency coil 2 to generate thermal plasma by a high frequency electromagnetic field (frequency 4 MHz). At this time, the plate power is 30 to 40 kW.
- a mixed powder of M element compound and tungsten compound obtained by the above-described synthesis method or a composite tungsten oxide is supplied from a gas supply device with 6 to 98 L / min argon gas as a carrier.
- the gas is introduced into the thermal plasma at a supply rate of 25 to 50 g / min and reacted for a predetermined time. After the reaction, the produced composite tungsten oxide ultrafine particles are deposited on the filter 8 and are collected.
- the carrier gas flow rate and the raw material supply speed greatly affect the generation time of ultrafine particles. Therefore, it is preferable to set the carrier gas flow rate to 6 L / min or more and 9 L / min or less and the raw material supply rate to 25 to 50 g / min. Further, it is preferable that the plasma gas flow rate is 30 L / min or more and 45 L / min or less, and the sheath gas flow rate is 60 L / min or more and 70 L / min or less.
- the plasma gas has a function of maintaining a thermal plasma region having a high temperature portion of 10,000 to 15000K, and the sheath gas has a function of cooling the inner wall surface of the quartz torch in the reaction vessel and preventing the quartz torch from melting.
- the flow rates of these gases are important parameters for controlling the shape of the plasma region.
- the shape of the plasma region extends in the gas flow direction and the temperature gradient of the plasma tail flame part becomes gentler, so the generation time of the generated ultrafine particles is lengthened and ultrafine particles with good crystallinity Can be generated.
- the value of the XRD peak top intensity ratio of the composite tungsten oxide ultrafine particles according to the present invention can be set to a desired value.
- the value of the ratio of the XRD peak top intensity of the composite tungsten oxide ultrafine particles according to the present invention can be set to a predetermined value.
- the composite tungsten oxide synthesized by the thermal plasma method has a crystallite diameter exceeding 200 nm, or in the composite tungsten oxide ultrafine particle dispersion obtained from the composite tungsten oxide synthesized by the thermal plasma method.
- the plasma conditions and the subsequent pulverization / dispersion treatment conditions are appropriately selected so that the value of the XRD peak top intensity ratio is 0.13 or more, If the difference between the average particle size and the crystallite size of the composite tungsten oxide ultrafine particles of the composite tungsten oxide ultrafine particle dispersion of the coating of the composite tungsten oxide ultrafine particle dispersion is 20% or less, The effect is demonstrated.
- Solid Phase Reaction Method The solid phase reaction method will be described in the order of (i) raw materials used for the solid phase reaction method, (ii) firing in the solid phase reaction method and its conditions.
- the tungsten compound is a tungsten hydrate obtained by adding water to tungstic acid (H 2 WO 4 ), ammonium tungstate, tungsten hexachloride, tungsten hexachloride dissolved in alcohol and hydrolyzing it, and then evaporating the solvent. It is preferable that it is 1 or more types chosen from.
- M element compound used for the production of the raw material of the composite tungsten oxide ultrafine particles includes M element oxide, hydroxide, nitrate, sulfate, chloride, carbonate, It is preferable that it is 1 or more types chosen from.
- a compound containing one or more impurity elements selected from Si, Al, and Zr may be included as a raw material.
- the impurity element compound does not react with the composite tungsten compound in the subsequent firing step, and functions to prevent crystal coarsening by suppressing the crystal growth of the composite tungsten oxide.
- the compound containing an impurity element is preferably at least one selected from oxides, hydroxides, nitrates, sulfates, chlorides, and carbonates, particularly colloidal silica or colloidal alumina having a particle size of 500 nm or less. preferable.
- the above tungsten compound and an aqueous solution containing the M element compound have a ratio of M element to W element of MxWyOz (where M is the M element, W is tungsten, O is oxygen, 0.001 ⁇ x / y ⁇ Wet mixing is performed so that the ratio of M element to W element is 1.0, 2.0 ⁇ z / y ⁇ 3.0).
- wet mixing is performed so that the impurity element compound is 0.5 mass% or less. Then, by drying the obtained mixed liquid, a mixed powder of the M element compound and the tungsten compound or a mixed powder of the M element compound containing the impurity element compound and the tungsten compound is obtained.
- (Ii) Firing in the solid-phase reaction method and its conditions A mixed powder of M element compound and tungsten compound produced by the wet mixing, or a mixed powder of M element compound and tungsten compound containing an impurity element compound is not used. Baking is performed in one stage in an atmosphere of a single active gas or a mixed gas of an inert gas and a reducing gas. At this time, the firing temperature is preferably close to the temperature at which the composite tungsten oxide ultrafine particles begin to crystallize. Specifically, the firing temperature is preferably 1000 ° C. or less, more preferably 800 ° C. or less, and 800 A temperature range of less than or equal to 500 ° C. is more preferred.
- the value of the ratio of the XRD peak top intensity of the composite tungsten oxide ultrafine particles according to the present invention can be set to a predetermined value.
- tungsten trioxide may be used instead of the tungsten compound.
- a composite tungsten oxide ultrafine particle dispersion described later was prepared using the composite tungsten oxide ultrafine particles obtained by the synthesis method by the thermal plasma method or the solid phase reaction method.
- the dispersion particle diameter of the ultrafine particles contained in the dispersion exceeds 200 nm, it may be pulverized and dispersed in the step of producing a composite tungsten oxide fine particle dispersion described later.
- the composite tungsten oxide ultrafine particles according to the present invention can realize excellent near-infrared shielding properties.
- the composite tungsten oxide ultrafine particles according to the present invention may contain a volatile component. It is preferable that it is 2.5 mass% or less. However, when the composite tungsten oxide ultrafine particles are exposed to the atmosphere and the content of volatile components exceeds 2.5% by mass, the content of the volatile components may be reduced by drying treatment. I can do it.
- the composite tungsten oxide synthesized by the above-described method is pulverized and dispersed into fine particles to produce a composite tungsten oxide ultrafine particle dispersion (pulverization / dispersion processing step), and
- the composite tungsten oxide ultrafine particles according to the present invention can be manufactured through a step of drying the composite tungsten oxide ultrafine particle dispersion and removing the solvent (drying step).
- the pulverization and dispersion step will be described in detail in the item of “[d] composite tungsten oxide ultrafine particle dispersion” described later, the step of the drying treatment will be described here.
- the composite tungsten oxide ultrafine particle dispersion obtained in the pulverization and dispersion process described later is dried to remove volatile components in the dispersion, and the composite tungsten oxide ultrafine particle according to the present invention is used. Is what you get.
- an air dryer As drying equipment, heating and / or decompression is possible, and from the viewpoint of easy mixing and recovery of the ultrafine particles, an air dryer, a universal mixer, a ribbon mixer, a vacuum fluidized dryer, an oscillatory fluid flow A dryer, a freeze dryer, a ribocorn, a rotary kiln, a spray dryer, a pulcon dryer, and the like are preferable, but not limited thereto.
- a drying process using an air dryer (2) a drying process using a vacuum fluidized dryer, and (3) a drying process using a spray dryer will be described.
- each drying process is demonstrated in order.
- Drying treatment by an air dryer This is a treatment method in which a composite tungsten oxide ultrafine particle dispersion obtained by a method described later is dried by an air dryer to remove volatile components in the dispersion.
- the drying treatment is desirably performed at a temperature higher than that at which the volatile component is volatilized from the composite tungsten oxide ultrafine particles and at a temperature at which the element M is not desorbed, and is desirably 150 ° C. or lower.
- the composite tungsten oxide ultrafine particles produced by drying with the air dryer are weak secondary aggregates.
- Drying process using a vacuum fluidized dryer This is a processing method for removing volatile components in the composite tungsten oxide ultrafine particle dispersion by performing a drying process using a vacuum fluidized dryer.
- the drying and pulverization processes are simultaneously performed in a reduced-pressure atmosphere, so that the drying speed is high and the agglomerates as seen in the above-mentioned dried products in the atmospheric dryer are not formed.
- the drying temperature is such that the element M does not desorb from the composite tungsten oxide ultrafine particles, and is higher than the volatile component volatilizes, and is preferably 150 ° C. or lower.
- Drying treatment by spray dryer This is a treatment method for removing volatile components of the composite tungsten oxide ultrafine particle dispersion by performing a drying treatment by a spray dryer.
- a spray dryer when removing volatile components in the drying process, secondary agglomeration due to the surface force of the volatile components is unlikely to occur, and composite tungsten oxidation that is not relatively secondary agglomerated without crushing treatment. Ultrafine particles can be obtained.
- the composite tungsten oxide ultrafine particles subjected to the drying treatment according to the above (1) to (3) in a resin or the like By dispersing the composite tungsten oxide ultrafine particles subjected to the drying treatment according to the above (1) to (3) in a resin or the like by an appropriate method, the high visible light transmittance and the expression of the near infrared absorption function are achieved. It is possible to form a composite tungsten oxide ultrafine particle dispersion which is a near-infrared shielding material fine particle dispersion having a low solar transmittance and an optical property of a low haze value.
- the composite tungsten oxide ultrafine particle dispersion according to the present invention includes the composite tungsten oxide ultrafine particles obtained by the above-described synthetic production method, water, an organic solvent, an oil, and a liquid. Grinding liquid medium of resin, liquid plasticizer for plastics, polymer monomer or mixture slurry selected from a mixture thereof, and appropriate amount of dispersant, coupling agent, surfactant, etc. with a medium stirring mill, It is dispersed.
- the dispersion state of the composite tungsten oxide ultrafine particles in the solvent is preferably good, and the dispersed particle diameter is preferably 1 to 200 nm.
- content of the composite tungsten oxide ultrafine particles contained in the composite tungsten oxide ultrafine particle dispersion is 0.01% by mass or more and 80% by mass or less.
- (1) solvent, (2) dispersant, (3) dispersion method, (4) binder, (5) additive, (6) coating film, 7) A coating method and (8) a method of mixing with a base resin will be described in this order.
- liquid solvent used in the composite tungsten oxide ultrafine particle dispersion is not particularly limited, and the coating conditions and application environment of the composite tungsten oxide ultrafine particle dispersion, and an appropriately added inorganic binder, What is necessary is just to select suitably according to a resin binder.
- the liquid solvent is water, an organic solvent, an oil or fat, a liquid resin, a liquid plasticizer for plastic, a polymer monomer, or a mixture thereof.
- organic solvent various solvents such as alcohol, ketone, hydrocarbon, glycol, and water can be selected.
- alcohol solvents such as methanol, ethanol, 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol and diacetone alcohol; ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone Ester solvents such as 3-methyl-methoxy-propionate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene Glycol derivatives such as glycol ethyl ether acetate; , N- methyl formamide, dimethylformamide, di
- chlorobenzene can be used.
- organic solvents dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether acetate, n-butyl acetate and the like are particularly preferable.
- the solvents described above can be used alone or in combination of two or more. Furthermore, you may adjust pH by adding an acid and an alkali to these solvents as needed.
- Vegetable oils include dry oils such as linseed oil, sunflower oil, tung oil, eno oil, semi-dry oils such as sesame oil, cottonseed oil, rapeseed oil, soybean oil, rice bran oil, poppy oil, olive oil, coconut oil, palm oil, dehydrated castor oil
- Non-drying oils such as are preferably used.
- As the compound derived from vegetable oil fatty acid monoesters, ethers, and the like obtained by directly esterifying fatty acids of plant oil and monoalcohols are preferably used.
- liquid plasticizer for plastics known liquid plasticizers typified by carboxylic acid esters and phosphate esters can be used.
- polymer monomer a polymer is formed by polymerization or the like. Examples of the monomer used in the present invention include methyl methacrylate monomer, acrylate monomer, and styrene resin monomer.
- Dispersant in order to further improve the dispersion stability of the composite tungsten oxide ultrafine particles in the composite tungsten oxide ultrafine particle dispersion and avoid the coarsening of the dispersed particle diameter due to reaggregation, It is also preferable to add a dispersant, a surfactant, a coupling agent and the like.
- the dispersant, the coupling agent, and the surfactant can be selected according to the use, but preferably have an amine-containing group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group. A polymer dispersant having any of these functional groups in the molecule is more desirable.
- These functional groups are adsorbed on the surface of the composite tungsten oxide ultrafine particles to prevent aggregation, and have an effect of uniformly dispersing the composite tungsten oxide ultrafine particles according to the present invention even in the near-infrared shielding film.
- the dispersion method of the composite tungsten oxide ultrafine particles in the dispersion is not particularly limited as long as the fine particles can be uniformly dispersed in the dispersion without agglomeration.
- the dispersion method include a dispersion treatment method using an apparatus such as a bead mill, a ball mill, a sand mill, a paint shaker, and an ultrasonic homogenizer.
- pulverization and dispersion with a medium agitation mill such as a bead mill using a medium medium (beads, balls, Ottawa sand), a ball mill, a sand mill, a paint shaker or the like is preferable because the time required for the desired dispersed particle size is short.
- the composite tungsten oxide ultrafine particles can be made finer and dispersed (that is, pulverized and dispersed).
- the dispersed particle diameter of the composite tungsten oxide ultrafine particles is 1 to 200 nm, light in the visible light region having a wavelength of 380 nm to 780 nm is not scattered by geometrical scattering or Mie scattering.
- haze is reduced and visible light transmittance can be increased, which is preferable.
- the scattered light is reduced in inverse proportion to the sixth power of the particle diameter, so that the scattering is reduced and the transparency is improved as the dispersed particle diameter is reduced. Therefore, it is preferable that the dispersed particle size is 200 nm or less because the scattered light is extremely reduced and the blue haze phenomenon can be suppressed, and thus the transparency is further increased.
