WO2021132450A1 - 近赤外線吸収材料粒子、近赤外線吸収材料粒子分散液、近赤外線吸収材料粒子分散体 - Google Patents

近赤外線吸収材料粒子、近赤外線吸収材料粒子分散液、近赤外線吸収材料粒子分散体 Download PDF

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WO2021132450A1
WO2021132450A1 PCT/JP2020/048402 JP2020048402W WO2021132450A1 WO 2021132450 A1 WO2021132450 A1 WO 2021132450A1 JP 2020048402 W JP2020048402 W JP 2020048402W WO 2021132450 A1 WO2021132450 A1 WO 2021132450A1
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Prior art keywords
absorbing material
infrared absorbing
particles
material particles
particle dispersion
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PCT/JP2020/048402
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English (en)
French (fr)
Japanese (ja)
Inventor
昭也 野下
中山　博貴
貢尚 川野
長南　武
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Sumitomo Metal Mining Co Ltd
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Sumitomo Metal Mining Co Ltd
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Priority to EP20906352.8A priority Critical patent/EP4082972B1/en
Priority to JP2021567603A priority patent/JP7753881B2/ja
Priority to US17/757,794 priority patent/US20230022949A1/en
Priority to IL294188A priority patent/IL294188A/en
Priority to CN202080093484.2A priority patent/CN114981214A/zh
Priority to KR1020227020077A priority patent/KR20220121797A/ko
Publication of WO2021132450A1 publication Critical patent/WO2021132450A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C01G41/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/38—Particle morphology extending in three dimensions cube-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/39—Particle morphology extending in three dimensions parallelepiped-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/40—Particle morphology extending in three dimensions prism-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2258—Oxides; Hydroxides of metals of tungsten
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter

Definitions

  • the present invention relates to near-infrared absorbing material particles, a near-infrared absorbing material particle dispersion, and a near-infrared absorbing material particle dispersion.
  • Near-infrared rays contained in the sun's rays pass through window materials, etc., enter the room, enter the room, raise the surface temperature of the walls and floor of the room, and raise the indoor temperature.
  • window materials etc.
  • Patent Document 1 proposes a light-shielding film containing a fine black powder containing an inorganic pigment such as carbon black or titanium black or an organic pigment such as aniline black. ..
  • Patent Document 2 discloses a heat-retaining sheet in which a band-shaped film having infrared reflection and a band-shaped film having infrared absorption are knitted as warp threads or weft threads, respectively. It is also described that, as a strip-shaped film having infrared reflectivity, a synthetic resin film obtained by subjecting an aluminum vapor deposition process and further laminating a synthetic resin film is used.
  • the infrared material fine particles are an infrared shielding material fine particle dispersion in which the infrared material fine particles are dispersed in a medium, and the infrared material fine particles are tungsten oxide fine particles and / or composite tungsten oxide fine particles.
  • Patent Document 1 and Patent Document 2 have the following problems.
  • the black fine powder described in Patent Document 1 has a large absorption in the visible light region. Therefore, it is considered that the color tone of the window material or the like to which the black fine powder is applied becomes dark, and the method of use and use are limited.
  • the window material or the like to which the metal vapor deposition film is applied has a half mirror shape in appearance. Therefore, when a window material or the like to which a metal vapor-deposited film is applied is used outdoors, it is considered that the reflection is dazzling and there is a problem in the landscape.
  • Patent Document 3 is made to solve the above-mentioned problems. Then, it sufficiently transmits visible light, does not have a half-mirror-like appearance, efficiently shields invisible near-infrared rays having a wavelength of 780 nm or more, and is transparent and does not change the color tone. Shielding Material Fine Particle Dispersion, Near Infrared Shielding Body, Near Infrared Shielding Material Fine Particles, and a method for producing the same have been provided. However, in recent years, performance such as weather resistance has also been required.
  • One aspect of the present invention is to provide near-infrared absorbing material particles having excellent weather resistance.
  • the general formula M x W y Oz (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, 0.001 ⁇ x / y ⁇ Provided are near-infrared absorbing material particles containing particles of a composite tungsten oxide represented by 1, 3.0 ⁇ z / y).
  • the near-infrared absorbing material particles, the near-infrared absorbing material particle dispersion, and the near-infrared absorbing material particle dispersion according to the present embodiment will be described in "1. Near-infrared absorbing material particles” and "2. Near-infrared absorbing material particles”. , “3. Near-infrared absorbing material particle dispersion", and “4. Near-infrared absorbing material particle dispersion” will be described in detail in this order. 1.
  • the near-infrared absorbing material particles according to the present embodiment may contain particles of a composite tungsten oxide represented by the general formula M x W y Oz.
  • the M elements in the above general formula are 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, One or more elements selected from Ta, Re, Be, Hf, Os, Bi, and I. W is tungsten and O is oxygen.
  • x, y, and z can satisfy 0.001 ⁇ x / y ⁇ 1, 3.0 ⁇ z / y.
  • the inventors of the present invention conducted diligent research in order to obtain near-infrared absorbing material particles having excellent weather resistance.
  • excellent weather resistance means that the near-infrared absorption characteristics do not change significantly even when placed in a high temperature environment.
  • a material containing free electrons exhibits a reflection absorption response due to plasma oscillation to an electromagnetic wave having a wavelength of 200 nm to 2600 nm around the region of sunlight rays.
  • the powder of the material containing the free electrons is made into particles smaller than the wavelength of light, geometric scattering in the visible light region (wavelength 380 nm or more and 780 nm or less) is reduced, and transparency in the visible light region can be obtained. It has been known.
  • "transparency” is used in the sense that there is little scattering and high transparency with respect to light in the visible light region.
  • Tungsten oxide represented by the general formula WO 3-a and so-called tungsten bronze obtained by adding a positive element such as Na to tungsten trioxide are known to be conductive materials and materials containing free electrons. There is. Analysis of single crystals and the like of these materials suggests the response of free electrons to light in the near-infrared region.
  • the inventors of the present invention further studied tungsten oxides and composite tungsten oxides in order to obtain near-infrared absorbing material particles having excellent weather resistance.
  • the near-infrared absorbing material particles containing the particles of the composite tungsten oxide represented by the general formula M x W y O z the y and z in the above general formula are set to 3.0 ⁇ z / y. Therefore, they have found that both near-infrared absorption characteristics and weather resistance can be achieved, and have completed the present invention.
  • Near-infrared-absorbing material particles of this embodiment can contain particles of the general formula M x W y O z composite tungsten oxide indicated by, as described above.
  • the near-infrared absorbing material particles of the present embodiment can also be composed of composite tungsten oxide particles represented by the above general formula. However, even in this case, it is not excluded that the unavoidable component mixed in the manufacturing process or the like is contained.
  • the M element in the above general formula is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, as described above, from the viewpoint of enhancing stability.
  • 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, and I are preferably one or more elements.
  • the M elements belong to alkali metals, alkaline earth metal elements, transition metal elements, group 4B elements, and group 5B elements. More preferred.
  • the particles of the composite tungsten oxide contain crystals having a hexagonal crystal structure
  • the transmittance of the particles in the visible light region is particularly improved, and the absorption in the near infrared region is particularly improved.
  • the hexagonal crystal structure six octahedrons formed in WO 6 units are assembled to form a hexagonal void (tunnel), and M elements are arranged in the voids to form one unit. However, it is composed of a large number of these one unit.
  • the composite tungsten oxide particles are not limited to the case where the particles contain a crystal having a hexagonal crystal structure.
  • the above unit structure that is, six octahedrons formed by WO 6 units are aggregated to form a hexagon. If the void is configured and the M element is arranged in the void, the transmittance in the visible light region can be particularly improved, and the absorption in the near infrared region can be particularly improved. Therefore, the particles of the composite tungsten oxide do not contain crystals having a hexagonal crystal structure, and even if they only have the above-mentioned unit structure, a high effect can be obtained.
  • the particles of the composite tungsten oxide contain a structure in which the cation of the M element is added to the hexagonal voids, the absorption in the near infrared region is particularly improved.
  • a hexagonal crystal or the above structure is likely to be formed.
  • the composite tungsten oxide contains one or more elements selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn as the M element. , Hexagonal crystals and the above structure are easily formed.
  • the particles of the composite tungsten oxide may contain one or more kinds of elements selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn as the M element. More preferably, the M element is one or more elements selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn.
  • the particles of the composite tungsten oxide containing at least one selected from Cs and Rb among these M elements having a large ionic radius hexagonal crystals and the above structure are likely to be formed, and absorption in the near infrared region is likely to occur. And transmission in the visible light region are compatible, and particularly high performance can be exhibited.
  • x / y indicating the content ratio of the M element to 1 mol of tungsten is preferably 0.2 or more and 0.5 or less. More preferably, it is 0.33.
  • the value of x / y is 0.33, it is considered that the element M is arranged in all the hexagonal voids.
  • Each of the cubic and tetragonal composite tungsten oxides also has a suitable range and upper limit for the amount of the element M added due to the structure, and the content ratio of the M element to 1 mol of tungsten is x / y.
  • the upper limit is 1 mol in the case of cubic crystals and about 0.5 mol in the case of tetragonal crystals.
  • the upper limit of x / y, which is the content ratio of M element to 1 mol of tungsten, varies depending on the type of M element, etc., but in the case of tetragonal crystals, industrial production is easy in about 0.5 mol. is there.
  • the absorption position in the near-infrared region tends to change depending on the crystal structure contained in the particles of the composite tungsten oxide, and the absorption position in the near-infrared region is on the long wavelength side of the cubic crystal rather than the cubic crystal. Hexagonal crystals tend to move to the longer wavelength side than cubic crystals. Further, with the fluctuation of the absorption position, the absorption in the visible light region is the least in the hexagonal crystal, followed by the tetragonal crystal, and the cubic crystal is the largest among them. Therefore, it is preferable to select the crystal system to be contained according to the required performance and the like.
  • the particles of the composite tungsten oxide when used in an application where it is required to transmit light in a more visible light region and absorb light in a closer infrared region, the particles of the composite tungsten oxide preferably contain hexagonal crystals.
  • the tendency of the optical characteristics described here is only a rough tendency, and changes depending on the type of added element, the amount of added element, and the amount of oxygen, and the present invention is not limited to this.
