Manganese oxide, manganese oxide particles, near-infrared transmitting material, and near-infrared transmitting film

Abstract

To provide a near-infrared transmission material that has low transmittance in the visible light region while having high transmittance in the near-infrared radiation region.SOLUTION: A manganese oxide according to the present invention has its constituent elements expressed as A-Mn-O, where the constituent element A includes at least one element selected from Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to manganese oxide, manganese oxide particles, near-infrared transmitting materials, and near-infrared transmitting films. [Background technology]

[0002] In recent years, infrared sensors and infrared cameras have been effectively utilized in a wide range of technical fields. For example, in the field of information and communication devices such as smartphones, face recognition has been introduced to enhance security, and infrared sensors and infrared cameras are used to accurately detect facial shapes. In addition, in the automotive field, infrared sensors and infrared cameras are attached to vehicles to detect the situation around the vehicle.

[0003] In order to accurately detect the shape of a face and the situation around the vehicle, high-precision infrared sensors and near-infrared cameras are required, and to achieve this, filters and paints that transmit only near-infrared light and block other wavelengths, such as visible light, are necessary.

[0004] As a material for such filters and paints, Patent Document 1 discloses an infrared-transmitting product in which a composition in which titanium oxide or zinc oxide is blended with a transparent resin is used as the paint. Patent Documents 2 and 3 also disclose a configuration in which a composition in which an azo-based dye or pigment is blended with a transparent resin is used as a coating film that transmits near-infrared rays. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 2021-56346 [Patent Document 2] Patent No. 6899061 [Patent Document 3] Patent Publication No. 2021-56345 Summary of the Invention [Problem to be solved by the invention]

[0006] However, there were concerns that increasing the transmittance in the near-infrared region of paints formed from compositions in which titanium oxide or zinc oxide is blended with a transparent resin, as disclosed in Patent Document 1, would also increase the transmittance in the visible light region, and that titanium oxide and zinc oxide, having photocatalytic properties, would deteriorate the resin they are blended in. Furthermore, organic dyes and pigments such as azo-based dyes and pigments are generally said to be weak against ultraviolet rays, and there were concerns about their weather resistance and durability.

[0007] In view of the above problems, the present invention provides manganese oxide, manganese oxide particles, near-infrared transparent materials, and near-infrared transparent films that have low transmittance in the visible light region and high transmittance in the near-infrared region. [Means for solving the problem]

[0008] The manganese oxide of the present invention, which has been made to solve the above problems, is a manganese oxide whose constituent elements are expressed as A-Mn-O, and is characterized in that the constituent element A contains one or more elements selected from Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu. The manganese oxide of the present invention is not limited to a powder form, but may be in a liquid form dispersed in a dispersion medium.

[0009] The constituent elements of the manganese oxide of the present invention can be expressed as A-Mn-O. Specifically, the constituent element A represents one or more elements selected from Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu. The constituent element Mn represents manganese, a transition metal, and can have a valence of 2 to 7 depending on the constituent element A bonded to it, and is particularly stable in the +2, +3, +4, +6, and +7 states.

[0010] Here, when the molar ratio A / Mn of the constituent element A to Mn is 0.001 to 2.0, a material having low transmittance in the visible light region and excellent transmittance in the near-infrared region can be obtained. Furthermore, the molar ratio A / Mn of the constituent element A to Mn is more preferably 0.1 to 1.0, even more preferably 0.3 to 0.7, particularly preferably 0.4 to 0.6, and most preferably 0.5. When the constituent element A is a plurality of elements, "A" in the above-mentioned molar ratio A / Mn is the sum of the number of moles of the plurality of elements that are the constituent element A.

[0011] The constituent element O represents an oxygen element, and may be in an amount that satisfies the condition for electrical neutrality, and may include an oxygen excess or oxygen deficiency.

[0012] The manganese oxide of the present invention is characterized in that the constituent element A contains one or more elements selected from H, alkali metals, alkaline earth metals, rare earth elements, B, F, Al, Si, P, S, Cl, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Br, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb, and Bi. The manganese oxide of the present invention is preferred in that it contains, as constituent element A, one or more elements selected from Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu, as well as one or more elements selected from H, alkali metals, alkaline earth metals, rare earth elements, B, F, Al, Si, P, S, Cl, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Br, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb, and Bi, as it has low transmittance in the visible light region and high transmittance in the near-infrared region. Rare earth elements are 17 elements, including 15 elements (lanthanoids) ranging from La (lanthanum) with atomic number 57 to Lu (lutetium) with atomic number 71, plus Sc (scandium) with atomic number 21 and Y (yttrium) with atomic number 29, and refer to Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

[0013] Furthermore, the manganese oxide of the present invention is preferably an inorganic compound and preferably contains a metal element and / or a metalloid element. In this specification, unless otherwise specified, Be and Mg are considered to be alkaline earth metals.

[0014] In the manganese oxide of the present invention, the constituent element A preferably includes one or more elements selected from the group consisting of Cr, Fe, Co, and Ni. The manganese oxide of the present invention is preferred in that it contains, as constituent element A, one or more elements selected from Cr, Fe, Co, and Ni in addition to one or more elements selected from Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu, resulting in low transmittance in the visible light region and high transmittance in the near-infrared region. For example, the manganese oxide of the present invention may have a portion of the Mn constituting the manganese oxide replaced with one or more elements selected from Cr, Fe, Co, and Ni.

[0015] The manganese oxide of the present invention is characterized in that, in the XRD spectrum of the manganese oxide, it has a peak derived from the (111) plane appearing at 2θ=28.0° to 32.0° and a peak derived from the (112) plane appearing at 2θ=31.0° to 35.0°. In the manganese oxide of the present invention, when its XRD spectrum using CuKα radiation has a peak derived from the (111) plane appearing at 2θ = 28.0° to 32.0° and a peak derived from the (112) plane appearing at 2θ = 31.0° to 35.0°, this indicates that the crystal system of the manganese oxide of the present invention contains a hexagonal system, and is preferable in that the transmittance increases sharply around a wavelength of 780 nm, which is the boundary between the visible light region and the near-infrared region. Furthermore, in the XRD spectrum using CuKα radiation of the manganese oxide of the present invention, it is more preferable that the peak derived from the (111) plane appears at 2θ = 29.5° to 31.0°, and it is even more preferable that the peak derived from the (112) plane appears at 2θ = 32.0° to 34.0°.

[0016] Specifically, the manganese oxide of the present invention was thoroughly mixed and pulverized in an agate mortar, then sieved through a 75 μm sieve. 0.5 g of the well-mixed powder in the center of the undersize container was dispensed onto a glass sample plate, and the resulting sample was packed with glass plates to ensure a smooth surface. Powder X-ray diffraction measurement was performed using CuKα radiation under the following powder X-ray diffraction measurement conditions to obtain an X-ray diffraction pattern. The peak appearing between 2θ = 28.0° and 33.0° in the obtained X-ray diffraction pattern is due to the (111) plane of hexagonal manganese oxide AMnO3, and the peak appearing between 2θ = 31.0° and 35.0° is due to the (112) plane of hexagonal manganese oxide AMnO3. The "A" in hexagonal manganese oxide AMnO3 represents the constituent element A described above.

[0017] = Powder X-ray diffraction measurement conditions = Equipment: MiniFlex II (Rigaku Corporation) Measurement range (2θ): 5 to 90° Sampling width: 0.02° Scan speed: 1.0° / min ·X-ray: CuKα ray Voltage: 30kV ·Current: 15mA Divergence slit: 1.25° Scattering slit: 1.25° Receiving slit: 0.3 mm X-ray analysis software: PDXL2 Version 2.9.1.0

[0018] The manganese oxide of the present invention is characterized in that the crystal system of the manganese oxide includes a hexagonal crystal. The manganese oxide of the present invention is preferably one whose crystal system includes a hexagonal system, since the transmittance increases sharply around a wavelength of 780 nm, which is the boundary between the visible light region and the near-infrared region.

[0019] The manganese oxide of the present invention is characterized in that the reflectance of the manganese oxide at wavelengths of 550 nm and 700 nm is 20%R or less. With this configuration, the manganese oxide of the present invention has low reflectance values ​​for light with wavelengths of 550 nm and 700 nm, which are in the visible light range. This means that the manganese oxide of the present invention has excellent anti-halation properties in the visible light range. In other words, it not only does not simply not transmit visible light in the visible light range, but also has excellent visible light absorption properties. Furthermore, the reflectance of light with wavelengths of 550 nm and 700 nm is more preferably 15%R or less, even more preferably 12%R or less, particularly preferably 10%R or less, even more particularly preferably 5%R or less, and most preferably 0%R. Furthermore, it is more preferable that the reflectance of the manganese oxide of the present invention for light with wavelengths of 550 nm, 600 nm, 650 nm, and 700 nm is below the upper limit values ​​mentioned above. It is even more preferable that the reflectance of the manganese oxide of the present invention for light with wavelengths of 550 nm to 700 nm is below the upper limit values ​​mentioned above. The reflectance of the manganese oxide of the present invention for light with wavelengths of 550 nm and 700 nm is typically 0.001%R to 10%R. Alternatively, the reflectance for light with wavelengths of 550 nm and 700 nm may be 0.1%R to 5%R, or may be 0.11%R to 3%R. Furthermore, the reflectance for light with wavelengths of 550 nm and 700 nm may be 0.001%R to 0.99%R, or may be 0.001%R to 0.1%R.

[0020] The reflectance is measured using a spectrophotometer equipped with a φ60 mm integrating sphere unit (UH4150 ultraviolet-visible-near-infrared spectrophotometer manufactured by Hitachi High-Tech Science Corporation). A sample filled with the manganese oxide according to the present invention is attached, and the reflectance for light with wavelengths of 550 nm and 700 nm is measured.

[0021] Furthermore, the manganese oxide of the present invention preferably has a band gap of 0.62 eV or more and 1.77 eV or less. The band gap of the manganese oxide of the present invention is preferably 0.62 eV or more and 1.77 eV or less, since this results in low transmittance in the visible light region and high transmittance in the near-infrared region. Specifically, 0.62 eV corresponds to light in the near-infrared region with a wavelength of 2000 nm, and 1.77 eV corresponds to light near the lower end of the visible light region with a wavelength of 700 nm. Furthermore, the band gap is more preferably 1.10 eV or more and 1.77 eV or less, even more preferably 1.18 eV or more and 1.55 eV or less, particularly preferably 1.20 eV or more and 1.53 eV or less, and even more particularly preferably 1.25 eV or more and 1.50 eV or less.

[0022] The manganese oxide of the present invention has low transmittance in the visible light region and high transmittance in the near-infrared region, i.e., the wavelength dependence of transmittance, which is directly related to the band gap of the manganese oxide. Substances with a band gap exhibit strong absorption of light with energies equal to or greater than the band gap energy, resulting in a significant change in absorbance around the band gap energy. Therefore, the band gap determines the wavelength region in which the transition occurs from the short wavelength region with low transmittance to the long wavelength region with high transmittance. For example, as the absorbance of light with a wavelength of 700 nm (i.e., 1.77 eV) increases, the transmittance for light with a wavelength of 700 nm (visible light region) tends to decrease, while as the absorbance of light with a wavelength of 2000 nm (i.e., 0.62 eV) decreases, the transmittance for light with a wavelength of 2000 nm (near-infrared region) tends to increase. To achieve this wavelength dependence of transmittance through light absorption by the band gap, it is desirable for the band gap to be between 0.62 eV and 1.77 eV. On the other hand, in the near-infrared transmitting material of the present invention, not only band gap absorption by the manganese oxide of the present invention occurs, but also scattering, refraction, and absorption by components other than the manganese oxide of the present invention. Therefore, although the wavelength dependence of the transmittance resulting from light absorption by the band gap of the manganese oxide of the present invention does not completely match the wavelength dependence of the transmittance of the near-infrared transmitting material of the present invention containing the manganese oxide of the present invention, a strong positive correlation is observed.

[0023] The band gap of the manganese oxide of the present invention can be determined as follows. First, the diffuse reflectance of the manganese oxide of the present invention from the ultraviolet to near-infrared region is measured using a standard integral type ultraviolet-visible-near-infrared spectrometer. Next, the measured diffuse reflectance from the ultraviolet to near-infrared region is subjected to Kubelka-Munk transformation to determine the Kubelka-Munk function f. Note that the Kubelka-Munk function f is expressed as (1-R) ​​where R is the diffuse reflectance. 2 It can be calculated using the formula / 2R.

[0024] The horizontal axis is the energy of light E=hν, and the vertical axis is (hνf) 1 / n A Tauc plot is created where n = 1 / 2. A tangent line is drawn at the inflection point of the curve, and the point where it intersects with the horizontal axis is taken as the band gap value of the manganese oxide of the present invention. Here, the band gap transition of the manganese oxide of the present invention, i.e., YMnO3, is a direct allowed transition, so n = 1 / 2.

[0025] Furthermore, the manganese oxide of the present invention is characterized in that the composition formula of the manganese oxide is expressed as AxMnyOz, where x / y is 0.001 or more and 5.00 or less. In the composition formula (AxMnyOz) of the manganese oxide of the present invention, the coefficient x of the constituent element A and the coefficient y of the constituent element Mn are preferably x / y = 0.001 or more and 5.00 or less, from the viewpoint of gradually improving transmittance from a wavelength around 1000 nm and exhibiting high transmittance in the long wavelength region around 2000 nm. Furthermore, x / y = 0.001 or more and 2.00 or less is more preferable, and x / y = 0.10 or more and 1.5 or less is even more preferable. When the oxide mainly contains an oxide in which the atomic ratio of the constituent element A to Mn is 1:2, x / y = 0.40 or more and 0.60 or less is more preferable. When the oxide mainly contains an oxide in which the atomic ratio of the constituent element A to Mn is 1:1, x / y = 0.90 or more and 1.10 or less is more preferable. Furthermore, when the constituent element A is a multiple element, the coefficient x of the constituent element A is the sum of the coefficients of the multiple elements that are the constituent elements A. The coefficient z of the constituent element O may be any value that neutralizes the sum of the charges of the constituent elements A and Mn. The coefficients x, y, and z each represent an atomic percentage when the entire AxMnyOz is taken as 100 atomic percentage.

[0026] Furthermore, when the constituent element A of the manganese oxide of the present invention contains Y, this is preferable from the viewpoint that it suppresses transmission in the visible light region, while exhibiting a steep rise in transmittance from the low wavelength side around 1000 nm in the near-infrared region, and subsequently exhibiting high transmittance.

[0027] Furthermore, in the manganese oxide of the present invention, when the constituent element A contains Y, x / y = 0.001 to 5.00 is preferred from the viewpoint of suppressing transmission in the visible light region while exhibiting high transmittance in the near-infrared region. Furthermore, x / y = 0.001 to 2.00 is more preferred, and x / y = 0.10 to 1.5 is even more preferred. When the oxide mainly contains an oxide in which the atomic ratio of the constituent element A to Mn is 1:2, x / y = 0.40 to 0.60 is more preferred. When the oxide mainly contains an oxide in which the atomic ratio of the constituent element A to Mn is 1:1, x / y = 0.90 to 1.10 is more preferred.

[0028] Furthermore, when the manganese oxide of the present invention contains Y as constituent element A, the intensity ratio (211) / (112) of the peak intensity originating from the (211) plane of Mn3O4 appearing at 2θ = 35.5 to 36.5° to the peak intensity originating from the (112) plane of the oxide appearing at 2θ = 32.5 to 33.5° in an XRD spectrum using CuKα radiation is preferably 2.50 or less, more preferably 0.10 to 1.00, and a ratio of 0 indicates the absence of Mn3O4. From the viewpoint of high uniformity and high blackness (CIE 1976, i.e., CIE 1976(L)), this oxide is preferable. * a * b * ) color space measured using a * (redness), b * (yellowness index) is close to 0) is particularly preferable.

[0029] Furthermore, the manganese oxide of the present invention is for use as a near-infrared transmitting material. As described above, the manganese oxide of the present invention has low transmittance in the visible light region and excellent transmittance in the near-infrared region, and therefore can be used as a near-infrared transmitting material.

[0030] The manganese oxide particles of the present invention are characterized by containing the manganese oxide of the present invention described above. The manganese oxide particles of the present invention are in powder form, are preferably inorganic compound particles, and preferably contain a metal element and / or a metalloid element.

[0031] The manganese oxide particles of the present invention are characterized in that the constituent elements are manganese oxides represented by A-Mn-O, and the constituent element A includes one or more elements selected from the group consisting of Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu.

[0032] The constituent elements of the manganese oxide particles of the present invention can be expressed as A-Mn-O. Specifically, the constituent element A represents one or more elements selected from Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu. The constituent element Mn represents manganese, a transition metal, and can have a valence of 2 to 7 depending on the constituent element A bonded to it, and is particularly stable in the +2, +3, +4, +6, and +7 states.

[0033] The constituent element O represents an oxygen element, and may be in an amount that satisfies the condition for electrical neutrality, and may include an oxygen excess or oxygen deficiency.

[0034] Furthermore, the manganese oxide particles of the present invention may contain, as constituent element A, one or more elements selected from Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu, as well as one or more elements selected from H, alkali metals, alkaline earth metals, rare earth elements, B, F, Al, Si, P, S, Cl, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Br, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb, and Bi.

[0035] Furthermore, the manganese oxide particles of the present invention preferably contain, as constituent element A, one or more elements selected from the group consisting of Cr, Fe, Co, and Ni. The manganese oxide particles of the present invention preferably contain, as constituent element A, one or more elements selected from Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu, as well as one or more elements selected from Cr, Fe, Co, and Ni, since this results in low transmittance in the visible light region and high transmittance in the near-infrared region. For example, the manganese oxide particles of the present invention may have a portion of the Mn that is substituted with one or more elements selected from Cr, Fe, Co, and Ni.

[0036] The manganese oxide particles of the present invention are characterized in that their XRD spectrum has a peak derived from the (111) plane appearing at 2θ=28.0° to 32.0° and a peak derived from the (112) plane appearing at 2θ=31.0° to 35.0°. In the XRD spectrum using CuKα radiation, the manganese oxide particles of the present invention have a peak derived from the (111) plane appearing at 2θ = 28.0° to 32.0° and a peak derived from the (112) plane appearing at 2θ = 31.0° to 35.0°, indicating that the crystal system of the manganese oxide particles of the present invention contains hexagonal crystals, and are preferable in that the transmittance increases sharply around a wavelength of 780 nm, which is the boundary between the visible light region and the near-infrared region.

[0037] The manganese oxide particles of the present invention are also characterized in that their crystal system includes hexagonal crystals. The manganese oxide particles of the present invention are preferably those having a hexagonal crystal system, since the transmittance increases sharply around a wavelength of 780 nm, which is the boundary between the visible light region and the near-infrared region.

[0038] The manganese oxide particles of the present invention are characterized in that the reflectance of the manganese oxide particles at wavelengths of 550 nm and 700 nm is 20%R or less. The manganese oxide particles of the present invention preferably have a reflectance of 20%R or less at wavelengths of 550 nm and 700 nm, not only because they do not simply transmit visible light but also because they have excellent visible light absorption properties. The reflectance of 550 nm and 700 nm wavelengths is more preferably 15%R or less, even more preferably 12%R or less, particularly preferably 10%R or less, even more particularly preferably 5%R or less, and most preferably 0%R. Furthermore, the reflectance of 550 nm, 600 nm, 650 nm, and 700 nm wavelengths of the manganese oxide particles of the present invention is more preferably equal to or less than the upper limit values ​​described above. It is even more preferable that the reflectance of 550 nm to 700 nm wavelengths of the manganese oxide particles of the present invention is equal to or less than the upper limit values ​​described above. The reflectance of 550 nm and 700 nm wavelengths of the manganese oxide particles of the present invention is typically 0.001%R to 10%R. Furthermore, the reflectance of light with wavelengths of 550 nm and 700 nm may be 0.1%R to 5%R, or may be 0.11%R to 3%R. Furthermore, the reflectance of light with wavelengths of 550 nm and 700 nm may be 0.001%R to 0.99%R, or may be 0.001%R to 0.1%R.

[0039] The manganese oxide particles of the present invention are characterized in that the composition formula of the manganese oxide particles is expressed as AxMnyOz, where x / y = 0.001 or more and 5.00 or less. In the manganese oxide particles of the present invention, the coefficient x of the constituent element A and the coefficient y of the constituent element Mn in the composition formula (AxMnyOz) are preferably x / y = 0.001 or more and 5.00 or less, from the viewpoint of gradually improving transmittance from wavelengths around 1000 nm and exhibiting high transmittance in the long wavelength region around 2000 nm. Furthermore, x / y = 0.001 or more and 2.00 or less is more preferable, and x / y = 0.10 or more and 1.5 or less is even more preferable. When the oxide mainly contains an oxide in which the atomic ratio of the constituent element A to Mn is 1:2, x / y = 0.40 or more and 0.60 or less is more preferable. When the oxide mainly contains an oxide in which the atomic ratio of the constituent element A to Mn is 1:1, x / y = 0.90 or more and 1.10 or less is more preferable. Furthermore, when the constituent element A is a multiple element, the coefficient x of the constituent element A is the sum of the coefficients of the multiple elements that are the constituent elements A. The coefficient z of the constituent element O may be any value that neutralizes the sum of the charges of the constituent elements A and Mn.

[0040] Furthermore, when the constituent element A of the manganese oxide particles of the present invention contains Y, this is preferable from the viewpoint of suppressing transmission in the visible light region, while exhibiting a steep rise in transmittance from the low wavelength side around 1000 nm in the near-infrared region, and subsequently exhibiting high transmittance.