- the dispersed particle size of the composite tungsten oxide ultrafine particles means the particle size of the single particles of the composite tungsten oxide ultrafine particles dispersed in the solvent or the aggregated particles obtained by aggregating the composite tungsten oxide ultrafine particles. It can be measured with various commercially available particle size distribution analyzers. For example, a sample of the composite tungsten oxide ultrafine particle dispersion can be collected, and the sample can be measured using a particle size measuring apparatus (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.) based on the dynamic light scattering method. .
- ELS-8000 manufactured by Otsuka Electronics Co., Ltd.
- the composite tungsten oxide ultrafine particle dispersion in which the content of the composite tungsten oxide ultrafine particles obtained by the above-described synthetic production method is 0.01% by mass or more and 80% by mass or less is excellent in liquid stability.
- a dispersant, a coupling agent, or a surfactant is selected, gelation of the dispersion or particle settling does not occur for more than 6 months even when placed in a constant temperature bath at a temperature of 40 ° C.
- the dispersed particle diameter can be maintained in the range of 1 to 200 nm.
- the binder By adding the binder to the composite tungsten oxide ultrafine particle dispersion, it is possible to control optical characteristics such as visible light transmittance by adjusting the amount of the binder added in the manufactured composite tungsten oxide ultrafine particle dispersion. This is because the adhesion of the composite tungsten oxide ultrafine particles to the substrate after application and curing on the substrate is improved, and the film hardness is further improved.
- the composite tungsten oxide ultrafine particle dispersion may appropriately contain one or more selected from an inorganic binder and a resin binder.
- the kind of the inorganic binder or resin binder contained in the composite tungsten oxide ultrafine particle dispersion is not particularly limited.
- the inorganic binder metal alkoxides of silicon, zirconium, titanium, or aluminum, partially hydrolyzed polycondensation products thereof, or organosilazanes can be applied.
- the resin binder a UV curable resin, a thermosetting resin, an electron beam curable resin, a room temperature curable resin, a thermoplastic resin, or the like can be selected according to the purpose.
- thermoplastic resins such as acrylic resins, thermosetting resins such as epoxy resins, polyethylene resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl alcohol resins, polystyrene resins, polypropylene resins, ethylene vinyl acetate copolymer
- thermoplastic resins such as acrylic resins, thermosetting resins such as epoxy resins, polyethylene resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl alcohol resins, polystyrene resins, polypropylene resins, ethylene vinyl acetate copolymer
- a coalescence a polyester resin, a polyethylene terephthalate resin, a fluorine resin, an ionomer resin, a polycarbonate resin, an acrylic resin, a polyvinyl butyral resin, a PET resin, a polyamide resin, a polyimide resin, an olefin resin, or the like can be applied.
- the dispersion according to the present invention is added to the general formula XBm (where X is an alkaline earth element, Alternatively, it is also a preferable configuration that a boride ultrafine particle represented by a metal element selected from rare earth elements including yttrium, 4 ⁇ m ⁇ 6.3) is appropriately added as desired. In addition, what is necessary is just to select the addition ratio at this time suitably according to the desired near-infrared shielding characteristic.
- a known inorganic pigment or a known organic pigment such as carbon black or a petrol can be added.
- a known ultraviolet absorber, a known near-infrared shielding material of an organic substance, or a phosphorus-based coloring inhibitor may be added.
- a coating method is convenient from the viewpoint of ease of film forming operation and cost.
- the content is preferably 40% by mass or less in terms of oxide in the coating obtained after heating.
- An oxide film such as silicon, zirconium, titanium, or aluminum can be easily formed by applying the coating liquid as a second layer on a film containing composite tungsten oxide ultrafine particles as a main component and heating. Is possible.
- an organosilazane solution as a binder component or a coating liquid component used in the coating liquid according to the present invention.
- the substrate heating temperature after application of the composite tungsten oxide ultrafine particle dispersion containing a metal alkoxide of silicon, zirconium, titanium, or aluminum and its hydrolysis polymer as an inorganic binder or coating film is 100
- the heating is preferably performed at a temperature equal to or higher than the boiling point of the solvent in the coating solution. This is because when the substrate heating temperature is 100 ° C. or higher, the polymerization reaction of the metal alkoxide or the hydrolysis polymer of the metal alkoxide contained in the coating film can be completed.
- the substrate heating temperature is 100 ° C. or higher, water or organic solvent as a solvent does not remain in the film, so that these solvents do not cause a reduction in visible light transmittance in the heated film. Because.
- a resin binder When a resin binder is added to the composite tungsten oxide ultrafine particle dispersion, it may be cured according to the curing method of each resin.
- the resin binder is an ultraviolet curable resin, it may be appropriately irradiated with ultraviolet rays, and if it is a room temperature curable resin, it may be left as it is after application. If this structure is taken, the application
- the method for applying the composite tungsten oxide ultrafine particle dispersion according to the present invention and the coating liquid is not particularly limited.
- a method of applying the treatment liquid flatly and thinly and uniformly such as a spin coating method, a bar coating method, a spray coating method, a dip coating method, a screen printing method, a roll coating method, and a flow coating method, can be preferably applied.
- the composite tungsten oxide ultrafine particles or composite tungsten oxide ultrafine particle dispersion according to the present invention is mixed into the base resin. You can also knead.
- any known method can be used as long as the composite tungsten oxide ultrafine particles are uniformly dispersed in the resin. A method may be selected as appropriate. Further, it can be melt-mixed at a temperature near the melting point of the resin and then pelletized, and formed into various shapes such as a plate shape, a sheet shape, or a film shape by a known method.
- the resin include PET resin, acrylic resin, polyamide resin, vinyl chloride resin, polycarbonate resin, olefin resin, epoxy resin, polyimide resin, and fluorine resin.
- the optical properties of the dispersions, coating films and cured films in the examples and comparative examples were measured using a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.), and the visible light transmittance and solar transmittance were , Calculated according to JIS R3106.
- the dispersed particle size was shown as an average value measured by a particle size measuring device (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.) based on the dynamic light scattering method.
- the average particle diameter of the composite tungsten oxide ultrafine particles dispersed in the cured film which is the composite tungsten oxide ultrafine particle dispersion was measured by observing a transmission electron microscope image of the cross section of the cured film.
- the transmission electron microscope image was observed using a transmission electron microscope (HF-2200 manufactured by Hitachi High-Technologies Corporation).
- the transmission electron microscope image was processed with an image processing apparatus, and the particle diameter of 100 ultrafine composite tungsten oxide particles was measured. The average value was defined as the average particle diameter.
- the X-ray diffraction pattern was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method) using a powder X-ray diffractometer (X'Pert-PRO / MPD manufactured by Spectris Co., Ltd.
- Example 1 Dissolve 0.216 kg of Cs 2 CO 3 in 0.330 kg of water, add this to 1.000 kg of H 2 WO 4, stir well, then dry and mix with Cs 0.33 WO 3 mixed powder which is the target composition Got the body.
- the inside of the reaction system is evacuated to about 0.1 Pa (about 0.001 Torr) using a high-frequency plasma reactor described in FIG. 1 and then completely replaced with argon gas.
- a pressure distribution system was used.
- argon gas as plasma gas was introduced into the reaction vessel at a flow rate of 30 L / min, and sheath gas was introduced spirally from the sheath gas supply port at a flow rate of argon gas 55 L / min and helium gas 5 L / min.
- high frequency power was applied to the water-cooled copper coil for high frequency plasma generation, and high frequency plasma was generated.
- the high frequency power was set to 40KW.
- the mixed powder was supplied into the thermal plasma at a rate of 50 g / min while supplying argon gas as a carrier gas from the gas supply device at a flow rate of 9 L / min.
- the mixed powder was instantly evaporated in the thermal plasma and rapidly solidified in the process of reaching the plasma tail flame part to become ultrafine particles.
- the produced ultrafine particles were deposited on the recovery filter.
- the deposited ultrafine particles were collected, and an X-ray diffraction pattern was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method) using a powder X-ray diffractometer (X'Pert-PRO / MPD manufactured by Spectris Co., Ltd. PANalytical). .
- the X-ray diffraction pattern of the obtained ultrafine particles is shown in FIG.
- the obtained ultrafine particles were identified as a hexagonal Cs 0.33 WO 3 single phase.
- the crystallite diameter of the obtained ultrafine particle was 18.8 nm.
- the value of peak top intensity of the X-ray diffraction pattern of the ultrafine particles obtained was 4200 counts.
- the composition of the ultrafine particles obtained was examined by ICP emission analysis. As a result, the Cs concentration was 13.6% by mass, the W concentration was 65.3% by mass, and the molar ratio of Cs / W was 0.29. The remainder other than Cs and W was oxygen, and it was confirmed that no other impurity element contained in an amount of 1% by mass or more was present.
- the BET specific surface area of the obtained ultrafine particles was measured using a BET specific surface area measuring device (HMmodel-1208 manufactured by Mountaintech), and was 60.0 m 2 / g.
- nitrogen gas having a purity of 99.9% was used for measurement of the BET specific surface area.
- the content rate of the volatile component of the composite tungsten oxide ultrafine particles according to Example 1 was measured using a moisture meter (MOC63u, manufactured by Shimadzu Corporation), it was 1.6% by mass.
- the temperature was raised from room temperature to 125 ° C. within 1 minute from the start of measurement, kept at a temperature of 125 ° C. for 9 minutes, and the weight reduction rate 10 minutes after the start of measurement was taken as the content of volatile components.
- Acrylic polymer dispersant (amine value 48 mgKOH / g, decomposition temperature 250 ° C.) having 20 parts by weight of the obtained composite tungsten oxide ultrafine particles, 64 parts by weight of methyl isobutyl ketone, and a group containing amine as a functional group.
- acrylic dispersant (hereinafter referred to as "dispersant a”) was mixed to prepare 3 kg of slurry. This slurry was put into a medium stirring mill together with beads and pulverized and dispersed for 1 hour.
- the medium stirring mill used was a horizontal cylindrical annular type (manufactured by Ashizawa Corporation), and the inner wall of the vessel and the rotor (rotary stirring portion) were made of zirconia.
- beads made of YSZ Yttria-Stabilized Zirconia having a diameter of 0.1 mm were used.
- the rotational speed of the rotor was 14 rpm / second, and pulverization and dispersion treatment was performed at a slurry flow rate of 0.5 kg / min.
- a composite tungsten oxide ultrafine particle dispersion liquid according to Example 1 was obtained.
- a silicon powder standard sample manufactured by NIST, 640c
- the value of the peak intensity on the basis of the (220) plane in the silicon powder standard sample was measured it was 19800 counts.
- the peak intensity value of the standard sample is 1, the value of the XRD peak intensity ratio of the composite tungsten oxide ultrafine particles after the pulverization and dispersion treatment according to Example 1 is found to be 0.15. did. Moreover, the crystallite diameter of the composite tungsten oxide ultrafine particles after the pulverization and dispersion treatment according to Example 1 was 16.9 nm.
- the dispersed particle size of the composite tungsten oxide ultrafine particle dispersion according to Example 1 was measured using a particle size measuring device based on a dynamic light scattering method (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.), it was found to be 70 nm. Met.
- the particle diameter measurement was set to a particle refractive index of 1.81 and a particle shape of aspherical.
- the background was measured using methyl isobutyl ketone, and the solvent refractive index was 1.40.
- the obtained composite tungsten oxide ultrafine particle dispersion was diluted with methyl isobutyl ketone in a spectrophotometer measurement glass cell so that the visible light transmittance was 70%, and the spectrophotometer (manufactured by Hitachi, Ltd.)
- the solar radiation transmittance was calculated by measuring at an interval of 5 nm in the wavelength range of 200 nm to 2600 nm according to U-4100) and found to be 34.8%.
- the visible light transmittance and solar transmittance were calculated based on JIS R3106.
- the incident direction of the light of the spectrophotometer was made into the direction perpendicular
- the blank liquid which put only the solvent methyl isobutyl ketone into the said glass cell for a measurement is made into the baseline of the light transmittance.
- Example 2 The composite tungsten oxide ultrafine particle dispersion obtained in Example 1 was mixed with an ultraviolet curable resin and a solvent, methyl isobutyl ketone, and coated on a 3 mm thick glass substrate with a bar coater (IMC-700 manufactured by Imoto Seisakusho). Then, a coating film was formed, and after evaporating the solvent from the coating film, irradiation with ultraviolet rays was performed to obtain a cured film that was a composite tungsten oxide ultrafine particle dispersion in which the coating film was cured. At this time, the concentration of the dispersion was adjusted in advance by dilution with methyl isobutyl ketone as a solvent so that the visible light transmittance of the cured film was 70%.
- the solar radiation transmittance was determined from the obtained transmission profile, it was 36.5%.
- the artificial solar illumination lamp (XC-100 manufactured by Celic Co., Ltd.) is used to irradiate the cured film according to Example 2 with the simulated sunlight, and the presence or absence of the blue haze phenomenon is visually confirmed, and there is no blue haze phenomenon. It was confirmed.
- Example 3 to 7 Except for changing the carrier gas flow rate, the plasma gas flow rate, the sheath gas flow rate, and the raw material supply speed, the composite tungsten oxide ultrafine particles according to Examples 3 to 7 were combined with the composite by performing the same operations as in Examples 1 and 2. A tungsten oxide ultrafine particle dispersion was produced. Table 1 shows the changed carrier gas flow rate conditions, raw material supply speed conditions, and other conditions. The same evaluations as in Examples 1 and 2 were performed on the composite tungsten oxide ultrafine particles, the composite tungsten oxide ultrafine particle dispersion, the coating film, and the cured film thereof according to Examples 3 to 7. The evaluation results are shown in Table 2.