  • the composite tungsten oxide which is a near-infrared absorbing material that combines the control of the amount of oxygen and the addition of an element that generates free electrons, is described as M x W y O z , x, y, It can be 0.001 ⁇ x / y ⁇ 1, and it is preferable that 0.20 ⁇ x / y ⁇ 0.37 is satisfied.
  • y and z of the above general formula preferably satisfy the relationship of 3.0 ⁇ z / y, preferably 3.0 ⁇ z / y ⁇ 3.4, and 3.0 ⁇ z / y ⁇ 3. It is more preferable to satisfy 3, and it is further preferable to satisfy 3.0 ⁇ z / y ⁇ 3.22.
  • the composite tungsten oxide particles contained in the near-infrared absorbing material particles according to the present embodiment exceeds 3.
  • the tungsten bronze structure may be adopted. Therefore, the composite tungsten oxide particles contained in the near-infrared absorbing material particles according to the present embodiment preferably contain crystals having one or more types of crystal structures selected from hexagonal crystals, tetragonal crystals, and cubic crystals. .. By containing a crystal having the above crystal structure, it is possible to exhibit particularly excellent near-infrared absorption characteristics and visible light transmission characteristics.
  • the oxygen atom when the z / y value exceeds 3 has entered the crystal of the composite tungsten oxide particle.
  • the oxygen atom enters the crystal, so that even if it is exposed to heat or moisture, the crystal of the composite tungsten oxide particle does not deteriorate and excellent weather resistance can be realized.
  • the crystal structure of the composite tungsten oxide particles contained in the near-infrared absorbing material particles according to the present embodiment can be confirmed by an X-ray diffraction pattern by a powder X-ray diffraction method ( ⁇ -2 ⁇ method).
  • the near-infrared absorbing material particles of the present embodiment have a maximum value in the wavelength range of 350 nm or more and 600 nm or less, and exhibit a light transmission characteristic having a minimum value in the wavelength range of 800 nm or more and 2100 nm or less, and have an excellent near-infrared absorbing effect. And weather resistance can be demonstrated. It is more preferable that the near-infrared absorbing material particles of the present embodiment have a maximum value in the wavelength range of 440 nm or more and 600 nm or less, and have a minimum value in the wavelength range of 1150 nm or more and 2100 nm or less.
  • the near-infrared absorbing material particles according to the present embodiment preferably have a particle size of 100 nm or less.
  • the particle size is more preferably 10 nm or more and 100 nm or less, further preferably 10 nm or more and 80 nm or less, particularly preferably 10 nm or more and 60 nm or less, and most preferably 10 nm or more and 40 nm or less.
  • the particle size of the near-infrared absorbing material particles is in the range of 10 nm or more and 40 nm or less, the most excellent near-infrared absorbing characteristics are exhibited.
  • the particle size is the diameter of each non-aggregated near-infrared absorbing material particle, that is, the particle size of the individual particles.
  • the particle size here does not include the diameter of the agglomerates of the near-infrared absorbing material particles, and is different from the dispersed particle size.
  • the particle size here can be calculated by measuring the particle size of a plurality of particles using, for example, a transmission electron microscope (TEM) in a state where the near-infrared absorbing material particles are dispersed. Since the near-infrared absorbing material particles are usually irregular, the diameter of the smallest circle circumscribing the particles can be used as the particle size of the particles. For example, when the particle size of a plurality of particles is measured for each particle using a transmission electron microscope as described above, it is preferable that the particle size of all the particles satisfies the above range.
  • the number of particles to be measured is not particularly limited, but is preferably 10 or more and 50 or less, for example.
  • the crystallite diameter of the composite tungsten oxide particles is preferably 10 nm or more and 100 nm or less, more preferably 10 nm or more and 80 nm or less, and 10 nm or more and 60 nm or less. It is more preferably 10 nm or more and 40 nm or less. This is because when the crystallite diameter is in the range of 10 nm or more and 40 nm or less, particularly excellent near-infrared absorption characteristics are exhibited.
  • the crystallite diameter of the composite tungsten oxide particles contained in the near-infrared absorbing material particles can be calculated by using the Rietveld method from the X-ray diffraction pattern measured by the powder X-ray diffraction method ( ⁇ -2 ⁇ method). ..
  • the general formula of the composite tungsten oxide composite tungsten oxide particles contain an M x W y O z as described above.
  • the lattice constant of the composite tungsten oxide is 7.3850 ⁇ or more on the a-axis. It is preferable that the size is 7.4186 ⁇ or less and the c-axis is 7.5600 ⁇ or more and 7.6240 ⁇ or less.
  • the M element is more preferably composed of one or more kinds of elements selected from Cs and Rb.
  • the lattice constant can be calculated using the Rietveld method.
  • the near-infrared absorbing material particle dispersion containing the particles of the composite tungsten oxide according to the present embodiment largely absorbs light in the near-infrared region, particularly in the vicinity of a wavelength of 1000 nm, its transmitted color tone varies from blue to green. There are many things that become.
  • the dispersed particle size of the near-infrared absorbing material particles of the present embodiment can be selected according to the purpose of use. First, when used for applications that maintain transparency, it is preferable to have a dispersed particle size of 800 nm or less. This is because particles having a dispersed particle diameter of 800 nm or less do not completely block light due to scattering, and can maintain visibility in the visible light region and at the same time efficiently maintain transparency.
  • the dispersed particle size includes the diameter of the agglomerates of the near-infrared absorbing material particles, and is different from the above-mentioned particle size.
  • the dispersed particle size of the near-infrared absorbing material particles of the present embodiment is preferably 200 nm or less, more preferably 10 nm or more and 200 nm or less, and further preferably 10 nm or more and 100 nm or less. This is because if the dispersed particle size is small, the scattering of light in the visible light region having a wavelength of 380 nm or more and 780 nm or less due to geometric scattering or Mie scattering is reduced, and as a result, the dispersion containing the near-infrared absorbing material particles of the present embodiment is contained. This is because it can be avoided that the light becomes like frosted glass and the clear transparency cannot be obtained.
  • the dispersed particle size when the dispersed particle size is 200 nm or less, the geometrical scattering or Mie scattering is reduced, and a Rayleigh scattering region is formed. This is because in the Rayleigh scattering region, the scattered light is proportional to the sixth power of the dispersed particle size, so that the scattering is reduced and the transparency is improved as the dispersed particle size is reduced. Further, when the dispersed particle size is 100 nm or less, the scattered light becomes very small, which is preferable. From the viewpoint of avoiding light scattering, it is preferable that the dispersed particle size is small, and if the dispersed particle size is 10 nm or more, industrial production is easy.
  • the haze (haze value) of the near-infrared absorbing material particle dispersion in which the near-infrared absorbing material particles are dispersed in the medium is 10% or less with a visible light transmittance of 85% or less.
  • the haze can be set to 1% or less.
  • the light scattering of the near-infrared absorbing material particle dispersion needs to consider the aggregation of the near-infrared absorbing material particles, and it is necessary to examine the dispersed particle size.
  • the near-infrared absorbing material particles of the present embodiment may have the surface of the particles coated with a compound containing one or more elements selected from Si, Ti, Zr, and Al.
  • a compound containing one or more elements selected from Si, Ti, Zr, and Al By coating the surface of the near-infrared absorbing material particles with the above compound, the weather resistance can be particularly enhanced.
  • Examples of the compound containing one or more elements selected from Si, Ti, Zr, and Al include a hydrolysis product of a metal chelate compound containing Si, Ti, Zr, and Al, and a hydrolysis product of a metal chelate compound.
  • a metal chelate compound containing Si, Ti, Zr, and Al containing Si, Ti, Zr, and Al
  • a hydrolysis product of a metal chelate compound containing Si, Ti, Zr, and Al
  • a hydrolysis product of a metal chelate compound One or more selected from the above-mentioned polymer, the hydrolysis product of the metal cyclic oligomer compound, and the polymerization product of the metal cyclic oligomer compound can be preferably used.
  • the metal chelate compound and the metal cyclic oligomer compound are preferably metal alkoxide, metal acetylacetonate, and metal carboxylate, they have one or more selected from ether bond, ester bond, alkoxy group, and
  • the operation of coating the surface of the near-infrared absorbing material particles with these compounds is preferably performed before preparing the near-infrared absorbing material particle dispersion liquid or the like.
  • the coating film material, etc. (1-1) metal chelate compound, (1) 1-2) Metallic cyclic oligomer compounds, (1-3) Hydrolysis products of metal chelate compounds and metallic cyclic oligomer compounds, and their polymers, (1-4) Amount of surface treatment agent added, in order of film thickness It will be explained in.
  • (1-1) Metal Chelate Compound The metal chelate compound is preferably one or more selected from Si-based, Ti-based, Zr-based, and Al-based chelate compounds containing an alkoxy group.
  • Si-based chelate compound examples include a tetrafunctional silane compound represented by the general formula Si (OR) 4 (where R is a monovalent hydrocarbon group having the same or different carbon atoms of 1 or more and 6 or less). Hydrolysis products can be used.
  • Specific examples of the tetrafunctional silane compound include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like.
  • Si-based chelate compound a silane monomer obtained by hydrolyzing a part or all of the alkoxy group of the alkoxysilane monomer to become a silanol group (Si—OH), an oligomer, and self-condensation through a hydrolysis reaction. Polymers can also be applied.
  • the hydrolysis product of the tetrafunctional silane compound a silane monomer in which a part or all of the alkoxy groups are hydrolyzed to become silanol (Si—OH) groups, tetramers or more and pentamers or less.
  • examples thereof include oligomers and polymers (silicone resins) having a weight average molecular weight (Mw) of about 800 or more and 8000 or less.
  • the hydrolysis product of the tetrafunctional silane compound means the entire hydrolysis product of the tetrafunctional silane compound. It is not necessary that all of the alkoxysilyl group (Si—OR) in the alkoxysilane monomer is hydrolyzed to silanol group (Si—OH) in the process of hydrolysis reaction.
  • Ti-based chelate compounds include titanium alcoholates such as methyl titanate, ethyl titanate, isopropyl titanate, butyl titanate, and 2-ethylhexyl titanate, and polymers thereof, titanium acetylacetonate, titanium tetraacetylacetonate, and titanium octylene glycote. Examples thereof include rates, titanium ethyl acetoacetate, titanium lactate, titanium triethanol aminated and the like.