[0041] Furthermore, in the manganese oxide particles of the present invention, the constituent element A includes Y, and the composition formula of the manganese oxide is expressed as AxMnyOz, where x / y = 0.001 to 5.00 is preferable from the viewpoint of suppressing transmission in the visible light region while exhibiting a steep rise in transmittance from the low wavelength side around 1000 nm in the near-infrared region and subsequently exhibiting high transmittance. Furthermore, x / y = 0.001 to 2.00 is more preferable, and x / y = 0.10 to 1.5 is even more preferable. When the oxide mainly contains an oxide in which the atomic ratio of the constituent element A to Mn is 1:2, x / y = 0.40 to 0.60 is more preferable. When the oxide mainly contains an oxide in which the atomic ratio of the constituent element A to Mn is 1:1, x / y = 0.90 to 1.10 is more preferable.

[0042] The manganese oxide particles of the present invention are also characterized in that the average secondary particle diameter of the manganese oxide particles, as determined by SEM observation, is 10 nm or more and 20 μm or less. It is preferable that the manganese oxide particles of the present invention have an average secondary particle size of 10 nm or more and 20 μm or less as determined by SEM observation, in that this improves transmittance to near-infrared rays.

[0043] The average secondary particle diameter is more preferably 50 nm or more, and even more preferably 100 nm or more. On the other hand, the average secondary particle diameter is more preferably 10 μm or less, even more preferably 2 μm or less, and particularly preferably 0.5 μm or less. Typically, it may be 50 nm to 1 μm, or 100 nm to 1 μm.

[0044] Here, the average secondary particle diameter of the manganese oxide particles as determined by SEM observation is determined by observing SEM images using a field emission scanning electron microscope (FE-SEM) at an acceleration voltage of 1 kV. Specifically, manganese oxide particles of the present invention (30 randomly selected particles) are directly observed, their secondary particle diameters are measured, and the arithmetic mean value is calculated to determine the average secondary particle diameter as determined by SEM observation. Note that the measurement magnification should be selected appropriately from the range of 500x to 100,000x, depending on the size of the secondary particle diameter.

[0045] The manganese oxide particles of the present invention have a specific surface area of ​​0.20 m2 measured by the BET method. 2 / g or more. The manganese oxide particles of the present invention have a specific surface area of ​​0.20 m as measured by the BET method. 2 A specific surface area of ​​10.0 m / g or more is preferable in that the dispersibility of the manganese oxide particles is improved. 2 / g or more, and the specific surface area is more preferably 15.0 m 2 Typically, the specific surface area measured by the BET method is 0.20 m / g or more. 2 / g~500m 2 / g, and 0.20m 2 / g~300m 2 / g, and 0.20m 2 / g~200m 2 / g, and 0.20m 2 / g~100m 2 / g.

[0046] The specific surface area (SSA) of the manganese oxide particles of the present invention can be determined by measurement using a Macsorb (HM model-1201) manufactured by Mountech Co., Ltd. in accordance with "6.2 Flow Method (3.5) Single Point Method" of JIS R 1626-1996 (Method for measuring the specific surface area of ​​fine ceramic powders by the gas adsorption BET method). A mixed gas of helium as the carrier gas and nitrogen as the adsorbate gas is used. Nitrogen gas is also used for calibration.

[0047] Furthermore, the manganese oxide particles of the present invention preferably have a particle size at an integrated volume fraction of 50% as measured by particle size distribution measurement using a laser diffraction / scattering method of 0.1 μm or more and 20 μm or less, more preferably 0.2 μm or more and 10 μm or less, and even more preferably 0.3 μm or more and 1 μm or less.

[0048] The particle size distribution of the particles is evaluated using a laser diffraction / scattering particle size distribution analyzer (Microtrac Bell Corporation: MT3300EXII) in accordance with JIS Z 8825: 2013. In addition, without filtering, the sample is subjected to ultrasonic treatment at an ultrasonic output of 40 W for 3 minutes before measurement.

[0049] Specifically, a slurry sample is fed into the sample inlet of the sample circulator installed in the measuring device until the measuring device determines that the sample is within the measurable range, then ultrasonic dispersion processing (ultrasonic output 40W, 3 minutes) is performed within the measuring device, and after confirming that the display has stabilized, measurements are performed.

[0050] Furthermore, the manganese oxide particles of the present invention have a L * is 45 or less. The manganese oxide particles of the present invention have an L measured by CIE 1976 * When the L is 45 or less, the appearance becomes blacker and the transmittance in the visible light region can be reduced, which is preferable, when it is 40 or less it is more preferable, when it is 35 or less it is even more preferable, when it is 30 or less it is particularly preferable, when it is 20 or less it is even more particularly preferable, when it is 10 or less it is most preferable, and when it is 0. In addition, in the manganese oxide particles of the present invention, the L measured by CIE1976 is typically * may be 1 to 45, may be 10 to 45, or may be 20 to 45.

[0051] Here, CIE1976, i.e. CIE1976(L * a * b * ) color space, measured using L * The value of L indicates the lightness. * The closer the value of is to 100, the lighter the color is, approaching white. * The closer the value of L is to 0, the closer the color is to black and the darker it becomes. * The value is determined using a color difference meter (Konica Minolta: CR-300) in accordance with JIS Z 8722:2009.

[0052] Furthermore, CIE1976(L * a * b * ) color space a * The value of is preferably from -5 to 20, more preferably from -5 to 15, even more preferably from -5 to 10, particularly preferably from -5 to 5, more particularly preferably from -2 to 2, and most preferably 0. * The closer the value is to 0, the more coloring is suppressed. * a * b * ) color space b *The value of b is preferably from -10 to 25, more preferably from -5 to 20, even more preferably from -5 to 15, particularly preferably from -5 to 5, more particularly preferably from -2 to 2, and most preferably 0. * The closer the value of a is to 0, the more the coloring is suppressed. * and b * The value of L * Similarly to the value of (1), it can be determined using a color difference meter (Konica Minolta: CR-300) in accordance with JIS Z 8722:2009.

[0053] Furthermore, the manganese oxide particles of the present invention are for use as near-infrared transmitting materials. As described above, the manganese oxide particles of the present invention have low transmittance in the visible light region and excellent transmission performance in the near-infrared region, making them suitable for use in near-infrared transmitting materials.

[0054] To enhance dispersibility, the manganese oxide particles of the present invention may be surface-treated or a surface treatment agent may be added to the system. Examples of surface treatment agents include silane coupling agents. The surface treatment agent may be one type, or two or more types may be used in any combination.

[0055] The near-infrared transmitting material of the present invention is characterized by having the above-mentioned manganese oxide particles of the present invention and a dispersion containing a component that transmits near-infrared light. The near-infrared transparent material of the present invention comprises the above-mentioned manganese oxide particles of the present invention and a dispersion containing a component that transmits near-infrared light, and may be a mixture of the manganese oxide particles and a dispersion, or the manganese oxide particles coated on the surface of a dispersion. Furthermore, the manganese oxide particles contained in the near-infrared transparent material of the present invention are preferably inorganic compound particles, and preferably contain a metal element and / or a metalloid element.

[0056] The manganese oxide particles contained in the near-infrared transmitting material of the present invention are not limited to manganese oxide particles of the same composition and the same properties. For example, in order to adjust the fluidity, manganese oxide particles having the same composition but different particle size distributions may be appropriately mixed. Furthermore, in order to adjust the transmittance in the near-infrared region, manganese oxide particles of different compositions may be appropriately mixed. Furthermore, depending on the application, manganese oxide particles with different compositions and properties may be appropriately mixed.

[0057] Furthermore, the manganese oxide particles contained in the near-infrared transmitting material of the present invention are preferably manganese oxide particles whose constituent elements are expressed as A-Mn-O, and the constituent element A includes one or more elements selected from Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu. If the constituent elements of the manganese oxide particles contained in the near-infrared transmitting material of the present invention are expressed as A-Mn-O, and the constituent element A includes one or more elements selected from Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu, this is preferable in that the transmittance in the visible light region is low and the transmittance in the near-infrared region is high.

[0058] Here, the constituent element Mn represents manganese, a transition metal, and can take a valence of 2 to 7 depending on the bound constituent element A, and is particularly stable in the states of +2, +3, +4, +6, and +7. The constituent element O represents oxygen, and may be in an amount that satisfies the electrical neutrality condition, including oxygen excess and oxygen deficiency.

[0059] Furthermore, the manganese oxide particles contained in the near-infrared transmitting material of the present invention may contain, as constituent element A, one or more elements selected from Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu, as well as one or more elements selected from H, alkali metals, alkaline earth metals, rare earth elements, B, F, Al, Si, P, S, Cl, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Br, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb, and Bi.

[0060] Furthermore, the manganese oxide particles contained in the near-infrared transmitting material of the present invention preferably contain, as constituent element A, one or more elements selected from Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu, as well as one or more elements selected from Cr, Fe, Co, and Ni. The manganese oxide particles contained in the near-infrared transparent material of the present invention preferably contain, as constituent element A, one or more elements selected from Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu, as well as one or more elements selected from Cr, Fe, Co, and Ni, in that they have low transmittance in the visible light region and high transmittance in the near-infrared region. For example, the manganese oxide particles contained in the near-infrared transparent material of the present invention may have a portion of the Mn constituting the manganese oxide particles replaced with one or more elements selected from Cr, Fe, Co, and Ni.

[0061] The dispersion may be any dispersion containing a component that transmits near-infrared rays, and does not necessarily mean that all components contained in the dispersion are components that transmit near-infrared rays.

[0062] The near-infrared transmitting material of the present invention includes not only a structure in which manganese oxide particles are uniformly dispersed in a dispersion, but also a structure in which a plurality of manganese oxide particles aggregate to form aggregates which are dispersed in a dispersion, or a state in which the manganese oxide particles are segregated in a dispersion.

[0063] The near-infrared transmitting material of the present invention is characterized in that the reflectance of the near-infrared transmitting material for light with a wavelength of 550 nm and light with a wavelength of 700 nm is 20%R or less. The near-infrared transmitting material of the present invention preferably has a reflectance of 20%R or less for light with wavelengths of 550 nm and 700 nm, not only because it does not simply transmit visible light but also because it has excellent visible light absorption performance. The reflectance of 550 nm and 700 nm light is more preferably 15%R or less, even more preferably 12%R or less, particularly preferably 10%R or less, even more particularly preferably 5%R or less, and most preferably 0%R. Furthermore, the reflectance of 550 nm, 600 nm, 650 nm, and 700 nm light by the near-infrared transmitting material of the present invention is more preferably equal to or less than the upper limit values ​​described above. It is even more preferable that the reflectance of 550 nm to 700 nm light by the near-infrared transmitting material of the present invention is equal to or less than the upper limit values ​​described above. The reflectance of 550 nm and 700 nm light by the near-infrared transmitting material of the present invention is typically 0.001%R to 10%R. Furthermore, the reflectance of light with wavelengths of 550 nm and 700 nm may be 0.1%R to 5%R, or may be 0.11%R to 3%R. Furthermore, the reflectance of light with wavelengths of 550 nm and 700 nm may be 0.001%R to 0.99%R, or may be 0.001%R to 0.1%R.

[0064] The manganese oxide particles according to the present invention used for measuring reflectance can be extracted from the near-infrared transparent material of the present invention by the following method. If the dispersion is a resin, the manganese oxide particles can be extracted by heating to a temperature and for a time that sufficiently burns off the resin. If the dispersion is a solvent such as an organic solvent or water, the manganese oxide particles can be extracted by volatilizing the solvent.

[0065] Furthermore, the near-infrared transmitting material of the present invention is characterized in that the transmittance at a wavelength of 700 nm (visible light region) is 30%T or less, and the transmittance at a wavelength of 2000 nm (near-infrared region) is 10%T or more, which are greater than the transmittance at a wavelength of 700 nm (visible light region). The transmittance of the near-infrared transmitting material of the present invention is measured using a spectrophotometer for a near-infrared transmitting film (sample) obtained by applying the near-infrared transmitting material of the present invention to a polyethylene terephthalate (hereinafter referred to as PET) film and baking it. If the transmittance at a wavelength of 700 nm, which is in the visible light region, is 30%T or less and the transmittance at a wavelength of 2000 nm (near-infrared region) is 10%T or more, which is greater than the transmittance at a wavelength of 700 nm, it is preferable in terms of minimizing transmission of visible light and transmitting near-infrared light.

[0066] Furthermore, the transmittance at a wavelength of 700 nm in the visible light region is more preferably 27% T or less, even more preferably 20% T or less, particularly preferably 15% T or less, more particularly preferably 10% T or less, even particularly preferably 5% T or less, and most preferably 0% T. The transmittance at a wavelength of 700 nm (visible light region) of the near-infrared transmitting material of the present invention may typically be 0.001% T to 30% T, 0.1% T to 20% T, 0.11% T to 13% T, 1% T to 10% T, or 5% T to 10% T.

[0067] On the other hand, the transmittance at a wavelength of 2000 nm (near-infrared region) is more preferably 30%T or more, even more preferably 50%T or more, and particularly preferably 80%T or more.

[0068] The transmittance at a wavelength of 550 nm in the visible light region is more preferably 15% T or less, even more preferably 10% T or less, particularly preferably 5% T or less, and most preferably 0% T. The transmittance at a wavelength of 550 nm (visible light region) of the near-infrared transmitting material of the present invention may typically be 0.001% T to 30% T, 0.1% T to 20% T, 0.11% T to 13% T, 1% T to 10% T, or 5% T to 10% T.

[0069] The near-infrared transmitting material of the present invention is characterized in that the transmittance of the near-infrared transmitting material at a wavelength of 700 nm (visible light region) is 30%T or less, and the transmittance of the near-infrared transmitting material at a wavelength of 1000 nm (near-infrared region) and a wavelength of 2000 nm (near-infrared region) is 10%T or more, which is greater than the transmittance at a wavelength of 700 nm (visible light region). It is preferable that the transmittance at a wavelength of 700 nm, which is the visible light region, is 30%T or less, and the transmittance at a wavelength of 1000 nm (near-infrared region) and a wavelength of 2000 nm (near-infrared region) is 10%T or more, which is greater than the transmittance at a wavelength of 700 nm, in that it transmits near-infrared light over a wide wavelength range while minimizing the transmission of visible light. Furthermore, it is more preferable that the transmittance at a wavelength of 700 nm, which is the visible light region, of the near-infrared transparent material of the present invention is 30%T or less, and the transmittance at wavelengths of 1000 nm, 1200 nm, 1400 nm, 1600 nm, 1800 nm, 2000 nm, 2200 nm, and 2400 nm, which are the near-infrared region, is 10%T or more, which is greater than the transmittance at a wavelength of 700 nm. It is more preferable that the near-infrared transmitting material of the present invention has a transmittance of 30%T or less at a wavelength of 700 nm, which is the visible light region, and a transmittance of 1000 nm to 2400 nm, which is the near-infrared region, of 10%T or more, which is greater than the transmittance at a wavelength of 700 nm.

[0070] Furthermore, the near-infrared transmitting material of the present invention has an L * is 45 or less. The near-infrared transmitting material of the present invention has an L * When the L is 45 or less, the appearance becomes blacker and the transmittance in the visible light region can be reduced, which is preferable, when the L is 40 or less, more preferably when the L is 35 or less, even more preferably when the L is 30 or less, particularly preferably when the L is 20 or less, even more particularly preferably when the L is 10 or less, and most preferably when the L is 0. The near-infrared transmitting material of the present invention has an L measured typically by CIE1976. * may be 1 to 45, may be 10 to 45, or may be 20 to 45.

[0071] Furthermore, CIE1976(L * a * b * ) color space a * The value of is preferably from -5 to 20, more preferably from -5 to 15, even more preferably from -5 to 10, particularly preferably from -5 to 5, more particularly preferably from -2 to 2, and most preferably 0. * The closer the value is to 0, the more coloring is suppressed. * a * b * ) color space b * The value of b is preferably from -10 to 25, more preferably from -5 to 20, even more preferably from -5 to 15, particularly preferably from -5 to 5, more particularly preferably from -2 to 2, and most preferably 0. * The closer the value is to 0, the more coloring is suppressed. * a * b * ) color space L * , a * , b * When the dispersion contained in the near-infrared transmitting material of the present invention is colorless and transparent or nearly colorless, the value of * a * b * ) color space L * , a * , b * indicates a value equivalent to the value of

[0072] The near-infrared transmitting material of the present invention is characterized in that the dispersion is a resin, glass, an organic solvent, or water, or a mixture of two or more of these. The dispersion preferably contains a component that transmits near-infrared rays.

[0073] The type of resin used in the dispersion is not particularly limited, and any resin that can be molded into a desired shape can be used. For example, a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, and a two-component mixed curable resin can be used.

[0074] Among these resins, it is preferable to use a thermoplastic resin as the matrix resin from the viewpoint of ease of molding into a thick sheet. Examples of thermoplastic resins include at least one of polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate resins, polyacrylic acid resins such as polyacrylic acid or its esters, polymethacrylic acid or its esters, polyvinyl resins such as polystyrene and polyvinyl chloride, cellulose resins such as triacetyl cellulose, and urethane resins such as polyurethane. Note that the thermoplastic resins also include those molded into multilayers, polymer blends, and copolymers.

[0075] Furthermore, from the viewpoint of ease of molding into a thin sheet, it is preferable to use at least one of a thermosetting resin, an ionizing radiation curable resin, and a two-component curable resin as the matrix resin. Examples of thermosetting resins include phenolic resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane resin, and polyimide resin. Furthermore, examples of ionizing radiation curable resins include acrylic resin, urethane resin, vinyl ester resin, and polyester alkyd resin. These resins can be used not only as polymers but also as oligomers and monomers. Furthermore, an example of a two-component curable resin is an epoxy resin.

[0076] Examples of glasses used in the dispersion include glass plates, water glass, quartz, and powdered glass.

[0077] Both water-soluble and water-insoluble organic solvents can be used as the organic solvent for the dispersion. When a water-soluble organic solvent is used, it can also be used as a mixed solvent obtained by mixing it with water. Specifically, as the water-soluble organic solvent, organic solvents compatible with water, such as monoalcohols, polyhydric alcohols, ketones, esters, amines, thiols, pyrrolidones, etc., can be used. Here, examples of monoalcohols include methanol, ethanol, industrial ethanol, and isopropyl alcohol. Examples of polyhydric alcohols include ethylene glycol, oligoethylene glycol, propylene glycol, oligopropylene glycol, copolymers of ethylene glycol and propylene glycol, and butylene glycol. Examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, and isophorone.

[0078] On the other hand, as the water-insoluble organic solvent, for example, organic solvents that are not miscible with water, such as saturated or unsaturated hydrocarbon compounds, halogenated hydrocarbons and their cyclic compounds, long-chain monoalcohols and polyalcohols, aromatic compounds, etc. These organic solvents can be used alone or in combination of two or more.

[0079] Examples of water that can be used in the dispersion include ordinary tap water (containing ionic components), ion-exchanged water, pure water, and ultrapure water.

[0080] Unless otherwise specified, the resin, glass, organic solvent, or water used as the dispersion does not affect the properties of the near-infrared transmitting material of the present invention.

[0081] The manganese oxide, manganese oxide particles, and near-infrared transparent material of the present invention may contain oxide particles of Nb, Ta, Ti, Si, Zr, Zn, Al, Y, V, or lanthanoids (La, Ce, Nd, Eu, Gd, Dy, Yb, etc.) as additives. The content of the additives in the manganese oxide, manganese oxide particles, and near-infrared transparent material of the present invention is preferably less than 1% by mass, more preferably less than 0.1% by mass, and even more preferably less than 0.01% by mass. However, the content of the additives may exceed the above-mentioned ranges as long as the properties of the manganese oxide, manganese oxide particles, and near-infrared transparent material of the present invention are not impaired.

[0082] Furthermore, the manganese oxide, manganese oxide particles, and near-infrared transparent material of the present invention may contain components other than those derived from the manganese oxide or manganese oxide particles and the dispersion (referred to as "other components"), provided that the effects of the components are not impaired. Examples of other components include Nb, Ta, Ti, Si, Zr, Zn, Al, Y, V, and lanthanoids (La, Ce, Nd, Eu, Gd, Dy, Yb, etc.). However, the content of other components in the manganese oxide, manganese oxide particles, and near-infrared transparent material of the present invention is preferably less than 5% by mass, more preferably less than 4% by mass, and even more preferably less than 3% by mass. It is anticipated that the manganese oxide, manganese oxide particles, and near-infrared transparent material of the present invention may contain unintended, unavoidable impurities. The total content of unavoidable impurities is preferably less than 10% by mass, more preferably less than 7% by mass, even more preferably less than 5% by mass, particularly preferably less than 3% by mass, and even more particularly preferably less than 1% by mass.

[0083] The method for producing the near-infrared transmitting material of the present invention described above will be described below.

[0084] First, as an example of a method for producing manganese oxide particles that constitute the near-infrared transmitting material of the present invention, a method for producing yttrium manganate (hereinafter referred to as the present YMO) in which the constituent element A of the manganese oxide particles is "Y" will be described below.

[0085] The present YMO is obtained by mixing a manganese raw material and an yttrium raw material, optionally granulating and drying the mixture, sintering the mixture, optionally classifying the mixture, optionally heat treating the mixture, and optionally classifying the mixture again.

[0086] Alternatively, the present YMO may be prepared by adding a boron compound to a manganese raw material and an yttrium raw material, mixing the mixture, wet-pulverizing the mixture, granulating the mixture, drying the mixture, and calcining the mixture.

[0087] Here, the manganese raw material is not particularly limited, but examples thereof include manganese oxide (II) (manganese monoxide), manganese oxide (II, III), manganese oxide (III), manganese oxide (IV) (manganese dioxide), manganese oxide (VI), and manganese oxide (VII).