- Example 8 A composite represented by Cs 0.33 WO 3 obtained by firing the mixed powder of Cs 2 CO 3 and H 2 WO 4 described in Example 1 at 800 ° C. in a mixed gas atmosphere of nitrogen gas and hydrogen gas. It changed to tungsten oxide and used as a raw material thrown into a high frequency plasma reactor. Otherwise, composite tungsten oxide ultrafine particles and composite tungsten oxide ultrafine particle dispersion according to Example 8 were produced in the same manner as in Examples 1 and 2. The obtained ultrafine particles and dispersions thereof were evaluated in the same manner as in Examples 1-7. The manufacturing conditions and evaluation results are shown in Tables 1 and 2.
- Example 9 A composite tungsten oxide ultrafine particle and a composite tungsten oxide ultrafine particle dispersion according to Example 9 were produced by performing the same operation as in Example 8 except that the carrier gas flow rate and the raw material supply speed were changed. The same evaluation as in Examples 1 to 8 was performed on the obtained ultrafine particles, the dispersion liquid, the coating film, and the cured film. The evaluation results are shown in Tables 1 and 2.
- Example 10 Dissolve 0.148 kg of Rb 2 CO 3 in 0.330 kg of water, add this to 1.000 kg of H 2 WO 4, stir well, then dry and mix with Rb 0.32 WO 3 mixed powder which is the target composition Got the body.
- the composite tungsten oxide ultrafine particle and the composite tungsten oxide ultrafine particle dispersion liquid according to Example 10 were used in the same manner as in Example 1 except that the mixed powder was used as a raw material to be charged into the high-frequency thermal plasma reactor. Manufactured. The same evaluation as in Examples 1 to 9 was performed on the obtained ultrafine particles, the dispersion liquid, the coating film, and the cured film. The manufacturing conditions and evaluation results are shown in Tables 1 and 2.
- Example 11 Dissolve 0.375 kg of K 2 CO 3 in 0.330 kg of water, add this to 1.000 kg of H 2 WO 4, stir well, and then dry, K 0.27 WO 3 mixed powder having the target composition Got the body.
- the composite tungsten oxide ultrafine particles and the composite tungsten oxide ultrafine particle dispersion liquid according to Example 11 were prepared in the same manner as in Example 1 except that the mixed powder was used as a raw material to be charged into the high-frequency thermal plasma reactor. Manufactured. Further, the same evaluation as in Examples 1 to 10 was performed on the obtained ultrafine particles, the dispersion thereof, the coating film, and the cured film. The manufacturing conditions and evaluation results are shown in Tables 1 and 2.
- Example 12 Dissolve 0.320 kg of TlNO 3 in 0.330 kg of water, add it to 1.000 kg of H 2 WO 4, stir well, and then dry, to obtain the target composition of Tl 0.19 WO 3 mixed powder. Obtained.
- the composite tungsten oxide ultrafine particles and the composite tungsten oxide ultrafine particle dispersion according to Example 12 were prepared in the same manner as in Example 1 except that the mixed powder was used as a raw material to be charged into the high-frequency thermal plasma reactor. Manufactured. The same evaluation as in Examples 1 to 11 was performed on the obtained ultrafine particles, the dispersion liquid, the coating film, and the cured film. The manufacturing conditions and evaluation results are shown in Tables 1 and 2.
- Example 13 Dissolve 0.111 kg of BaCO 3 in 0.330 kg of water, add this to 1.000 kg of H 2 WO 4, stir well, and then dry the powder to obtain the target composition of Ba 0.14 WO 3 mixed powder. Obtained.
- the composite tungsten oxide ultrafine particles and the composite tungsten oxide ultrafine particle dispersion according to Example 13 were prepared in the same manner as in Example 1 except that the mixed powder was used as a raw material to be charged into the high-frequency thermal plasma reactor. Manufactured. The same evaluation as in Examples 1 to 12 was performed on the obtained ultrafine particles, the dispersion liquid, the coating film, and the cured film. The manufacturing conditions and evaluation results are shown in Tables 1 and 2.
- Example 14 Dissolve 0.0663 kg of K 2 CO 3 and 0.0978 kg of Cs 2 CO 3 in 0.330 kg of water, add this to 1.000 kg of H 2 WO 4, stir well, then dry and have the desired composition A K 0.24 Cs 0.15 WO 3 mixed powder was obtained.
- the composite tungsten oxide ultrafine particles and the composite tungsten oxide ultrafine particle dispersion according to Example 14 were prepared in the same manner as in Example 1 except that the mixed powder was used as a raw material to be charged into the high-frequency thermal plasma reactor. Manufactured. The same evaluation as in Examples 1 to 13 was performed on the obtained ultrafine particles, the dispersion liquid, the coating film, and the cured film. The manufacturing conditions and evaluation results are shown in Tables 1 and 2.
- Example 15 10.8 g of Cs 2 CO 3 was dissolved in 16.5 g of water, the solution was added to 50 g of H 2 WO 4 and sufficiently stirred, and then dried. The dried product was heated while supplying 2% H 2 gas using N 2 gas as a carrier, and calcined at a temperature of 800 ° C. for 30 minutes. Thereafter, composite tungsten oxide ultrafine particles according to Example 15 were obtained by a solid phase method of baking at 800 ° C. for 90 minutes in an N 2 gas atmosphere. A composite tungsten oxide ultrafine particle dispersion according to Example 15 was produced in the same manner as Example 1 except for the above. However, the pulverization / dispersion processing time by the medium stirring mill was 4 hours.
- the same evaluation as in Examples 1 to 14 was performed on the obtained ultrafine particles, the dispersion liquid, the coating film, and the cured film.
- the manufacturing conditions and evaluation results are shown in Tables 1 and 2.
- the BET specific surface area is a value before pulverization / dispersion treatment.
- Example 16 to 25 Dissolve 0.044 kg of Li 2 CO 3 in 0.330 kg of water, add this to 1.000 kg of H 2 WO 4, stir well, and then dry and conduct the target composition of Li 0.3 WO 3 A mixed powder according to Example 16 was obtained.
- Example 20 of Ca 0.1 WO 3 which is a target composition, was prepared by dissolving 0.040 kg of CaCO 3 in 0.330 kg of water, adding this to 1.000 kg of H 2 WO 4, stirring sufficiently, and drying. To obtain a mixed powder.
- Snow Chemicals S manufactured by Nissan Chemical Co., Ltd., 0.115 kg and 1.000 kg of H 2 WO 4 are sufficiently mixed in a crusher , and the mixed powder according to Example 25 of Si 0.043 WO 2.839 , which is the target composition Got. Snowtech S is ultrafine silica powder.
- the composite tungsten oxide ultrafine particles according to Examples 16 to 25 were prepared in the same manner as in Example 1 except that the mixed powder according to Examples 16 to 25 was used as a raw material to be charged into the high-frequency thermal plasma reactor. A composite tungsten oxide ultrafine particle dispersion was produced. The same evaluation as in Examples 1 to 15 was performed on the obtained ultrafine particles, the dispersion liquid, the coating film, and the cured film. The manufacturing conditions and evaluation results are shown in Tables 1 and 2.
- Example 26 0.230 kg of Cs 2 CO 3 was dissolved in 0.330 kg of water, and the resulting solution was added to 1.000 kg of H 2 WO 4 and stirred sufficiently, followed by drying to obtain a dried product.
- the dried product was heated while supplying 5% H 2 gas using N 2 gas as a carrier, and baked at a temperature of 800 ° C. for 1 hour. Thereafter, a solid-state reaction method in which baking was performed at 800 ° C. for 2 hours in an N 2 gas atmosphere was performed to obtain a composite tungsten oxide.
- the rotational speed of the rotor was 14 rpm / second, and pulverization and dispersion treatment was performed at a slurry flow rate of 0.5 kg / min to obtain a composite tungsten oxide ultrafine particle aqueous dispersion.
- the dispersion particle diameter of the composite tungsten oxide ultrafine particle aqueous dispersion according to Example 26 was measured and found to be 70 nm.
- the particle refractive index was 1.81, and the particle shape was non-spherical.
- the background was measured with water, and the solvent refractive index was 1.33.
- Example 26 Next, about 3 kg of the obtained composite tungsten oxide ultrafine particle aqueous dispersion was dried with an air dryer, to obtain composite tungsten oxide ultrafine particles according to Example 26.
- a constant temperature oven SPH-201 type manufactured by ESPEC Corporation was used as the atmospheric dryer, and the drying temperature was 70 ° C. and the drying time was 96 hours.
- the obtained ultrafine particle was identified as a hexagonal Cs 0.33 WO 3 single phase.
- a silicon powder standard sample manufactured by NIST, 640c
- the value of the peak intensity on the basis of the (220) plane in the silicon powder standard sample was measured it was 19800 counts.
- the value of the peak intensity of the standard sample is 1, the value of the ratio of the XRD peak intensity of the composite tungsten oxide ultrafine particles after pulverization and dispersion treatment according to Example 1 is found to be 0.21. did.
- the composition of the ultrafine particles obtained was examined by ICP emission analysis. As a result, the Cs concentration was 15.2% by mass, the W concentration was 64.6% by mass, and the molar ratio of Cs / W was 0.33. The remainder other than Cs and W was oxygen, and it was confirmed that no other impurity element contained in an amount of 1% by mass or more was present.
- the content of the volatile component of the composite tungsten oxide ultrafine particle according to Example 26 was measured and found to be 2.2% by mass.
- the dispersion particle diameter of the composite tungsten oxide ultrafine particle dispersion according to Example 26 was measured and found to be 80 nm.
- the particle refractive index was 1.81, and the particle shape was non-spherical.
- the background was measured with methyl isobutyl ketone, and the solvent refractive index was 1.40.
- the obtained composite tungsten oxide ultrafine particle dispersion was diluted with methyl isobutyl ketone in a spectrophotometer measurement glass cell so that the visible light transmittance was 70%, and the spectrophotometer (manufactured by Hitachi, Ltd.)
- the solar radiation transmittance was calculated by measuring at an interval of 5 nm in the wavelength range of 200 nm to 2600 nm according to U-4100) and found to be 34.1%.
- the visible light transmittance and solar transmittance were calculated based on JIS R3106.
- the incident direction of the light of the spectrophotometer was made into the direction perpendicular
- the blank liquid which put only the solvent methyl isobutyl ketone into the said glass cell for a measurement is made into the baseline of the light transmittance.
- the obtained composite tungsten oxide ultrafine particle dispersion was mixed with an ultraviolet curable resin and a solvent such as methyl isobutyl ketone to prepare a coating solution.
- the coating solution was applied onto a 3 mm thick glass substrate using a bar coater to form a coating film. After evaporating the solvent from the coating film, the coating film was cured by irradiating with ultraviolet rays to obtain a cured film.
- the concentration of the dispersion was adjusted in advance by dilution with methyl isobutyl ketone as a solvent so that the visible light transmittance of the cured film was 70%.
- the average particle diameter of the composite tungsten oxide ultrafine particles dispersed in the obtained cured film according to Example 26 was calculated by an image processing apparatus using a transmission electron microscope image, and found to be 23 nm. It was almost the same value as the child diameter of 23.7 nm. It was 0.3% when the haze of the cured film which concerns on obtained Example 26 was measured. Further, the transmittance of the obtained cured film according to Example 1 was measured at intervals of 5 nm in the wavelength range of 200 nm to 2600 nm, and the transmission profile shown in FIG. 3 was obtained. When the solar radiation transmittance was determined from the obtained transmission profile, it was 35.7%.
- Tables 1 and 2 show the production conditions of the composite tungsten oxide ultrafine particles according to Example 26 and the evaluation results of the dispersion, the coating film, and the cured film.
- Example 27 The composite tungsten oxide ultrafine particles according to Example 27 and the composite tungsten oxide ultrafine particles according to the same method as in Example 26, except that the drying process by the air dryer is changed to the vacuum drying process by the vacuum stirring crusher. A dispersion was produced.
- the vacuum stir crusher uses an Ishikawa stir crusher 24P type (manufactured by Tajima Chemical Machinery Co., Ltd.), the drying temperature in the vacuum drying process is 80 ° C., the drying time is 32 hours, the rotational frequency of the kneading mixer is 40 Hz, The pressure in the vacuum vessel was 0.001 MPa or less.
- the same evaluations as in Examples 1 and 2 were performed on the obtained ultrafine particles, the dispersion liquid, the coating film, and the cured film. The manufacturing conditions and evaluation results are shown in Tables 1 and 2.
- Example 28 The composite tungsten oxide ultrafine particles according to Example 28 and the composite tungsten oxide ultrafine particle dispersion liquid were treated in the same manner as in Example 26 except that the drying process by the air dryer was changed to the spray drying process by the spray dryer. And manufactured.
- a spray dryer ODL-20 type manufactured by Okawara Chemical Co., Ltd.
- the manufacturing conditions and evaluation results are shown in Tables 1 and 2.
- Examples 29 to 31 The composite tungsten oxide ultrafine particles according to Examples 29 to 31 and the composite tungsten oxide ultrafine particle dispersion were prepared in the same manner as in Examples 26 to 28 except that the pulverization and dispersion treatment time by the medium stirring mill was changed to 2 hours. And manufactured. However, the pulverization and dispersion treatment time by the medium stirring mill was 2 hours. The same evaluations as in Examples 1 and 2 were performed on the obtained ultrafine particles, the dispersion liquid, the coating film, and the cured film. The manufacturing conditions and evaluation results are shown in Tables 1 and 2.