  • Zr-based chelating compounds include zirconium alkylates such as zirconium ethylate and zirconium butyrate or polymers thereof, zirconium tributoxystearate, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, and zirconium dibutoxybis ( Acetylacetate), zirconium tributoxyethylacetate, zirconium butoxyacetylacetonate bis (ethylacetate) and the like can be exemplified.
  • Al-based chelate compound examples include aluminum alcoholates such as aluminum ethylate, aluminum isopropylate, aluminum sec-butyrate, and mono-sec-butoxyaluminum diisopropyrate, or polymers thereof, ethylacetacetate aluminum diisopropyrate, and aluminum.
  • Tris ethylacetate acetate
  • octylacetoacetate aluminum diisoproplate stearylacetoaluminum diisopropyrate
  • aluminum monoacetylacetonatebis ethylacetate acetate
  • aluminum tris acetylacetonate
  • aluminum ethylacetacetate diisopropyrate etc.
  • aluminum alcoholate is dissolved in an aproton solvent, a petroleum solvent, a hydrocarbon solvent, an ester solvent, a ketone solvent, an ether solvent, an amide solvent, etc., and ⁇ - It is an alkoxy group-containing aluminum chelate compound obtained by adding a diketone, ⁇ -ketoester, monovalent or polyhydric alcohol, fatty acid, etc., heating and refluxing, and performing a ligand substitution reaction.
  • the metal cyclic oligomer compound is preferably one or more selected from Al-based, Zr-based, Ti-based, and Si-based cyclic oligomer compounds.
  • cyclic aluminum oxide octylate, cyclic aluminum oxide isopropylate, cyclic aluminum oxide stelate and the like can be mentioned.
  • Hydrolysis products of metal chelate compounds and metal cyclic oligomer compounds, and their polymers include the above-mentioned metal chelate. Hydrolyzed products in which all of the alkoxy groups, ether bonds, and ester bonds in the compound or metal cyclic oligomer compound are hydrolyzed to become hydroxyl groups or carboxyl groups, partially hydrolyzed partial hydrolysis products, and One or more selected from the compounds self-condensed through the hydrolysis reaction can be used.
  • the surface of the near-infrared absorbing material particles can be coated with one or more kinds selected from the above-mentioned hydrolysis products and polymers to form a coating film, and the near-infrared absorbing material particles of the present embodiment can be obtained.
  • the above-mentioned hydrolysis product is not limited to the hydrolysis product obtained by hydrolyzing the entire amount of the alkoxy group and the like, but is a concept including a partial hydrolysis product.
  • a hydrolysis product of a metal chelate compound on the surface of the near-infrared absorbing material particles, a hydrolysis product of a metal chelate compound, a polymer of a hydrolysis product of a metal chelate compound, a hydrolysis product of a metal cyclic oligomer compound, and a metal ring
  • a "coating film formed by using one or more selected from a polymer of a hydrolysis product of an oligomer compound” may be simply referred to as a "coating film”.
  • the coating film may contain one or more selected from undecomposed metal chelate compounds and metal cyclic oligomer compounds, but to the extent that near-infrared absorbing material particles do not aggregate. There is no particular problem if the amount is very small.
  • the coating film contains one or more selected from undecomposed metal chelate compounds and metal cyclic oligomer compounds, it is considered that the dispersion used when preparing a near-infrared absorbing material dispersion or the like in a subsequent step.
  • the hydrolysis reaction of the silane coupling agent, silane alkoxide, and polysilazane in the liquid (coating liquid) and the dehydration condensation reaction will proceed rapidly.
  • a polymer of a silane coupling agent, a silane-based alkoxide, and polysilazane acts as a cross-linking agent to agglomerate the near-infrared absorbing material particles in the near-infrared absorbing material particle dispersion liquid for surface treatment. May cause.
  • the near-infrared absorbing material particles aggregate, properties such as visible light transparency may deteriorate.
  • the coating film contains an undecomposed metal chelate compound or metal cyclic oligomer compound
  • the decomposition of these compounds is promoted in the "(2-5) heat treatment step" described later. It is preferable to react until a polymer of the reactive hydrolysis product is obtained.
  • the coating film that covers the surface of the near-infrared absorbing material particles a part or all of the alkoxy groups, ether bonds, and ester bonds contained in the above-mentioned metal chelate compound and metal cyclic oligomer compound are hydrolyzed.
  • the hydrolysis product that has become a hydroxyl group or a carboxyl group is preferably a self-condensed polymer that has undergone the hydrolysis reaction.
  • (1-4) Amount of surface treatment agent added and film thickness The amount of the above-mentioned metal chelate compound and metal cyclic oligomer compound added when forming the coating film is not particularly limited, but is limited to 100 parts by mass of the near-infrared absorbing material particles.
  • it is preferably 0.05 parts by mass or more and 1000 parts by mass or less, more preferably 5 parts by mass or more and 500 parts by mass or less, and 50 parts by mass or more and 250 parts by mass or less in terms of metal elements. More preferred.
  • the amount of the metal chelate compound or the metal cyclic oligomer compound added is 0.05 parts by mass or more in terms of metal element, the near infrared ray is produced by the hydrolysis product of the above compound or the polymer of the hydrolysis product. This is because the effect of coating the surface of the absorbent material particles is exhibited. That is, a particularly high effect can be obtained for improving weather resistance.
  • the amount of the metal chelate compound or the metal cyclic oligomer compound added is 1000 parts by mass or less in terms of metal elements, it is possible to avoid an excessive amount of adsorption to the near-infrared absorbing material particles. Further, the improvement of the weather resistance by the surface coating is not saturated, and the improvement of the coating effect can be expected.
  • the addition amount of the metal chelate compound or the metal cyclic oligomer compound to 1000 parts by mass or less in terms of metal elements, it is possible to avoid an excessive adsorption amount for the near-infrared absorbing material particles. Therefore, when the medium is removed after the coating film is formed, the near-infrared absorbing material particles are easily granulated via the hydrolysis product of the metal chelate compound or the metal cyclic oligomer compound or the polymer of the hydrolysis product. This is because it can be avoided. Good transparency can be ensured by suppressing granulation by the near-infrared absorbing material particles.
  • the amount of the metal chelate compound or the metal cyclic oligomer compound added is preferably 1000 parts by mass or less in terms of metal elements.
  • the film thickness of the coating film of the near-infrared absorbing material particles is not particularly limited, but is preferably 0.5 nm or more, for example. This is because if the film thickness of the coating film is 0.5 nm or more, the near-infrared absorbing material particles are considered to exhibit particularly excellent weather resistance and chemical stability. On the other hand, from the viewpoint of sufficiently ensuring the optical characteristics of the near-infrared absorbing material particles, it is considered that the film thickness of the coating film is preferably 100 nm or less.
  • the film thickness of the coating film is more preferably 0.5 nm or more and 20 nm or less, and further preferably 1 nm or more and 10 nm or less.
  • the film thickness of the coating film can be measured from a transmission electron microscope image of surface-treated infrared absorbing material particles.
  • (2) Method for producing surface-coated near-infrared absorbing material particles In order to produce surface-coated near-infrared absorbing material particles, first, the near-infrared absorbing material particles are dispersed in water or an organic solvent containing water and covered. A near-infrared absorbing material particle dispersion liquid for covering film formation (hereinafter, may be referred to as “dispersion liquid for coating film formation”) is prepared (dispersion liquid preparation step for coating film formation). The surface-coated near-infrared absorbing material particles can be produced by the method described in "2. Method for producing near-infrared absorbing material particles" described later.
  • the surface treatment agent is added to the dispersion liquid for forming the coating film while mixing and stirring (surface treatment agent addition step).
  • the solvent in the solvent mixture such as the coating film-forming dispersion liquid, the surface treatment agent, and water can be removed by an appropriate drying treatment. Can be done (drying process).
  • the dispersion liquid preparation step for coating film formation the dispersion liquid for coating film formation is prepared by previously pulverizing near-infrared absorbing material particles as necessary. , Water, or an appropriate organic solvent containing water to disperse the particles in a monodisperse state.
  • the dispersion concentration of the near-infrared absorbing material particles in the dispersion is preferably 0.01% by mass or more and 80% by mass or less. By setting the dispersion concentration range, the liquid stability of the dispersion can be improved.
  • the near-infrared absorbing material particles ensure the dispersed state and do not agglomerate the particles. This is to prevent the near-infrared absorbing material particles from agglomerating and being surface-coated in the state of aggregates in the next step, the surface treatment agent addition step of surface-treating the near-infrared absorbing material particles. Further, this is to avoid a situation in which the agglomerates remain in the near-infrared absorbing material particle dispersion described later and the transparency of the near-infrared absorbing material particle dispersion is lowered.
  • the specific method of pulverizing / dispersing the near-infrared absorbing material particles in the dispersion liquid preparation step for forming a coating film is not particularly limited, and for example, a device such as a bead mill, a ball mill, a sand mill, a paint shaker, or an ultrasonic homogenizer is used. Examples include the crushing / dispersion treatment method used. Among them, it is necessary to reach a desired dispersed particle size by performing pulverization and dispersion treatment with a medium stirring mill such as a bead mill, a ball mill, a sand mill, or a paint shaker using a medium medium such as beads, balls, or Ottawa sand. It is preferable because the time is short.
  • the surface of the near-infrared absorbing material particles is a hydrolysis product of a metal chelate compound, a polymer of a hydrolysis product of a metal chelate compound, a hydrolysis product of a metal cyclic oligomer compound, and a metal cyclic oligomer. It is coated with a coating film containing one or more selected from a polymer of the hydrolysis product of the compound.
  • the surface treatment agent is added while mixing and stirring the prepared dispersion liquid for forming a coating film.
  • (2-3-1) a method for surface coating near-infrared absorbing material particles using a dispersion liquid for forming a coating film using water as a medium, and (2--3-2) an organic solvent containing water.
  • the method of surface-coating the near-infrared absorbing material particles using the dispersion liquid for forming a coating film using the medium as a medium will be described in this order.
  • (2-3-1) Surface coating method for near-infrared absorbing material particles using a dispersion liquid for forming a coating film using water as a medium
  • the inventors of the present invention prepare the above-mentioned dispersion liquid for forming a coating film.
  • a surface treatment agent is added to the dispersion liquid while stirring and mixing the dispersion liquid for forming a coating film using water as a medium, and further, a hydrolysis reaction of the added metal chelate compound and metal cyclic oligomer compound. It was found that it is preferable to complete the procedure immediately. From the viewpoint of uniformly surface-coating the near-infrared absorbing material particles, it is preferable to add the surface treatment agent in a dropping manner.