[0088] The yttrium raw material is not particularly limited, but examples thereof include yttrium oxide (YO), yttrium carbonate (Y(CO) 3H0), yttrium acetate (Y(CHCOO) 4H0), yttrium fluoride (YF), yttrium nitrate (Y(NO) nH0), etc. Yttrium oxide (YO) is particularly preferred.

[0089] The boron compound is added as a flux component to promote the composite formation of the manganese raw material and the yttrium raw material. After firing, the boron compound does not form a solid solution but remains as an impurity on the surface of the manganese oxide particles that constitute the near-infrared transmitting material of the present invention. However, this can be removed by washing with water or wet grinding. The content of the boron compound in the near-infrared transmitting material of the present invention is preferably less than 5% by mass, more preferably less than 3% by mass, and even more preferably less than 1% by mass. The content of the boron compound is calculated as the weight ratio of the element "boron (B)" by ICP emission spectrometry (AG-5110, manufactured by Agilent Technologies).

[0090] Here, the boron compound is preferably boric acid or lithium borate. Lithium borate may take various forms, such as lithium metaborate (LiBO), lithium tetraborate (LiBO), lithium pentaborate (LiBO), and lithium perborate (LiBO), with lithium tetraborate (LiBO) being particularly preferred.

[0091] The method for mixing the various raw materials described above is not particularly limited as long as they are mixed uniformly. For example, the raw materials may be added simultaneously or in an appropriate order using a known mixer such as a mixer, and then stirred and mixed in a wet or dry manner. In the case of wet mixing, it is preferable to add a liquid medium such as water or a dispersant and wet mix the raw materials to form a slurry, and then pulverize the resulting slurry using a wet pulverizer. It is particularly preferable to pulverize the raw materials to the submicron order. After pulverization to the submicron order, granulation and firing can increase the uniformity of the particles before the firing reaction, thereby increasing reactivity. As described above, the mixed raw materials may be fired as is, or they may be granulated to a predetermined size and then fired.

[0092] The granulation method may be either wet or dry, as long as the various pulverized raw materials are dispersed within the granulated particles without separation. Examples include extrusion granulation, tumbling granulation, fluidized bed granulation, mixed granulation, spray-drying granulation, pressure molding granulation, and flake granulation using a roll or the like. However, when wet granulation is used, it is necessary to thoroughly dry the granulated material before firing. Known drying methods such as spray-heat drying, hot-air drying, vacuum drying, and freeze-drying may be used, with spray-heat drying being particularly preferred. Spray-heat drying is preferably carried out using a thermal spray dryer (spray dryer). Granulation using a thermal spray dryer (spray dryer) not only makes it possible to achieve a sharper particle size distribution, but also allows the granulated material to be prepared so as to contain round, aggregated particles (secondary particles).

[0093] The calcination is preferably carried out in a calcination furnace in the air, oxygen gas, an atmosphere with adjusted oxygen partial pressure, carbon dioxide gas, or other atmosphere, by increasing the temperature at a rate of 50 to 200°C / hr and maintaining the temperature at 400 to 1500°C (meaning the temperature when a thermocouple is in contact with the calcined product in the calcination furnace) for 0.5 to 30 hours. However, when calcining together with a boron compound, calcination can be carried out at a temperature range lower than the above-mentioned calcination temperatures. The type of calcination furnace is not particularly limited. For example, a rotary kiln, a static furnace, or other calcination furnaces can be used.

[0094] The calcined product obtained by calcination may be used as is as the present YMO (manganese oxide particles). Alternatively, the calcined product may be pulverized and used as the present YMO (manganese oxide particles). Regardless of whether it is pulverized or not, the calcined product may be classified using a sieve or the like, and the resulting undersized particles (fine particles) may be used as the present YMO (manganese oxide particles). The oversized particles (coarse particles) may be pulverized again and classified before use.

[0095] The pulverization method can be either dry or wet. In the dry method, the sintered product can be pulverized using commercially available dry pulverization equipment such as an attritor, blade pulverizer, jet mill, or ball mill. On the other hand, in the wet method, the sintered product is mixed with water or an organic solvent to form a slurry in which the sintered product is dispersed in water or an organic solvent. The slurry can then be pulverized using commercially available wet pulverization equipment such as a media mill such as a ball mill or a bead mill, or an emulsifier / disperser that utilizes high-speed shear. Examples of beads that can be used include zirconia beads, alumina beads, and glass beads. Alternatively, a media-less pulverizer that pulverizes particles by interparticle collisions under high-pressure conditions without using pulverization media can be used, which is preferable from the viewpoint of reducing the risk of contamination, such as metal powder, generated by the pulverization media. A dispersant may be added to the slurry, if necessary.

[0096] In the case of wet milling, the milled fired product is separated from the solvent using a filter or centrifuge, and then dried at a temperature at which the solvent evaporates, yielding the milled YMO (manganese oxide particles).

[0097] Alternatively, the pulverization method may involve a two-stage pulverization process in which the above-described pulverization is repeated twice to produce smaller-sized YMO (manganese oxide particles). Examples of the first-stage pulverization method include a pulverization method using the above-described dry pulverization device or wet pulverization device. Examples of the second-stage pulverization method include a pulverization method using the above-described dry pulverization device or wet pulverization device.

[0098] The manganese oxide particles of the present invention are not limited to the above-described present YMO, but can also be obtained by mixing a manganese raw material and an ytterbium raw material, optionally granulating and drying the mixture, firing the mixture, optionally classifying the mixture, optionally heat treating the mixture, and optionally classifying the mixture again.

[0099] Examples of ytterbium raw materials include ytterbium oxide (Yb2O3), ytterbium (III) fluoride (YbF3), ytterbium (III) chloride (YbCl3), ytterbium (III) isopropoxide (Yb(OC3H7)3), etc. Ytterbium oxide is particularly preferred.

[0100] Other raw materials include the following raw materials containing elements such as Sc, Dy, Ho, Er, Tm, and Lu in addition to Y and Yb.

[0101] Examples of scandium raw materials include scandium oxide (Sc2O3), scandium nitrate pentahydrate (Sc(NO3)3·5H2O), etc. Scandium oxide (Sc2O3) is particularly preferred.

[0102] Examples of dysprosium raw materials include dysprosium oxide (Dy2O3), dysprosium carbonate dihydrate (Dy2(CO3)3·2H2O), dysprosium(III) fluoride (DyF3), and dysprosium nitrate hexahydrate (Dy(NO3)3·6H2O). Dysprosium oxide (Dy2O3) is particularly preferred.

[0103] Examples of holmium raw materials include holmium oxide (Ho2O3), holmium acetate monohydrate (Ho(OOCCH3)3·H2O), and holmium carbonate dihydrate (Ho2(CO3)3·2H2O). Holmium oxide (Ho2O3) is particularly preferred.

[0104] Examples of erbium raw materials include erbium oxide (Er2O3), erbium fluoride (ErF3), erbium (III) acetate tetrahydrate (Er(CH3COO)3·4H2O), etc. Erbium oxide (Er2O3) is particularly preferred.

[0105] Examples of thulium raw materials include thulium oxide (Tm2O3) and thulium (III) acetate tetrahydrate (Tm(OOCCH3)3·4H2O). Thulium oxide (Tm2O3) is particularly preferred.

[0106] Examples of lutetium raw materials include lutetium oxide (Lu2O3), lutetium acetate tetrahydrate ((CH3COO)3Lu·4H2O), lutetium(III) chloride hexahydrate (LuCl3·6H2O), etc. Lutetium oxide (Lu2O3) is particularly preferred.

[0107] Furthermore, raw materials other than Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu include the following raw materials: Examples of lithium raw materials include lithium hydroxide (LiOH), lithium carbonate (Li2CO3), lithium nitrate (LiNO3), lithium hydroxide hydrate (LiOH·H2O), lithium oxide (Li2O), other lithium fatty acids, and lithium halide compounds. Particularly preferred are lithium hydroxides, carbonates, and nitrates.

[0108] Examples of magnesium raw materials include magnesium oxide (MgO), magnesium hydroxide (Mg(OH)2), magnesium fluoride (MgF2), magnesium nitrate (Mg(NO3)2), magnesium chloride (MgCl2), magnesium sulfate (MgSO4), etc. Magnesium oxide is particularly preferred.

[0109] Examples of aluminum raw materials include aluminum hydroxide (Al(OH)3), aluminum fluoride (AlF3), etc. Aluminum hydroxide is particularly preferred. Zinc raw materials include zinc oxide (ZnO), zinc sulfide (ZnS), zinc fluoride tetrahydrate (ZnF2·4H2O), zinc stearate ([CH3(CH2) 16 COO]2Zn), etc. Zinc oxide (ZnO) is particularly preferred.

[0110] Examples of sodium raw materials include sodium carbonate (Na2CO3), sodium hydroxide (NaOH), sodium bicarbonate (NaHCO3), sodium nitrate (NaNO3), sodium sulfate (Na2SO4), sodium chloride (NaCl), etc. Sodium carbonate (Na2CO3) is particularly preferred.

[0111] Examples of calcium raw materials include calcium carbonate (CaCO3), calcium oxide (CaO), calcium hydroxide (CaOH), calcium nitrate (Ca(NO3)2), calcium sulfate (CaSO4), etc. Calcium carbonate (CaCO3) is particularly preferred.

[0112] Examples of strontium raw materials include strontium carbonate (SrCo3), strontium sulfate (SrSO4), strontium nitrate (Sr(NO3)2), and strontium chloride (SrCl2).

[0113] Examples of barium raw materials include barium carbonate (BaCO3), barium sulfate (BaSO4), barium hydroxide (Ba(OH)2), barium fluoride (BaF2), etc. Barium carbonate (BaCO3) is particularly preferred.

[0114] Examples of bismuth raw materials include bismuth oxide (Bi2O3), basic bismuth carbonate ((BiO)2CO3), bismuth sulfate (Bi2(SO4)3), and bismuth nitrate pentahydrate (Bi(NO3)3·5H2O). Basic bismuth carbonate ((BiO)2CO3) is particularly preferred.

[0115] Examples of lanthanum raw materials include lanthanum oxide (La2O3), lanthanum carbonate (La2(CO3)3), lanthanum hydroxide (La(OH)3), lanthanum sulfate (La2(SO4)3·9H2O), and lanthanum nitrate (La(NO3)3·6H2O). Lanthanum carbonate (La2(CO3)3) is particularly preferred.

[0116] The praseodymium raw material is, for example, praseodymium oxide (PrO 11 ), praseodymium acetate ((CH3COO)3Pr·nH2O), praseodymium fluoride (PrF3), and praseodymium carbonate octahydrate (Pr2(CO3)3·8H2O). 11 ) is preferred.

[0117] Examples of neodymium raw materials include neodymium oxide (Nd2O3), neodymium carbonate (Nd2(CO3)3·8H2O), neodymium fluoride (NdF3), etc. Neodymium carbonate (Nd2(CO3)3·8H2O) is particularly preferred.

[0118] Examples of iron raw materials include iron oxide (Fe2O3), iron oxide (Fe3O4), iron sulfate (FeSO4), iron carbonate (FeCO3), iron nitrate (Fe(NO3)3), etc. Iron oxide (Fe2O3) is particularly preferred.

[0119] Examples of titanium raw materials include titanium oxide (TiO2) (rutile, anatase, brookite, bronze), titanium tetraisopropoxide ([(CH3)2CHO]4Ti), etc. Titanium oxide (TiO2) (anatase) is particularly preferred.

[0120] Nickel raw materials include basic nickel(II) carbonate (NiCO3 2Ni(OH)2 4H2O), nickel(II) oxide (NiO), nickel(II) sulfate hexahydrate (NiSO4 6H2O), nickel(II) chloride hexahydrate (NiCl2 6H2O), nickel(II) nitrate hexahydrate (Ni(NO3)2 6H2O), nickel(II) acetate tetrahydrate ((CH3COO)2Ni 4H2O), and nickel(II) hydroxide (Ni(OH)2). Basic nickel(II) carbonate (NiCO3 2Ni(OH)2 4H2O) is particularly preferred.

[0121] Examples of chromium raw materials include chromium(III) oxide (Cr2O3), chromium(III) acetate (Cr(CH3COO)3), chromium(III) chloride (CrCl3), chromium(III) fluoride (CrF3), chromium(III) nitrate nonahydrate (Cr(NO3)3·9H2O), and chromium(III) sulfate (Cr2(SO4)3). Chromium(III) oxide (Cr2O3) is particularly preferred.

[0122] Examples of cobalt raw materials include cobalt(II) hydroxide (Co(OH)2), cobalt(II, III) oxide (Co3O4), cobalt(II) oxide (CoO), cobalt(II) carbonate (CoCO3), cobalt(II) acetate ((CH3COO)2Co), cobalt(II) nitrate hexahydrate (Co(NO3)2·6H2O), and cobalt(II) sulfate heptahydrate (CoSO4·7H2O). Cobalt(II) hydroxide (Co(OH)2) is particularly preferred.

[0123] The YMO (manganese oxide particles) thus obtained are mixed with a dispersion as follows to obtain the near-infrared transmitting material of the present invention.

[0124] When the dispersion is a resin, the near-infrared transmitting material (dispersion: resin) of the present invention can be obtained by mixing the resin dispersion with the present YMO in a predetermined ratio. Specifically, when the dispersion is a thermosetting resin, the present YMO and the thermosetting resin can be mixed before heating, or an organic solvent for diluting the thermosetting resin can be added and mixed. Here, a planetary mixer, agitator, three-roll mill, etc. can be used to mix the present YMO and the thermosetting resin. Thereafter, the near-infrared transmitting material (dispersion: resin) of the present invention can be obtained by heating to a temperature at which the thermosetting resin hardens and hardens.

[0125] Furthermore, when the dispersion is a thermoplastic resin, the near-infrared transmitting material (dispersion: resin) of the present invention can be obtained by mixing the present YMO into the thermoplastic resin heated, for example, in a kneader. Furthermore, when the dispersion is a resin film, the near-infrared transmitting material (dispersion: resin) of the present invention can be obtained by coating the present YMO onto a film made of PET or polyethylene naphthalate (PEN). During this coating, a mixture of the present YMO, resin, and organic solvent can be applied using a bar coater or blade. Furthermore, the mixture of the present YMO and resin can be extrusion-molded to form a film.

[0126] In the near-infrared transmitting material (dispersion: resin) of the present invention, it is preferable that the present YMO is dispersed uniformly in the resin that is the dispersion.

[0127] When the dispersion is glass, the near-infrared transmitting material of the present invention (dispersion: glass) can be obtained by mixing the present YMO with the glass dispersion, such as powdered glass, in a predetermined ratio. Note that the near-infrared transmitting material of the present invention (dispersion: glass) is preferably prepared by uniformly dispersing the present YMO in the glass dispersion.

[0128] When the dispersion is an organic solvent, the near-infrared transmitting material of the present invention (dispersion: organic solvent) can be obtained by mixing the organic solvent as the dispersion with the present YMO in a predetermined ratio.

[0129] First, the present YMO is mixed with an organic solvent to obtain a slurry in which the present YMO particles are dispersed in the organic solvent. A dispersant may be added during this process. The obtained slurry is then wet-pulverized and dispersed using a media mill such as a bead mill, a high-pressure jet mill, or a homogenizer to obtain the near-infrared transmitting material (dispersion: organic solvent) of the present invention. Examples of beads used in the bead mill include zirconia beads and alumina beads. Furthermore, a dispersant may be added to the slurry during wet-pulverization, or to the oil-based dispersion obtained by wet-pulverization. The amount of dispersant added may be adjusted appropriately.

[0130] In the near-infrared transmitting material of the present invention (dispersion: organic solvent), it is preferable that the present YMO is dispersed uniformly in the organic solvent that is the dispersion.

[0131] When the dispersion is water, the near-infrared transmitting material of the present invention (dispersion: water) can be obtained by mixing the water dispersion with the present YMO in a predetermined ratio.

[0132] First, the present YMO and water are mixed to obtain a slurry in which the present YMO particles are dispersed in water. A dispersant may be added at this time. The obtained slurry is then wet-pulverized and dispersed using a media mill such as a bead mill, a high-pressure jet mill, or a homogenizer to obtain the near-infrared transmitting material (dispersion: water) of the present invention. Examples of beads used in the bead mill include zirconia beads and alumina beads. Furthermore, a dispersant may be added to the slurry during wet-pulverization, or to the oil-based dispersion obtained by wet-pulverization. The amount of dispersant added may be adjusted appropriately.

[0133] In the near-infrared transmitting material of the present invention (dispersion: water), it is preferable that the present YMO is dispersed uniformly in the water that is the dispersion.

[0134] The near-infrared transmitting material of the present invention is not limited to one containing the present YMO and the above-mentioned dispersion, but may also contain the manganese oxide particles of the present invention and the dispersion.

[0135] When mixing the manganese oxide particles of the present invention with the dispersion, a dispersant may be added to the near-infrared transmitting material of the present invention. Examples of dispersants include phosphoric acids, silane coupling agents, and one or more selected from the group consisting of polycarboxylic acids, polycarboxylates, salts of naphthalenesulfonic acid-formalin condensates, polyvinyl alcohol, polyethylene glucose, polyvinylpyrrolidone, and copolymers thereof. Examples of silane coupling agents include vinyltrimethoxysilane (functional group: vinyl), 3-glycidoxypropyltrimethoxysilane (functional group: epoxy), 3-methacryloxypropyltrimethoxysilane (functional group: methacryl), 3-acryloxypropyltrimethoxysilane (functional group: acrylic), and N-phenyl-3-aminopropyltrimethoxysilane (functional group: amino).

[0136] The near-infrared transmitting film of the present invention is characterized by containing the near-infrared transmitting material of the present invention described above. The near-infrared transmitting film of the present invention contains the near-infrared transmitting material of the present invention described above, and can be used as an optical filter in infrared sensors and infrared cameras.

[0137] The near-infrared sensor of the present invention is characterized by having an optical filter on which the above-described near-infrared transmitting film of the present invention is formed. The near-infrared sensor of the present invention is preferable in that it has an optical filter formed with the near-infrared transmitting film of the present invention described above, and thus can transmit near-infrared rays while minimizing the transmission of visible light.

[0138] The method for producing the near-infrared transmitting film of the present invention described above will be described below.

[0139] The method for producing a near-infrared transmitting film of the present invention includes a step of applying the above-described near-infrared transmitting material of the present invention to a substrate and drying the applied material to produce a near-infrared transmitting film. The substrate may be glass, acrylic, a resin molded body, or the like.

[0140] The near-infrared transparent material produced by the above-described method for producing a near-infrared transparent material of the present invention is applied to a substrate using a bar coater. The substrate coated with the near-infrared transparent material of the present invention is then placed in a static furnace and dried at room temperature (25°C) for 3 hours to obtain the near-infrared transparent film of the present invention. Alternatively, the substrate coated with the near-infrared transparent material of the present invention may be placed in a static furnace, heated to 110°C, and dried for 6 hours, or heated to 600°C and fired for 3 hours.

[0141] The heat-shielding member of the present invention includes a substrate, a near-infrared-reflective lower film formed on the substrate, and a near-infrared-transparent upper film formed on the near-infrared-reflective lower film, wherein the near-infrared-reflective lower film contains a near-infrared-reflective material, and the near-infrared-transparent upper film contains a near-infrared-transparent material having compound particles containing two or more elements selected from H, alkali metals, alkaline earth metals, rare earth elements, B, F, Al, Si, P, S, Cl, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Br, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Hf, Ta, W, Re, Os, Ir, Pt, Tl, Pb, and Bi, and wherein the heat-shielding member has a maximum reflectance of 40%R or more for light having a wavelength of 8000 nm to 2500 nm. With the above-described configuration, the heat shield of the present invention has heat shielding properties and a blackish appearance, and therefore can be used for applications such as vehicles and the exterior walls of buildings.

[0142] Examples of the substrate for the heat shield of the present invention include stainless steel (SUS), aluminum, aluminum alloys, and high-tensile steel.

[0143] The near-infrared reflective undercoat of the heat-shielding member of the present invention is formed on a substrate and contains a near-infrared reflective material.

[0144] Here, the near-infrared reflective material has high reflectivity in the infrared band. Specifically, the near-infrared reflective material preferably reflects light in the near-infrared wavelength range of 800 nm to 2500 nm, and more preferably reflects light in the near-infrared wavelength range of 1000 nm to 2000 nm from the viewpoint of heat-shielding properties. The maximum reflectivity of light in this wavelength range is preferably 40%R or more, more preferably 60%R or more, even more preferably 70%R or more, particularly preferably 80%R or more, even more particularly preferably 90%R or more, and most preferably 100%R or more. Note that, due to measurement errors, etc., the measured value of the maximum reflectivity of the light may exceed 100%R, but since the theoretical upper limit is 100%R, if the measured value exceeds 100%R, it is considered to be 100%R.

[0145] Furthermore, the near-infrared reflective material preferably has a minimum reflectance of 40%R or more for light at a wavelength of 1000 nm or 2000 nm, more preferably 60%R or more, even more preferably 70%R or more, particularly preferably 80%R or more, even more particularly preferably 90%R or more, and most preferably 100%R or more.

[0146] Furthermore, the near-infrared reflective material preferably has a minimum reflectance of 40%R or more for light in the wavelength range, more preferably 60%R or more, even more preferably 70%R or more, particularly preferably 80%R or more, even more particularly preferably 90%R or more, and most preferably 100%R or more.

[0147] The near-infrared reflective material may be, for example, an inorganic material, an organic material, or a combination thereof.