- Examples 32 to 34 Except that 20 parts by weight of the composite tungsten oxide and 80 parts by weight of propylene glycol monoethyl ether were mixed during the preparation of the slurry, the same methods as in Examples 29 to 31 described above were used to produce Examples 32 to No. 34 composite tungsten oxide ultrafine particles and composite tungsten oxide ultrafine particle dispersion were produced. The same evaluations as in Examples 1 and 2 were performed on the obtained ultrafine particles, dispersions, coating films, and cured films according to Examples 32 to 34. In measuring the dispersed particle size, the background was measured with propylene glycol monoethyl ether, and the solvent refractive index was 1.40. The manufacturing conditions and evaluation results are shown in Tables 1 and 2.
- Example 35 Composite tungsten oxide ultrafine particles were obtained in the same manner as in the method according to Example 1. Thereafter, 20 weights of the obtained ultrafine particles, 64 parts by weight of methyl isobutyl ketone, and 16 parts by weight of dispersant a were mixed to prepare 50 g of a slurry. The slurry was subjected to a dispersion treatment for 1 hour using an ultrasonic homogenizer (US-600TCVP, manufactured by Nippon Seiki Seisakusho Co., Ltd.) to obtain a composite tungsten oxide ultrafine particle dispersion liquid according to Example 35. The same evaluation as in Examples 1 and 2 was performed on the composite tungsten oxide ultrafine particle dispersion, the coating film, and the cured film thereof according to Example 35. The evaluation results are shown in Table 2.
- Comparative Example 3 In order to generate a thermal plasma having a high temperature part of 5000 to 10000 K, the composite tungsten oxide superconductor according to Comparative Example 3 is obtained by performing the same operation as in Example 1 except that the high frequency power is 15 kW. Fine particles and composite tungsten oxide ultrafine particle dispersion were prepared. The same evaluations as in Examples 1 and 2 were performed on the obtained ultrafine particles, the dispersion liquid, the coating film, and the cured film. The manufacturing conditions and evaluation results are shown in Tables 1 and 2.
- Example 4 A comparison was made by performing the same operation as in Example 26, except that the composite tungsten oxide ultrafine particle aqueous dispersion according to Example 26 was obtained in a pulverization dispersion treatment time of 4 hours, except that the pulverization dispersion treatment was performed for 40 hours. A composite tungsten oxide ultrafine particle aqueous dispersion according to Example 4 was obtained. The dispersion particle diameter of the composite tungsten oxide ultrafine particle aqueous dispersion according to Comparative Example 4 was measured and found to be 120 nm. In addition, as a setting for the measurement of the dispersed particle size, the particle refractive index was 1.81, and the particle shape was non-spherical.
- the background was measured with water, and the solvent refractive index was 1.33.
- the obtained ultrafine particle was identified as a hexagonal Cs 0.33 WO 3 single phase.
- the composite tungsten oxide ultrafine particle dispersion according to Comparative Example 4 was diluted with methyl isobutyl ketone in a spectrophotometer measurement glass cell so that the visible light transmittance was 70%.
- the solar radiation transmittance was calculated by measuring at an interval of 5 nm in the wavelength range of 200 nm to 2600 nm by U-4100 manufactured by Seisakusho, it was 47.2%.
- the visible light transmittance and solar transmittance were calculated based on JIS R3106.
- the incident direction of the light of the spectrophotometer was made into the direction perpendicular
- the blank liquid which put only the solvent methyl isobutyl ketone into the said glass cell for a measurement is made into the baseline of the light transmittance.
- the composite tungsten oxide ultrafine particle dispersion according to Comparative Example 4 was mixed with an ultraviolet curable resin and methyl isobutyl ketone as a solvent to prepare a coating solution.
- the coating solution was applied onto a 3 mm thick glass substrate using a bar coater to form a coating film. After evaporating the solvent from the coating film, the coating film was cured by irradiating with ultraviolet rays to obtain a cured film.
- the concentration of the dispersion was adjusted in advance by dilution with methyl isobutyl ketone as a solvent so that the visible light transmittance of the cured film was 70%.
- the average particle diameter of the composite tungsten oxide ultrafine particles dispersed in the obtained cured film according to Comparative Example 4 was calculated by an image processing apparatus using a transmission electron microscope image to be 120 nm.
- the haze of the cured film according to Comparative Example 4 obtained was measured, it was 1.8%.
- the transmittance of the obtained cured film according to Comparative Example 4 was measured at an interval of 5 nm in the wavelength range of 200 nm to 2600 nm, and the solar radiation transmittance was obtained from the obtained transmission profile, which was 48.3%. there were.
- the presence or absence of the blue haze phenomenon of the cured film which concerns on the comparative example 4 was confirmed visually similarly to Example 2, and it confirmed that there was a blue haze phenomenon.
- Tables 1 and 2 show the production conditions of the composite tungsten oxide ultrafine particles according to Comparative Example 4, and the evaluation results of the dispersion, the coating film, and the cured film.
- the composite tungsten oxide ultrafine particles according to Examples 1 to 35 have excellent solar transmittance of 47% or less compared to the composite tungsten oxide ultrafine particles of Comparative Examples 1 to 4. Infrared shielding properties were demonstrated.
- the composite tungsten oxide ultrafine particles contained in the dispersions according to Examples 2 to 35 are the XRD of the previous composite tungsten oxide ultrafine particles with respect to the XRD peak intensity of the silicon powder standard sample (manufactured by NIST, 640c) (220).
- the composite was a composite tungsten oxide ultrafine particle having a peak top intensity ratio of 0.13 or more, a crystallite diameter of 1 nm or more, and no heterogeneous phase.
- the average particle diameter and the crystallite diameter of the composite tungsten oxide ultrafine particles in the cured film are almost the same value, so that the single-crystal composite tungsten oxide whose volume ratio of the amorphous phase is less than 50% is used. It is considered to be ultrafine particles.