  • the surface treatment agent When the surface treatment agent is added dropwise, it is also preferable to add the surface treatment agent diluted with an appropriate solvent by dropping in order to adjust the amount of the surface treatment agent added per hour.
  • a solvent that does not react with the surface treatment agent and has high compatibility with water which is a medium of the dispersion liquid for forming a coating film, is preferable.
  • alcohol-based, ketone-based, glycol-based solvents and the like can be preferably used.
  • the dilution ratio of the surface treatment agent is not particularly limited. However, from the viewpoint of ensuring productivity, the dilution ratio is preferably 100 times or less.
  • the metal chelate compound, the metal cyclic oligomer compound, the hydrolysis products thereof, and the polymer of the hydrolysis product are metal ions immediately after addition. It is decomposed to. However, when the saturated aqueous solution is obtained, the decomposition to the metal ion is completed.
  • the near-infrared absorbing material particles maintain their dispersion by electrostatic repulsion in the dispersion liquid for forming a coating film using the water as a medium.
  • the surfaces of all the near-infrared absorbing material particles are of the hydrolysis product of the metal chelate compound, the polymer of the hydrolysis product of the metal chelate compound, the hydrolysis product of the metal cyclic oligomer compound, and the metal cyclic oligomer compound.
  • Near-infrared absorbing material particles coated with a coating film containing one or more selected from a polymer of hydrolysis products are produced.
  • (2-3-2) Surface coating method of near-infrared absorbing material particles using a dispersion liquid for forming a coating film using an organic solvent containing water The above-mentioned dispersion liquid for forming a coating film using water as a medium is used.
  • an organic solvent containing water was used as the medium of the dispersion liquid for forming the coating film, and the above reaction sequence was carried out while adjusting the amount of water to be added to an appropriate value. The method of doing so is also preferable.
  • the preparation method is suitable, for example, when it is desired to reduce the amount of water contained in the dispersion liquid for forming a coating film due to the convenience of a subsequent process.
  • the above-mentioned surface treatment agent and pure water are dropped in parallel while stirring and mixing the dispersion liquid for forming a coating film using an organic solvent containing water as a medium.
  • the medium temperature that affects the reaction rate and the dropping rate of the surface treatment agent and pure water are appropriately controlled.
  • the organic solvent any solvent such as alcohol-based, ketone-based, glycol-based, etc. that dissolves in water at room temperature may be used, and various solvents can be selected.
  • the solvent used for dilution is preferably one that does not react with the surface treatment agent and has high compatibility with an organic solvent containing water, which is a medium of the dispersion liquid for forming a coating film.
  • an organic solvent containing water which is a medium of the dispersion liquid for forming a coating film.
  • alcohol-based, ketone-based, glycol-based solvents and the like can be preferably used.
  • the dilution ratio of the surface treatment agent is the same as in the case of "(2-3-1) Surface coating method of near-infrared absorbing material particles using a dispersion liquid for forming a coating film using water as a medium". You can do the same.
  • (2-4) Drying Step In the drying step, after the near-infrared absorbing material particles are surface-coated by the surface treatment agent addition step, the dispersion liquid for coating film formation, the surface treatment agent, water, etc. are subjected to an appropriate drying treatment. The solvent in the mixture of solvents can be removed.
  • the drying treatment equipment one or more types of operations selected from heating and depressurization are possible, and from the viewpoint of easy mixing and recovery of surface-coated near-infrared absorbing material particles, an air dryer and a universal mixer. , Ribbon type mixer, vacuum flow dryer, vibration flow dryer, freeze dryer, ribocorn, rotary kiln, spray dryer, Palcon dryer, etc. are preferable, but the present invention is not limited thereto.
  • the drying temperature in the drying step is not particularly limited, but the temperature is higher than the solvent in the dispersion liquid volatilizes, and the element M does not desorb even in the air atmosphere in the composite tungsten oxide contained in the near-infrared absorbing material particles. It is preferable to carry out the drying treatment at a temperature.
  • the drying temperature is preferably 150 ° C. or lower.
  • the conditions of the heat treatment are not particularly limited, but it can be carried out in an air atmosphere or an inert gas atmosphere.
  • the heat treatment atmosphere is preferably an inert gas atmosphere.
  • the heat treatment temperature is also not particularly limited, but is preferably a temperature equal to or higher than the temperature at which the metal chelate compound or the metallic cyclic oligomer compound contained in the coating film is decomposed and lower than the temperature at which the near-infrared absorbing material particles start to crystallize.
  • the heat treatment temperature is preferably in the temperature range of 200 ° C. or higher and lower than 500 ° C.
  • Composite tungsten oxide particles near-infrared-absorbing material particles of this embodiment are denoted by the aforementioned general formula M x W y O z containing, for example following the solid-phase reaction method or can be produced by plasma method.
  • Tungsten compound and M element compound are mixed to prepare a raw material mixture (mixing step).
  • the substance amount ratio (molar ratio) of the M element and tungsten is blended and mixed so as to be the ratio of x and y in the above general formula of the target composite tungsten oxide particles. Is preferable.
  • the raw material mixture obtained in the mixing step is heat-treated in an atmosphere containing oxygen (first heat treatment step).
  • the heat-treated product obtained after the first heat treatment step is heat-treated in a reducing gas atmosphere or a mixed gas atmosphere of a reducing gas and an inert gas, or in an inert gas atmosphere (second heat treatment step).
  • the near-infrared absorbing material particles can be pulverized so as to have a desired particle size.
  • the near-infrared absorbing material particles of the present embodiment including the composite tungsten oxide particles obtained by the above steps, have sufficient near-infrared absorbing power and have preferable properties as near-infrared absorbing material particles. Further, it can be a near-infrared absorbing material particle having excellent weather resistance.
  • Examples of the tungsten compound to be used in the mixing step include tungstic acid (H 2 WO 4 ), ammonium tungstic acid, tungsten hexachloride, and tungsten hexachloride dissolved in alcohol, hydrolyzed by adding water, and then the solvent is evaporated.
  • tungstic acid H 2 WO 4
  • ammonium tungstic acid tungsten hexachloride
  • tungsten hexachloride tungsten hexachloride dissolved in alcohol, hydrolyzed by adding water, and then the solvent is evaporated.
  • One or more selected from the hydrates of the above can be used.
  • M element compound to be used in the mixing step for example, one or more selected from M element oxides, hydroxides, nitrates, sulfates, chlorides and carbonates can be used.
  • the substance amount ratio (M: W) of the M element (M) and the tungsten (W) in the obtained raw material mixture is a general object. It is preferable to mix and mix each raw material so as to be equal to x: y of the formula M x W y O z.
  • the mixing method is not particularly limited, and either wet mixing or dry mixing can be used.
  • wet mixing a mixed powder of the M element compound and the tungsten compound can be obtained by drying the mixed solution obtained after the wet mixing.
  • the drying temperature and time after wet mixing are not particularly limited.
  • the dry mixing may be performed by a known mixing device such as a commercially available grinder, kneader, ball mill, sand mill, paint shaker, etc., and the mixing conditions such as mixing time and mixing speed are not particularly limited.
  • the heat treatment temperature in the first heat treatment step is not particularly limited, but is preferably higher than the temperature at which the composite tungsten oxide particles crystallize. Specifically, for example, 500 ° C. or higher and 1000 ° C. or lower is preferable, and 500 ° C. or higher and 800 ° C. or lower is more preferable.
  • Second heat treatment step In the second heat treatment step, heat treatment is performed at a temperature of 500 ° C. or higher and 1200 ° C. or lower in a reducing gas atmosphere, a mixed gas atmosphere of a reducing gas and an inert gas, or an inert gas atmosphere as described above. be able to.
  • the type of the reducing gas is not particularly limited, but hydrogen (H 2 ) is preferable.
  • hydrogen H 2
  • its concentration may be appropriately selected according to the firing temperature, the quantity of the starting raw material, and the like, and is not particularly limited. For example, it is 20 vol% or less, preferably 10 vol% or less, and more preferably 7 vol% or less. This is because if the concentration of the reducing gas is 20 vol% or less, it is possible to avoid the formation of WO 2 having no solar shielding function due to rapid reduction.
  • the raw material mixture of a tungsten compound and M element compound, or the general formula M x W y O composite tungsten oxide precursor is prepared which is represented by z '(raw material preparation step).
  • the starting material prepared in the raw material preparation step is supplied into the plasma together with the carrier gas, and the desired composite tungsten oxide particles are produced through evaporation and condensation processes (reaction step).
  • reaction step evaporation and condensation processes
  • Raw material preparation process When preparing a raw material mixture of a tungsten compound and an M element compound as a starting material, the substance amount ratio (M: W) of M element (M) and tungsten (W) in the raw material mixture of the tungsten compound and the M element compound. ) Is preferably equal to the ratio x: y of x to y in the above-mentioned general formula of the target composite tungsten oxide, and each raw material is blended and mixed.
  • the same materials as those described in the solid phase reaction method can be preferably used, and thus the description thereof will be omitted here.
  • M can be the above-mentioned M element
  • W can be tungsten
  • O can be oxygen
  • x, y, z It is preferable that ′ satisfies 0.001 ⁇ x / y ⁇ 1 and 2.0 ⁇ z ′ / y.
  • X / y in the composite tungsten oxide precursor according is preferably a material that matches the x / y in the general formula M x W y O z particles of composite tungsten oxide expressed by the intended.
  • a mixed gas of an inert gas and an oxygen gas can be used as the carrier gas for transporting the starting material in the reaction step.
  • Plasma can be generated, for example, in an inert gas alone or in a mixed gas atmosphere of an inert gas and a hydrogen gas.
  • the plasma is not particularly limited, but thermal plasma is preferable.
  • the raw material supplied into the plasma evaporates instantaneously, and the evaporated raw material condenses in the process of reaching the plasma tail flame portion and is rapidly cooled and solidified outside the plasma frame to generate particles of composite tungsten oxide.
  • the plasma method for example, particles of a composite tungsten oxide having a single phase crystal phase can be generated.
  • the plasma used in the method for producing near-infrared absorbing material particles of the present embodiment is, for example, any one of DC arc plasma, high frequency plasma, microwave plasma, low frequency AC plasma, a superposition of these, or a magnetic field on the DC plasma. It is preferable that it is obtained by an electric method to which the above is applied, by a high-power laser, or by a high-power electron beam or an ion beam. Whichever thermal plasma is used, it is a thermal plasma having a high temperature portion of 10000 K or more, more preferably 10000 K or more and 25000 K or less, and in particular, a plasma capable of controlling the generation time of particles is preferable.