[0148] The inorganic material may be a metal such as aluminum, gold, silver, copper, brass, tin, iron, stainless steel, or titanium, or an alloy containing these metals; a metal oxide, a lower metal oxide, a composite metal oxide, or a composite lower metal oxide such as titanium dioxide, low-order titanium oxide, zinc oxide, low-order zinc oxide, aluminum oxide, Yingmin blue, cobalt blue, or low-order aluminum oxide; or a compound salt or mixed compound salt such as barium sulfate, zinc sulfide, or magnesium carbonate.

[0149] Examples of organic materials include copper phthalocyanine pigments, phthalocyanine pigments containing different metals (nickel, cobalt, iron, etc.), metal-free phthalocyanine pigments, chlorinated phthalocyanine pigments, chlorinated / brominated phthalocyanine pigments, brominated phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, diketopyrrolopyrrole pigments, perylene pigments, monoazo pigments, disazo pigments, condensed azo pigments, metal complex pigments, quinophthalone pigments, indanthrene blue pigments, dioxazine violet pigments, anthraquinone pigments, metal complex pigments, and benzimidazolone pigments.

[0150] Furthermore, the near-infrared reflective material may be one or more selected from the inorganic materials or organic materials described above.

[0151] The near-infrared-transmitting upper film of the heat-shielding member of the present invention is formed on the near-infrared-reflective lower film, and contains a near-infrared-transmitting material having compound particles containing, as constituent elements, two or more elements selected from H, alkali metals, alkaline earth metals, rare earth elements, B, F, Al, Si, P, S, Cl, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Br, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Hf, Ta, W, Re, Os, Ir, Pt, Tl, Pb, and Bi.

[0152] The near-infrared transmitting material having compound particles contained in the near-infrared transmitting upper film is the near-infrared transmitting material of the present invention described above, and therefore a detailed description thereof will be omitted.

[0153] The heat-shielding member of the present invention preferably reflects light in the near-infrared wavelength range of 800 nm to 2500 nm, and more preferably reflects light in the near-infrared wavelength range of 1000 nm to 2000 nm from the viewpoint of heat-shielding properties. A maximum reflectance of 40%R or more for light in this wavelength range improves the reflectance of light in the near-infrared wavelength range at the outermost surface of the heat-shielding member of the present invention, which is preferable in terms of enhancing the heat-shielding effect. The maximum reflectance of this light is more preferably 60%R or more, even more preferably 70%R or more, particularly preferably 80%R or more, even more particularly preferably 90%R or more, and most preferably 100%R or more. Note that, due to measurement errors or the like, the measured value of the maximum reflectance of this light may exceed 100%R. However, since the theoretical upper limit is 100%R, if the measured value exceeds 100%R, it is considered to be 100%R.

[0154] Furthermore, the heat-shielding member of the present invention preferably has a minimum reflectance of 40%R or more for light at a wavelength of 1000 nm or 2000 nm, more preferably 60%R or more, even more preferably 70%R or more, particularly preferably 80%R or more, even more particularly preferably 90%R or more, and most preferably 100%R or more.

[0155] Furthermore, the heat-shielding member of the present invention preferably has a minimum reflectance of 40%R or more for light in the wavelength range, more preferably 60%R or more, even more preferably 70%R or more, particularly preferably 80%R or more, even more particularly preferably 90%R or more, and most preferably 100%R or more.

[0156] The heat-shielding member of the present invention is a heat-shielding member having a substrate, a near-infrared reflective lower film formed on the substrate, and a near-infrared transparent upper film formed on the near-infrared reflective lower film, wherein the near-infrared reflective lower film contains a near-infrared reflective material, and the near-infrared transparent upper film contains, as constituent elements, H, alkali metals, alkaline earth metals, rare earth elements, B, F, Al, Si, P, S, Cl, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Br, Z The near-infrared reflective lower film has a maximum reflectance of 40%R or more for light with a wavelength of 800 nm to 2500 nm, and the near-infrared reflective upper film has a maximum transmittance of 40%T or more for light with a wavelength of 800 nm to 2500 nm. With the above-described configuration, the heat shield of the present invention has heat shielding properties and a blackish appearance, and therefore can be used for applications such as vehicles and the exterior walls of buildings.

[0157] The near-infrared reflective undercoat of the present invention preferably reflects light in the near-infrared wavelength range of 800 nm to 2500 nm, and more preferably reflects light in the near-infrared wavelength range of 1000 nm to 2000 nm from the viewpoint of heat-shielding properties. A maximum reflectance of 40%R or more for light in this wavelength range improves the reflectance of light in the near-infrared wavelength range on the surface of the near-infrared reflective undercoat of the present invention, which is preferable in terms of enhancing the heat-shielding effect. A maximum reflectance of 60%R or more is more preferred, 70%R or more is even more preferred, 80%R or more is particularly preferred, 90%R or more is even more particularly preferred, and 100%R or more is most preferred. Note that, due to measurement errors or the like, the measured value of the maximum reflectance of the light may exceed 100%R. However, since the theoretical upper limit is 100%R, if the measured value exceeds 100%R, it is considered to be 100%R.

[0158] Furthermore, the near-infrared reflective undercoat of the present invention preferably has a minimum reflectance of 40%R or more for light at a wavelength of 1000 nm or 2000 nm, more preferably 60%R or more, even more preferably 70%R or more, particularly preferably 80%R or more, even more particularly preferably 90%R or more, and most preferably 100%R or more.

[0159] Furthermore, the near-infrared reflective undercoat of the present invention preferably has a minimum reflectance of 40%R or more for light in the wavelength range, more preferably 60%R or more, even more preferably 70%R or more, particularly preferably 80%R or more, even more particularly preferably 90%R or more, and most preferably 100%R or more.

[0160] The near-infrared-transmitting upper film of the present invention preferably transmits light in the near-infrared wavelength range of 800 nm to 2500 nm, and more preferably transmits light in the near-infrared wavelength range of 1000 nm to 2000 nm from the viewpoint of heat-shielding properties. A maximum transmittance of 40%T or more for light in this wavelength range improves the reflectance of light in the near-infrared wavelength range on the surface of the near-infrared-reflective lower film of the present invention, which is preferable in terms of enhancing the heat-shielding effect. The maximum transmittance of light is more preferably 60%T or more, even more preferably 70%T or more, particularly preferably 80%T or more, even more particularly preferably 90%T or more, and most preferably 100%T or more. Note that, due to measurement error or the like, the measured value of the maximum transmittance of light may exceed 100%T. However, since the theoretical upper limit is 100%T, if the measured value exceeds 100%T, it is considered to be 100%T.

[0161] Furthermore, the near-infrared transmitting upper film of the present invention preferably has a minimum transmittance of 40%T or more for light at a wavelength of 1000 nm or 2000 nm, more preferably 60%T or more, even more preferably 70%T or more, particularly preferably 80%T or more, even more particularly preferably 90%T or more, and most preferably 100%T or more.

[0162] Furthermore, the near-infrared transmitting upper film of the present invention preferably has a minimum transmittance of 40%T or more for light in the wavelength range, more preferably 60%T or more, even more preferably 70%T or more, particularly preferably 80%T or more, even more particularly preferably 90%T or more, and most preferably 100%T or more.

[0163] The method for producing a heat-shielding member of the present invention includes a lower film-forming step of forming a near-infrared-reflective lower film containing a near-infrared-reflective material on a substrate, and a top film-forming step of forming a near-infrared-transparent upper film on the near-infrared-reflective lower film, the near-infrared-transparent upper film containing a near-infrared-transparent material having compound particles containing, as constituent elements, two or more elements selected from H, alkali metals, alkaline earth metals, rare earth elements, B, F, Al, Si, P, S, Cl, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Br, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Hf, Ta, W, Re, Os, Ir, Pt, Tl, Pb, and Bi.

[0164] The undercoat formation process can be carried out by a method of placing a foil-shaped near-infrared reflective material on a substrate, a method of applying a paint containing a mixture of a near-infrared reflective material and a dispersion, or a thin film formation method such as vacuum deposition, sputtering, or electrolytic or electroless plating.

[0165] By these methods, a near-infrared reflective undercoat containing a near-infrared reflective material is formed on a substrate.

[0166] The upper film formation process can be carried out by applying a near-infrared transmitting material having compound particles containing two or more elements selected from H, alkali metals, alkaline earth metals, rare earth elements, B, F, Al, Si, P, S, Cl, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Br, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Hf, Ta, W, Re, Os, Ir, Pt, Tl, Pb, and Bi as constituent elements onto the near-infrared reflective lower film formed in the lower film formation process, or by using a thin film formation method such as vacuum deposition, sputtering, or electrolytic or electroless plating.

[0167] By these methods, a near-infrared transparent upper film is formed on the near-infrared reflective lower film, which contains a near-infrared transparent material having compound particles containing, as constituent elements, two or more elements selected from H, alkali metals, alkaline earth metals, rare earth elements, B, F, Al, Si, P, S, Cl, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Br, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Hf, Ta, W, Re, Os, Ir, Pt, Tl, Pb, and Bi.

[0168] In this manner, the heat shield of the present invention is obtained.

[0169] In this specification, when "X to Y" (X and Y are any numbers) is expressed, unless otherwise specified, it means "X or more and Y or less," and also includes the meaning "preferably larger than X" or "preferably smaller than Y." Furthermore, when "X or more" (X is any number) or "Y or less" (Y is any number), it also includes the meaning "preferably larger than X" or "preferably smaller than Y." [Effects of the Invention]

[0170] The manganese oxide, manganese oxide particles, near-infrared-transmitting material, and near-infrared-transmitting film of the present invention are able to transmit near-infrared light while minimizing the transmission of visible light. [Brief explanation of the drawings]

[0171] [Figure 1] 1 is a table listing the physical property values ​​and measurement results of near-infrared transmitting materials according to Examples 1 to 7 of the present invention, a titanium oxide mixture according to Comparative Example 1, and a carbon black mixture according to Comparative Example 2. [Figure 2] 1 is a graph showing the transmittance of coating films formed from near-infrared transmitting materials according to Examples 1 to 7 of the present invention at wavelengths of 400 nm to 2400 nm. [Figure 3] 1 is a table listing the physical property values ​​and measurement results of the heat shields according to Example C1 of the present invention and Comparative Examples C1 to C4. [Figure 4] 1 is a graph showing the reflectance at wavelengths of 550 nm to 2000 nm of heat shielding members according to Example C1 of the present invention and Comparative Examples C1 to C4. [Figure 5] 1 is a table listing the physical property values ​​and measurement results of near-infrared transmitting materials according to Experimental Examples 1 to 3 of the present invention, a titanium oxide mixture according to Comparative Example 1, and a carbon black mixture according to Comparative Example 2. [Figure 6] 1 is a table listing the physical property values ​​and measurement results of near-infrared transmitting materials according to Experimental Examples 4 to 14 of the present invention. [Figure 7] 1 is a table listing the physical property values ​​and measurement results of near-infrared transmitting materials according to Experimental Examples 15 to 20 of the present invention. [Figure 8] 1 is a table listing the physical property values ​​and measurement results of near-infrared transmitting materials according to Experimental Examples 21 to 26 of the present invention. [Figure 9] 1 is a table listing the physical property values ​​and measurement results of near-infrared transmitting materials according to Experimental Examples 1 to 3, 10, and 26 of the present invention. [Figure 10] 1 is a table listing the physical property values ​​and measurement results of near-infrared transmitting materials according to Experimental Examples 27 to 30 of the present invention. [Figure 11] 1 is a table listing the physical property values ​​and measurement results of near-infrared transmitting materials according to Experimental Examples 31 to 38 of the present invention. [Figure 12] 1 is a table listing the physical property values ​​and measurement results of near-infrared transmitting materials according to Experimental Examples 39 to 41 of the present invention. [Figure 13]1 is a graph showing the transmittance of coating films formed from near-infrared transmitting materials according to Experimental Examples 1 to 3 of the present invention at wavelengths of 400 nm to 2400 nm. [Figure 14] Graph (a) shows the transmittance of coating films formed from near-infrared transmitting materials according to Experimental Examples 4 to 9 of the present invention at wavelengths of 400 nm to 2400 nm, and graph (b) shows the transmittance of coating films formed from near-infrared transmitting materials according to Experimental Examples 10 to 14 of the present invention at wavelengths of 400 nm to 2400 nm. [Figure 15] 1 is a graph showing the transmittance of coating films formed from near-infrared transmitting materials according to Experimental Examples 15 to 20 of the present invention at wavelengths of 400 nm to 2400 nm. [Figure 16] 1 is a graph showing the transmittance of coating films formed from near-infrared transmitting materials according to Experimental Examples 21 to 26 of the present invention at wavelengths of 400 nm to 2400 nm. [Figure 17] 1 is a graph showing the transmittance of coating films formed from near-infrared transmitting materials according to Experimental Examples 1 to 3, 10, and 26 of the present invention at wavelengths of 400 nm to 2400 nm. [Figure 18] 1 is a graph showing the transmittance of coating films formed from near-infrared transmitting materials according to Experimental Examples 27 to 30 of the present invention at wavelengths of 400 nm to 2400 nm. [Figure 19] 1 is a graph showing the transmittance of coating films formed from near-infrared transmitting materials according to Experimental Examples 31 to 38 of the present invention at wavelengths of 400 nm to 2400 nm. [Figure 20] 1 is a graph showing the transmittance of coating films formed from near-infrared transmitting materials according to Experimental Examples 39 to 41 of the present invention at wavelengths of 400 nm to 2400 nm. [Figure 21] 1 is a graph showing the transmittance of coating films formed from near-infrared transmitting materials according to Experimental Examples 10, 35, and 36 of the present invention at wavelengths of 400 nm to 2400 nm. BEST MODE FOR CARRYING OUT THE INVENTION

[0172] The manganese oxide, manganese oxide particles, near-infrared transparent material, and near-infrared transparent film according to the embodiments of the present invention will be further described below with reference to the following examples, although the present invention is not limited to these examples.

[0173] Example 1 The manganese oxide according to Example 1 is yttrium manganate particles (YMO) in which, when its composition formula is expressed as AxXyOz, the constituent element A is Y and the constituent element X is Mn.

[0174] The yttrium manganate particles (YMO) according to Example 1 had a molar number of the constituent element A (Y) of 1.000 mol, a molar number of the constituent element X (Mn) of 1.000 mol, a molar number of A+X of 2.000 mol, a molar ratio of A / (A+X) of 0.500, a molar ratio of X / (A+X) of 0.500, and a molar ratio of A / X of 1.000.

[0175] Specifically, trimanganese tetroxide (228.81 g / mol) and yttrium oxide (225.81 g / mol) were weighed out so that the molar ratio of Mn:Y was 1.0:1.0, and mixed to obtain a mixed raw material.

[0176] The obtained mixed raw material was placed in an alumina crucible and maintained at a firing temperature (holding temperature) of 1200°C for 20 hours in an air atmosphere using a static electric furnace, and then naturally cooled to room temperature.The fired powder obtained by firing was crushed in a mortar and classified using a sieve with 75 μm openings, and the powder that fell through the sieve was obtained as the fired powder.

[0177] The fired powder thus obtained was subjected to a two-stage crushing treatment as follows.

[0178] First, in the first stage of pulverization, 30 g of the sintered powder, 100 g of 0.8 mm zirconia beads, and 45 g of pure water were placed in a 100 mL plastic container, which was then placed in a rocking shaker manufactured by Seiwa Giken Co., Ltd. The mixture was pulverized for 4 hours using the rocking shaker. The zirconia beads were then separated using a mesh, followed by solid-liquid separation using a small centrifuge (Eppendorf-Himac Technologies Co., Ltd.: CT6E). The solids were then dried at 110 °C in a dryer to obtain a dried powder obtained by the first stage of pulverization.

[0179] Next, in the second stage of pulverization, 30 g of the dried powder pulverized in the first stage, 100 g of 0.2 mm zirconia beads, and 45 g of pure water were placed in a 100 mL plastic container, and the plastic container was placed in a rocking shaker manufactured by Seiwa Giken Co., Ltd. The mixture was pulverized for 4 hours using the rocking shaker. The zirconia beads were then separated using a mesh, followed by solid-liquid separation using a small centrifuge (Eppendorf-Himac Technologies Co., Ltd.: CT6E). The solid content was then dried at 110°C using a dryer to obtain yttrium manganate particles (YMO) according to Example 1.

[0180] The yttrium manganate particles (YMO) obtained in this manner according to Example 1 were thoroughly mixed and pulverized in an agate mortar, then sieved using a 75 μm mesh sieve. 0.5 g of the well-mixed powder in the center of the undersize container was dispensed onto a glass sample plate. The glass plate was then filled to a smooth surface, and the resulting sample was subjected to powder X-ray diffraction measurement using CuKα radiation under the powder X-ray diffraction measurement conditions described above to obtain an X-ray diffraction pattern. The obtained X-ray diffraction pattern showed a peak at 2θ = 28.0° to 33.0° due to the YMnO3 (111) plane and a peak at 2θ = 31.0° to 35.0° due to the YMnO3 (112) plane. It was confirmed that the crystal system of the yttrium manganate particles (YMO) according to Example 1 included a hexagonal crystal system.

[0181] Then, 20.0 g of the yttrium manganate particles (YMO) according to Example 1, 11.1 g of acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 60%, and the resulting mixture was dispersed using a paint shaker for 2 hours to obtain a near-infrared transmitting material according to Example 1.

[0182] The near-infrared transmitting material of Example 1 obtained in this manner was applied to a PET film ("Lumirror (registered trademark)": #100-T60, manufactured by Toray Industries, Inc.) using a bar coater (No. 10) to form a coating film, thereby obtaining a near-infrared transmitting film of Example 1 (film thickness 5 μm).

[0183] Example 2 When the composition formula of the manganese oxide according to Example 2 is expressed as AxXyOz, the constituent element A is Yb and the constituent element X is Mn, that is, ytterbium manganate particles (YbMO).

[0184] The ytterbium manganate particles (YbMO) according to Example 2 had a molar number of constituent element A (Yb) of 1.000 mol, a molar number of constituent element X (Mn) of 1.000 mol, a molar number of A+X of 2.000 mol, a molar ratio of A / (A+X) of 0.500, a molar ratio of X / (A+X) of 0.500, and a molar ratio of A / X of 1.000.

[0185] The ytterbium manganate particles (YbMO) of Example 2 were obtained in the same manner as Example 1, except that trimanganese tetroxide (228.81 g / mol) and ytterbium oxide (394.08 g / mol) were weighed out so that the molar ratio of Mn:Yb=1.0:1.0, and mixed to obtain a mixed raw material.

[0186] The ytterbium manganate particles (YbMO) obtained in this manner according to Example 2 were thoroughly mixed and pulverized in an agate mortar, then sieved using a 75 μm mesh sieve. 0.5 g of the powder in the center of the undersize container, which was well mixed, was dispensed onto a glass sample plate. The glass plate was then filled to a smooth surface, and the resulting sample was subjected to powder X-ray diffraction measurement using CuKα radiation under the powder X-ray diffraction measurement conditions described above to obtain an X-ray diffraction pattern. The obtained X-ray diffraction pattern showed a peak at 2θ = 28.0° to 33.0° due to the YbMnO3 (111) plane and a peak at 2θ = 31.0° to 35.0° due to the YbMnO3 (112) plane. Therefore, it was confirmed that the crystal system of the ytterbium manganate particles (YbMO) according to Example 2 included a hexagonal crystal system.

[0187] The near-infrared transmitting material according to Example 2 and the near-infrared transmitting film (film thickness: 5 μm) according to Example 2 were obtained in the same manner as in Example 1.

[0188] Example 3 The compound according to Example 3, when expressed by the composition formula AxXyOz, is yttrium manganate particles (YMO-Fe) in which the constituent element A is Y and Fe, and the constituent element X is Mn.

[0189] The yttrium manganate particles (YMO-Fe) according to Example 3 had a molar number of constituent element A (Y, Fe) of 1.010 mol, a molar number of constituent element X (Mn) of 0.990 mol, a molar number of A+X of 2.000 mol, a molar ratio of A / (A+X) of 0.505, a molar ratio of X / (A+X) of 0.495, and a molar ratio of A / X of 1.020.

[0190] The yttrium manganate particles (YMO-Fe) according to Example 3 were obtained in the same manner as in Example 1, except that manganese trioxide (228.81 g / mol), yttrium oxide (225.81 g / mol), and iron oxide (159.69 g / mol) were weighed out and mixed to give a molar ratio of Mn:Y:Fe=0.99:1.0:0.01 to obtain a mixed raw material.

[0191] The yttrium manganate particles (YMO-Fe) according to Example 3 obtained in this manner were subjected to powder X-ray diffraction measurement to obtain an X-ray diffraction pattern in the same manner as in Example 1. It was confirmed that the crystal system of the yttrium manganate particles (YMO-Fe) according to Example 3 contains hexagonal crystals.

[0192] The near-infrared transmitting material according to Example 3 and the near-infrared transmitting film (film thickness: 5 μm) according to Example 3 were obtained in the same manner as in Example 1.

[0193] Example 4 The compound according to Example 4, when expressed by the composition formula AxXyOz, is yttrium manganate particles (YMO-Fe) in which the constituent element A is Y and Fe, and the constituent element X is Mn.

[0194] The yttrium manganate particles (YMO-Fe) according to Example 4 had a molar number of constituent element A (Y, Fe) of 1.050 mol, a molar number of constituent element X (Mn) of 0.950 mol, a molar number of A+X of 2.000 mol, a molar ratio of A / (A+X) of 0.525, a molar ratio of X / (A+X) of 0.475, and a molar ratio of A / X of 1.105.