- Comparative Examples 1, 2, and 4 since the average particle diameter of the composite tungsten oxide ultrafine particles in the cured film is larger than the crystallite diameter, these composite tungsten oxide ultrafine particles are not single crystals. it is conceivable that. Further, in Comparative Example 3, different phases (WO 2 and W) were generated.
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Abstract
Description
一方、特許文献7にもプラズマ反応を用いた複合タングステン酸化物超微粒子の製造方法が記載されている。
そして、複合タングステン酸化物超微粒子のX線回折(本発明において「XRD」と記載する場合がある。)パターンにおいて、ピークトップ強度の比の値が所定の値である複合タングステン酸化物超微粒子を知見した。具体的には、シリコン粉末標準試料(NIST製、640c)の(220)面に係るXRDピーク強度の値を1としたときの、前記複合タングステン酸化物超微粒子のXRDピークトップ強度の比の値が0.13以上である複合タングステン酸化物超微粒子である。
当該複合タングステン酸化物超微粒子は、可視光領域で透明性があり優れた近赤外線遮蔽特性を有しながら、分散液を高い生産性をもって製造可能な汎用性のある複合タングステン酸化物超微粒子であった。
さらに、当該複合タングステン酸化物超微粒子を用いた分散液において、複合タングステン酸化物超微粒子の分散粒子径が200nm以下であれば、ブルーヘイズ現象を抑制できることも知見し本発明を完成した。
近赤外線遮蔽特性を有する複合タングステン酸化物超微粒子であって、
シリコン粉末標準試料(NIST製、640c)の(220)面に係るXRDピーク強度を1としたときの、前記複合タングステン酸化物超微粒子のXRDピークトップ強度の比の値が0.13以上であることを特徴とする複合タングステン酸化物超微粒子である。
第2の発明は、
一般式MxWyOz(但し、Mは、H、He、アルカリ金属、アルカリ土類金属、希土類元素、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、Ybの内から選択される1種以上の元素、Wはタングステン、Oは酸素、0.001≦x/y≦1、2.0<z/y≦3.0)で標記されることを特徴とする第1の発明に記載の複合タングステン酸化物超微粒子である。
第3の発明は、
前記複合タングステン酸化物超微粒子の結晶子径が1nm以上であることを特徴とする第1または2の発明に記載の複合タングステン酸化物超微粒子である。
第4の発明は、
前記複合タングステン酸化物超微粒子が六方晶の結晶構造を含むことを特徴とする第1から3の発明のいずれかに記載の複合タングステン酸化物超微粒子である。
第5の発明は、
前記複合タングステン酸化物超微粒子における揮発成分の含有率が、2.5質量%以下であることを特徴とする第1から4の発明のいずれかに記載の複合タングステン酸化物超微粒子である。
第6の発明は、
第1から5の発明のいずれかに記載の複合タングステン酸化物超微粒子が、液状媒体中に分散して含有されている分散液であって、前記液状媒体は、水、有機溶媒、油脂、液状樹脂、液状プラスチック用可塑剤、高分子単量体から選択される1種以上であることを特徴とする複合タングステン酸化物超微粒子分散液である。
第7の発明は、
前記複合タングステン酸化物超微粒子分散液に含有されている複合タングステン酸化物超微粒子の分散粒子径が、1nm以上200nm以下であることを特徴とする第6の発明に記載の複合タングステン酸化物超微粒子分散液である。
第8の発明は、
前記複合タングステン酸化物超微粒子分散液に含有されている複合タングステン酸化物超微粒子の含有量が、0.01質量%以上80質量%以下であることを特徴とする第6または7の発明に記載の複合タングステン酸化物超微粒子分散液である。
本発明に係る複合タングステン酸化物超微粒子は近赤外線遮蔽特性を有し、シリコン粉末標準試料(NIST製、640c)の(220)面に係るXRDピーク強度の値を1としたときの、前記複合タングステン酸化物超微粒子のXRDピークトップ強度の比の値が0.13以上のものである。
以下、本発明に係る複合タングステン酸化物超微粒子について、(1)XRDピークトップ強度の比、(2)組成、(3)結晶構造、(4)BET比表面積、(5)分散粒子径、(6)揮発成分、(7)まとめ、の順に説明する。
上述した複合タングステン酸化物超微粒子のXRDピークトップ強度の測定には、粉末X線回折法を用いる。このとき、複合タングステン酸化物超微粒子の試料間において、測定結果に客観的な定量性を持たせるため、標準試料を定めて、当該標準試料のピーク強度を測定し、当該標準試料のピーク強度に対する当該超微粒子試料のXRDピークトップ強度の比の値をもって、各超微粒子試料のXRDピークトップ強度を表記することとした。
具体的には、深さ1.0mmの試料ホルダーへ、X線回折測定の際における公知の操作によって超微粒子試料を充填する。具体的には、超微粒子試料において優先方位(結晶の配向)が生じるのを回避する為、ランダム且つ徐々に充填し、尚且つムラなく出来るだけ密に充填することが好ましい。
X線源として、陽極のターゲット材質がCuであるX線管球を45kV/40mAの出力設定で使用し、ステップスキャンモード(ステップサイズ:0.0165°(2θ)および計数時間:0.022m秒/ステップ)のθ-2θの粉末X線回折法で測定することとしたものである。
このとき、X線管球の使用時間によってXRDピーク強度は変化するので、X線管球の使用時間は試料間で殆ど同じであることが望ましい。客観的な定量性を確保するため、X線管球使用時間の試料間の差は、最大でもX線管球の予測寿命の20分の1以下に収めることが必要である。より望ましい測定方法として、複合タングステン酸化物超微粒子のX線回折パターンの測定毎に、シリコン粉末標準試料の測定を実施して、前記XRDピークトップ強度の比を算出する方法が挙げられる。本発明ではこの測定方法を用いた。市販のX線装置のX線管球予測寿命は数千時間以上で且つ1試料当たりの測定時間は数時間以下のものが殆どであるため、上述の望ましい測定方法を実施することで、X線管球使用時間によるXRDピークトップ強度の比への影響を無視できるほど小さくすることが出来る。
また、X線管球の温度を一定とするため、X線管球用の冷却水温度も一定とすることが望ましい。
前記複合タングステン酸化物超微粒子のXRDピークトップ比の値が0.13以上であることは、異相が殆ど含まれていない結晶性の良い複合タングステン酸化物超微粒子が得られていることを表す。即ち、得られる複合タングステン酸化物超微粒子がアモルファス(非晶質)化していないと考えられる。この結果、可視光を透過する有機溶媒などの液体媒体や、可視光を透過する樹脂などの固体媒体へ、当該異相が殆ど含まれていない複合タングステン酸化物超微粒子を分散させることにより、近赤外線遮蔽特性が十分得られると考えられる。
尚、本発明において「異相」とは、複合タングステン酸化物以外の化合物の相をいう。また、XRDピークトップ強度を測定する際に得られるX線回折パターンを解析することで、複合タングステン酸化物微粒子の結晶構造や結晶子径を求めることが出来る。
そして、本発明に係る複合タングステン酸化物超微粒子は、一般式MxWyOz(但し、Mは、H、He、アルカリ金属、アルカリ土類金属、希土類元素、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、Ybの内から選択される1種以上の元素、Wはタングステン、Oは酸素、0.001≦x/y≦1、2.0<z/y≦3.0)で表記される、複合タングステン酸化物超微粒子であることが好ましい。
一般式MxWyOz中のM元素、x、y、zおよびその結晶構造は、複合タングステン酸化物超微粒子の自由電子密度と密接な関係があり、近赤外線遮蔽特性に大きな影響を及ぼす。
ここで本発明者らは、当該タングステン酸化物へ、M元素(但し、M元素は、H、He、アルカリ金属、アルカリ土類金属、希土類元素、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、Ybの内から選択される1種以上の元素を添加して複合タングステン酸化物とすることで、当該複合タングステン酸化物中に自由電子が生成され、近赤外線領域に自由電子由来の遮蔽特性が発現し、波長1000nm付近の近赤外線遮蔽材料として有効なものとなり、且つ、当該複合タングステン酸化物は化学的に安定な状態を保ち、耐候性に優れた近赤外線遮蔽材料として有効なものとなることを知見したものである。さらに、M元素は、Cs、Rb、K、Tl,Ba、Cu、Al、Mn、Inが好ましいこと、なかでも、M元素がCs、Rbであると、当該複合タングステン酸化物が六方晶構造を取り易くなる。この結果、可視光線を透過し、近赤外線を吸収し遮蔽することから、後述する理由により特に好ましいことも知見したものである。
x/yの値が0.001以上であれば、十分な量の自由電子が生成され目的とする近赤外線遮蔽特性を得ることが出来る。そして、M元素の添加量が多いほど、自由電子の供給量が増加し、近赤外線遮蔽特性も上昇するが、x/yの値が1程度で当該効果も飽和する。また、x/yの値が1以下であれば、複合タングステン超微粒子に不純物相が生成されるのを回避できるので好ましい。
一般式MxWyOzで示される複合タングステン酸化物超微粒子において、z/yの値は、2.0<z/y≦3.0であることが好ましく、より好ましくは2.2≦z/y≦3.0であり、さらに好ましくは2.6≦z/y≦3.0、最も好ましくは2.7≦z/y≦3.0である。このz/yの値が2.0以上であれば、当該複合タングステン酸化物中に目的以外であるWO2の結晶相が現れるのを回避することが出来ると伴に、材料としての化学的安定性を得ることが出来るので、有効な赤外線遮蔽材料として適用できるためである。一方、このz/yの値が3.0以下であれば、当該タングステン酸化物中に必要とされる量の自由電子が生成され、効率よい赤外線遮蔽材料となる。
複合タングステン酸化物超微粒子は、六方晶以外に、正方晶、立方晶のタングステンブロンズの構造をとるが、いずれの構造をとるときも近赤外線遮蔽材料として有効である。しかしながら、当該複合タングステン酸化物微超粒子がとる結晶構造によって、近赤外線領域の遮蔽位置が変化する傾向がある。即ち、近赤外線領域の遮蔽位置は、立方晶よりも正方晶のときが長波長側に移動し、六方晶のときは正方晶のときよりも、さらに長波長側へ移動する傾向がある。また、当該遮蔽位置の変動に付随して、可視光線領域の遮蔽は六方晶が最も少なく、次に正方晶であり、立方晶はこの中では最も大きい。
以上の知見から、可視光領域の光をより透過させ、近赤外線領域の光をより遮蔽する用途には、六方晶のタングステンブロンズを用いることが最も好ましい。複合タングステン酸化物超微粒子が六方晶の結晶構造を有する場合、当該微粒子の可視光領域の透過が向上し、近赤外領域の遮蔽が向上する。
複合タングステン酸化物超微粒子が、アモルファス相の体積比率50%未満である単結晶であると、XRDピークトップ強度を維持しながら結晶子径を200nm以下にすることが出来る。複合タングステン酸化物超微粒子の結晶子径を200nm以下とすることで、その分散粒子径を1nm以上200nm以下とすることが出来る。
これに対し、複合タングステン超微粒子において、分散粒子径が1nm以上200nm以下ではあるが、アモルファス相が体積比率で50%以上存在する場合や、多結晶の場合、当該複合タングステン超微粒子のXRDピークトップ強度比の値が0.13未満となり、結果的に、近赤外線吸収特性が不十分で近赤外線遮蔽特性を発現が不十分となる場合がある。
そして、複合タングステン酸化物超微粒子の結晶子径が200nm以下10nm以上であることが、より好ましい。結晶子径が200nm以下10nm以上の範囲であれば、XRDピークトップ強度比の値が0.13を超え、さらに優れた赤外線遮蔽特性が発揮されるからである。
尚、後述する解砕、粉砕または分散された後の複合タングステン酸化物超微粒子分散液中の複合タングステン酸化物超微粒子のX線回折パターンは、本発明に係る複合タングステン酸化物超微粒子分散液中の揮発成分を除去して得られた複合タングステン酸化物超微粒子のX線回折パターンや、前記分散液から得られる分散体中に含まれる複合タングステン酸化物超微粒子のX線回折パターンにおいても維持される。
結果的に、複合タングステン酸化物超微粒子分散液や該分散液から得られる複合タングステン超微粒子分散体中の複合タングステン酸化物超微粒子のXRDパターン、XRDピークトップ強度、結晶子径など結晶の状態が、本発明で用いることができる複合タングステン酸化物超微粒子の結晶の状態であれば、本発明の効果は発揮される。
一方、複合タングステン酸化物超微粒子が、複合タングステン酸化物超微粒子分散体を構成する塗布膜、塗布膜に所定の操作を施して当該塗布膜の樹脂を硬化させた膜(本発明において「硬化膜」と記載する場合がある。)、樹脂等の内部で分散している場合、当該分散している複合タングステン酸化物超微粒子の平均粒子径から結晶子径を引いた差の値が当該平均粒子径の20%以下であれば、当該複合タングステン酸化物超微粒子は、アモルファス相の体積比率50%未満の単結晶であると言える。
ここで、複合タングステン酸化物超微粒子の平均粒子径は、複合タングステン酸化物超微粒子分散体の透過型電子顕微鏡像から画像処理装置を用いて複合タングステン酸化物超微粒子100個の粒子径を測定し、その平均値を算出することで求めることが出来る。そして、複合タングステン酸化物超微粒子分散体に分散された複合タングステン酸化物超微粒子の平均粒子径と結晶子径との差が20%以下になるように、複合タングステン酸化物超微粒子の合成工程、粉砕工程、分散工程を、製造設備に応じて適宜調整すればよい。
上述した複合タングステン酸化物超微粒子のBET比表面積は、当該超微粒子の粒度分布に密接な関係があるが、それと共に、当該超微粒子を原料とする近赤外線遮蔽分散液の生産性や、当該超微粒子自体の近赤外線遮蔽特性や光着色を抑制する耐光性に大きく影響する。
複合タングステン酸化物超微粒子の分散粒子径は、200nm以下であることが好ましく、さらに好ましくは、分散粒子径は、200nm以下10nm以上である。複合タングステン酸化物超微粒子の分散粒子径が、200nm以下であることが好ましいことは、複合タングステン酸化物超微粒子分散液中の複合タングステン酸化物超微粒子においても同様である。これは、当該複合タングステン酸化物超微粒子の結晶子径が、最大でも200nm以下であることが好ましいことに拠る。一方、当該複合タングステン酸化物超微粒子の近赤外線吸収特性の観点から、結晶粒径は1nm以上であることが好ましく、より好ましくは10nm以上である。
上述した複合タングステン酸化物超微粒子は、加熱により揮発する成分(本発明において「揮発成分」と記載する場合がある。)を含む場合がある。当該揮発成分とは、複合タングステン酸化物超微粒子が、保管雰囲気や大気中に暴露された際や、合成工程途中において吸着する成分のことである。ここで、当該揮発成分の具体例としては、水である場合や、後述する分散液の溶媒である場合があり、例えば150℃、またはそれ以下の加熱により、当該複合タングステン酸化物超微粒子から揮発する成分である。
例えば、後述する近赤外線吸収分散体に使用する樹脂と、当該超微粒子に吸着されている揮発成分との相溶性が悪い場合であって、さらに当該超微粒子において当該揮発成分含有量が多い場合、製造される近赤外線吸収分散体のヘイズ発生(透明性悪化)の原因となる可能性がある。また、製造される当該近赤外線吸収分散体が、長期間室外に設置され太陽光や風雨に暴露されたときに、複合タングステン酸化物超微粒子が近赤外線吸収分散体外へと脱離したり、膜の剥がれが生じたりする可能性がある。即ち、当該超微粒子と樹脂との相溶性悪化は、製造される当該近赤外線吸収分散体の劣化の原因となる。つまり、揮発成分を大量に含む複合タングステン酸化物超微粒子は、分散系に用いられる分散媒との相性によって、当該超微粒子の分散が良好であるか否かが、左右される可能性が有るということを意味する。従って、本発明に係る複合タングステン酸化物超微粒子において揮発成分含有率が所定量以下であれば、広い汎用性が発揮される。