  • the device shown in FIG. 1 is a hybrid plasma reactor 10 in which a DC plasma device and a high-frequency plasma device are superimposed.
  • the hybrid plasma reactor 10 has a water-cooled quartz double tube 11 and a reaction vessel 12 connected to the water-cooled quartz double tube 11. Further, a vacuum exhaust device 13 is connected to the reaction vessel 12.
  • a DC plasma torch 14 is provided above the water-cooled quartz double tube 11, and the DC plasma torch 14 is provided with a gas supply port 15 for plasma generation.
  • sheath gas for generating high-frequency plasma and protecting the quartz tube is configured to be supplied, and the upper flange of the water-cooled quartz double tube 11 is provided.
  • a sheath gas introduction port 16 is provided.
  • a water-cooled copper coil 17 for generating high-frequency plasma is arranged around the water-cooled quartz double tube 11.
  • a raw material powder carrier gas supply port 18 is provided in the vicinity of the DC plasma torch 14, and is connected to a raw material powder supply device 19 for supplying the raw material powder by piping.
  • a gas supply device 20 can be connected to the plasma generation gas supply port 15, the sheath gas introduction port 16, and the raw material powder supply device 19 by piping so that a predetermined gas can be supplied from the gas supply device 20 to each member. .. If necessary, the members in the device may be cooled, or a supply port may be provided in addition to the members so as to create a predetermined atmosphere, and the members may be connected to the gas supply device 20.
  • the vacuum exhaust device 13 evacuates the inside of the reaction system composed of the inside of the water-cooled quartz double tube 11 and the inside of the reaction vessel 12.
  • the degree of vacuum at this time is not particularly limited, but can be evacuated to, for example, about 0.1 Pa (about 0.001 Torr).
  • argon gas can be supplied from the gas supply device 20 to fill the inside of the reaction system with argon gas.
  • plasma gas can be supplied into the reaction vessel 12.
  • the plasma gas is not particularly limited, but is, for example, from argon gas, a mixed gas of argon and helium (Ar-He mixed gas), a mixed gas of argon and nitrogen (Ar-N 2 mixed gas), neon, helium, and xenone. Any gas of choice can be used.
  • the supply flow rate of the plasma gas is also not particularly limited, but for example, it can be introduced from the plasma generation gas supply port 15 at a flow rate of preferably 3 L / min or more and 30 L / min or less, more preferably 3 L / min or more and 15 L / min or less. Then, DC plasma can be generated.
  • sheath gas for generating high-frequency plasma and protecting the quartz tube can be supplied in a swirling manner from the sheath gas introduction port 16 along the inner wall of the water-cooled quartz double tube 11 outside the plasma region.
  • the type of sheath gas and the supply speed are not particularly limited, but for example, argon gas is flowed at 20 L / min or more and 50 L / min or less and hydrogen gas at 1 L / min or more and 5 L / min or less to generate high-frequency plasma.
  • a high frequency power supply can be applied to the water-cooled copper coil 17 for generating high frequency plasma.
  • the conditions of the high frequency power supply are not particularly limited, but for example, a high frequency power supply having a frequency of about 4 MHz can be added at 15 kW or more and 50 kW or less.
  • the raw material can be introduced from the raw material powder carrier gas supply port 18 by the raw material powder supply device 19 using the carrier gas.
  • the carrier gas is also not particularly limited, and for example, a mixed gas composed of an argon gas of 1 L / min or more and 8 L / min or less and an oxygen gas of 0.001 L / min or more and 0.8 L / min or less can be used.
  • the reaction is carried out by introducing a raw material mixture or a composite tungsten oxide precursor, which is a starting material supplied into the plasma, into the plasma.
  • the supply rate of the starting material from the raw material powder carrier gas supply port 18 is not particularly limited, but for example, it is preferably supplied at a ratio of 1 g / min or more and 50 g / min or less, and more preferably 1 g / min or more and 20 g / min or less.
  • the supply rate of the starting material By setting the supply rate of the starting material to 50 g / min or less, the ratio of the starting material passing through the center of the plasma flame is sufficiently increased, the ratio of unreacted substances and intermediate products is suppressed, and the desired composite tungsten is obtained.
  • the production rate of oxide particles can be increased. Further, the productivity can be improved by setting the supply rate of the starting raw material to 1 g / min or more.
  • the starting material supplied into the plasma evaporates instantly in the plasma, and through a condensation process, composite tungsten oxide particles having an average primary particle size of 100 nm or less are generated.
  • the particle size of the composite tungsten oxide particles obtained by the production method of the present embodiment can be easily controlled by the plasma output, the plasma flow rate, the amount of raw material powder to be supplied, and the like.
  • the generated composite tungsten oxide particles are deposited in the reaction vessel 12, so that they can be recovered.
  • the surface of the near-infrared absorbing material particles obtained by the manufacturing method described so far can also be coated with a coating film. Since the method of forming the coating film has already been described, the description thereof will be omitted here.
  • the method for producing the near-infrared absorbing material particles of the present embodiment has been described above, but the near-infrared absorbing material particles obtained by the manufacturing method can be evaluated and confirmed by, for example, the following method.
  • the analysis method is not particularly limited, but for example, element M and tungsten can be analyzed by plasma emission spectroscopy, and oxygen can be analyzed by an inert gas impulse heating / melting infrared absorption method.
  • the crystal structure of the composite tungsten oxide particles contained in the near-infrared absorbing material particles can be confirmed by the powder X-ray diffraction method.
  • the particle size of the near-infrared absorbing material particles can be confirmed by TEM observation or particle size measurement based on the dynamic light scattering method. 3.
  • the near-infrared absorbing material particle dispersion liquid of the present embodiment can include the above-mentioned near-infrared absorbing material particles and a dispersion medium.
  • the near-infrared absorbing material particles are preferably dispersed in a dispersion medium.
  • the near-infrared absorbing material particle dispersion liquid according to the present embodiment is obtained by mixing and dispersing the above-mentioned near-infrared absorbing material particles containing the composite tungsten oxide particles in an appropriate dispersion medium (solvent).
  • the type of dispersion medium used in the near-infrared absorbing material particle dispersion liquid of the present embodiment is not particularly limited. For example, it can be selected according to the conditions, environment, etc. when the dispersion liquid is applied or kneaded into another material. Further, when the near-infrared absorbing material particle dispersion liquid of the present embodiment further contains other components such as an inorganic binder and a binder such as a resin binder, a dispersion medium is used in accordance with other components such as a binder. You can choose.
  • dispersion medium examples include water, ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol, diacetone alcohol and other alcohols, methyl ether, ethyl ether, propyl ether and other ethers, esters, acetone, methyl ethyl ketone and diethyl ketone.
  • Cyclohexanone, isobutyl ketone, ketones such as methyl isobutyl ketone, water such as aromatic hydrocarbons such as toluene, and one or more selected from various organic solvents can be used.
  • a resin monomer or oligomer may be used as the dispersion medium.
  • the content ratio of the dispersion medium in the near-infrared absorbing material particle dispersion is not particularly limited, but it is preferable that the dispersion medium is contained in an amount of 80 parts by mass or more with respect to 100 parts by mass of the near-infrared absorbing material particles.
  • the dispersion medium is contained in an amount of 80 parts by mass or more with respect to 100 parts by mass of the near-infrared absorbing material particles.
  • the near-infrared absorbing material particle dispersion liquid of the present embodiment may contain any component other than the near-infrared absorbing material particles and the dispersion medium.
  • an acid or an alkali may be added to the near-infrared absorbing material particle dispersion liquid of the present embodiment to adjust the pH of the dispersion liquid.
  • the near-infrared absorbing material particle dispersion of the present embodiment further contains various dispersants, surfactants, coupling agents and the like. You can also do it.
  • the method of dispersing the near-infrared absorbing material particles in the dispersion medium is not particularly limited.
  • the near-infrared absorbing material particles are uniformly dispersed in the dispersion medium, and the particle size of the near-infrared absorbing material particles can be adjusted.
  • it is a method of uniformly dispersing the near-infrared absorbing material particles in a dispersion medium, preferably a method in which the particle size of the near-infrared absorbing material particles is 100 nm or less, and is preferably 10 nm or more and 100 nm or less.
  • the method is more preferably 10 nm or more and 80 nm or less, particularly preferably 10 nm or more and 60 nm or less, and most preferably 10 nm or more and 40 nm or less.
  • Examples of the method of dispersing the near-infrared absorbing material particles in the dispersion medium include one or more selected from a bead mill, a ball mill, a sand mill, a paint shaker, an ultrasonic homogenizer, and the like.
  • the particles of the near-infrared absorbing material are dispersed in the dispersion medium, and at the same time, the particles of the near-infrared absorbing material are atomized due to collisions with each other.
  • the state of the near-infrared absorbing material particle dispersion liquid of the present embodiment can be confirmed by measuring the dispersed state of the near-infrared absorbing material particles when the near-infrared absorbing material particles are dispersed in the dispersion medium.
  • the near-infrared absorbing material particles of the present embodiment are confirmed by sampling a sample from the particles and a liquid existing as an aggregated state of the particles in the dispersion medium and measuring with various commercially available particle size distribution meters. Can be done.
  • the particle size distribution meter for example, a known measuring device such as ELS-8000 manufactured by Otsuka Electronics Co., Ltd. based on the dynamic light scattering method can be used.
  • the dispersed particle size of the near-infrared absorbing material particles is preferably 800 nm or less, more preferably 200 nm or less, and further preferably 100 nm or less from the viewpoint of optical characteristics.
  • the lower limit of the dispersed particle size of the near-infrared absorbing material is not particularly limited, but is preferably 10 nm or more, for example.
  • the near-infrared absorbing material particles are uniformly dispersed in the dispersion medium.
  • the dispersed particle size of the near-infrared absorbing material particles is 800 nm or less, for example, a near-infrared absorbing film (near-infrared shielding film) or a molded body (plate, sheet, etc.) manufactured by using a near-infrared absorbing material particle dispersion liquid.
  • a near-infrared absorbing film near-infrared shielding film
  • a molded body plate, sheet, etc.