[0195] The yttrium manganate particles (YMO-Fe) according to Example 4 were obtained in the same manner as in Example 1, except that manganese trioxide (228.81 g / mol), yttrium oxide (225.81 g / mol), and iron oxide (159.69 g / mol) were weighed and mixed to give a molar ratio of Mn:Y:Fe=0.95:1.0:0.05 to obtain a mixed raw material.

[0196] The yttrium manganate particles (YMO-Fe) according to Example 4 obtained in this manner were subjected to powder X-ray diffraction measurement to obtain an X-ray diffraction pattern in the same manner as in Example 1. It was confirmed that the crystal system of the yttrium manganate particles (YMO-Fe) according to Example 4 contains hexagonal crystals.

[0197] The near-infrared transmitting material according to Example 4 and the near-infrared transmitting film (film thickness: 5 μm) according to Example 4 were obtained in the same manner as in Example 1.

[0198] Example 5 The compound according to Example 5, when expressed by the composition formula AxXyOz, is yttrium manganate particles (YMO-Fe) in which the constituent element A is Y and Fe, and the constituent element X is Mn.

[0199] The yttrium manganate particles (YMO-Fe) according to Example 5 had a molar number of constituent element A (Y, Fe) of 1.200 mol, a molar number of constituent element X (Mn) of 0.800 mol, a molar number of A+X of 2.000 mol, a molar ratio of A / (A+X) of 0.600, a molar ratio of X / (A+X) of 0.400, and a molar ratio of A / X of 1.500.

[0200] The yttrium manganate particles (YMO-Fe) according to Example 5 were obtained in the same manner as in Example 1, except that manganese trioxide (228.81 g / mol), yttrium oxide (225.81 g / mol), and iron oxide (159.69 g / mol) were weighed out and mixed to give a molar ratio of Mn:Y:Fe=0.8:1.0:0.2 to obtain a mixed raw material.

[0201] The yttrium manganate particles (YMO-Fe) according to Example 5 thus obtained were subjected to powder X-ray diffraction measurement to obtain an X-ray diffraction pattern in the same manner as in Example 1. It was confirmed that the crystal system of the yttrium manganate particles (YMO-Fe) according to Example 5 contains hexagonal crystals.

[0202] The near-infrared transmitting material according to Example 5 and the near-infrared transmitting film (film thickness: 5 μm) according to Example 5 were obtained in the same manner as in Example 1.

[0203] Example 6 The compound according to Example 6, when expressed by the composition formula AxXyOz, is yttrium manganate particles (YMO-La) in which the constituent element A is Y and La, and the constituent element X is Mn.

[0204] The yttrium manganate particles (YMO-La) according to Example 6 had a molar number of constituent element A (Y, La) of 1.000 mol, a molar number of constituent element X (Mn) of 1.000 mol, a molar number of A+X of 2.000 mol, a molar ratio of A / (A+X) of 0.500, a molar ratio of X / (A+X) of 0.500, and a molar ratio of A / X of 1.500.

[0205] The yttrium manganate particles (YMO-La) of Example 6 were obtained in the same manner as in Example 1, except that manganese trioxide (228.81 g / mol), yttrium oxide (225.81 g / mol), and lanthanum carbonate (457.84 g / mol) were weighed out and mixed to give a molar ratio of Mn:Y:La=1.0:0.99:0.01 to obtain a mixed raw material.

[0206] The yttrium manganate particles (YMO-Fe) according to Example 6 thus obtained were subjected to powder X-ray diffraction measurement to obtain an X-ray diffraction pattern in the same manner as in Example 1. It was confirmed that the crystal system of the yttrium manganate particles (YMO-La) according to Example 6 contains hexagonal crystals.

[0207] The near-infrared transmitting material according to Example 6 and the near-infrared transmitting film (film thickness: 5 μm) according to Example 6 were obtained in the same manner as in Example 1.

[0208] Example 7 The compound of Example 7, when expressed by its composition formula AxXyOz, is yttrium manganate particles (YMO-La) in which the constituent element A is Y and La, and the constituent element X is Mn.

[0209] The yttrium manganate particles (YMO-La) according to Example 7 had a molar number of constituent element A (Y, La) of 1.000 mol, a molar number of constituent element X (Mn) of 1.000 mol, a molar number of A+X of 2.000 mol, a molar ratio of A / (A+X) of 0.500, a molar ratio of X / (A+X) of 0.500, and a molar ratio of A / X of 1.500.

[0210] The yttrium manganate particles (YMO-La) of Example 7 were obtained in the same manner as Example 1, except that manganese trioxide (228.81 g / mol), yttrium oxide (225.81 g / mol), and lanthanum carbonate (457.84 g / mol) were weighed out and mixed to give a molar ratio of Mn:Y:La=1.0:0.95:0.05 to obtain a mixed raw material.

[0211] The yttrium manganate particles (YMO-Fe) according to Example 7 thus obtained were subjected to powder X-ray diffraction measurement to obtain an X-ray diffraction pattern in the same manner as in Example 1. It was confirmed that the crystal system of the yttrium manganate particles (YMO-La) according to Example 7 contains hexagonal crystals.

[0212] The near-infrared transmitting material according to Example 7 and the near-infrared transmitting film (film thickness: 5 μm) according to Example 7 were obtained in the same manner as in Example 1.

[0213] (Comparative Example 1) In Comparative Example 1, a titanium oxide mixture according to Comparative Example 1 was obtained by blending titanium oxide aggregates (7 parts by mass) having a primary particle diameter of 35 nm and a secondary particle diameter of 140 nm with a transparent resin (acrylic polyol; 100 parts by mass) and a curing agent (hexamethylene diisocyanate; 20 parts by mass), and melt-mixing them.

[0214] (Comparative Example 2) Comparative Example 2 has a primary particle diameter of 15 nm and a BET specific surface area of ​​120 m 2Carbon black, a single black pigment, was used in an amount of 1 / g. Specifically, the carbon black aggregates (20 parts by mass) were blended and kneaded with a transparent resin (methyl methacrylate / methacrylic acid copolymer; 100 parts by mass) and PGMEA (120 parts by mass) using a three-roll mill to obtain a carbon black mixture according to Comparative Example 2.

[0215] The heat shield according to the embodiment of the present invention will be further described below with reference to the following examples, although the present invention is not limited to these examples.

[0216] Example C1 First, 7.6 g of titanium oxide (TiO2), a near-infrared reflective material, 11.1 g of acrylic resin, and 18.9 g of ethyl acetate were mixed in a container, and the resulting mixture was dispersed for 10 minutes using a paint shaker to obtain the mixed paint of Example C1.

[0217] The mixed coating material of Example C1 was applied to a substrate (SUS304) with a brush and dried at 110°C for 1 hour to form a near-infrared reflective undercoat (film thickness 53.5 μm) of Example C1.

[0218] Next, yttrium manganate particles (YMO) according to Example 8, which are compound particles constituting the near-infrared transmitting material, and 7.6 g of YMnO5, 11.1 g of acrylic resin, and 18.9 g of ethyl acetate were mixed in a container, and the resulting mixture was subjected to a dispersion treatment for 2 hours using a paint shaker to obtain the YMO paint according to Example C1.

[0219] The YMO coating material of Example C1 was applied to the near-infrared-reflecting lower film of Example C1 using a spin coater (1000 rpm, 20 s) and dried to form the near-infrared-transmitting upper film of Example C1 (film thickness 14 μm).

[0220] In this way, a heat shield according to Example C1 was obtained.

[0221] (Comparative Example C1) In the heat-shielding member of Comparative Example C1, neither a near-infrared reflective lower film nor a near-infrared transparent upper film was formed on the substrate (SUS304).

[0222] (Comparative Example C2) First, 2.12 g of carbon black, 11.1 g of acrylic resin, and 18.9 g of ethyl acetate were mixed in a container, and the resulting mixture was subjected to a dispersion treatment for 2 hours using a paint shaker to obtain a mixed paint according to Comparative Example C2.

[0223] The mixed coating material of Comparative Example C2 was applied to a substrate (SUS304) using a spin coater (1000 rpm, 20 s) and dried at 110°C for 1 hour to form a base film (film thickness 17 μm) of Comparative Example C2.

[0224] In this way, the heat shield of Comparative Example C2 was obtained. However, no near-infrared transmitting upper film was formed on the lower film of Comparative Example C2.

[0225] (Comparative Example C3) First, 7.6 g of titanium oxide (TiO2), a near-infrared reflective material, 11.1 g of acrylic resin, and 18.9 g of ethyl acetate were mixed in a container, and the resulting mixture was dispersed for 10 minutes using a paint shaker to obtain a mixed paint according to Comparative Example C3.

[0226] The mixed coating material of Comparative Example C3 was applied to a substrate (SUS304) with a brush and dried at 110°C for 1 hour to form a near-infrared reflective undercoat (film thickness 58 μm) of Comparative Example C3.

[0227] In this way, the heat shield of Comparative Example C3 was obtained. Note that no near-infrared-transmitting upper film was formed on the near-infrared-reflective lower film of Comparative Example C3.

[0228] (Comparative example C4) First, 2.12 g of carbon black, 11.1 g of acrylic resin, and 18.9 g of ethyl acetate were mixed in a container, and the resulting mixture was subjected to a dispersion treatment for 2 hours using a paint shaker to obtain a mixed paint according to Comparative Example C4.

[0229] The mixed coating material of Comparative Example C4 was applied onto a substrate (SUS304) using a spin coater (1000 rpm, 20 s) and dried at 110°C for 1 hour to form a base film (film thickness 17 μm) of Comparative Example C4.

[0230] Next, yttrium manganate particles (YMO) according to Example 8, which are compound particles constituting the near-infrared transmitting material, and 7.6 g of YMnO5, 11.1 g of acrylic resin, and 18.9 g of ethyl acetate were mixed in a container, and the resulting mixture was subjected to a dispersion treatment for 2 hours using a paint shaker to obtain a YMO paint according to Comparative Example C4.

[0231] The YMO paint of Comparative Example C4 was applied to the lower film of Comparative Example C4 using a spin coater (1000 rpm, 20 s) and dried to form a near-infrared-transmitting upper film (film thickness 14 μm) of Comparative Example C4.

[0232] In this manner, a heat shield according to Comparative Example C4 was obtained.

[0233] The manganese oxide, manganese oxide particles, near-infrared transparent material, and near-infrared transparent film according to embodiments of the present invention will be further described by the following experimental examples related to the present invention, although the present invention is not limited to these examples.

[0234] (Experimental Example 1) The manganese oxide according to Experimental Example 1 is lithium manganese oxide particles (LMO-MgAl) in which the constituent element A is Li, Mg, or Al.

[0235] The lithium manganese oxide particles (LMO-MgAl) according to Experimental Example 1 had a molar number of constituent elements A (Li, Mg, Al) of 0.625 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 1.625 mol, a molar ratio of A / (A+Mn) of 0.385, a molar ratio of Mn / (A+Mn) of 0.615, and a molar ratio of A / Mn of 0.625.

[0236] Specifically, manganese dioxide (228.81 g / mol), lithium carbonate (73.891 g / mol), magnesium oxide (40.304 g / mol), and aluminum hydroxide (78.000 g / mol) were weighed out to a molar ratio of Mn:Li:Mg:Al=1.04:0.60:0.004:0.044 and mixed to obtain a mixed raw material.

[0237] The resulting mixed raw material was placed in an alumina crucible and kept at a firing temperature (holding temperature) of 770°C for 20 hours in an air atmosphere using a static electric furnace, and then naturally cooled to room temperature to obtain a fired powder.

[0238] The fired powder obtained by firing was crushed in a mortar and classified using a sieve with 75 μm openings, and the powder that fell through the sieve was obtained as lithium manganate particles (LMO-MgAl) according to Experimental Example 1.

[0239] Next, 20.0 g of the lithium manganese oxide particles (LMO-MgAl) of Experimental Example 1, 11.1 g of acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 80%, and the resulting mixture was dispersed using a paint shaker for 2 hours to obtain a near-infrared transmitting material of Experimental Example 1.

[0240] The near-infrared transmitting material according to Experimental Example 1 obtained in this manner was applied to a PET film ("Lumirror (registered trademark)" manufactured by Toray Industries, Inc.: #100-T60) using a bar coater (No. 10) to form a coating film, thereby obtaining a near-infrared transmitting film according to Experimental Example 1 (film thickness 5 μm).

[0241] (Experimental Example 2) The manganese oxide according to Experimental Example 2 is lithium manganese oxide particles (LMO-MgAl) in which the constituent element A is Li, Mg, or Al.

[0242] The lithium manganese oxide particles (LMO-MgAl) of Experimental Example 2 had a molar number of constituent elements A (Li, Mg, Al) of 0.625 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 1.625 mol, a molar ratio of A / (A+Mn) of 0.385, a molar ratio of Mn / (A+Mn) of 0.615, and a molar ratio of A / Mn of 0.625.

[0243] The lithium manganese oxide particles (LMO-MgAl) of Experimental Example 2 were obtained in the same manner as Experimental Example 1, except that (i) the firing temperature for firing the mixed raw materials was 570°C, and (ii) a pulverization treatment, which will be described later, was carried out.

[0244] In the pulverization process in Experimental Example 2, 100 g of φ0.8 mm zirconia beads were placed in a 100 ml plastic container together with 30 g of the calcined powder and 45 g of pure water, and pulverized for 4 hours using a rocking shaker manufactured by Seiwa Giken Co., Ltd. Next, the zirconia beads were separated using a mesh, and then solid-liquid separation was performed using a small centrifuge (Eppendorf-Himac Technologies Co., Ltd.: CT6E). The solid content was dried at 110°C using a dryer to obtain lithium manganese oxide particles (LMO-MgAl) according to Experimental Example 2.

[0245] The near-infrared transmitting material according to Experimental Example 2 was obtained in the same manner as Experimental Example 1. The near-infrared transmitting film according to Experimental Example 2 (film thickness 9 μm) was obtained in the same manner as Experimental Example 1, except that the coating film of the near-infrared transmitting material according to Experimental Example 2 was formed by applying twice using a bar coater.

[0246] (Experimental Example 3) The manganese oxide according to Experimental Example 3 is lithium manganate particles (LMO-MgAl) in which the constituent element A is Li, Mg, or Al.

[0247] The lithium manganese oxide particles (LMO-MgAl) of Experimental Example 3 had a molar number of constituent elements A (Li, Mg, Al) of 0.625 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 1.625 mol, a molar ratio of A / (A+Mn) of 0.385, a molar ratio of Mn / (A+Mn) of 0.615, and a molar ratio of A / Mn of 0.625.

[0248] The lithium manganate particles (LMO-MgAl) according to Experimental Example 3 were obtained in the same manner as in Experimental Example 1, except that (i) the temperature for firing the mixed raw materials was 570°C, (ii) a two-stage pulverization process described below was performed, and (iii) when the lithium manganate particles (LMO-MgAl) according to Experimental Example 3 were mixed with the acrylic resin and ethyl acetate, they were mixed so that the pigment concentration in terms of solids (PWC) was 60%.

[0249] In the two-stage milling process of Experimental Example 3, the milling process of Experimental Example 2 was performed as the first stage. Next, in the second stage, 30 g of the dried powder obtained by the milling process of Experimental Example 2 and 45 g of pure water were added to a 100 ml plastic container along with 100 g of 0.2 mm zirconia beads, and the mixture was milled for 4 hours using a rocking shaker manufactured by Seiwa Giken Co., Ltd. Next, the zirconia beads were separated using a mesh, followed by solid-liquid separation using a small centrifuge (Eppendorf-Himac Technologies Co., Ltd.: CT6E). The solid content was dried at 110 °C using a dryer to obtain lithium manganese oxide particles (LMO-MgAl) according to Experimental Example 3.

[0250] The near-infrared transmitting material according to Experimental Example 3 was obtained in the same manner as in Experimental Example 1. The coating film of the near-infrared transmitting material according to Experimental Example 3 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 3 was obtained.

[0251] (Experimental Example 4) The manganese oxide according to Experimental Example 4 is sodium manganate particles (NaMnO) in which the constituent element A is Na.

[0252] In the sodium manganate particles (NaMnO) according to Experimental Example 4, the number of moles of constituent element A (Na) was 0.5 mol, the number of moles of Mn was 1 mol, the number of moles of A+Mn was 1.5 mol, the molar ratio of A / (A+Mn) was 0.3, the molar ratio of Mn / (A+Mn) was 0.7, and the molar ratio of A / Mn was 0.5.

[0253] Sodium manganate particles (NaMnO) according to Experimental Example 4 were obtained in the same manner as Experimental Example 1, except that trimanganese tetroxide (228.81 g / mol) and sodium carbonate (105.99 g / mol) were weighed and mixed so that the molar ratio was Mn:Na=1.00:0.50 to obtain a mixed raw material.

[0254] Next, the near-infrared transmitting material according to Experimental Example 4 was obtained in the same manner as Experimental Example 1, except that 7.6 g of sodium manganate particles (NaMnO) according to Experimental Example 4, 11.1 g of acrylic resin (manufactured by Mitsubishi Rayon: Dianal LR167), and 18.9 g of ethyl acetate were mixed in a container so that the solid content equivalent pigment concentration (PWC) was 80%.

[0255] The coating film of the near-infrared transmitting material according to Experimental Example 4 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 4 was obtained.

[0256] (Experimental Example 5) The manganese oxide according to Experimental Example 5 is calcium manganate particles (CaMnO) in which the constituent element A is Ca.

[0257] In the calcium manganate particles (CaMnO) according to Experimental Example 5, the number of moles of constituent element A (Ca) was 0.5 mol, the number of moles of Mn was 1 mol, the number of moles of A+Mn was 1.5 mol, the molar ratio of A / (A+Mn) was 0.3, the molar ratio of Mn / (A+Mn) was 0.7, and the molar ratio of A / Mn was 0.5.

[0258] The calcium manganate particles (CaMnO) of Experimental Example 5 were obtained in the same manner as in Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol) and calcium carbonate (100.09 g / mol) were weighed and mixed to obtain a mixed raw material with a molar ratio of Mn:Ca=1.00:0.50, and (ii) the mixed raw material was fired at 1000°C.

[0259] Next, the near-infrared transmitting material according to Experimental Example 5 was obtained in the same manner as in Experimental Example 1, except that 7.6 g of the calcium manganate particles (CaMnO) according to Experimental Example 5, 11.1 g of an acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 80%.

[0260] The coating film of the near-infrared transmitting material according to Experimental Example 5 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 5 was obtained.

[0261] (Experimental Example 6) The manganese oxide according to Experimental Example 6 is strontium manganate particles (SrMnO) in which the constituent element A is Sr.

[0262] The strontium manganate particles (SrMnO) according to Experimental Example 6 had a molar number of the constituent element A (Sr) of 0.5 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 1.5 mol, a molar ratio of A / (A+Mn) of 0.3, a molar ratio of Mn / (A+Mn) of 0.7, and a molar ratio of A / Mn of 0.5.

[0263] Strontium manganate particles (SrMnO) according to Experimental Example 6 were obtained in the same manner as in Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol) and strontium carbonate (147.63 g / mol) were weighed and mixed to obtain a mixed raw material with a molar ratio of Mn:Sr=1.00:0.50, and (ii) the mixed raw material was fired at 1000°C.

[0264] Next, the near-infrared transmitting material according to Experimental Example 6 was obtained in the same manner as in Experimental Example 1, except that 7.6 g of the strontium manganate particles (SrMnO) according to Experimental Example 6, 11.1 g of an acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 80%.

[0265] The coating film of the near-infrared transmitting material according to Experimental Example 6 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 6 was obtained.

[0266] (Experimental Example 7) The manganese oxide according to Experimental Example 7 is barium manganate particles (BaMnO) in which the constituent element A is Ba.

[0267] The barium manganate particles (BaMnO) according to Experimental Example 7 had a molar number of the constituent element A (Ba) of 0.5 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 1.5 mol, a molar ratio of A / (A+Mn) of 0.3, a molar ratio of Mn / (A+Mn) of 0.7, and a molar ratio of A / Mn of 0.5.

[0268] Barium manganate particles (BaMnO) according to Experimental Example 7 were obtained in the same manner as in Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol) and barium carbonate (197.34 g / mol) were weighed and mixed to obtain a mixed raw material with a molar ratio of Mn:Ba=1.00:0.50, and (ii) the mixed raw material was fired at a firing temperature of 1000°C.

[0269] Next, the near-infrared transmitting material according to Experimental Example 7 was obtained in the same manner as in Experimental Example 1, except that 7.6 g of the barium manganate particles (BaMnO) according to Experimental Example 7, 11.1 g of an acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 80%.

[0270] The coating film of the near-infrared transmitting material according to Experimental Example 7 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 7 was obtained.

[0271] (Experimental Example 8) The manganese oxide of Experimental Example 8 is yttrium manganate particles (YMO) in which the constituent element A is Y.

[0272] The yttrium manganate particles (YMO) of Experimental Example 8 had a molar number of the constituent element A (Y) of 0.5 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 1.5 mol, a molar ratio of A / (A+Mn) of 0.3, a molar ratio of Mn / (A+Mn) of 0.7, and a molar ratio of A / Mn of 0.5.

[0273] The yttrium manganate particles (YMO) of Experimental Example 8 were obtained in the same manner as Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol) and yttrium oxide (225.81 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Y=1.00:0.50, (ii) the mixed raw material was fired at a firing temperature of 1000°C, and (iii) the pulverization treatment of Experimental Example 2 was performed.

[0274] Next, the near-infrared transmitting material of Experimental Example 8 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the yttrium manganate particles (YMO) of Experimental Example 8, 11.1 g of acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in solids equivalent (PWC) was 80%.

[0275] The coating film of the near-infrared transmitting material according to Experimental Example 8 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 8 was obtained.