一方、当該揮発成分の含有率の下限には、特に制限はないことも知見した。
この結果、揮発成分の含有率が2.5質量%以下である超微粒子が過度に二次凝集していない場合であれば、タンブラー、ナウターミキサー、ヘンシェルミキサー、スーパーミキサー、プラネタリーミキサーなどの混合機、及びバンバリーミキサー、ニーダー、ロール、一軸押出機、二軸押出機などの混練機で均一に混合(溶融混合も含む)する方法を用いて、当該超微粒子を樹脂等に分散可能となる。
以上、詳細に説明した、複合タングステン酸化物超微粒子のXRDピークトップ強度の値やBET比表面積は、所定の製造条件によって制御可能である。具体的には、熱プラズマ法や固相反応法などで該超微粒子が生成される際の温度(焼成温度)、生成時間(焼成時間)、生成雰囲気(焼成雰囲気)、前駆体原料の形態、生成後のアニール処理、不純物元素のドープなどの製造条件の適宜な設定によって制御可能である。一方、複合タングステン酸化物超微粒子の揮発成分の含有率は、当該超微粒子の保存方法や保存雰囲気、当該超微粒子分散液を乾燥させる際の温度、乾燥時間、乾燥方法などの製造条件の適宜な設定によって制御可能である。尚、複合タングステン酸化物超微粒子の揮発成分の含有率は、複合タングステン酸化物超微粒子の結晶構造や、後述する熱プラズマ法や固相反応等の合成方法に依存しない。
本発明に係る複合タングステン酸化物超微粒子の合成方法について説明する。
本発明に係る複合タングステン酸化物超微粒子の合成方法としては、熱プラズマ中にタングステン化合物出発原料を投入する熱プラズマ法や、タングステン化合物出発原料を還元性ガス雰囲気中で熱処理する固相反応法が挙げられる。熱プラズマ法や固相反応法で合成された複合タングステン酸化物微粒子は、分散処理または粉砕・分散処理される。
以下、(1)熱プラズマ法、(2)固相反応法、(3)合成された複合タングステン酸化物超微粒子、の順に説明する。
熱プラズマ法について(i)熱プラズマ法に用いる原料、(ii)熱プラズマ法とその条件、の順に説明する。
本発明に係る複合タングステン酸化物超微粒子を熱プラズマ法で合成する際には、タングステン化合物と、M元素化合物との混合粉体を原料として用いることができる。
タングステン化合物としては、タングステン酸(H2WO4)、タングステン酸アンモニウム、六塩化タングステン、アルコールに溶解した六塩化タングステンに水を添加して加水分解した後溶媒を蒸発させたタングステンの水和物、から選ばれる1種以上であることが好ましい。
また、M元素化合物としては、M元素の酸化物、水酸化物、硝酸塩、硫酸塩、塩化物、炭酸塩、から選ばれる1種以上を用いることが好ましい。
本発明で用いる熱プラズマとして、例えば、直流アークプラズマ、高周波プラズマ、マイクロ波プラズマ、低周波交流プラズマ、のいずれか、または、これらのプラズマの重畳したもの、または、直流プラズマに磁場を印加した電気的な方法により生成するプラズマ、大出力レーザーの照射により生成するプラズマ、大出力電子ビームやイオンビームにより生成するプラズマ、が適用出来る。尤も、いずれの熱プラズマを用いるにしても、10000~15000Kの高温部を有する熱プラズマであり、特に、超微粒子の生成時間を制御できるプラズマであることが好ましい。
その後、反応容器内にプラズマガスとして、アルゴンガス、アルゴンとヘリウムの混合ガス(Ar-He混合ガス)、またはアルゴンと窒素の混合ガス(Ar-N2混合ガス)から選択されるいずれかのガスを30~45L/minの流量で導入する。一方、プラズマ領域のすぐ外側に流すシースガスとして、Ar-He混合ガスを60~70L/minの流量で導入する。
そして、高周波コイル2に交流電流をかけて、高周波電磁場(周波数4MHz)により熱プラズマを発生させる。このとき、プレート電力は30~40kWとする。
また、プラズマガス流量を30L/min以上45L/min以下、シースガス流量を60L/min以上70L/min以下とすることが好ましい。プラズマガスは10000~15000Kの高温部を有する熱プラズマ領域を保つ機能があり、シースガスは反応容器内における石英トーチの内壁面を冷やし、石英トーチの溶融を防止する機能がある。それと同時に、プラズマガスとシースガスはプラズマ領域の形状に影響を及ぼすため、それらのガスの流量はプラズマ領域の形状制御に重要なパラメータとなる。プラズマガスとシースガス流量を上げるほどプラズマ領域の形状がガスの流れ方向に延び、プラズマ尾炎部の温度勾配が緩やかなるので、生成される超微粒子の生成時間を長くし、結晶性の良い超微粒子を生成できるようになる。これにより、本発明に係る複合タングステン酸化物超微粒子のXRDピークトップ強度比の値を所望の値とすることが出来る。逆に、プラズマガスとシースガス流量を下げるほどプラズマ領域の形状がガスの流れ方向に縮み、プラズマ尾炎部の温度勾配が急になるので、生成される超微粒子の生成時間を短くし、BET比表面積の大きい超微粒子を生成できるようになる。これにより本発明に係る複合タングステン酸化物超微粒子のXRDピークトップ強度の比の値を所定の値に設定することが出来る。
熱プラズマ法で合成し得られる複合タングステン酸化物が、その結晶子径が200nmを超える場合や、熱プラズマ法で合成し得られる複合タングステン酸化物から得られる複合タングステン酸化物超微粒子分散液中の複合タングステン酸化物の分散粒子径が200nmを超える場合は、後述する、粉砕・分散処理を行うことができる。熱プラズマ法で複合タングステン酸化物を合成する場合は、そのプラズマ条件や、その後の粉砕・分散処理条件を適宜選択して、XRDピークトップ強度比の値が0.13以上となるようして、複合タングステン酸化物超微粒子分散液の被膜の複合タングステン酸化物超微粒子分散体の複合タングステン酸化物超微粒子の平均粒子径と結晶子径の差が20%以下となるようにすれば、本発明の効果が発揮される。
固相反応法について(i)固相反応法に用いる原料、(ii)固相反応法における焼成とその条件、の順に説明する。
本発明に係る複合タングステン酸化物超微粒子を固相反応法で合成する際には、原料としてタングステン化合物およびM元素化合物を用いる。
タングステン化合物は、タングステン酸(H2WO4)、タングステン酸アンモニウム、六塩化タングステン、アルコールに溶解した六塩化タングステンに水を添加して加水分解した後、溶媒を蒸発させたタングステンの水和物、から選ばれる1種以上であることが好ましい。
また、より好ましい実施形態である一般式MxWyOz(但し、Mは、Cs、Rb、K、Tl、Baから選択される1種類以上の元素、0.001≦x/y≦1、2.0<z/y≦3.0)で示される複合タングステン酸化物超微粒子の原料の製造に用いるM元素化合物には、M元素の酸化物、水酸化物、硝酸塩、硫酸塩、塩化物、炭酸塩、から選ばれる1種以上であることが好ましい。
また、Si、Al、Zrから選ばれる1種以上の不純物元素を含有する化合物(本発明において「不純物元素化合物」と記載する場合がある。)を、原料として含んでもよい。当該不純物元素化合物は、後の焼成工程において複合タングステン化合物と反応せず、複合タングステン酸化物の結晶成長を抑制して、結晶の粗大化を防ぐ働きをするものである。不純物元素を含む化合物は、酸化物、水酸化物、硝酸塩、硫酸塩、塩化物、炭酸塩、から選ばれる1種以上であることが好ましく、粒径が500nm以下のコロイダルシリカやコロイダルアルミナが特に好ましい。
当該湿式混合で製造したM元素化合物とタングステン化合物との混合粉体、もしくは不純物元素化合物を含むM元素化合物とタングステン化合物との混合粉体を、不活性ガス単独または不活性ガスと還元性ガスとの混合ガス雰囲気下、1段階で焼成する。このとき、焼成温度は複合タングステン酸化物超微粒子が結晶化し始める温度に近いことが好ましく、具体的には焼成温度が1000℃以下であることが好ましく、800℃以下であることがより好ましく、800℃以下500℃以上の温度範囲がさらに好ましい。この焼成温度の制御により、本発明に係る複合タングステン酸化物超微粒子のXRDピークトップ強度の比の値を所定の値に設定することが出来る。
尤も、当該複合タングステン酸化物超微粒子の合成において、前記タングステン化合物に替えて、三酸化タングステンを用いても良い。
熱プラズマ法や固相反応法による合成法で得られた複合タングステン酸化物超微粒子を用いて、後述する複合タングステン酸化物超微粒子分散液を作製した場合、当該分散液に含有されている超微粒子の分散粒子径が、200nmを超える場合は、後述する複合タングステン酸化物微粒子分散液を製造する工程において、粉砕・分散処理すればよい。そして、粉砕・分散処理を経て得られた複合タングステン酸化物超微粒子のXRDピークトップ強度の比の値が、本発明の範囲を実現できていれば、本発明に係る複合タングステン酸化物超微粒子やその分散液から得られる複合タングステン酸化物超微粒子分散体は、優れた近赤外線遮蔽特性を実現できるのである。
上述したように、本発明に係る複合タングステン酸化物超微粒子は、揮発成分を含む場合があるが、当該揮発成分の含有率は2.5質量%以下であることが好ましい。しかし、複合タングステン酸化物超微粒子が大気中に暴露されるなどして、揮発成分の含有率が2.5質量%を超えた場合は、乾燥処理により当該揮発成分の含有率を低減させることが出来る。
具体的には、上述の方法で合成された複合タングステン酸化物を、粉砕・分散処理して微粒化し、複合タングステン酸化物超微粒子分散液を製造する工程(粉砕・分散処理工程)と、製造された複合タングステン酸化物超微粒子分散液を乾燥処理して溶媒を除去する工程(乾燥工程)とを経ることで、本発明に係る複合タングステン酸化物超微粒子を製造することができる。
当該乾燥処理の工程は、後述する粉砕分散工程で得られる複合タングステン酸化物超微粒子分散液を、乾燥処理して当該分散液中の揮発成分を除去し、本発明に係る複合タングステン酸化物超微粒子を得るものである。
以下、その一例として、(1)大気乾燥機による乾燥処理、(2)真空流動乾燥機による乾燥処理、(3)噴霧乾燥機による乾燥処理、について説明する。以下、それぞれの乾燥処理について順に説明する。
後述する方法で得られた複合タングステン酸化物超微粒子分散液を、大気乾燥機によって乾燥処理して当該分散液中の揮発成分を除去する処理方法である。この場合、複合タングステン酸化物超微粒子から当該揮発成分が揮発するよりも高い温度であって、元素Mが脱離しない温度で乾燥処理することが望ましく、150℃以下であることが望ましい。
当該大気乾燥機により、乾燥処理して製造した複合タングステン酸化物超微粒子は、弱い二次凝集体となっている。この状態でも、当該複合タングステン酸化物超微粒子を樹脂等に分散させることは可能であるが、より分散し易くするために、当該超微粒子を擂潰機等によって解砕することも好ましい一例である。
真空流動乾燥機による乾燥処理を行うことで、複合タングステン酸化物超微粒子分散液中の揮発成分を除去する処理方法である。当該真空流動乾燥機では、減圧雰囲気下で乾燥と解砕の処理を同時に行うため、乾燥速度が速い上に、上述した大気乾燥機での乾燥処理品に見られるような凝集体を形成しない。また、減圧雰囲気下での乾燥のため、比較的低温でも揮発成分を除去することができ、残存する揮発成分量も限りなく少なくすることができる。
乾燥温度は複合タングステン酸化物超微粒子から元素Mが脱離しない温度で乾燥処理することが望ましく、当該揮発成分が揮発するよりも高い温度であって、150℃以下であることが望ましい。
噴霧乾燥機による乾燥処理を行うことで、複合タングステン酸化物超微粒子分散液の揮発成分を除去する処理方法である。当該噴霧乾燥機では、乾燥処理における揮発成分除去の際に、揮発成分の表面力に起因する二次凝集が発生しにくく、解砕処理を施さずとも比較的二次凝集していない複合タングステン酸化物超微粒子が得られる。
本発明に係る複合タングステン酸化物超微粒子分散液は、上述した合成製造方法で得られた複合タングステン酸化物超微粒子と、水、有機溶媒、油脂、液状樹脂、プラスチック用の液状可塑剤、高分子単量体またはこれらの混合物から選択される混合スラリーの液状媒体、および適量の分散剤、カップリング剤、界面活性剤等を、媒体攪拌ミルで粉砕、分散させたものである。
そして、当該溶媒中における複合タングステン酸化物超微粒子の分散状態が良好で、その分散粒子径が1~200nmであることが好ましい。また、当該複合タングステン酸化物超微粒子分散液に含有されている複合タングステン酸化物超微粒子の含有量が、0.01質量%以上80質量%以下であることが好ましい。
以下、本発明に係る複合タングステン酸化物超微粒子分散液について(1)溶媒、(2)分散剤、(3)分散方法、(4)バインダー、(5)添加剤、(6)コーティング膜、(7)塗布方法、(8)基材樹脂への混合方法、の順に説明する。
複合タングステン酸化物超微粒子分散液に用いられる液状溶媒は特に限定されるものではなく、複合タングステン酸化物超微粒子分散液の塗布条件、塗布環境、および、適宜添加される無機バインダーや樹脂バインダーなどに合わせて適宜選択すればよい。例えば、液状溶媒は、水、有機溶媒、油脂、液状樹脂、プラスチック用の液状可塑剤、高分子単量体または、これらの混合物などである。
以上、説明した溶媒は、1種または2種以上を組み合わせて用いることができる。さらに、必要に応じて、これらの溶媒へ酸やアルカリを添加してpH調整してもよい。
プラスチック用の液状可塑剤としては、カルボン酸エステル系やリン酸エステル系等に代表される公知の液状可塑剤を用いることができる。
高分子単量体としては、重合等により高分子を形成する。本発明で用いることがメチルメタクリレート単量体、アクレリート単量体やスチレン樹脂単量体などが挙げられる。
さらに、当該複合タングステン酸化物超微粒子分散液中における複合タングステン酸化物超微粒子の分散安定性を一層向上させ、再凝集による分散粒子径の粗大化を回避するために、各種の分散剤、界面活性剤、カップリング剤などを添加することも好ましい。当該分散剤、カップリング剤、界面活性剤は用途に合わせて選定可能であるが、アミンを含有する基、水酸基、カルボキシル基、または、エポキシ基を官能基として有するものであることが好ましい。これらの官能基のいずれかを分子中にもつ高分子系分散剤は、さらに望ましい。
これらの官能基は、複合タングステン酸化物超微粒子の表面に吸着して凝集を防ぎ、近赤外線遮蔽膜中においても本発明に係る複合タングステン酸化物超微粒子を均一に分散させる効果を持つ。
当該複合タングステン酸化物超微粒子分散液を、適宜な方法で透明基材上に塗布、または、基材に練り込むことで、高い可視光透過率と、低い日射透過率を有しながら、ヘイズ値が低いという近赤外線遮蔽特性を有する複合タングステン酸化物超微粒子分散体を形成することができる。
当該複合タングステン酸化物超微粒子分散液を透明基材上に塗布し固着させて被膜形成した複合タングステン酸化物超微粒子分散体は、基材上に複合タングステン酸化物超微粒子のみが堆積した膜の構造になる。この膜は、このままでも近赤外線遮蔽効果を示すが、上述した複合タングステン酸化物超微粒子分散液の製造工程において、複合タングステン酸化物超微粒子の分散時に無機バインダー、樹脂バインダーから選ばれる1種以上を添加するのも好ましい構成である。複合タングステン酸化物超微粒子分散液へ当該バインダーを添加することで、製造される複合タングステン酸化物超微粒子分散体において、当該バインダーの添加量の加減による可視光透過率などの光学特性制御が可能になると伴に、基材上へ塗布、硬化後における複合タングステン酸化物超微粒子の基材への密着性が向上し、さらに膜の硬度を向上させる効果があるからである。