  • the dispersed particle size means the particle size of the single particles of the near-infrared absorbing material particles dispersed in the near-infrared absorbing material particle dispersion, or the particle size of the agglomerated particles in which the near-infrared absorbing material particles are aggregated.
  • the near-infrared absorbing material particles aggregate to form coarse agglomerates, and when a large number of the coarsened particles are present, the coarse particles become a light scattering source.
  • a near-infrared absorbing material particle dispersion such as a near-infrared absorbing film or a molded body is produced using the near-infrared absorbing material particle dispersion, haze becomes large and the visible light transmittance decreases. May cause Therefore, it is preferable to disperse the near-infrared absorbing material particles sufficiently so as to avoid the formation of coarse particles. 4.
  • the near-infrared absorbing material particle dispersion of the present embodiment can include the above-mentioned near-infrared absorbing material particles and a solid medium.
  • the near-infrared absorbing material particles are preferably dispersed in a solid medium.
  • the near-infrared absorbing material particle dispersion of the present embodiment is obtained by dispersing the above-mentioned near-infrared absorbing material particles in an appropriate solid medium.
  • the near-infrared absorbing material particles are mechanically pulverized under predetermined conditions and then dispersed in a solid medium such as resin to maintain the dispersed state. Therefore, it can be applied to a base material having a low heat resistant temperature such as a resin material, and has an advantage that it does not require a large device for formation and is inexpensive.
  • the near-infrared absorbing material of this embodiment is a conductive material, when it is used as a continuous film, it may absorb and reflect radio waves of a mobile phone or the like and interfere with it.
  • the near-infrared absorbing material is dispersed as particles in a matrix of a solid medium, each particle is dispersed in an isolated state, so that radio wave transmission can be exhibited and the material has versatility.
  • the average particle size of the near-infrared absorbing material particles dispersed in the matrix of the solid medium of the near-infrared absorbing material particle dispersion and the near-infrared absorbing material particle dispersion used to form the near-infrared absorbing material particle dispersion may be different.
  • the solid medium of the near-infrared absorbing material particle dispersion is not particularly limited, but for example, resin or glass can be used.
  • the type of resin is not particularly limited, and the resin is, for example, polyethylene terephthalate resin, polycarbonate resin, acrylic resin, polystyrene resin, polyamide resin, polyethylene resin, vinyl chloride resin, polyvinyl butyral resin, polyester. It may be one or more kinds selected from a resin, an olefin resin, an epoxy resin, a polyimide resin, a fluororesin, an ethylene / vinyl acetate copolymer resin, and a polyvinyl acetal resin.
  • the content ratio of the near-infrared absorbing material particles in the near-infrared absorbing material particle dispersion is not particularly limited, but the near-infrared absorbing material particle dispersion contains the near-infrared absorbing material particles in an amount of 0.001% by mass or more and 80% by mass or less. It is preferably contained in a proportion. This is because a sufficient near-infrared ray shielding function can be exhibited by containing 0.001% by mass or more of the near-infrared ray absorbing material particles.
  • the ratio of the solid medium contained in the near-infrared absorbing material particle dispersion can be increased, and the strength of the dispersion can be increased. is there.
  • the shape and the like of the near-infrared absorbing material particle dispersion of the present embodiment are not particularly limited and can be arbitrarily selected according to the application and the like.
  • the near-infrared absorbing material particle dispersion of the present embodiment is preferably in the form of a sheet, a board, or a film.
  • the method for producing the near-infrared absorbing material particle dispersion of the present embodiment is not particularly limited, and the near-infrared absorbing material particles described above can be produced by adding them to a solid medium and dispersing them as necessary.
  • the near-infrared absorbing material particle dispersion of the present embodiment can be produced, for example, by the following procedure.
  • a dispersion liquid for forming a particle dispersion of a near-infrared absorbing material can be prepared.
  • the near-infrared absorbing material particle dispersion forming dispersion can be prepared, for example, by adding and dissolving a resin as a solid medium to the near-infrared absorbing material particle dispersion. Further, it can be prepared by adding one or more selected from a silane coupling agent, a silane-based alkoxide, polysilazane, and polyorganosilane, which are precursors of a silicate compound or the like to be glass, to the near-infrared absorbing material particle dispersion.
  • the prepared dispersion liquid for forming a particle dispersion of a near-infrared absorbing material is applied to a glass plate or a transparent base material such as a plate-shaped plastic.
  • the dispersion medium of the near-infrared absorbing material particle dispersion contained in the dispersion for forming the near-infrared absorbing material particle dispersion was dried and volatilized to form a cured near-infrared absorbing material particle dispersion on the surface of the transparent substrate.
  • the formed near-infrared absorbing transparent substrate can be obtained.
  • Example 1 23.5 g of Cs 2 CO 3 was dissolved in 36 g of water , this was added to 109 g of H 2 WO 4 and sufficiently stirred, and then dried to obtain a raw material mixture according to Example 1 (raw material preparation step).
  • the reaction step was carried out using the hybrid plasma reactor 10 in which the DC plasma and the high frequency plasma shown in FIG. 1 were superimposed.
  • the inside of the reaction system was evacuated to about 0.1 Pa (about 0.001 torr) by the vacuum exhaust device 13, and then completely replaced with argon gas to obtain an argon flow system at 1 atm.
  • Argon gas 8 L / min was flowed from the plasma generation gas supply port 15 to generate DC plasma.
  • the DC power input at this time is 6 kW.
  • argon gas 40 L / min and hydrogen gas 3 L / min are spirally flowed from the sheath gas introduction port 16 to obtain high frequency. A plasma was generated.
  • the high frequency power input at this time was set to 45 kW.
  • the particle size of the recovered tungsten oxide particles a was determined by TEM observation, it was confirmed that the particle size of the 30 particles evaluated was 10 nm or more and 50 nm or less.
  • the particle size was calculated by using the diameter of the smallest circle circumscribing the particle to be evaluated as the particle size of the particle.
  • Cs was evaluated by a frame atomic absorption spectrophotometer (manufactured by VARIAN, model: SpecterAA 220FS). W was evaluated by an ICP emission spectroscopic analyzer (manufactured by Shimadzu Corporation, model: ICPE9000). O was evaluated by an oxygen-nitrogen simultaneous analyzer (manufactured by LECO, model: ON836).
  • VARIAN frame atomic absorption spectrophotometer
  • ICP emission spectroscopic analyzer manufactured by Shimadzu Corporation, model: ICPE9000
  • O was evaluated by an oxygen-nitrogen simultaneous analyzer (manufactured by LECO, model: ON836).
  • the X-ray diffraction pattern of the cesium tungsten oxide particles a was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method) using a powder X-ray diffractometer (X'Pert-PRO / MPD manufactured by PANalytical Co., Ltd.).
  • a powder X-ray diffractometer X'Pert-PRO / MPD manufactured by PANalytical Co., Ltd.
  • the crystal structure of the compound contained in the particles of the composite tungsten oxide as described above coincides with the peak of the similar hexagonal composite tungsten oxide. Therefore, it can be confirmed that the crystal structure of the composite tungsten oxide obtained in this example, that is, tungsten cesium oxide, is hexagonal.
  • Acrylic polymer dispersant having 20.0% by mass of cesium oxide tungsten particles a and an amine-containing group as a functional group (amine value 48 mgKOH / g, acrylic dispersant having a decomposition temperature of 250 ° C.) (hereinafter, " Dispersant a ”.) 16.0% by mass and 64.0% by mass of methylisobutylketone as a dispersion medium were weighed and placed in a paint shaker (manufactured by Asada Iron Works Co., Ltd.) containing 0.3 mm ⁇ ZrO 2 beads. A near-infrared absorbing material particle dispersion liquid (A-1 liquid) was prepared by loading and crushing / dispersing treatment for 50 minutes.
  • a near-infrared absorbing material particle dispersion liquid (A-1 liquid) was prepared by loading and crushing / dispersing treatment for 50 minutes.
  • the particle size of the cesium tungsten oxide particles a in the near-infrared absorbing material particle dispersion (A-1 solution) is measured by a particle size measuring device based on a dynamic light scattering method (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.). It was 50 nm as measured by.
  • the dispersion medium was removed from the near-infrared absorbing material particle dispersion liquid (A-1 liquid), and the recovered near-infrared absorbing material particles were subjected to a powder X-ray diffractometer (X'Pert-PRO / MPD manufactured by Spectris Co., Ltd.
  • the X-ray diffraction pattern was measured using the above, and the crystallite diameter was determined from the X-ray diffraction pattern by the Rietveld method. As a result, the crystallite diameter was 25.0 nm.
  • the lattice constants obtained by the Rietveld method were 7.4099 ⁇ for the a-axis and 7.6090 ⁇ for the c-axis. In the other examples and comparative examples below, the crystallite diameter and lattice constant were determined by the Rietveld method.
  • the obtained near-infrared absorbing material particle dispersion liquid (A-1 liquid) and the UV curable resin (Aronix UV-3701 (Toa Synthetic Co., Ltd.)) were weighed so as to have a weight ratio of 1: 9. , Mixing and stirring to prepare a dispersion liquid (AA-1 liquid) for forming a particle dispersion of a near-infrared absorbing material.
  • a dispersion liquid (AA-1 liquid) for forming a near-infrared absorbing material particle dispersion was applied onto a soda-lime glass substrate having a thickness of 3 mm, and then at 70 ° C. for 1 minute. It was dried. Next, a high-pressure mercury lamp was irradiated to obtain a near-infrared absorber A, which is a particle dispersion of near-infrared absorbing material according to Example 1.
  • the optical characteristics of the near-infrared absorber A were measured. As a result, the visible light transmittance was 69.7% and the solar radiation transmittance was 47.0%.
  • optical characteristics were measured using a spectrophotometer U-4000 manufactured by Hitachi, Ltd. The following other optical characteristics are also measured by the same photometer. Visible light transmittance and solar radiation transmittance were calculated according to JIS R 3106 (2019).
  • the visible light transmittance and the solar radiation transmittance were measured.
  • the solar transmittance after exposure was 45.7%
  • the change ⁇ ST (post-exposure solar transmittance-pre-exposure solar transmittance) before and after 120 ° C exposure was -1.3%. It had excellent heat resistance.
  • a dispersion liquid (AA-1 liquid) for forming a near-infrared absorbing material particle dispersion was applied onto a PET film substrate having a thickness of 0.05 mm, and then the conditions were 70 ° C. for 1 minute. It was dried with.