[0276] (Experimental Example 9) The manganese oxide of Experimental Example 9 is bismuth manganate particles (BiMnO) in which the constituent element A is Bi.

[0277] The bismuth manganate particles (BiMnO) according to Experimental Example 9 had a molar number of the constituent element A (Bi) of 0.5 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 1.5 mol, a molar ratio of A / (A+Mn) of 0.3, a molar ratio of Mn / (A+Mn) of 0.7, and a molar ratio of A / Mn of 0.5.

[0278] Bismuth manganate particles (BiMnO) according to Experimental Example 9 were obtained in the same manner as in Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol) and basic bismuth carbonate (509.97 g / mol) were weighed and mixed to obtain a mixed raw material with a molar ratio of Mn:Bi=1.00:0.50, and (ii) the mixed raw material was fired at a firing temperature of 800°C.

[0279] Next, the near-infrared transmitting material of Experimental Example 9 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the bismuth manganate particles (BiMnO) of Experimental Example 9, 11.1 g of an acrylic resin (Dianal LR167, manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 80%.

[0280] The coating film of the near-infrared transmitting material according to Experimental Example 9 was formed in the same manner as in Experimental Example 1, to obtain a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 9.

[0281] (Experimental Example 10) The manganese oxide of Experimental Example 10 is yttrium manganate particles (YMnO) in which the constituent element A is Y.

[0282] The yttrium manganate particles (YMO) of Experimental Example 10 had a molar number of the constituent element A (Y) of 1 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 2 mol, a molar ratio of A / (A+Mn) of 0.5, a molar ratio of Mn / (A+Mn) of 0.5, and a molar ratio of A / Mn of 1.0.

[0283] The yttrium manganate particles (YMnO) of Experimental Example 10 were obtained in the same manner as in Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol) and yttrium oxide (225.81 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Y=1.00:1.00, (ii) the mixed raw material was fired at a firing temperature of 1200°C, and (iii) the pulverization treatment of Experimental Example 2 was performed.

[0284] Next, the near-infrared transmitting material of Experimental Example 10 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the yttrium manganate particles (YMnO) of Experimental Example 10, 11.1 g of an acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 60%.

[0285] The coating film of the near-infrared transmitting material according to Experimental Example 10 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 10 was obtained.

[0286] (Experimental Example 11) The manganese oxide of Experimental Example 11 is lanthanum manganate particles (LaMnO) in which the constituent element A is La.

[0287] The lanthanum manganate particles (LaMnO) according to Experimental Example 11 had a molar number of the constituent element A (La) of 1 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 2 mol, a molar ratio of A / (A+Mn) of 0.5, a molar ratio of Mn / (A+Mn) of 0.5, and a molar ratio of A / Mn of 1.0.

[0288] Lanthanum manganate particles (LaMnO) according to Experimental Example 11 were obtained in the same manner as in Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol) and lanthanum carbonate (457.84 g / mol) were weighed and mixed to give a molar ratio of Mn:La=1.00:1.00 to obtain a mixed raw material, (ii) the mixed raw material was fired at a firing temperature of 1200°C, and (iii) the pulverization treatment of Experimental Example 2 was performed.

[0289] Next, a near-infrared transmitting material according to Experimental Example 11 was obtained in the same manner as in Experimental Example 1, except that 7.6 g of the lanthanum manganate particles (LaMnO) according to Experimental Example 11, 11.1 g of an acrylic resin (Dianal LR167, manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 60%.

[0290] The coating film of the near-infrared transmitting material according to Experimental Example 11 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 11 was obtained.

[0291] (Experimental Example 12) The manganese oxide according to Experimental Example 12 is praseodymium manganate particles (PrMnO) in which the constituent element A is Pr.

[0292] The praseodymium manganate particles (PrMnO) according to Experimental Example 12 had a molar number of the constituent element A (Pr) of 1 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 2 mol, a molar ratio of A / (A+Mn) of 0.5, a molar ratio of Mn / (A+Mn) of 0.5, and a molar ratio of A / Mn of 1.0.

[0293] The praseodymium manganate particles (PrMnO) of Experimental Example 12 were obtained in the same manner as in Experimental Example 1, except that (i) manganese dioxide (228.81 g / mol) and praseodymium oxide (1021.44 g / mol) were weighed out to a molar ratio of Mn:Pr=1.00:1.00 and mixed to obtain a mixed raw material, (ii) the mixed raw material was fired at a firing temperature of 1200°C, and (iii) the pulverization treatment of Experimental Example 2 was performed.

[0294] Next, the near-infrared transmitting material of Experimental Example 12 was obtained in the same manner as in Experimental Example 1, except that 7.6 g of the praseodymium manganate particles (PrMnO) of Experimental Example 12, 11.1 g of an acrylic resin (Dianal LR167, manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 60%.

[0295] The coating film of the near-infrared transmitting material according to Experimental Example 12 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 12 was obtained.

[0296] (Experimental Example 13) The manganese oxide of Experimental Example 13 is neodymium manganate particles (NdMnO) in which the constituent element A is Nd.

[0297] The neodymium manganate particles (NdMnO) according to Experimental Example 13 had a molar number of the constituent element A (Nd) of 1 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 2 mol, a molar ratio of A / (A+Mn) of 0.5, a molar ratio of Mn / (A+Mn) of 0.5, and a molar ratio of A / Mn of 1.0.

[0298] Neodymium manganate particles (NdMnO) according to Experimental Example 13 were obtained in the same manner as in Experimental Example 1, except that (i) manganese tetroxide (228.81 g / mol) and neodymium carbonate octahydrate (612.62 g / mol) were weighed out and mixed to give a molar ratio of Mn:Nd=1.00:1.00 to obtain a mixed raw material, (ii) the firing temperature for firing the mixed raw material was 1200°C, and (iii) the pulverization treatment of Experimental Example 2 was performed.

[0299] Next, the near-infrared transmitting material of Experimental Example 13 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the neodymium manganate particles (NdMnO) of Experimental Example 13, 11.1 g of acrylic resin (Dianal LR167, manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 60%.

[0300] The coating film of the near-infrared transmitting material according to Experimental Example 13 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 13 was obtained.

[0301] (Experimental Example 14) The manganese oxide of Experimental Example 14 is iron manganate particles (FeMnO) in which the constituent element A is Fe.

[0302] The iron manganate particles (FeMnO) according to Experimental Example 14 had a molar number of the constituent element A (Fe) of 2 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 3 mol, a molar ratio of A / (A+Mn) of 0.7, a molar ratio of Mn / (A+Mn) of 0.3, and a molar ratio of A / Mn of 2.0.

[0303] The iron manganate particles (FeMnO) of Experimental Example 14 were obtained in the same manner as in Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol) and iron (III) oxide (159.69 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Fe=0.50:1.00, (ii) the mixed raw material was fired at a firing temperature of 1200°C, and (iii) the pulverization treatment of Experimental Example 2 was performed.

[0304] Next, the near-infrared transmitting material of Experimental Example 14 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the iron manganate particles (FeMnO) of Experimental Example 14, 11.1 g of acrylic resin (Dianal LR167, manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 60%.

[0305] The coating film of the near-infrared transmitting material according to Experimental Example 14 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 14 was obtained.

[0306] (Experimental Example 15) The manganese oxide of Experimental Example 15 is lithium manganese oxide particles (LMO) in which the constituent element A is Li.

[0307] The lithium manganese oxide particles (LMO) of Experimental Example 15 had a molar number of the constituent element A (Li) of 0.001 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 1.001 mol, a molar ratio of A / (A+Mn) of 0.001, a molar ratio of Mn / (A+Mn) of 0.999, and a molar ratio of A / Mn of 0.001.

[0308] The lithium manganese oxide particles (LMO) of Experimental Example 15 were obtained in the same manner as Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol) and lithium carbonate (73.891 g / mol) were weighed and mixed to obtain a mixed raw material with a molar ratio of Mn:Li=1.00:0.001, and (ii) the mixed raw material was fired at 620°C for 24 hours.

[0309] Next, a near-infrared transmitting material according to Experimental Example 15 was obtained in the same manner as in Experimental Example 1. Then, a coating film of the near-infrared transmitting material according to Experimental Example 15 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 15 was obtained.

[0310] (Experimental Example 16) The manganese oxide of Experimental Example 16 is lithium manganese oxide particles (LMO) in which the constituent element A is Li.

[0311] The lithium manganese oxide particles (LMO) of Experimental Example 16 had a molar number of the constituent element A (Li) of 0.012 mol, a molar number of Mn of 1 mol, a molar number of A + Mn of 1.012 mol, a molar ratio of A / (A + Mn) of 0.012, a molar ratio of Mn / (A + Mn) of 0.988, and a molar ratio of A / Mn of 0.012.

[0312] The lithium manganese oxide particles (LMO) of Experimental Example 16 were obtained in the same manner as Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol) and lithium carbonate (73.891 g / mol) were weighed and mixed to obtain a mixed raw material with a molar ratio of Mn:Li=1.00:0.012, and (ii) the mixed raw material was fired at 620°C for 24 hours.

[0313] Next, a near-infrared transmitting material according to Experimental Example 16 was obtained in the same manner as in Experimental Example 1. Then, a coating film of the near-infrared transmitting material according to Experimental Example 16 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 16 was obtained.

[0314] (Experimental Example 17) The manganese oxide of Experimental Example 17 is lithium manganese oxide particles (LMO) in which the constituent element A is Li.

[0315] The lithium manganese oxide particles (LMO) of Experimental Example 17 had a molar number of the constituent element A (Li) of 0.1 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 1.1 mol, a molar ratio of A / (A+Mn) of 0.09, a molar ratio of Mn / (A+Mn) of 0.91, and a molar ratio of A / Mn of 0.1.

[0316] The lithium manganese oxide particles (LMO) of Experimental Example 17 were obtained in the same manner as Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol) and lithium carbonate (73.891 g / mol) were weighed and mixed to obtain a mixed raw material with a molar ratio of Mn:Li=1.00:0.10, and (ii) the mixed raw material was fired at 620°C for 24 hours.

[0317] Next, a near-infrared transmitting material according to Experimental Example 17 was obtained in the same manner as in Experimental Example 1. Then, a coating film of the near-infrared transmitting material according to Experimental Example 17 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 17 was obtained.

[0318] (Experimental Example 18) The manganese oxide of Experimental Example 18 is lithium manganese oxide particles (LMO) in which the constituent element A is Li.

[0319] The lithium manganese oxide particles (LMO) of Experimental Example 18 had a molar number of the constituent element A (Li) of 0.5 mol, a molar number of Mn of 1 mol, a molar number of A + Mn of 1.5 mol, a molar ratio of A / (A + Mn) of 0.33, a molar ratio of Mn / (A + Mn) of 0.67, and a molar ratio of A / Mn of 0.5.

[0320] The lithium manganese oxide particles (LMO) of Experimental Example 18 were obtained in the same manner as Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol) and lithium carbonate (73.891 g / mol) were weighed and mixed to obtain a mixed raw material with a molar ratio of Mn:Li=1.00:0.50, and (ii) the mixed raw material was fired at a firing temperature of 620°C for 24 hours.

[0321] Next, a near-infrared transmitting material according to Experimental Example 18 was obtained in the same manner as in Experimental Example 1. Then, a coating film of the near-infrared transmitting material according to Experimental Example 18 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 18 was obtained.

[0322] (Experimental Example 19) The manganese oxide of Experimental Example 19 is lithium manganese oxide particles (LMO) in which the constituent element A is Li.

[0323] The lithium manganese oxide particles (LMO) of Experimental Example 19 had a molar number of the constituent element A (Li) of 1 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 2 mol, a molar ratio of A / (A+Mn) of 0.50, a molar ratio of Mn / (A+Mn) of 0.50, and a molar ratio of A / Mn of 1.

[0324] The lithium manganese oxide particles (LMO) of Experimental Example 19 were obtained in the same manner as Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol) and lithium carbonate (73.891 g / mol) were weighed and mixed to obtain a mixed raw material with a molar ratio of Mn:Li=1.00:1.00, and (ii) the mixed raw material was fired at a firing temperature of 620°C for 24 hours.

[0325] Next, a near-infrared transmitting material according to Experimental Example 19 was obtained in the same manner as in Experimental Example 1. Then, a coating film of the near-infrared transmitting material according to Experimental Example 19 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 19 was obtained.

[0326] (Experimental Example 20) The manganese oxide of Experimental Example 20 is lithium manganese oxide particles (LMO) in which the constituent element A is Li.

[0327] The lithium manganese oxide particles (LMO) of Experimental Example 20 had a molar number of the constituent element A (Li) of 1.5 mol, a molar number of Mn of 1 mol, a molar number of A + Mn of 2.5 mol, a molar ratio of A / (A + Mn) of 0.60, a molar ratio of Mn / (A + Mn) of 0.40, and a molar ratio of A / Mn of 1.5.

[0328] The lithium manganese oxide particles (LMO) of Experimental Example 20 were obtained in the same manner as Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol) and lithium carbonate (73.891 g / mol) were weighed and mixed to obtain a mixed raw material with a molar ratio of Mn:Li=1.00:1.50, and (ii) the mixed raw material was fired at a firing temperature of 620°C for 24 hours.

[0329] Next, a near-infrared transmitting material according to Experimental Example 20 was obtained in the same manner as in Experimental Example 1. Then, a coating film of the near-infrared transmitting material according to Experimental Example 20 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 20 was obtained.

[0330] (Experimental Example 21) The manganese oxide of Experimental Example 21 is yttrium manganate particles (YMO) in which the constituent element A is Y.

[0331] The yttrium manganate particles (YMO) of Experimental Example 21 had a molar number of the constituent element A (Y) of 0.1 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 1.1 mol, a molar ratio of A / (A+Mn) of 0.1, a molar ratio of Mn / (A+Mn) of 0.9, and a molar ratio of A / Mn of 0.1.

[0332] The yttrium manganate particles (YMO) of Experimental Example 21 were obtained in the same manner as Experimental Example 1, except that (i) manganese tetroxide (228.81 g / mol) and yttrium oxide (225.81 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Y=1.00:0.10, (ii) the mixed raw material was fired at a firing temperature of 1200°C, and (iii) the two-stage crushing process of Experimental Example 3 was performed.

[0333] Next, the near-infrared transmitting material of Experimental Example 21 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the yttrium manganate particles (YMO) of Experimental Example 21, 11.1 g of acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in solids equivalent (PWC) was 60%.

[0334] The coating film of the near-infrared transmitting material according to Experimental Example 21 was formed in the same manner as in Experimental Example 1, to obtain a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 21.

[0335] (Experimental Example 22) The manganese oxide of Experimental Example 22 is yttrium manganate particles (YMO) in which the constituent element A is Y.

[0336] The yttrium manganate particles (YMO) of Experimental Example 22 had a molar number of the constituent element A (Y) of 0.4 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 1.4 mol, a molar ratio of A / (A+Mn) of 0.3, a molar ratio of Mn / (A+Mn) of 0.7, and a molar ratio of A / Mn of 0.4.

[0337] The yttrium manganate particles (YMO) of Experimental Example 22 were obtained in the same manner as Experimental Example 1, except that (i) manganese tetroxide (228.81 g / mol) and yttrium oxide (225.81 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Y=1.00:0.40, (ii) the mixed raw material was fired at a firing temperature of 1200°C, and (iii) the two-stage crushing process of Experimental Example 3 was performed.

[0338] Next, the near-infrared transmitting material of Experimental Example 22 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the yttrium manganate particles (YMO) of Experimental Example 22, 11.1 g of acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in solids equivalent (PWC) was 60%.

[0339] The coating film of the near-infrared transmitting material according to Experimental Example 22 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 22 was obtained.

[0340] (Experimental Example 23) The manganese oxide of Experimental Example 23 is yttrium manganate particles (YMO) in which the constituent element A is Y.

[0341] The yttrium manganate particles (YMO) of Experimental Example 23 had a molar number of the constituent element A (Y) of 0.5 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 1.5 mol, a molar ratio of A / (A+Mn) of 0.3, a molar ratio of Mn / (A+Mn) of 0.7, and a molar ratio of A / Mn of 0.5.

[0342] The yttrium manganate particles (YMO) of Experimental Example 23 were obtained in the same manner as Experimental Example 1, except that (i) manganese tetroxide (228.81 g / mol) and yttrium oxide (225.81 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Y=1.00:0.50, (ii) the mixed raw material was fired at a firing temperature of 1200°C, and (iii) the two-stage crushing process of Experimental Example 3 was performed.

[0343] Next, the near-infrared transmitting material of Experimental Example 23 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the yttrium manganate particles (YMO) of Experimental Example 23, 11.1 g of acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in solids equivalent (PWC) was 60%.

[0344] The coating film of the near-infrared transmitting material according to Experimental Example 23 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 23 was obtained.

[0345] (Experimental Example 24) The manganese oxide of Experimental Example 24 is yttrium manganate particles (YMO) in which the constituent element A is Y.

[0346] The yttrium manganate particles (YMO) of Experimental Example 24 had a molar number of the constituent element A (Y) of 0.6 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 1.6 mol, a molar ratio of A / (A+Mn) of 0.4, a molar ratio of Mn / (A+Mn) of 0.6, and a molar ratio of A / Mn of 0.6.

[0347] The yttrium manganate particles (YMO) of Experimental Example 24 were obtained in the same manner as Experimental Example 1, except that (i) manganese tetroxide (228.81 g / mol) and yttrium oxide (225.81 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Y=1.00:0.60, (ii) the mixed raw material was fired at a firing temperature of 1200°C, and (iii) the two-stage crushing process of Experimental Example 3 was performed.

[0348] Next, the near-infrared transmitting material of Experimental Example 24 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the yttrium manganate particles (YMO) of Experimental Example 24, 11.1 g of acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in solids equivalent (PWC) was 60%.

[0349] The coating film of the near-infrared transmitting material according to Experimental Example 24 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 24 was obtained.

[0350] (Experimental Example 25) The manganese oxide of Experimental Example 25 is yttrium manganate particles (YMO) in which the constituent element A is Y.

[0351] The yttrium manganate particles (YMO) of Experimental Example 25 had a molar number of the constituent element A (Y) of 0.75 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 1.75 mol, a molar ratio of A / (A+Mn) of 0.43, a molar ratio of Mn / (A+Mn) of 0.57, and a molar ratio of A / Mn of 0.75.

[0352] The yttrium manganate particles (YMO) of Experimental Example 25 were obtained in the same manner as Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol) and yttrium oxide (225.81 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Y=1.00:0.75, (ii) the mixed raw material was fired at a firing temperature of 1200°C, and (iii) the two-stage crushing process of Experimental Example 3 was performed.

[0353] Next, the near-infrared transmitting material of Experimental Example 25 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the yttrium manganate particles (YMO) of Experimental Example 25, 11.1 g of acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 60%.

[0354] The coating film of the near-infrared transmitting material according to Experimental Example 25 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 25 was obtained.

[0355] (Experimental Example 26) The manganese oxide of Experimental Example 26 is yttrium manganate particles (YMO) in which the constituent element A is Y.

[0356] The yttrium manganate particles (YMO) of Experimental Example 26 had a molar number of the constituent element A (Y) of 1 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 2 mol, a molar ratio of A / (A+Mn) of 0.5, a molar ratio of Mn / (A+Mn) of 0.5, and a molar ratio of A / Mn of 1.0.

[0357] The yttrium manganate particles (YMO) of Experimental Example 26 were obtained in the same manner as Experimental Example 1, except that (i) manganese tetroxide (228.81 g / mol) and yttrium oxide (225.81 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Y=1.00:1.00, (ii) the mixed raw material was fired at a firing temperature of 1200°C, and (iii) the two-stage crushing process of Experimental Example 3 was performed.

[0358] Next, the near-infrared transmitting material of Experimental Example 26 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the yttrium manganate particles (YMO) of Experimental Example 26, 11.1 g of acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 60%.

[0359] The coating film of the near-infrared transmitting material according to Experimental Example 26 was formed in the same manner as in Experimental Example 1, to obtain a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 26.

[0360] (Experimental Example 27) The manganese oxide of Experimental Example 27 is lithium manganate particles (LMO-Ti) in which the constituent element A is Li and Ti.

[0361] The lithium manganese oxide particles (LMO-Ti) of Experimental Example 27 had a molar number of constituent elements A (Li, Ti) of 1.1 mol, a molar number of Mn of 1.9 mol, a molar number of A+Mn of 3 mol, a molar ratio of A / (A+Mn) of 0.4, a molar ratio of Mn / (A+Mn) of 0.6, and a molar ratio of A / Mn of 0.58.

[0362] The lithium manganese oxide particles (LMO-Ti) of Experimental Example 27 were obtained in the same manner as Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol), lithium carbonate (73.891 g / mol), and titanium oxide (79.87 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Li:Ti:=1.90:1.00:0.10, (ii) the mixed raw material was fired at a firing temperature of 1000°C, and (iii) the pulverization treatment of Experimental Example 2 was performed.

[0363] Next, a near-infrared transmitting material according to Experimental Example 27 was obtained in the same manner as in Experimental Example 1. Then, a coating film of the near-infrared transmitting material according to Experimental Example 27 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 27 was obtained.

[0364] (Experimental Example 28) The manganese oxide of Experimental Example 28 is lithium manganate particles (LMO-Ti) in which the constituent element A is Li and Ti.

[0365] The lithium manganese oxide particles (LMO-Ti) of Experimental Example 28 had a molar number of constituent elements A (Li, Ti) of 1.5 mol, a molar number of Mn of 1.5 mol, a molar number of A+Mn of 3 mol, a molar ratio of A / (A+Mn) of 0.5, a molar ratio of Mn / (A+Mn) of 0.5, and a molar ratio of A / Mn of 1.00.