また、本発明に係る複合タングステン酸化物超微粒子分散体の近赤外線遮蔽特性を向上させるために、本発明に係る分散液へ一般式XBm(但し、Xはアルカリ土類元素、またはイットリウムを含む希土類元素から選ばれた金属元素、4≦m≦6.3)で表されるホウ化物超微粒子を、所望に応じて適宜添加することも好ましい構成である。尚、このときの添加割合は、所望とする近赤外線遮蔽特性に応じて適宜選択すればよい。
また、複合タングステン酸化物超微粒子分散体の色調を調整する為に、カーボンブラックや弁柄等の、公知の無機顔料や公知の有機顔料も添加できる。
複合タングステン酸化物超微粒子分散液には、公知の紫外線吸収剤や有機物の公知の近赤外線遮蔽材やリン系の着色防止剤を添加してもよい。
基材上に複合タングステン酸化物超微粒子分散液が被膜形成した膜上へ、珪素、ジルコニウム、チタン、アルミニウムのいずれか1種以上を含むアルコキシド、および/または、当該アルコキシドの部分加水分解縮重合物、を含有する塗布液を塗布した後、加熱することで、当該膜上へ、珪素、ジルコニウム、チタン、アルミニウムのいずれか1種以上を含む酸化物のコーティング膜を形成し、多層膜とするのも好ましい構成である。当該構成を採ることにより、コーティングされた成分が、第1層である複合タングステン酸化物超微粒子の堆積した間隙を埋めて成膜され、可視光の屈折を抑制するために、膜のヘイズ値がより低減して可視光透過率が向上し、また複合タングステン酸化物超微粒子の基材への結着性が向上するからである。ここで、複合タングステン酸化物超微粒子単体あるいは複合タングステン酸化物超微粒子を主成分とする膜上に、珪素、ジルコニウム、チタン、アルミニウムのいずれか1種以上を含むアルコキシドや、これらの部分加水分解縮重合物からなるコーティング膜を形成する方法としては、成膜操作の容易さやコストの観点から塗布法が便宜である。
無機バインダーやコーティング膜として、珪素、ジルコニウム、チタン、もしくはアルミニウムの金属アルコキシドおよびその加水分解重合物を含む複合タングステン酸化物超微粒子分散液の塗布後の基材加熱温度は、100℃以上が好ましく、さらに好ましくは塗布液中の溶媒の沸点以上で加熱を行う。これは、基材加熱温度が100℃以上であると、塗膜中に含まれる金属アルコキシドまたは当該金属アルコキシドの加水分解重合物の重合反応が完結出来るからである。また、基材加熱温度が100℃以上であると、溶媒である水や有機溶媒が膜中に残留することがないので、加熱後の膜において、これら溶媒が可視光透過率低減の原因とならないからである。
また、上述した基材への塗布とは別に、本発明に係る複合タングステン酸化物超微粒子や複合タングステン酸化物超微粒子分散液を、基材樹脂へ混合して練り込むことも出来る。
基材の樹脂へ、上述した複合タングステン酸化物超微粒子または複合タングステン酸化物超微粒子分散液を練り込むときは、当該複合タングステン酸化物超微粒子が樹脂中に均一に分散する方法であれば公知の方法を適宜選択すればよい。さらに、当該樹脂の融点付近の温度で溶融混合した後ペレット化し、公知の各方式で板状、シート状、またはフィルム状、等、種々の形状に成形することが可能である。
当該樹脂としては、例えばPET樹脂、アクリル樹脂、ポリアミド樹脂、塩化ビニル樹脂、ポリカーボネート樹脂、オレフィン樹脂、エポキシ樹脂、ポリイミド樹脂、フッ素樹脂などが挙げられる。
尚、実施例および比較例中の分散液、塗布膜および硬化膜の光学特性は、分光光度計(日立製作所株式会社製U-4100)を用いて測定し、可視光透過率と日射透過率は、JISR3106に従って算出した。また、分散粒子径は、動的光散乱法に基づく粒径測定装置(大塚電子株式会社製ELS-8000)により測定した平均値をもって示した。複合タングステン酸化物超微粒子分散体である硬化膜中に分散された複合タングステン酸化物超微粒子の平均粒子径は、当該硬化膜の断面の透過型電子顕微鏡像を観察することによって測定した。透過型電子顕微鏡像は、透過型電子顕微鏡(株式会社日立ハイテクノロジーズ製 HF-2200)を用いて観察した。当該透過型電子顕微鏡像を画像処理装置にて処理し、複合タングステン酸化物超微粒子100個の粒子径を測定して、その平均値を平均粒子径とした。X線回折パターンは、粉末X線回折装置(スペクトリス株式会社PANalytical製X‘Pert-PRO/MPD)を用いて粉末X線回折法(θ―2θ法)により測定した。また、客観的な定量性を確保するため、複合タングステン酸化物超微粒子のX線回折パターンの測定毎に、シリコン粉末標準試料のX線回折パターンの測定を実施して、都度ピーク強度の比を算出した。
水0.330kgにCs2CO30.216kgを溶解し、これをH2WO41.000kgに添加して十分攪拌した後、乾燥し、狙いの組成であるCs0.33WO3混合粉体を得た。
その結果、混合粉体は熱プラズマ中にて瞬時に蒸発し、プラズマ尾炎部に至る過程で急冷凝固して超微粒化した。当該生成した超微粒子は、回収フィルターに堆積した。
一方、シリコン粉末標準試料(NIST製、640c)を準備し、当該シリコン粉末標準試料における(220)面を基準としたピーク強度の値を測定したところ、19800カウントであった。従って、当該標準試料のピーク強度の値を1としたときの、実施例1に係る粉砕分散処理後の複合タングステン酸化物超微粒子のXRDピーク強度の比の値は0.15であることが判明した。
また、実施例1に係る粉砕分散処理後の複合タングステン酸化物超微粒子の結晶子径は16.9nmであった。
実施例1で得られた複合タングステン酸化物超微粒子分散液に紫外線硬化樹脂および溶媒のメチルイソブチルケトンと混合し、厚さ3mmのガラス基板上にバーコーター(井元製作所製IMC-700)で塗布して塗布膜を形成し、この塗布膜から溶媒を蒸発させた後、紫外線照射して、塗布膜を硬化させた複合タングステン酸化物超微粒子分散体である硬化膜を得た。このとき、硬化膜の可視光透過率が70%になるように予め溶媒のメチルイソブチルケトンによる希釈で分散液の濃度を調整した。
実施例2に係る硬化膜のヘイズを、ヘイズメーター(村上色彩技術研究所製HM-150)を用いて、JISK7105に基づき測定したところ、0.4%であった。また、得られた実施例2に係る硬化膜の透過率を、分光光度計(日立製作所製U-4100)により波長200nm~2600nmの範囲において5nmの間隔で測定した結果、図3に示す透過プロファイルが得られた。得られた透過プロファイルから日射透過率を求めたところ、36.5%であった。また、人工太陽照明灯(セリック株式会社製XC-100)を用いて疑似太陽光を実施例2に係る硬化膜に照射して、ブルーヘイズ現象の有無を目視で確認し、ブルーヘイズ現象がないことを確認した。
キャリアガス流量、プラズマガス流量、シースガス流量、原料供給速度を変更したこと以外は、実施例1~2と同様の操作をすることで、実施例3~7に係る複合タングステン酸化物超微粒子と複合タングステン酸化物超微粒子分散液を製造した。変更したキャリアガス流量条件と原料供給速度条件、およびその他の条件を表1に記載する。実施例3~7に係る複合タングステン酸化物超微粒子と複合タングステン酸化物超微粒子分散液とその塗布膜とその硬化膜とに対して、実施例1および2と同様の評価を実施した。当該評価結果を表2に示す。
実施例1に記載のCs2CO3とH2WO4との混合粉体を、窒素ガスと水素ガスとの混合ガス雰囲気下、800℃で焼成したCs0.33WO3で表される複合タングステン酸化物に変更して、高周波プラズマ反応装置に投入する原料として用いた。それ以外は実施例1~2と同様の方法で実施例8に係る複合タングステン酸化物超微粒子と複合タングステン酸化物超微粒子分散液を製造した。得られた超微粒子とその分散液に対して、実施例1~7と同様の評価を実施した。当該製造条件と評価結果を表1、2に示す。
キャリアガス流量と原料供給速度を変更したこと以外は、実施例8と同様の操作をすることで、実施例9に係る複合タングステン酸化物超微粒子と複合タングステン酸化物超微粒子分散液を製造した。得られた超微粒子とその分散液とその塗布膜とその硬化膜とに対して、実施例1~8と同様の評価を実施した。当該評価結果を表1、2に示す。
水0.330kgにRb2CO30.148kgを溶解し、これをH2WO41.000kgに添加して十分攪拌した後、乾燥し、狙いの組成であるRb0.32WO3混合粉体を得た。
水0.330kgにK2CO30.375kgを溶解し、これをH2WO41.000kgに添加して十分攪拌した後、乾燥し、狙いの組成であるK0.27WO3混合粉体を得た。
水0.330kgにTlNO30.320kgを溶解し、これをH2WO41.000kgに添加して十分攪拌した後、乾燥し、狙いの組成であるTl0.19WO3混合粉体を得た。
水0.330kgにBaCO30.111kgを溶解し、これをH2WO41.000kgに添加して十分攪拌した後、乾燥し、狙いの組成であるBa0.14WO3混合粉体を得た。
水0.330kgにK2CO30.0663kgとCs2CO30.0978kgを溶解し、これをH2WO41.000kgに添加して十分攪拌した後、乾燥し、狙いの組成であるK0.24Cs0.15WO3混合粉体を得た。
水16.5gにCs2CO310.8gを溶解し、当該溶液をH2WO450gに添加して十分攪拌した後、乾燥した。当該乾燥物へN2ガスをキャリアーとした2%H2ガスを供給しながら加熱し、800℃の温度で30分間焼成した。その後、N2ガス雰囲気下800℃で90分間焼成する固相法にて実施例15に係る複合タングステン酸化物超微粒子を得た。
これ以外は実施例1と同様にして、実施例15に係る複合タングステン酸化物超微粒子分散液を製造した。但し、媒体攪拌ミルによる粉砕・分散処理時間は4時間とした。得られた超微粒子とその分散液とその塗布膜とその硬化膜とに対して、実施例1~14と同様の評価を実施した。当該製造条件と評価結果を表1、2に示す。尚、BET比表面積は、粉砕・分散処理前の値である。
水0.330kgにLi2CO30.044kgを溶解し、これをH2WO41.000kgに添加して十分攪拌した後、乾燥し、狙いの組成であるLi0.3WO3の実施例16に係る混合粉体を得た。
水0.330kgにCs2CO30.216kgを溶解し、得られた溶液をH2WO41.000kgに添加して十分攪拌した後、乾燥して乾燥物を得た。N2ガスをキャリアーとした5%H2ガスを供給しながら当該乾燥物を加熱し、800℃の温度で1時間焼成した。その後、さらにN2ガス雰囲気下800℃で2時間焼成する固相反応法を実施して、複合タングステン酸化物を得た。
実施例26に係る複合タングステン酸化物超微粒子水分散液の分散粒子径を測定したところ、70nmであった。尚、分散粒子径測定の設定として、粒子屈折率は1.81とし、粒子形状は非球形とした。また、バックグラウンドは水で測定し、溶媒屈折率は1.33とした。
得られた超微粒子の組成を、ICP発光分析法により調べた。その結果、Cs濃度が15.2質量%、W濃度が64.6質量%であり、Cs/Wのモル比は0.33であった。CsとW以外の残部は酸素であり、1質量%以上含有されるその他不純物元素は存在していないことを確認した。
次に、得られた複合タングステン酸化物超微粒子分散液をメチルイソブチルケトンで分光光度計の測定用ガラスセルにて可視光透過率が70%となるように希釈し、分光光度計(日立製作所製U-4100)により波長200nm~2600nmの範囲において5nmの間隔で測定して日射透過率を算出したところ、34.1%であった。尚、可視光透過率、日射透過率はJISR3106に基づき算出した。また、当該測定において、分光光度計の光の入射方向は測定用ガラスセルに垂直な方向とした。また、当該測定用ガラスセルに溶媒のメチルイソブチルケトンのみを入れたブランク液を、光の透過率のベースラインとしている。
得られた実施例26に係る硬化膜のヘイズを測定したところ、0.3%であった。また、得られた実施例1に係る硬化膜の透過率を、波長200nm~2600nmの範囲において5nmの間隔で測定し、図3に示す透過プロファイルが得られた。得られた透過プロファイルから日射透過率を求めたところ、35.7%であった。また、実施例26に係る硬化膜のブルーヘイズ現象の有無を、実施例2と同様に目視で確認し、ブルーヘイズ現象がないことを確認した。
実施例26に係る複合タングステン酸化物超微粒子の製造条件と分散液と塗布膜と硬化膜との評価結果とを、表1および表2に示す。
大気乾燥機による乾燥処理を、真空攪拌擂潰機による真空乾燥処理に変更した以外は、実施例26と同様の方法で実施例27に係る複合タングステン酸化物超微粒子と、複合タングステン酸化物超微粒子分散液とを製造した。真空攪拌擂潰機は石川式攪拌擂潰機24P型(田島化学機械株式会社製)を使用し、真空乾燥処理における乾燥温度は80℃、乾燥時間は32時間、混練ミキサーの回転周波数は40Hz、真空容器内の圧力は0.001MPa以下とした。得られた超微粒子とその分散液とその塗布膜とその硬化膜とに対して、実施例1~2と同様の評価を実施した。当該製造条件と評価結果とを表1、2に示す。
大気乾燥機による乾燥処理を、噴霧乾燥機による噴霧乾燥処理に変更した以外は、実施例26と同様の方法で実施例28に係る複合タングステン酸化物超微粒子と、複合タングステン酸化物超微粒子分散液とを製造した。噴霧乾燥機は噴霧乾燥機ODL-20型(大川原化工機株式会社製)を使用した。得られた超微粒子とその分散液とその塗布膜とその硬化膜とその硬化膜とに対して、実施例1~2と同様の評価を実施した。当該製造条件と評価結果とを表1、2に示す。
媒体攪拌ミルによる粉砕分散処理時間を2時間に変更した以外は、実施例26~28と同様の方法で実施例29~31に係る複合タングステン酸化物超微粒子と、複合タングステン酸化物超微粒子分散液とを製造した。但し、媒体攪拌ミルによる粉砕分散処理時間は2時間とした。得られた超微粒子とその分散液とその塗布膜とその硬化膜とに対して、実施例1~2と同様の評価を実施した。当該製造条件と評価結果とを表1、2に示す。
スラリーの調製の際、複合タングステン酸化物20重量部と、プロピレングリコールモノエチルエーテル80重量部とを混合したこと以外は、上述した実施例29~31と同様の合成製造方法により、実施例32~34に係る複合タングステン酸化物超微粒子と複合タングステン酸化物超微粒子分散液とを製造した。得られた実施例32~34に係る超微粒子とその分散液とその塗布膜とその硬化膜とに対して、実施例1~2と同様の評価を実施した。尚、分散粒子径を測定する際に、バックグラウンドはプロピレングリコールモノエチルエーテルで測定し、溶媒屈折率は1.40とした。当該製造条件と評価結果とを表1、2に示す。
実施例1に係る方法と同様にして複合タングステン酸化物超微粒子を得た。その後、得られた超微粒子20重量と、メチルイソブチルケトン64重量部と、分散剤a16重量部とを混合し、50gのスラリーを調製した。このスラリーへ、超音波ホモジナイザー(株式会社日本精機製作所製US-600TCVP)によって1時間分散処理を行い、実施例35に係る複合タングステン酸化物超微粒子分散液を得た。実施例35に係る複合タングステン酸化物超微粒子分散液とその塗布膜とその硬化膜とに対して、実施例1~2と同様の評価を実施した。当該評価結果を表2に示す。
キャリアガス流量、プラズマガス流量、シースガス流量、原料供給速度を変更したこと以外は、実施例1と同様の操作をすることで、比較例1、2に係る複合タングステン酸化物超微粒子と複合タングステン酸化物超微粒子分散液を製造した。変更したキャリアガス流量条件と原料供給速度条件、およびその他の条件を表1に記載する。得られた超微粒子とその分散液とその塗布膜とその硬化膜とに対して、実施例1~2と同様の評価を実施した。当該評価結果を表2に示す。