  • the near-infrared absorber B which is the near-infrared absorbing material particle dispersion according to Example 1, was obtained by irradiating with a high-pressure mercury lamp.
  • the optical characteristics of the near-infrared absorber B were measured. As a result, the visible light transmittance was 70.3% and the solar radiation transmittance was 49.6%.
  • the visible light transmittance and the solar radiation transmittance were measured.
  • the solar transmittance was 49.3%, and the change ⁇ ST of the solar transmittance before and after the moisture resistance test was ⁇ 0.3%, which was excellent in moisture resistance.
  • Example 2 the same tests and evaluations as in Example 1 were carried out in Examples 2 to 21 and Comparative Examples 1 and 2. The results are shown in Tables 1 and 2.
  • Example 2 Near-infrared absorbing material particles were prepared using the high-frequency plasma reactor 30 shown in FIG.
  • the high-frequency plasma reactor 30 has a water-cooled quartz double tube 31 and a reaction vessel 32 connected to the water-cooled quartz double tube 31. Further, a vacuum exhaust device 33 is connected to the reaction vessel 32.
  • a gas supply port 34 for plasma generation is provided above the water-cooled quartz double tube 31.
  • sheath gas for generating high-frequency plasma and for protecting the quartz tube is configured to be supplied, and the sheath gas introduction port 36 is provided on the upper flange of the water-cooled quartz double tube 31. Is provided.
  • a water-cooled copper coil 37 for generating high-frequency plasma is arranged around the water-cooled quartz double tube 31.
  • a raw material powder carrier gas supply port 38 is provided in the vicinity of the plasma generation gas supply port 34, and is connected to the raw material powder supply device 39 for supplying the raw material powder by piping.
  • the plasma generation gas supply port 34, the sheath gas introduction port 36, and the raw material powder supply device 39 can be connected to the gas supply device 40 by piping so that a predetermined gas can be supplied from the gas supply device 40 to each member. If necessary, the members in the device may be cooled, or a supply port may be provided in addition to the members so as to create a predetermined atmosphere, and the members may be connected to the gas supply device 40.
  • the raw material mixture prepared in Example 1 is plasma at a ratio of 2 g / min from the raw material powder supply device 39. Supplied inside.
  • the particle size of the near-infrared absorbing material particles recovered at the bottom of the reaction vessel 32 was 10 nm or more and 50 nm or less as observed by TEM.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 2 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of hexagonal Cs 0.3 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 2 were used.
  • the crystallite diameter of the composite tungsten oxide particles which are the near-infrared absorbing material particles recovered from the dispersion medium by removing the dispersion medium from the near-infrared absorbing material particle dispersion, is 25.2 nm, and the lattice constant is the a-axis.
  • the crystallite diameter of the composite tungsten oxide particles which are the near-infrared absorbing material particles recovered from the dispersion medium by removing the dispersion medium from the near-infrared absorbing material particle dispersion
  • Example 3 6.65 g of Li 2 CO 3 was dissolved in 50 g of water , this was added to 150 g of H 2 WO 4 and sufficiently stirred, and then dried to obtain a raw material mixture according to Example 3.
  • Li 0.31 WO 3 which is a near-infrared absorbing material particle according to Example 3 by the same operation as in Example 2 except that the raw material mixture according to Example 3 was supplied into the plasma in the same manner as in Example 2. A powder of .16 particles was obtained.
  • the particle size of the recovered near-infrared absorbing material particles was 10 nm or more and 50 nm or less as observed by TEM.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 3 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of cubic Li 0.3 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 3 were used. Further, the dispersion medium was removed from the near-infrared absorbing material particle dispersion, and the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered from the dispersion, was 24.9 nm.
  • Example 4 2.74 g of Na 2 CO 3 was dissolved in 43 g of water , this was added to 130 g of H 2 WO 4 and sufficiently stirred, and then dried to obtain a raw material mixture according to Example 4.
  • the raw material mixture according to Example 4 was supplied into plasma in the same manner as in Example 2 to obtain a powder of Na 0.1 WO 3.19 particles, which are near-infrared absorbing material particles according to Example 4.
  • the particle size of the recovered near-infrared absorbing material particles was 10 nm or more and 50 nm or less as observed by TEM.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 4 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of tetragonal Na 0.1 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 4 were used. Further, the dispersion medium was removed from the near-infrared absorbing material particle dispersion, and the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered from the dispersion, was 25.5 nm.
  • Example 5 13.43 g of K 2 CO 3 was dissolved in 59 g of water, this was added to 180 g of H 2 WO 4 and sufficiently stirred, and then dried to obtain a raw material mixture according to Example 5.
  • the raw material mixture according to Example 5 was supplied into plasma in the same manner as in Example 2 to obtain a powder of K 0.27 WO 3.14 particles, which are composite tungsten oxide particles according to Example 5.
  • the particle size of the recovered near-infrared absorbing material particles was 10 nm or more and 50 nm or less as observed by TEM.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 5 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of hexagonal K 0.27 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 5 were used. Further, the dispersion medium was removed from the near-infrared absorbing material particle dispersion, and the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered from the dispersion, was 24.4 nm.
  • Example 6 22.17 g of Rb 2 CO 3 was dissolved in 50 g of water , this was added to 150 g of H 2 WO 4 and sufficiently stirred, and then dried to obtain a raw material mixture according to Example 6.
  • the raw material mixture according to Example 6 was supplied into plasma in the same manner as in Example 2 to obtain a powder of Rb 0.3 WO 3.16 particles, which are composite tungsten oxide particles according to Example 6.
  • the particle size of the recovered near-infrared absorbing material particles was 10 nm or more and 50 nm or less as observed by TEM.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 6 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of hexagonal Rb 0.3 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 6 were used.
  • the crystallite diameter of the composite tungsten oxide particles which are the near-infrared absorbing material particles recovered from the dispersion medium by removing the dispersion medium from the near-infrared absorbing material particle dispersion, is 23.9 nm, and the lattice constant is a.
  • the axis was 7.3958 ⁇ and the c-axis was 7.5605 ⁇ .
  • Example 7 It was dissolved Cu (NO 3) 2 3H 2 O30.16g water 40 g, which was sufficiently stirred and added to the H 2 WO 4 120 g, and dried to obtain a raw material mixture according to Example 7.
  • the raw material mixture according to Example 7 was supplied into plasma in the same manner as in Example 2 to obtain a powder of Cu 0.2 WO 3.14 particles, which are composite tungsten oxide particles according to Example 7.
  • the particle size of the recovered near-infrared absorbing material particles was 10 nm or more and 50 nm or less as observed by TEM.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 7 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of orthorhombic Cu 0.26 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 7 were used. Further, the dispersion medium was removed from the near-infrared absorbing material particle dispersion, and the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered from the dispersion, was 26.1 nm.
  • Example 8 0.66 g of Ag 2 CO 3 was dissolved in 40 g of water , this was added to 120 g of H 2 WO 4 and sufficiently stirred, and then dried to obtain a raw material mixture according to Example 8.
  • the raw material mixture according to Example 8 was supplied into plasma in the same manner as in Example 2 to obtain a powder of Ag 0.01 WO 3.16 particles, which are composite tungsten oxide particles according to Example 8.
  • the particle size of the recovered near-infrared absorbing material particles was 10 nm or more and 50 nm or less as observed by TEM.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 8 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of orthorhombic Ag 0.01 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 8 were used. Further, the dispersion medium was removed from the near-infrared absorbing material particle dispersion, and the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered from the dispersion, was 23.7 nm.
  • Example 9 6.42 g of CaCO 3 was dissolved in 53 g of water , this was added to 160 g of H 2 WO 4 and sufficiently stirred, and then dried to obtain a raw material mixture according to Example 9.
  • the raw material mixture according to Example 9 was supplied into plasma in the same manner as in Example 2 to obtain a powder of Ca 0.09 WO 3.14 particles, which are composite tungsten oxide particles according to Example 9.
  • the particle size of the recovered near-infrared absorbing material particles was 10 nm or more and 50 nm or less as observed by TEM.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 9 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of hexagonal Ca 0.1 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 9 were used. Further, the dispersion medium was removed from the near-infrared absorbing material particle dispersion, and the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered from the dispersion, was 23.5 nm.
  • Example 10 8.50 g of SrCO 3 was dissolved in 59 g of water, this was added to 180 g of H 2 WO 4 and sufficiently stirred, and then dried to obtain a raw material mixture according to Example 10.
  • the raw material mixture according to Example 10 was supplied into plasma in the same manner as in Example 2 to obtain a powder of Sr 0.01 WO 3.16 particles, which are composite tungsten oxide particles according to Example 10.
  • the particle size of the recovered near-infrared absorbing material particles was 10 nm or more and 50 nm or less as observed by TEM.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 10 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of hexagonal Sr 0.08 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 10 were used. Further, the dispersion medium was removed from the near-infrared absorbing material particle dispersion, and the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered from the dispersion, was 26.4 nm.
  • Example 11 13.26 g of BaCO 3 was dissolved in 40 g of water , this was added to 120 g of H 2 WO 4 and sufficiently stirred, and then dried to obtain a raw material mixture according to Example 11.
  • the raw material mixture according to Example 11 was supplied into plasma in the same manner as in Example 2 to obtain a powder of Ba 0.14 WO 3.14 particles, which are composite tungsten oxide particles according to Example 11.
  • the particle size of the recovered near-infrared absorbing material particles was 10 nm or more and 50 nm or less as observed by TEM.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 11 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of hexagonal Ba 0.14 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 11 were used. Further, the dispersion medium was removed from the near-infrared absorbing material particle dispersion, and the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered from the dispersion, was 24.7 nm.
  • Example 12 1.67 g of In 2 O 3 and 150 g of H 2 WO 4 were sufficiently mixed with a grinder to obtain a raw material mixture according to Example 12.
  • the raw material mixture according to Example 12 was supplied into plasma in the same manner as in Example 2 to obtain a powder of In 0.02 WO 3.18 particles, which are composite tungsten oxide particles according to Example 12.
  • the particle size of the recovered near-infrared absorbing material particles was 10 nm or more and 50 nm or less as observed by TEM.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 12 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of tetragonal In 0.02 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 12 were used. Further, the dispersion medium was removed from the near-infrared absorbing material particle dispersion, and the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered from the dispersion, was 25.0 nm.