[0366] The lithium manganese oxide particles (LMO-Ti) of Experimental Example 28 were obtained in the same manner as Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol), lithium carbonate (73.891 g / mol), and titanium oxide (79.87 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Li:Ti:=1.50:1.00:0.50, (ii) the mixed raw material was fired at a firing temperature of 1000°C, and (iii) the pulverization treatment of Experimental Example 2 was performed.

[0367] Next, a near-infrared transmitting material according to Experimental Example 28 was obtained in the same manner as in Experimental Example 1. Then, a coating film of the near-infrared transmitting material according to Experimental Example 28 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 28 was obtained.

[0368] (Experimental Example 29) The manganese oxide of Experimental Example 29 is lithium manganate particles (LMO-Y) in which the constituent element A is Li and Y.

[0369] The lithium manganate particles (LMO-Y) of Experimental Example 29 had a molar number of the constituent element A (Li, Y) of 1.1 mol, a molar number of Mn of 1.9 mol, a molar number of A+Mn of 3 mol, a molar ratio of A / (A+Mn) of 0.4, a molar ratio of Mn / (A+Mn) of 0.6, and a molar ratio of A / Mn of 0.58.

[0370] The lithium manganese oxide particles (LMO-Y) of Experimental Example 29 were obtained in the same manner as Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol), lithium carbonate (73.891 g / mol), and yttrium oxide (225.81 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Li:Y=1.90:1.00:0.10, (ii) the mixed raw material was fired at 1000°C, and (iii) the pulverization treatment of Experimental Example 2 was performed.

[0371] Next, a near-infrared transmitting material according to Experimental Example 29 was obtained in the same manner as in Experimental Example 1. Then, a coating film of the near-infrared transmitting material according to Experimental Example 29 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 29 was obtained.

[0372] (Experimental Example 30) The manganese oxide of Experimental Example 30 is lithium manganate particles (LMO-Y) in which the constituent element A is Li and Y.

[0373] The lithium manganese oxide particles (LMO-Y) of Experimental Example 30 had a molar number of the constituent element A (Li, Y) of 1.5 mol, a molar number of Mn of 1.5 mol, a molar number of A+Mn of 3 mol, a molar ratio of A / (A+Mn) of 0.5, a molar ratio of Mn / (A+Mn) of 0.5, and a molar ratio of A / Mn of 1.00.

[0374] The lithium manganese oxide particles (LMO-Y) of Experimental Example 30 were obtained in the same manner as Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol), lithium carbonate (73.891 g / mol), and yttrium oxide (225.81 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Li:Y=1.50:1.00:0.50, (ii) the mixed raw material was fired at a firing temperature of 1000°C, and (iii) the pulverization treatment of Experimental Example 2 was performed.

[0375] Next, a near-infrared transmitting material according to Experimental Example 30 was obtained in the same manner as in Experimental Example 1. Then, a coating film of the near-infrared transmitting material according to Experimental Example 30 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 30 was obtained.

[0376] (Experimental Example 31) The manganese oxide of Experimental Example 31 is yttrium manganate particles (YMO-Ti) in which the constituent element A is Y and Ti.

[0377] The yttrium manganate particles (YMO-Ti) of Experimental Example 31 had a molar number of constituent elements A (Y, Ti) of 1.1 mol, a molar number of Mn of 0.9 mol, a molar number of A+Mn of 2 mol, a molar ratio of A / (A+Mn) of 0.55, a molar ratio of Mn / (A+Mn) of 0.45, and a molar ratio of A / Mn of 1.22.

[0378] The yttrium manganate particles (YMO-Ti) of Experimental Example 31 were obtained in the same manner as Experimental Example 1, except that (i) manganese tetroxide (228.81 g / mol), yttrium oxide (225.81 g / mol):1 mol, and titanium oxide (79.87 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Y:Ti=0.90:1.00:0.1, (ii) the mixed raw material was fired at a firing temperature of 1200°C, and (iii) the pulverization treatment of Experimental Example 2 was performed.

[0379] Next, the near-infrared transmitting material of Experimental Example 31 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the yttrium manganate particles (YMO-Ti) of Experimental Example 31, 11.1 g of acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in solids equivalent (PWC) was 60%.

[0380] The coating film of the near-infrared transmitting material according to Experimental Example 31 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 31 was obtained.

[0381] (Experimental Example 32) The manganese oxide of Experimental Example 32 is yttrium manganate particles (YMO-Ti) in which the constituent element A is Y and Ti.

[0382] The yttrium manganate particles (YMO-Ti) of Experimental Example 32 had a molar number of constituent elements A (Y, Ti) of 1.3 mol, a molar number of Mn of 0.7 mol, a molar number of A+Mn of 2 mol, a molar ratio of A / (A+Mn) of 0.65, a molar ratio of Mn / (A+Mn) of 0.35, and a molar ratio of A / Mn of 1.86.

[0383] The yttrium manganate particles (YMO-Ti) of Experimental Example 32 were obtained in the same manner as Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol), lithium carbonate (73.891 g / mol), and yttrium oxide (225.81 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Li:Y=1.70:1.00:0.30, (ii) the mixed raw material was fired at a firing temperature of 1200°C, and (iii) the grinding process of Experimental Example 2 was performed.

[0384] Next, the near-infrared transmitting material of Experimental Example 32 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the yttrium manganate particles (YMO-Ti) of Experimental Example 32, 11.1 g of acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in solids equivalent (PWC) was 60%.

[0385] The coating film of the near-infrared transmitting material according to Experimental Example 32 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 32 was obtained.

[0386] (Experimental Example 33) The manganese oxide of Experimental Example 33 is yttrium manganate particles (YMO-Ti) in which the constituent element A is Y and Ti.

[0387] The yttrium manganate particles (YMO-Ti) of Experimental Example 33 had a molar number of constituent elements A (Y, Ti) of 1 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 2 mol, a molar ratio of A / (A+Mn) of 0.5, a molar ratio of Mn / (A+Mn) of 0.5, and a molar ratio of A / Mn of 1.00.

[0388] The yttrium manganate particles (YMO-Ti) of Experimental Example 33 were obtained in the same manner as Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol), lithium carbonate (73.891 g / mol), and yttrium oxide (225.81 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Li:Y=1.00:0.90:0.10, (ii) the mixed raw material was fired at a firing temperature of 1200°C, and (iii) the pulverization treatment of Experimental Example 2 was performed.

[0389] Next, the near-infrared transmitting material of Experimental Example 33 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the yttrium manganate particles (YMO-Ti) of Experimental Example 33, 11.1 g of acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in solids equivalent (PWC) was 60%.

[0390] The coating film of the near-infrared transmitting material according to Experimental Example 33 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 33 was obtained.

[0391] (Experimental Example 34) The manganese oxide of Experimental Example 34 is yttrium manganate particles (YMO-Ti) in which the constituent element A is Y and Ti.

[0392] The yttrium manganate particles (YMO-Ti) of Experimental Example 34 had a molar number of constituent elements A (Y, Ti) of 1 mol, a molar number of Mn of 1 mol, a molar number of A + Mn of 2 mol, a molar ratio of A / (A + Mn) of 0.5, a molar ratio of Mn / (A + Mn) of 0.5, and a molar ratio of A / Mn of 1.00.

[0393] The yttrium manganate particles (YMO-Ti) of Experimental Example 34 were obtained in the same manner as Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol), lithium carbonate (73.891 g / mol), and yttrium oxide (225.81 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Li:Y=1.00:0.70:0.30, (ii) the mixed raw material was fired at a firing temperature of 1200°C, and (iii) the pulverization treatment of Experimental Example 2 was performed.

[0394] Next, the near-infrared transmitting material of Experimental Example 34 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the yttrium manganate particles (YMO-Ti) of Experimental Example 34, 11.1 g of acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in solids equivalent (PWC) was 60%.

[0395] The coating film of the near-infrared transmitting material according to Experimental Example 34 was formed in the same manner as in Experimental Example 1, to obtain a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 34.

[0396] (Experimental Example 35) The manganese oxide of Experimental Example 35 is yttrium manganate particles (YMO-Zn) in which the constituent elements A are Y and Zn.

[0397] The yttrium manganate particles (YMO-Zn) of Experimental Example 35 had a molar number of constituent elements A (Y, Zn) of 1 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 2 mol, a molar ratio of A / (A+Mn) of 0.5, a molar ratio of Mn / (A+Mn) of 0.5, and a molar ratio of A / Mn of 1.00.

[0398] The yttrium manganate particles (YMO-Zn) of Experimental Example 35 were obtained in the same manner as Experimental Example 1, except that (i) manganese tetroxide (228.81 g / mol), yttrium oxide (225.81 g / mol), and zinc oxide (81.41 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Y:Zn=1.00:0.90:0.10, (ii) the mixed raw material was fired at a firing temperature of 1200°C, and (iii) the pulverization treatment of Experimental Example 2 was performed.

[0399] Next, the near-infrared transmitting material of Experimental Example 35 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the yttrium manganate particles (YMO-Zn) of Experimental Example 35, 11.1 g of acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in solids equivalent (PWC) was 60%.

[0400] The coating film of the near-infrared transmitting material according to Experimental Example 35 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 35 was obtained.

[0401] (Experimental Example 36) The manganese oxide of Experimental Example 36 is yttrium manganate particles (YMO-Zn) in which the constituent elements A are Y and Zn.

[0402] The yttrium manganate particles (YMO-Zn) of Experimental Example 36 had a molar number of constituent elements A (Y, Zn) of 1 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 2 mol, a molar ratio of A / (A+Mn) of 0.5, a molar ratio of Mn / (A+Mn) of 0.5, and a molar ratio of A / Mn of 1.00.

[0403] The yttrium manganate particles (YMO-Zn) of Experimental Example 36 were obtained in the same manner as Experimental Example 1, except that (i) manganese tetroxide (228.81 g / mol), yttrium oxide (225.81 g / mol), and zinc oxide (81.41 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Y:Zn=1.00:0.90:0.10, (ii) the mixed raw material was fired at a firing temperature of 1200°C, and (iii) the two-stage crushing process of Experimental Example 3 was performed.

[0404] Next, the near-infrared transmitting material of Experimental Example 36 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the yttrium manganate particles (YMO-Zn) of Experimental Example 36, 11.1 g of acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 60%.

[0405] The coating film of the near-infrared transmitting material according to Experimental Example 36 was formed in the same manner as in Experimental Example 1, to obtain a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 36.

[0406] (Experimental Example 37) Experimental Example 37 is directed to yttrium manganate particles (YMO-Zn) in which the constituent elements A are Y and Zn.

[0407] The yttrium manganate particles (YMO-Zn) of Experimental Example 37 had a molar number of constituent elements A (Y, Zn) of 1 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 2 mol, a molar ratio of A / (A+Mn) of 0.5, a molar ratio of Mn / (A+Mn) of 0.5, and a molar ratio of A / Mn of 1.00.

[0408] The yttrium manganate particles (YMO-Zn) of Experimental Example 37 were obtained in the same manner as Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol), yttrium oxide (225.81 g / mol), and zinc oxide (81.41 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Y:Zn=1.00:0.95:0.05, (ii) the mixed raw material was fired at a firing temperature of 1200°C, and (iii) the two-stage crushing process of Experimental Example 3 was performed.

[0409] Next, the near-infrared transmitting material of Experimental Example 37 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the yttrium manganate particles (YMO-Zn) of Experimental Example 37, 11.1 g of acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in solids equivalent (PWC) was 60%.

[0410] The coating film of the near-infrared transmitting material according to Experimental Example 37 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 37 was obtained.

[0411] (Example 38) Experimental Example 38 is directed to yttrium manganate particles (YMO-Zn) in which the constituent elements A are Y and Zn.

[0412] The yttrium manganate particles (YMO-Zn) of Experimental Example 38 had a molar number of constituent elements A (Y, Zn) of 1 mol, a molar number of Mn of 1 mol, a molar number of A+Mn of 2 mol, a molar ratio of A / (A+Mn) of 0.5, a molar ratio of Mn / (A+Mn) of 0.5, and a molar ratio of A / Mn of 1.00.

[0413] The yttrium manganate particles (YMO-Zn) of Experimental Example 38 were obtained in the same manner as Experimental Example 1, except that (i) manganese trioxide (228.81 g / mol), yttrium oxide (225.81 g / mol), and zinc oxide (81.41 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Y:Zn=1.00:0.70:0.30, (ii) the mixed raw material was fired at a firing temperature of 1200°C, and (iii) the two-stage crushing process of Experimental Example 3 was performed.

[0414] Next, the near-infrared transmitting material of Experimental Example 38 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the yttrium manganate particles (YMO-Zn) of Experimental Example 38, 11.1 g of acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 60%.

[0415] The coating film of the near-infrared transmitting material according to Experimental Example 38 was formed in the same manner as in Experimental Example 1, to obtain a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 38.

[0416] (Experimental Example 39) The manganese oxide of Experimental Example 39 is yttrium manganate particles (YMO-CaAlTiFeZnBi) in which the constituent element A is Y, Ca, Al, Ti, Fe, Zn, or Bi.

[0417] The yttrium manganate particles (YMO-CaAlTiFeZnBi) of Experimental Example 39 had a molar number of constituent elements A (Y, Ca, Al, Ti, Fe, Zn, Bi) of 1 mol, a molar number of Mn of 1 mol, a molar ratio of A / (A+Mn) of 0.5, a molar ratio of Mn / (A+Mn) of 0.5, and a molar ratio of A / Mn of 1.00.

[0418] The yttrium manganate particles (YMO-CaAlTiFeZnBi) according to Experimental Example 39 were composed of (i) manganese tetroxide (228.81 g / mol), yttrium oxide (225.81 g / mol), calcium carbonate (100.09 g / mol), aluminum hydroxide (78.00 g / mol), titanium oxide (79.87 g / mol), iron oxide (159.69 g / mol), and zinc oxide (81.41 g / mol). The mixture was obtained in the same manner as in Experimental Example 1, except that (i) the mixed raw materials were weighed out and mixed with basic bismuth carbonate (509.97 g / mol) in a molar ratio of Mn:Y:Ca:Al:Ti:Fe:Zn:Bi=1.00:0.94:0.01:0.01:0.01:0.01:0.01:0.01 to obtain a mixed raw material, (ii) the mixed raw material was fired at 800°C for 15 hours, and (iii) the grinding treatment of Experimental Example 2 was carried out.

[0419] Next, the near-infrared transmitting material of Experimental Example 39 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the yttrium manganate particles (YMO-CaAlTiFeZnBi) of Experimental Example 39, 11.1 g of acrylic resin (Dianal LR167, manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 60%.

[0420] The coating film of the near-infrared transmitting material according to Experimental Example 39 was formed in the same manner as in Experimental Example 1, to obtain a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 39.

[0421] (Experimental Example 40) The manganese oxide of Experimental Example 40 is lithium manganate particles (LMO-CaAlTiFeZnBi) in which the constituent element A is Li, Ca, Al, Ti, Fe, Zn, or Bi.

[0422] The lithium manganese oxide particles (LMO-CaAlTiFeZnBi) of Experimental Example 40 had a molar number of constituent elements A (Li, Ca, Al, Ti, Fe, Zn, Bi) of 1 mol, a molar number of Mn of 2 mol, a molar number of A+Mn of 3 mol, a molar ratio of A / (A+Mn) of 0.33, a molar ratio of Mn / (A+Mn) of 0.67, and a molar ratio of A / Mn of 0.5.

[0423] The lithium manganate particles (LMO-CaAlTiFeZnBi) according to Experimental Example 40 were prepared by mixing (i) manganese trioxide (228.81 g / mol), lithium carbonate (73.891 g / mol), calcium carbonate (100.09 g / mol), aluminum hydroxide (78.00 g / mol), titanium oxide (79.87 g / mol), iron oxide (159.69 g / mol), zinc oxide (81.41 g / mol), and salt. The mixed raw material was obtained in the same manner as in Experimental Example 1, except that (i) basic bismuth carbonate (509.97 g / mol) was weighed out and mixed to give a molar ratio of Mn:Li:Ca:Al:Ti:Fe:Zn:Bi=1.00:0.94:0.01:0.01:0.01:0.01:0.01:0.01 to obtain a mixed raw material, (ii) the mixed raw material was fired at a firing temperature of 800°C for 15 hours, and (iii) the grinding treatment of Experimental Example 2 was carried out.

[0424] Next, the near-infrared transmitting material of Experimental Example 40 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the lithium manganese oxide particles (LMO-CaAlTiFeZnBi) of Experimental Example 40, 11.1 g of acrylic resin (Dianal LR167 manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 60%.

[0425] The coating film of the near-infrared transmitting material according to Experimental Example 40 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 40 was obtained.

[0426] (Example 41) The manganese oxide of Experimental Example 41 is lithium yttrium manganate particles (LYMO-CaAlTiFeZnBi) in which the constituent element A is Li, Y, Ca, Al, Ti, Fe, Zn, or Bi.

[0427] The lithium yttrium manganese oxide particles (LYMO-CaAlTiFeZnBi) according to Experimental Example 41 had a molar number of constituent elements A (Li, Y, Ca, Al, Ti, Fe, Zn, Bi) of 1.06 mol, a molar number of Mn of 0.94 mol, a molar number of A+Mn of 2 mol, a molar ratio of A / (A+Mn) of 0.53, a molar ratio of Mn / (A+Mn) of 0.47, and a molar ratio of A / Mn of 1.13.

[0428] The lithium yttrium manganate particles (LYMO-CaAlTiFeZnBi) according to Experimental Example 41 were composed of (i) manganese tetroxide (228.81 g / mol), lithium carbonate (73.891 g / mol), yttrium oxide (225.81 g / mol), calcium carbonate (100.09 g / mol), aluminum hydroxide (78.00 g / mol), titanium oxide (79.87 g / mol), iron oxide (159.69 g / mol), and zinc oxide (81. The procedure for Experimental Example 1 was repeated except that (i) Mn:Li:Y:Ca:Al:Ti:Fe:Zn:Bi (41 g / mol) and basic bismuth carbonate (509.97 g / mol) were weighed and mixed to obtain a mixed raw material in a molar ratio of Mn:Li:Y:Ca:Al:Ti:Fe:Zn:Bi=0.94:0.50:0.50:0.01:0.01:0.01:0.01:0.01:0.01, (ii) the mixed raw material was fired at 800°C for 15 hours, and (iii) the grinding treatment of Experimental Example 2 was performed.

[0429] Next, the near-infrared transmitting material of Experimental Example 41 was obtained in the same manner as Experimental Example 1, except that 7.6 g of the lithium yttrium manganate particles (LYMO-CaAlTiFeZnBi) of Experimental Example 41, 11.1 g of acrylic resin (Dianal LR167, manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 60%.

[0430] The coating film of the near-infrared transmitting material according to Experimental Example 41 was formed in the same manner as in Experimental Example 1, and a near-infrared transmitting film (film thickness 5 μm) according to Experimental Example 41 was obtained.

[0431] (Comparative Example 3) Comparative Example 3 is a manganese oxide mixture consisting only of trimanganese tetroxide.

[0432] The manganate particles of Comparative Example 3 had a molar number of Mn of 1 mol, a molar number of A + Mn of 1 mol, a molar ratio of A / (A + Mn) of 0.0, a molar ratio of Mn / (A + Mn) of 1.0, and a molar ratio of A / Mn of 0.0.

[0433] The manganate particles of Comparative Example 3 were obtained in the same manner as in Experimental Example 1, except that (i) they consisted only of manganese trioxide (228.81 g / mol), (ii) the firing temperature for firing the raw materials was 1200°C, and (iii) the two-stage crushing process of Experimental Example 3 was carried out.

[0434] Next, the manganese oxide mixture of Comparative Example 3 was obtained in the same manner as in Experimental Example 1, except that 7.6 g of the manganic acid particles of Comparative Example 3, 11.1 g of acrylic resin (Dianal LR167, manufactured by Mitsubishi Rayon Co., Ltd.), and 18.9 g of ethyl acetate were mixed in a container so that the pigment concentration in terms of solids (PWC) was 60%.

[0435] The manganese oxide mixture coating film according to Comparative Example 3 was formed in the same manner as in Experimental Example 1, and a manganese oxide mixture film according to Comparative Example 3 (film thickness: 5 μm) was obtained.

[0436] The following physical properties were measured for the near-infrared transparent materials according to Examples 1 to 7, the near-infrared transparent materials according to Experimental Examples 1 to 41, the titanium oxide mixture according to Comparative Example 1, the carbon black mixture according to Comparative Example 2, and the manganese oxide mixture according to Comparative Example 3. The measured physical property values ​​and the methods for measuring the physical property values ​​are shown below, and the measurement results are shown in Figures 1 to 19.

[0437] <Elemental analysis> The compositions (atomic ratios) of the manganese oxide particles contained in the near-infrared transparent materials according to Examples 1 to 7 and Experimental Examples 1 to 41 were analyzed using an ICP-OES (Inductivity Coupled Plasma Optical Emission Spectrometry) multi-type ICP optical emission spectrometer. The ICP-OES used for the analysis was an ICP-OES (700 Series) manufactured by Agilent Technologies, Inc.

[0438] <Laser diffraction and scattering method> The particle size distribution of the particles was evaluated using a laser diffraction / scattering particle size distribution analyzer (MT3300EXII manufactured by Microtrac-Bell Corporation) in accordance with JIS Z 8825:2013. Furthermore, without filtering, the samples were subjected to ultrasonic treatment at an ultrasonic output of 40 W for 3 minutes, followed by measurement. Here, the near-infrared transparent materials according to Examples 1 to 7 or Experimental Examples 1 to 41 are mixtures of manganese oxide particles, which are particles for near-infrared transparent materials, with a dispersion, and therefore particle size distribution evaluation is not possible as is. Therefore, particle size distribution evaluation was performed using manganese oxide particles before mixing with a dispersion. Note that D50 indicates the particle size at which the volume fraction reaches 50%.