5000~10000Kの高温部を有している熱プラズマを発生させるために、高周波電力を15KWとした以外は、実施例1と同様の操作をすることで、比較例3に係る複合タングステン酸化物超微粒子と複合タングステン酸化物超微粒子分散液を製造した。得られた超微粒子とその分散液とその塗布膜とその硬化膜とに対して、実施例1~2と同様の評価を実施した。当該製造条件と評価結果を表1、2に示す。
実施例26に係る複合タングステン酸化物超微粒子水分散液を4時間の粉砕分散処理時間で得るところを、40時間の粉砕分散処理とした以外は、実施例26と同様の操作を行って、比較例4に係る複合タングステン酸化物超微粒子水分散液を得た。比較例4に係る複合タングステン酸化物超微粒子水分散液の分散粒子径を測定したところ、120nmであった。尚、分散粒子径測定の設定として、粒子屈折率は1.81とし、粒子形状は非球形とした。また、バックグラウンドは水で測定し、溶媒屈折率は1.33とした。
比較例4に係る複合タングステン酸化物超微粒子のX線回折パターンを測定し、相の同定を行った結果、得られた超微粒子は、六方晶Cs0.33WO3単相と同定された。また、得られた超微粒子のX線回折パターンのピークトップ強度の値は1300カウント、ピーク位置は2θ=27.8°であり、結晶子径は8.1nmであった。一方、シリコン粉末標準試料(NIST製、640c)を準備し、当該シリコン粉末標準試料における(220)面を基準としたピーク強度の値を測定したところ、19800カウントであった。従って、当該標準試料のピーク強度の値を1としたときの、実施例1に係る粉砕分散処理後の複合タングステン酸化物超微粒子のXRDピーク強度の比の値は0.07であることが判明した。
また、比較例4に係る複合タングステン酸化物超微粒子の揮発成分の含有率を測定したところ2.2質量%であった。
次に、比較例4に係る複合タングステン酸化物超微粒子分散液をメチルイソブチルケトンで分光光度計の測定用ガラスセルにて可視光透過率が70%となるように希釈し、分光光度計(日立製作所製U-4100)により波長200nm~2600nmの範囲において5nmの間隔で測定して日射透過率を算出したところ、47.2%であった。尚、可視光透過率、日射透過率はJISR3106に基づき算出した。また、当該測定において、分光光度計の光の入射方向は測定用ガラスセルに垂直な方向とした。また、当該測定用ガラスセルに溶媒のメチルイソブチルケトンのみを入れたブランク液を、光の透過率のベースラインとしている。
得られた比較例4に係る硬化膜のヘイズを測定したところ、1.8%であった。また、得られた比較例4に係る硬化膜の透過率を、波長200nm~2600nmの範囲において5nmの間隔で測定し、得られた透過プロファイルから日射透過率を求めたところ、48.3%であった。また、比較例4に係る硬化膜のブルーヘイズ現象の有無を、実施例2と同様に目視で確認し、ブルーヘイズ現象があることを確認した。
比較例4に係る複合タングステン酸化物超微粒子の製造条件と分散液と塗布膜と硬化膜との評価結果とを、表1および表2に示す。
表2から明らかなように、実施例1~35に係る複合タングステン酸化物超微粒子は、比較例1~4の複合タングステン酸化物超微粒子と比べて、日射透過率が47%以下の優れた近赤外線遮蔽特性を発揮した。
そして、実施例2~35に係る分散液に含まれる複合タングステン酸化物超微粒子は、シリコン粉末標準試料(NIST製、640c)(220)面のXRDピーク強度に対する前期複合タングステン酸化物超微粒子のXRDピークトップ強度の比が0.13以上であり、結晶子径が1nm以上であり、異相の無い複合タングステン酸化物超微粒子であった。また、実施例においては硬化膜中の複合タングステン酸化物超微粒子の平均粒子径と結晶子径とがほぼ同値であることから、アモルファス相の体積比率が50%未満である単結晶の複合タングステン酸化物超微粒子であると考えられる。一方、比較例1、2、4においては、硬化膜中の複合タングステン酸化物超微粒子の平均粒子径が結晶子径よりも大きいことから、これらの複合タングステン酸化物超微粒子は、単結晶ではないと考えられる。また、比較例3においては異相(WO2とW)が発生していた。
2 高周波コイル
3 シースガス供給ノズル
4 プラズマガス供給ノズル
5 原料粉末供給ノズル
6 反応容器
7 吸引管
8 フィルター
Claims (8)
- 近赤外線遮蔽特性を有する複合タングステン酸化物超微粒子であって、
シリコン粉末標準試料(NIST製、640c)の(220)面に係るXRDピーク強度を1としたときの、前記複合タングステン酸化物超微粒子のXRDピークトップ強度の比の値が0.13以上であることを特徴とする複合タングステン酸化物超微粒子。 - 一般式MxWyOz(但し、Mは、H、He、アルカリ金属、アルカリ土類金属、希土類元素、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、Ybの内から選択される1種以上の元素、Wはタングステン、Oは酸素、0.001≦x/y≦1、2.0<z/y≦3.0)で標記されることを特徴とする請求項1に記載の複合タングステン酸化物超微粒子。
- 前記複合タングステン酸化物超微粒子の結晶子径が1nm以上であることを特徴とする請求項1または2に記載の複合タングステン酸化物超微粒子。
- 前記複合タングステン酸化物超微粒子が六方晶の結晶構造を含むことを特徴とする請求項1から3のいずれかに記載の複合タングステン酸化物超微粒子。
- 前記複合タングステン酸化物超微粒子における揮発成分の含有率が、2.5質量%以下であることを特徴とする請求項1から4のいずれかに記載の複合タングステン酸化物超微粒子。
- 請求項1から5のいずれかに記載の複合タングステン酸化物超微粒子が、液状媒体中に分散して含有されている分散液であって、前記液状媒体は、水、有機溶媒、油脂、液状樹脂、液状プラスチック用可塑剤、高分子単量体から選択される1種以上であることを特徴とする複合タングステン酸化物超微粒子分散液。
- 前記複合タングステン酸化物超微粒子分散液に含有されている複合タングステン酸化物超微粒子の分散粒子径が、1nm以上200nm以下であることを特徴とする請求項6に記載の複合タングステン酸化物超微粒子分散液。
- 前記複合タングステン酸化物超微粒子分散液に含有されている複合タングステン酸化物超微粒子の含有量が、0.01質量%以上80質量%以下であることを特徴とする請求項6または7に記載の複合タングステン酸化物超微粒子分散液。
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02136230A (ja) | 1988-11-16 | 1990-05-24 | Takiron Co Ltd | 赤外線吸収性合成樹脂成型品 |
JPH08259279A (ja) | 1995-01-23 | 1996-10-08 | Central Glass Co Ltd | 合せガラス及びその製造方法 |
JPH11181336A (ja) | 1997-09-30 | 1999-07-06 | Sumitomo Metal Mining Co Ltd | 選択透過膜用塗布液、選択透過膜および選択透過多層膜 |
WO2005037932A1 (ja) | 2003-10-20 | 2005-04-28 | Sumitomo Metal Mining Co., Ltd. | 赤外線遮蔽材料微粒子分散体、赤外線遮蔽体、及び赤外線遮蔽材料微粒子の製造方法、並びに赤外線遮蔽材料微粒子 |
JP2005187323A (ja) * | 2003-12-05 | 2005-07-14 | Sumitomo Metal Mining Co Ltd | 日射遮蔽体形成用タングステン酸化物微粒子の製造方法、日射遮蔽体形成用タングステン酸化物微粒子および日射遮蔽体形成用分散液並びに日射遮蔽体 |
JP2009215487A (ja) | 2008-03-12 | 2009-09-24 | Sumitomo Metal Mining Co Ltd | 赤外線遮蔽材料微粒子分散液、赤外線遮蔽膜と赤外線遮蔽光学部材およびプラズマディスプレイパネル用近赤外線吸収フィルター |
JP2010265144A (ja) | 2009-05-15 | 2010-11-25 | Sumitomo Metal Mining Co Ltd | 複合タングステン酸化物超微粒子の製造方法 |
JP2012506463A (ja) | 2008-10-23 | 2012-03-15 | データレース リミテッド | 熱吸収添加剤 |
JP2012532822A (ja) * | 2009-07-07 | 2012-12-20 | ビーエーエスエフ ソシエタス・ヨーロピア | カリウム・セシウム・タングステンブロンズ粒子 |
WO2015186663A1 (ja) * | 2014-06-05 | 2015-12-10 | 日清エンジニアリング株式会社 | タングステン複合酸化物粒子の製造方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6060154A (en) | 1997-09-30 | 2000-05-09 | Sumitomo Metal Mining Co., Ltd. | Coating liquid for selective permeable membrane, selective permeable membrane and selective permeable multilayered membrane |
CN101023498B (zh) * | 2004-08-31 | 2012-02-29 | 住友金属矿山株式会社 | 导电性粒子、可见光透过型粒子分散导电体及其制造方法、透明导电薄膜及其制造方法、使用它的透明导电物品、红外线屏蔽物品 |
BRPI0514795B1 (pt) * | 2004-08-31 | 2018-05-08 | Sumitomo Metal Mining Co | condutor elétrico dispersado em partícula que transmite luz visível, e, película eletrocondutora transparente |
JP5176492B2 (ja) * | 2007-11-06 | 2013-04-03 | 住友金属鉱山株式会社 | 近赤外線吸収粘着体、プラズマディスプレイパネル用近赤外線吸収フィルターおよびプラズマディスプレイパネル |
CN102282229B (zh) * | 2008-11-13 | 2015-05-06 | 住友金属矿山株式会社 | 红外线屏蔽用微粒及其制造方法、以及使用该红外线屏蔽用微粒的红外线屏蔽用微粒分散体、红外线屏蔽用基体材料 |
JP5493225B2 (ja) | 2009-11-02 | 2014-05-14 | 平岡織染株式会社 | 近赤外線遮蔽性シート及びその製造方法 |
JP5942466B2 (ja) | 2012-02-22 | 2016-06-29 | 住友金属鉱山株式会社 | 複合タングステン酸化物微粒子分散ポリカーボネート樹脂組成物およびそれを用いた熱線遮蔽成形体並びに熱線遮蔽積層体 |
-
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Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02136230A (ja) | 1988-11-16 | 1990-05-24 | Takiron Co Ltd | 赤外線吸収性合成樹脂成型品 |
JPH08259279A (ja) | 1995-01-23 | 1996-10-08 | Central Glass Co Ltd | 合せガラス及びその製造方法 |
JPH11181336A (ja) | 1997-09-30 | 1999-07-06 | Sumitomo Metal Mining Co Ltd | 選択透過膜用塗布液、選択透過膜および選択透過多層膜 |
WO2005037932A1 (ja) | 2003-10-20 | 2005-04-28 | Sumitomo Metal Mining Co., Ltd. | 赤外線遮蔽材料微粒子分散体、赤外線遮蔽体、及び赤外線遮蔽材料微粒子の製造方法、並びに赤外線遮蔽材料微粒子 |
JP2005187323A (ja) * | 2003-12-05 | 2005-07-14 | Sumitomo Metal Mining Co Ltd | 日射遮蔽体形成用タングステン酸化物微粒子の製造方法、日射遮蔽体形成用タングステン酸化物微粒子および日射遮蔽体形成用分散液並びに日射遮蔽体 |
JP2009215487A (ja) | 2008-03-12 | 2009-09-24 | Sumitomo Metal Mining Co Ltd | 赤外線遮蔽材料微粒子分散液、赤外線遮蔽膜と赤外線遮蔽光学部材およびプラズマディスプレイパネル用近赤外線吸収フィルター |
JP2012506463A (ja) | 2008-10-23 | 2012-03-15 | データレース リミテッド | 熱吸収添加剤 |
JP2010265144A (ja) | 2009-05-15 | 2010-11-25 | Sumitomo Metal Mining Co Ltd | 複合タングステン酸化物超微粒子の製造方法 |
JP2012532822A (ja) * | 2009-07-07 | 2012-12-20 | ビーエーエスエフ ソシエタス・ヨーロピア | カリウム・セシウム・タングステンブロンズ粒子 |
WO2015186663A1 (ja) * | 2014-06-05 | 2015-12-10 | 日清エンジニアリング株式会社 | タングステン複合酸化物粒子の製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3392199A4 |
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Also Published As
Publication number | Publication date |
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CN108779000A (zh) | 2018-11-09 |
KR102534292B1 (ko) | 2023-05-18 |
US20180370813A1 (en) | 2018-12-27 |
CN108779000B (zh) | 2021-03-09 |
IL260088A (en) | 2018-07-31 |
IL260088B (en) | 2022-06-01 |
TWI699335B (zh) | 2020-07-21 |
EP3392199A1 (en) | 2018-10-24 |
MX2018007488A (es) | 2019-01-31 |
US10752512B2 (en) | 2020-08-25 |
KR20180095875A (ko) | 2018-08-28 |
JPWO2017104853A1 (ja) | 2018-11-08 |
EP3392199A4 (en) | 2019-08-07 |
JP6825577B2 (ja) | 2021-02-03 |
BR112018012241B1 (pt) | 2023-02-23 |
EP3392199B1 (en) | 2024-02-07 |
BR112018012241A2 (pt) | 2020-10-27 |
TW201736276A (zh) | 2017-10-16 |
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