  • Example 13 Water 180g dissolving TlNO 3 12.15g, which was sufficiently stirred and added to the H 2 WO 4 60 g, and dried to obtain a raw material mixture according to Example 13.
  • the raw material mixture according to Example 13 was supplied into plasma in the same manner as in Example 2 to obtain a powder of Tl 0.19 WO 3.19 particles, which are composite tungsten oxide particles according to Example 13.
  • the particle size of the recovered near-infrared absorbing material particles was 10 nm or more and 50 nm or less as observed by TEM.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 13 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of hexagonal Tl 0.19 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 13 were used. Further, the dispersion medium was removed from the near-infrared absorbing material particle dispersion, and the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered from the dispersion, was 26.4 nm.
  • Example 14 17.18 g of SnO 2 and 150 g of H 2 WO 4 were sufficiently mixed with a grinder to obtain a raw material mixture according to Example 14.
  • the raw material mixture according to Example 14 was supplied into plasma in the same manner as in Example 2 to obtain a powder of Sn 0.19 WO 3.16 particles, which are composite tungsten oxide particles according to Example 14.
  • the particle size of the recovered near-infrared absorbing material particles was 10 nm or more and 50 nm or less as observed by TEM.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 14 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of tetragonal Sn 0.19 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 14 were used. Further, the dispersion medium was removed from the near-infrared absorbing material particle dispersion, and the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered from the dispersion, was 23.9 nm.
  • Example 15 17.98 g of Yb 2 O 3 and 120 g of H 2 WO 4 were sufficiently mixed with a grinder to obtain a raw material mixture according to Example 15.
  • the raw material mixture according to Example 15 was supplied into plasma in the same manner as in Example 2 to obtain a powder of Yb 0.18 WO 3.16 particles, which are composite tungsten oxide particles according to Example 15.
  • the particle size of the recovered near-infrared absorbing material particles was 10 nm or more and 50 nm or less as observed by TEM.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 15 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of cubic Yb 0.19 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 15 were used. Further, the dispersion medium was removed from the near-infrared absorbing material particle dispersion, and the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered from the dispersion, was 24.3 nm.
  • Example 16 After thorough mixing with grinder to Nissan Chemical Industries, Ltd. Snowtex S17.25g and H 2 WO 4 150 g, dried to obtain a raw material mixture according to Example 16.
  • the raw material mixture according to Example 16 was supplied into plasma in the same manner as in Example 2 to obtain a powder of Si 0.04 WO 3.14 particles, which are composite tungsten oxide particles according to Example 16.
  • the particle size of the recovered near-infrared absorbing material particles was 10 nm or more and 50 nm or less as observed by TEM.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 16 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of cubic Si 0.04 WO 2.839 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 16 were used. Further, the dispersion medium was removed from the near-infrared absorbing material particle dispersion, and the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered from the dispersion, was 26.2 nm.
  • Example 17 Composite tungsten oxide particles according to Example 17 in the same manner as in Example 2 except that a mixed gas of 5 L / min argon gas and 0.01 L / min oxygen gas was used as a carrier gas in Example 2. was prepared and evaluated.
  • the particle size of the near-infrared absorbing material particles recovered from the high-frequency plasma reactor 30 was 10 nm or more and 50 nm or less according to TEM observation.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 17 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of hexagonal Cs 0.3 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 17 were used. Further, the dispersion medium was removed from the near-infrared absorbing material particle dispersion, and the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered from the dispersion, was 24.5 nm.
  • the lattice constants obtained by the Rietveld method were 7.4148 ⁇ on the a-axis and 7.5995 ⁇ on the c-axis.
  • Example 18 Composite tungsten oxide particles according to Example 18 in the same manner as in Example 2 except that a mixed gas of 4 L / min argon gas and 0.01 L / min oxygen gas was used as a carrier gas in Example 2. was prepared and evaluated.
  • the particle size of the near-infrared absorbing material particles recovered from the high-frequency plasma reactor 30 was 10 nm or more and 50 nm or less according to TEM observation.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 18 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of hexagonal Cs 0.3 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 18 were used. Further, the dispersion medium was removed from the near-infrared absorbing material particle dispersion, and the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered from the dispersion, was 21.7 nm.
  • the lattice constants obtained by the Rietveld method were 7.4116 ⁇ on the a-axis and 7.5955 ⁇ on the c-axis.
  • Example 19 In Example 2, a mixed gas of 5 L / min of argon gas and 0.02 L / min of oxygen gas was used as a carrier gas, and the raw material mixture prepared in Example 1 was put into plasma at a ratio of 2.5 g / min. Composite tungsten oxide particles according to Example 19 were prepared and evaluated in the same manner as in Example 2 except for the points supplied.
  • the particle size of the near-infrared absorbing material particles recovered from the high-frequency plasma reactor 30 was 10 nm or more and 50 nm or less according to TEM observation.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 19 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of hexagonal Cs 0.3 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 18 were used. Further, the dispersion medium was removed from the near-infrared absorbing material particle dispersion, and the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered from the dispersion, was 19.1 nm.
  • the lattice constants obtained by the Rietveld method were 7.4137 ⁇ on the a-axis and 7.6029 ⁇ on the c-axis.
  • Example 20 In Example 2, a mixed gas of 4.5 L / min of argon gas and 0.02 L / min of oxygen gas is used as a carrier gas, and the raw material mixture prepared in Example 1 is plasma at a ratio of 2.5 g / min.
  • the composite tungsten oxide particles according to Example 20 were prepared and evaluated in the same manner as in Example 2 except for the points supplied inside.
  • the particle size of the near-infrared absorbing material particles recovered from the high-frequency plasma reactor 30 was 10 nm or more and 50 nm or less according to TEM observation.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Example 20 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of hexagonal Cs 0.3 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion and a near-infrared absorbing material particle dispersion were prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particles according to Example 18 were used. Further, the dispersion medium was removed from the near-infrared absorbing material particle dispersion, and the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered from the dispersion, was 16.8 nm.
  • the lattice constant obtained by the Rietveld method was 7.4149 ⁇ on the a-axis and 7.5997 ⁇ on the c-axis.
  • Example 21 The near-infrared absorbing material particles 14.0% by mass and 86.0% by mass of pure water obtained in Example 19 were weighed and loaded into a paint shaker (manufactured by Asada Iron Works Co., Ltd.) containing 0.3 mm ⁇ ZrO 2 beads.
  • a dispersion liquid for forming a coating film was prepared by 50 decomposition crushing and dispersion treatment. While the dispersion was stirred, a 44.0% by mass isopropyl alcohol (IPA) solution of aluminum ethylacetate acetate diisopropylate was added dropwise over 5 hours as an aluminum-based chelate compound. Next, using a large-scale vacuum crusher, the medium was evaporated to obtain a near-infrared absorbing material particle powder having undergone the surface treatment according to Example 21. The infrared absorbing material particles are coated with a compound containing Al.
  • IPA isopropyl alcohol
  • the near-infrared absorbing material particle dispersion according to Example 21 was prepared by loading into a paint shaker (manufactured by Asada Iron Works) containing beads and dispersing the particles for 1 minute.
  • a near-infrared absorbing material particle dispersion was prepared and evaluated in the same manner as in Example 1 except that the near-infrared absorbing material particle dispersion liquid according to Example 21 was used.
  • near-infrared-absorbing material particles according to Comparative Example 1 3% H 2 under a gas atmosphere 500 ° C. in calcined effect 1 hour, coarse because near-infrared-absorbing material particles than the near-infrared absorbing material particles according to Example 1
  • the near-infrared absorbing material particle dispersion and the near-infrared absorbing material are the same as in Example 1 except that the dispersion / crushing time of the dispersion is 2 hours and the near-infrared absorbing material particles according to Comparative Example 1 are used.
  • a material particle dispersion was prepared and evaluated.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Comparative Example 1 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method).
  • ⁇ -2 ⁇ method powder X-ray diffraction method
  • the same peak as that of hexagonal Cs 0.3 WO 3 was confirmed.
  • the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered by removing the dispersion medium from the near-infrared absorbing material particle dispersion is 9 nm, and the lattice constant is 7.4100 ⁇ on the a-axis.
  • the c-axis was 7.6300 ⁇ .
  • the dried product was fired at 800 ° C. for 5.5 hours in a 5% H 2 gas atmosphere using N 2 gas as a carrier gas, and then the supplied gas was switched to N 2 gas only and the temperature was lowered to room temperature.
  • Tungsten oxide particles of cesium oxide, which are near-infrared absorbing material particles according to Comparative Example 2 were obtained.
  • the X-ray diffraction pattern of the obtained near-infrared absorbing material particles according to Comparative Example 2 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, the same peak as that of hexagonal Cs 0.3 WO 3 was confirmed.
  • a near-infrared absorbing material particle dispersion according to Comparative Example 2 was prepared by loading into a paint shaker (manufactured by Asada Iron Works) and pulverizing and dispersing for 30 hours.
  • a near-infrared absorbing material particle dispersion was produced in the same manner as in Example 1 except that the near-infrared absorbing material particle dispersion liquid according to Comparative Example 2 was used. Further, the crystallite diameter of the composite tungsten oxide particles, which are the near-infrared absorbing material particles recovered by removing the dispersion medium from the near-infrared absorbing material particle dispersion, is 9 nm, and the lattice constant is 7.4080 ⁇ on the a-axis. The c-axis was 7.6310 ⁇ .
  • the near-infrared absorption of Examples 1 to 21 produced by using the near-infrared absorbing material particle dispersion liquid containing the near-infrared absorbing material particles according to Examples 1 to 20.
  • the body emits sunlight, especially light in the near-infrared region, at the same level. It was confirmed that it absorbs and shields infrared rays, at the same time maintains high transmittance in the visible light region, and has excellent weather resistance.
  • the rate of change ( ⁇ ST) of the solar transmittance before and after the heat resistance evaluation and the weather resistance evaluation, which is the moist heat resistance evaluation is almost 0, or even if it changes, the rate of change. Is on the minus side.
  • the rate of change of the solar transmittance exceeds 1 and is on the positive side, it means that the composite tungsten oxide particles are deteriorated by the exposure and the ability to absorb infrared rays is deteriorated. From these facts, the results in Table 2 show that the composite tungsten oxide particles of the present embodiment have excellent weather resistance.
  • the present invention is not limited to the above-described embodiments and examples. Various modifications and changes are possible within the scope of the gist of the present invention described in the claims.

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