[0439] Specifically, a slurry sample was fed into the sample inlet of a sample circulator provided in the measuring device until the measuring device determined that the sample was within the measurable range, and then ultrasonic dispersion treatment (ultrasonic output 40 W, 3 minutes) was performed within the measuring device, and after confirming that the display had stabilized, measurements were performed. On the other hand, the titanium oxide mixture of Comparative Example 1, the carbon black mixture of Comparative Example 2, and the manganese oxide mixture of Comparative Example 3 were also measured in the same manner.

[0440] <Particle size measurement> The average secondary particle size of the manganese oxide particles contained in the near-infrared transparent materials according to Examples 1 to 7 or Experimental Examples 1 to 41 was calculated by analyzing particle images taken with a field emission scanning electron microscope (FE-SEM) (S-4800, manufactured by Hitachi High-Tech Science Corporation).

[0441] Specifically, the horizontal Feret diameters of 20 secondary particles were measured, and the number-average value was taken as the average secondary particle diameter. Since the near-infrared transparent materials according to Examples 1 to 7 or Experimental Examples 1 to 41 are mixtures of manganese oxide particles, which are particles for near-infrared transparent materials, with a dispersion, the manganese oxide particles before being mixed with the dispersion were observed with an SEM under an accelerating voltage of 1 kV and directly measured using an FE-SEM. Similarly, the titanium oxide mixture according to Comparative Example 1, the carbon black mixture according to Comparative Example 2, and the manganese oxide mixture according to Comparative Example 3 were also measured.

[0442] <Specific surface area (SSA)> The specific surface area (SSA) was measured using a Macsorb (HM model-1201) manufactured by Mountech Co., Ltd. in accordance with "6.2 Fluidized Method (3.5) Single-Point Method" of JIS R 1626-1996 (Method for Measuring Specific Surface Area of ​​Fine Ceramic Powders by Gas Adsorption BET Method). A mixed gas of helium as a carrier gas and nitrogen as an adsorbate gas was used. Nitrogen gas was used for calibration. The near-infrared transparent materials of Examples 1, 3 to 7, and Experimental Examples 1 to 41 were prepared by mixing manganese oxide particles, which are particles for near-infrared transparent materials, with a dispersion. Therefore, the specific surface area (SSA) could not be measured as is. Therefore, the specific surface area (SSA) was measured using the manganese oxide particles before mixing with the dispersion. The titanium oxide mixture of Comparative Example 1, the carbon black mixture of Comparative Example 2, and the manganese oxide mixture of Comparative Example 3 were also similarly measured.

[0443] <Reflectance measurement> The reflectance of each sample filled with the manganese oxide particles contained in the near-infrared transparent materials of Examples 1 to 7 or Experimental Examples 1 to 41, the titanium oxide mixture of Comparative Example 1, the carbon black mixture of Comparative Example 2, and the manganese oxide mixture of Comparative Example 3 was measured using a spectrophotometer (UH4150 ultraviolet-visible-near-infrared spectrophotometer manufactured by Hitachi High-Tech Science Corporation) equipped with a φ60 mm integrating sphere unit, measuring the reflectance at a wavelength of 550 nm. Here, the near-infrared transparent materials of Examples 1 to 7 or Experimental Examples 1 to 41 are a mixture of manganese oxide particles, which are particles for near-infrared transparent materials, and a dispersion, and the reflectance cannot be measured as is. Therefore, the reflectance was measured using the manganese oxide particles before being mixed with the dispersion. The titanium oxide mixture of Comparative Example 1, the carbon black mixture of Comparative Example 2, and the manganese oxide mixture of Comparative Example 3 were also measured in the same manner.

[0444] <Ultraviolet-visible near-infrared spectroscopy (UV-vis)> A test cell for optical measurement was prepared by filling an aluminum sample cell with a powder sample of the manganese oxide particles contained in the near-infrared transmitting materials according to Examples 1 to 7, and covering and sealing the surface of the sample cell with quartz glass. This test cell was loaded into a standard integral-class ultraviolet-visible-near-infrared spectrometer, and the diffuse reflectance from the ultraviolet region to the near-infrared region was determined according to the following diffuse reflectance measurement conditions.

[0445] = Diffuse reflectance measurement conditions = Measurement equipment: UV-Vis-NIR spectrophotometer UH4150 (Hitachi High-Tech Science Corporation) Measurement mode: Wavelength scan Data mode: %R (reflectance) Measurement wavelength range: 240~2500nm Scan speed: 600nm / min in the wavelength range of 240nm to 850nm, 1500nm / min in the wavelength range of 850nm to 2400nm Sampling interval: 2nm

[0446] <Band gap calculation> The band gap of the powder samples of manganese oxide particles contained in the near-infrared transmitting materials of Examples 1 to 7 was determined as follows. First, the diffuse reflectance from the ultraviolet region to the near-infrared region measured by the above-mentioned ultraviolet-visible-near-infrared spectroscopy (UV-vis) was subjected to Kubelka-Munk transformation to determine the Kubelka-Munk function f. The Kubelka-Munk function f is given by (1-R) ​​where R is the diffuse reflectance. 2 It can be calculated using the formula / 2R.

[0447] Next, the horizontal axis is the energy of light E=hν and the vertical axis is (hνf) 1 / n A Tauc plot was created in which the following equation was used: A tangent line was drawn at the position of the inflection point of the curve, and the point where it intersects with the horizontal axis was taken as the band gap value of the powder sample of manganese oxide particles contained in the near-infrared transparent material according to Examples 1 to 7. Here, n = 1 / 2 was set because the band gap transition of the manganese oxide particles contained in the near-infrared transparent material according to Examples 1 to 7, i.e., YMnO3, is a direct allowed transition.

[0448] <L * a * b * measurement> As described above, the near-infrared transmitting materials according to Examples 1 to 7 or Experimental Examples 1 to 41 were applied onto a PET film ("Lumirror (registered trademark)": #100-T60, manufactured by Toray Industries, Inc.) using a bar coater (No. 10). The coating film samples formed in Examples 1 to 7 or Experimental Examples 1 and 3 to 41 had a film thickness of 5 μm, and in Experimental Example 2 had a film thickness of 9 μm. The coating film samples were measured for CIE1976 (L) color difference using a colorimeter (manufactured by Konica Minolta, Inc.: CR-300) in accordance with JIS Z 8722:2009. * a * b * ) color space * , a * , b * The value of L * The value of indicates the brightness, and * (positive values ​​are redder, negative values ​​are greener) and b *The value (positive values ​​are yellowish, negative values ​​are blueish) indicates chromaticity. On the other hand, coating samples were also prepared for the titanium oxide mixture of Comparative Example 1, the carbon black mixture of Comparative Example 2, and the manganese oxide mixture of Comparative Example 3, and measurements were carried out.

[0449] <Transmittance measurement> The near-infrared transmitting materials according to Examples 1 to 7 or Experimental Examples 1 to 41 were applied to a PET film ("Lumirror (registered trademark): #100-T60" manufactured by Toray Industries, Inc.), and the transmittance of the resulting near-infrared transmitting films (samples) according to Examples 1 to 7 or Experimental Examples 1 to 41 was measured by ultraviolet-visible absorption spectrum (UV-Vis absorption spectrum) according to JIS K 0115, 2004 "General Rules for Spectrophotometric Analysis Methods" under the transmittance measurement conditions described below. The transmittance of the titanium oxide mixture film (sample) according to Comparative Example 1, which was produced by applying the titanium oxide mixture to the PET film, the carbon black mixture according to Comparative Example 2, which was produced by applying the carbon black mixture to the PET film, and the manganese oxide mixture film (sample) according to Comparative Example 3, which was produced by applying the manganese oxide mixture to the PET film, was also measured by a spectrophotometer under the transmittance measurement conditions described below.

[0450] =Transmittance measurement conditions= Measurement equipment: UV-Vis-NIR spectrophotometer UH4150 (Hitachi High-Tech Science Corporation) Measurement mode: Wavelength scan Data mode: %T (transparent) Measurement wavelength range: 240~2500nm Scan speed: 600nm / min Sampling interval: 2nm

[0451] Based on the transmittance measurement conditions, the transmittances at wavelengths of 500 nm and 700 nm, and the transmittances at wavelengths of 1000 nm and 2000 nm were calculated from the transmittances measured.

[0452] <Measurement of reflectance of heat shielding material> The reflectance of the heat shields of Example C1 and Comparative Examples C1 to C4 at wavelengths of 240 to 2500 nm was measured using a spectrophotometer equipped with a φ60 mm integrating sphere unit under the following reflectance measurement conditions. From the measured reflectances, the reflectances at wavelengths of 550 nm, 700 nm, 1000 nm, and 2000 nm were calculated.

[0453] =Reflectance measurement conditions= Measurement equipment: UV-Vis-NIR spectrophotometer UH4150 (Hitachi High-Tech Science Corporation) Measurement mode: Wavelength scan Data mode: %R (reflection) Measurement wavelength range: 240~2500nm Scan speed: 600nm / min Sampling interval: 2nm

[0454] <L of heat insulating material * a * b * measurement> The outermost layers of the heat-shielding members according to Example C1 and Comparative Examples C1 to C4 were measured using a colorimeter (Konica Minolta: CR-300) in accordance with JIS Z 8722:2009, using CIE1976(L * a * b * ) color space * , a * , b * The value of L * The value of indicates the brightness, and * (positive values ​​are redder, negative values ​​are greener) and b * The value of indicates chromaticity (positive values ​​are yellowish, negative values ​​are blueish).

[0455] 1, the manganese oxide, manganese oxide particles, and near-infrared transparent materials according to Examples 1 to 7, whose constituent elements are expressed as A-Mn-O, where constituent element A includes one or more elements selected from Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu, were able to transmit near-infrared light while minimizing the transmission of visible light. The manganese oxide, manganese oxide particles, and near-infrared transparent materials according to Experimental Examples 8, 10, 21 to 26, 29 to 39, and 41 were also able to transmit near-infrared light while minimizing the transmission of visible light (see FIGS. 5 to 12).

[0456] The manganese oxides, manganese oxide particles, and near-infrared transmitting materials according to Examples 1 to 7, in which the constituent element A contained one or more elements selected from H, alkali metals, alkaline earth metals, rare earth elements, B, F, Al, Si, P, S, Cl, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Br, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Hf, Ta, W, Re, Os, Ir, Pt, Tl, Pb, and Bi, were able to transmit near-infrared light while minimizing visible light transmission. Similarly, the manganese oxides, manganese oxide particles, and near-infrared transmitting materials according to Experimental Examples 1 to 41 were able to transmit near-infrared light while minimizing visible light transmission (see FIGS. 5 to 12).

[0457] The manganese oxide, manganese oxide particles, and near-infrared transmitting material according to Experimental Example 41, in which the constituent element A contained one or more elements selected from Cr, Fe, Co, and Ni, were able to transmit near-infrared light while minimizing the transmission of visible light (see FIG. 12).

[0458] The manganese oxides and manganese oxide particles according to Examples 1 to 7 had, in their XRD spectra, a peak derived from the (111) plane appearing at 2θ=28.0° to 32.0° and a peak derived from the (112) plane appearing at 2θ=31.0° to 35.0°, and exhibited a steep increase in transmittance at a wavelength of around 780 nm, which is the boundary between the visible light region and the near-infrared region.

[0459] When the manganese oxide and manganese oxide particles according to Examples 1 to 7 contained a hexagonal crystal system, the transmittance increased sharply around a wavelength of 780 nm, which is the boundary between the visible light region and the near-infrared region.

[0460] Furthermore, the manganese oxide, manganese oxide particles, and near-infrared transmitting materials according to Examples 1 to 7 had a reflectance of 20%R or less for light with a wavelength of 550 nm, and were therefore able to transmit near-infrared light while minimizing the transmission of visible light. Similarly, the manganese oxide, manganese oxide particles, and near-infrared transmitting materials according to Experimental Examples 1 to 41 were also able to transmit near-infrared light while minimizing the transmission of visible light (see FIGS. 5 to 12).

[0461] Furthermore, when the average secondary particle diameter of the manganese oxide particles according to Examples 1 to 7, as determined by SEM observation, was 10 nm or more and 20 μm or less, the transmittance in the near-infrared region was improved. Similarly, the manganese oxide particles according to Experimental Examples 1 to 41 also had improved transmittance in the near-infrared region (see FIGS. 5 to 12).

[0462] Furthermore, the specific surface area of ​​the manganese oxide particles according to Examples 1 and 3 to 7 measured by the BET method was 0.20 m 2 / g or more, the dispersibility of the manganese oxide particles was improved. Similarly, the manganese oxide particles according to Experimental Examples 1 to 41 also showed improved dispersibility (see FIGS. 5 to 12).

[0463] The near-infrared transmitting materials according to Examples 1 to 7 have an L *When the L value is 45 or less, the appearance becomes blacker and the transmittance in the visible light region can be reduced. * , a * , b * The values ​​are measured values ​​for near-infrared transparent materials, but because the near-infrared transparent materials of Examples 1 to 7 were prepared by adding acrylic resin and ethyl acetate to the manganese oxide particles of Examples 1 to 7, they showed values ​​equivalent to those measured for the manganese oxide particles of Examples 1 to 7. Similarly, the near-infrared transparent materials of Experimental Examples 1 to 41 also appeared blacker, and were able to reduce transmittance in the visible light region (see FIGS. 5 to 12).

[0464] 2, the near-infrared transmitting materials according to Examples 1 to 7 had a transmittance of 30%T or less at a wavelength of 700 nm (visible light region) and a transmittance of 10%T or more at a wavelength of 2000 nm (near-infrared region), which was greater than the transmittance at a wavelength of 700 nm (visible light region), and thus minimized the transmission of visible light while transmitting near-infrared light. Similarly, the near-infrared transmitting materials according to Experimental Examples 1 to 41 also minimized the transmission of visible light while transmitting near-infrared light (see FIGS. 13 to 21).

[0465] Furthermore, the near-infrared transmitting materials according to Examples 1 to 7 had a transmittance of 30%T or less at a wavelength of 700 nm (visible light region) and a transmittance of 1000 nm and 2000 nm (near-infrared region) of 10%T or more, which was greater than the transmittance at a wavelength of 700 nm (visible light region), and thus minimized the transmission of visible light while transmitting near-infrared light. Similarly, the near-infrared transmitting materials according to Experimental Examples 3, 5, 8 to 10, 13, 14, 17, 21 to 26, and 31 to 41 also minimized the transmission of visible light while transmitting near-infrared light (see FIGS. 13 to 21).

[0466] Furthermore, the L measured by CIE1976 in the outermost layer of the heat shielding member according to Example C1 shown in FIG. *When the value was 45 or less, the appearance became blacker and the transmittance in the visible light region could be reduced.

[0467] 3 and 4, the heat-shielding member of Example C1 had a reflectance of 20%R or more for light with wavelengths of 550 nm and 700 nm (visible light region), indicating that it absorbed visible light. Furthermore, the heat-shielding member of Example C1 had a reflectance of 40%R or more for light with wavelengths of 1000 nm and 2000 nm (near-infrared region), indicating that it had heat-shielding properties.

[0468] In the heat-shielding member of Example C1 shown in Figures 3 and 4, reflected light is observed due to the near-infrared reflective material (titanium oxide) contained in the near-infrared-reflective lower film, and low reflectance is achieved in the visible light region due to the near-infrared-transparent material contained in the near-infrared-transparent upper film. Reflection characteristics are maintained in the near-infrared region due to the near-infrared-transparent material contained in the near-infrared-transparent upper film. Therefore, the heat-shielding member of Example C1 has heat-shielding properties. On the other hand, Comparative Examples C2 and C4 absorb most of the light due to the inclusion of carbon black in the lower film. Furthermore, Comparative Example C3 has a near-infrared-reflective lower film containing titanium oxide, but does not have a near-infrared-transparent upper film, so it reflects both the visible light region and the near-infrared region.

[0469] The inventions disclosed in this specification include, in addition to the configurations of each invention and embodiment, those specified by changing these partial configurations to other configurations disclosed in this specification, to the extent applicable, or those specified by adding other configurations disclosed in this specification to these configurations, or those specified as higher-level concepts specified by deleting these partial configurations to the extent that partial effects can be obtained. [Industrial Applicability]

[0470] The manganese oxide, manganese oxide particles, near-infrared transparent material, and near-infrared transparent film according to the present invention have low transmittance in the visible light region but high transmittance in the near-infrared region, making them suitable for applications such as optical filters for infrared sensors and infrared cameras. Furthermore, the heat-shielding member according to the present invention has heat-shielding properties and a blackish appearance, making it suitable for applications such as vehicle and building exterior walls. Furthermore, the manganese oxide according to the present invention has excellent weather resistance and durability, and can reduce the rate of defective products due to deterioration over time, thereby reducing waste and energy costs for waste disposal. Furthermore, the manganese oxide according to the present invention also forms a good coating film, so the coated material can also reduce waste and the rate of defective products. These features contribute to the sustainable management and efficient benefits of natural resources and the achievement of decarbonization (carbon neutrality).

Claims

1. A near-infrared transmitting material comprising manganese oxide particles containing a manganese oxide represented by A-Mn-O as a constituent element, and a dispersion containing a component that transmits near-infrared rays, the constituent element A includes two or more elements selected from Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu, In the XRD spectrum of the manganese oxide, A peak originating from the (111) plane appears at 2θ = 28.0 ° to 32.0 °; A peak originating from the (112) plane appears at 2θ = 31.0 ° to 35.0 °; appears, The near-infrared transparent material has a transmittance of 30%T or less at a wavelength of 700 nm (visible light region) and a transmittance of 10%T or more at a wavelength of 2000 nm (near-infrared region), which is greater than the transmittance at a wavelength of 700 nm (visible light region).

2. Manganese oxide whose constituent elements are expressed as A-Mn-O (hexagonal YMnO ３ A near-infrared transmitting material comprising manganese oxide particles containing manganese oxide particles (excluding the above-mentioned compounds) and a dispersion containing a component that transmits near-infrared rays, The constituent element A includes one or more elements selected from Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu, In the XRD spectrum of the manganese oxide, A peak originating from the (111) plane appears at 2θ = 28.0 ° to 32.0 °; A peak originating from the (112) plane appears at 2θ = 31.0 ° to 35.0 °; appears, The near-infrared transparent material has a transmittance of 30%T or less at a wavelength of 700 nm (visible light region) and a transmittance of 10%T or more at a wavelength of 2000 nm (near-infrared region), which is greater than the transmittance at a wavelength of 700 nm (visible light region).

3. A near-infrared transmitting material comprising manganese oxide particles containing a manganese oxide represented by A-Mn-O as a constituent element, and a dispersion containing a component that transmits near-infrared rays, the constituent element A includes two or more elements selected from Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu, The crystal system of the manganese oxide includes a hexagonal crystal, The near-infrared transparent material has a transmittance of 30%T or less at a wavelength of 700 nm (visible light region) and a transmittance of 10%T or more at a wavelength of 2000 nm (near-infrared region), which is greater than the transmittance at a wavelength of 700 nm (visible light region).

4. Manganese oxide whose constituent elements are expressed as A-Mn-O (hexagonal YMnO ３ A near-infrared transmitting material comprising manganese oxide particles containing manganese oxide particles (excluding the above-mentioned compounds) and a dispersion containing a component that transmits near-infrared rays, The constituent element A includes one or more elements selected from Sc, Y, Dy, Ho, Er, Tm, Yb, and Lu, The crystal system of the manganese oxide includes a hexagonal crystal, The near-infrared transparent material has a transmittance of 30%T or less at a wavelength of 700 nm (visible light region) and a transmittance of 10%T or more at a wavelength of 2000 nm (near-infrared region), which is greater than the transmittance at a wavelength of 700 nm (visible light region).

5. 5. The near-infrared transmitting material according to claim 1, wherein the constituent element A comprises one or more elements selected from H, alkali metals, alkaline earth metals, rare earth elements, B, F, Al, Si, P, S, Cl, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Br, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb, and Bi.

6. 5. The near-infrared transmitting material according to claim 1, wherein the constituent element A includes one or more elements selected from the group consisting of Cr, Fe, Co, and Ni.

7. The composition formula of the manganese oxide is expressed as AxMnyOz, 5. The near-infrared transmitting material according to claim 1, wherein x / y is 0.001 or more and 5.00 or less.

8. 5. The near-infrared transparent material according to claim 1, wherein the near-infrared transparent material has a transmittance of 30%T or less at a wavelength of 700 nm (visible light region), and a transmittance of 1000 nm (near-infrared region) and a wavelength of 2000 nm (near-infrared region) of 10%T or more, which are greater than the transmittance at a wavelength of 700 nm (visible light region).

9. 5. The near-infrared transmitting material according to claim 1, wherein the reflectance of the near-infrared transmitting material for light having a wavelength of 550 nm and a wavelength of 700 nm is 20% R or less.

10. 5. The near-infrared transmitting material according to claim 1, wherein the dispersion is a resin, a glass, an organic solvent, or water, or a mixture of two or more of these.

11. A near-infrared transmitting film comprising the near-infrared transmitting material according to any one of claims 1 to 4.

12. A near-infrared sensor comprising an optical filter having the near-infrared transmitting film according to claim 11 formed thereon.

13. A method for producing a near-infrared transmitting film, comprising the steps of applying the near-infrared transmitting material according to any one of claims 1 to 4 onto a substrate and drying the applied material to produce a near-infrared transmitting film.

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