WO2020110906A1 - Liquide de dispersion de particules fines à absorption infrarouge traitées en surface et son procédé de production - Google Patents

Liquide de dispersion de particules fines à absorption infrarouge traitées en surface et son procédé de production Download PDF

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WO2020110906A1
WO2020110906A1 PCT/JP2019/045630 JP2019045630W WO2020110906A1 WO 2020110906 A1 WO2020110906 A1 WO 2020110906A1 JP 2019045630 W JP2019045630 W JP 2019045630W WO 2020110906 A1 WO2020110906 A1 WO 2020110906A1
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infrared absorbing
absorbing fine
fine particles
fine particle
particle dispersion
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PCT/JP2019/045630
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English (en)
Japanese (ja)
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裕史 常松
長南　武
中山　博貴
健二 福田
佐藤　啓一
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住友金属鉱山株式会社
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Priority to JP2020557626A priority Critical patent/JP7371638B2/ja
Publication of WO2020110906A1 publication Critical patent/WO2020110906A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C01G41/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

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  • the present invention relates to a surface-treated infrared absorption fine particle dispersion liquid in which surface-treated infrared absorption fine particles are dispersed in a solvent containing water, and a method for producing the same.
  • a transparent glass substrate is selected from the substrate side as a first layer from the group consisting of IIIa group, IVa group, Vb group, VIb group and VIIb group of the periodic table.
  • a composite tungsten oxide film containing at least one metal ion is provided, a transparent dielectric film is provided as a second layer on the first layer, and a IIIa group of the periodic table is provided as a third layer on the second layer.
  • a composite tungsten oxide film containing at least one metal ion selected from the group consisting of IVa group, Vb group, VIb group and VIIb group is provided, and the refractive index of the transparent dielectric film of the second layer is
  • the refractive index of the composite tungsten oxide film of the first layer and the third layer is lower than that of the composite tungsten oxide film.
  • the infrared ray shielding glass can be suitably used in a region where high visible light transmittance and good infrared ray shielding performance are required. Is proposed.
  • Patent Document 2 in the same manner as in Patent Document 1, a first dielectric film is provided as a first layer on the transparent glass substrate from the substrate side, and a tungsten oxide film is provided as a second layer on the first layer.
  • an infrared shielding glass provided with a second dielectric film as a third layer on the second layer.
  • Patent Document 3 a composite tungsten oxide film containing a metal element similar to that in Patent Document 1 is provided as a first layer from the substrate side on a transparent glass substrate by the same method as in Patent Document 1, and the first layer is formed on the first layer.
  • a heat ray-shielding glass provided with a transparent dielectric film as a second layer.
  • Patent Document 4 tungsten trioxide (WO 3 ), molybdenum trioxide (MoO 3 ), niobium pentoxide (Nb 2 O 5 ), tantalum pentoxide (containing additional elements such as hydrogen, lithium, sodium or potassium) ( Ta 2 O 5 ), vanadium pentoxide (V 2 O 5 ), and vanadium dioxide (VO 2 ) selected from at least one metal oxide film, which is coated at about 250° C. by a CVD method or a spray method.
  • a solar control glass sheet having a sunlight shielding property, which is formed by being thermally decomposed in.
  • Patent Document 5 proposes a solar light-modulating light heat insulating material in which tungsten oxide obtained by hydrolyzing tungstic acid is used, and an organic polymer having a specific structure called polyvinylpyrrolidone is added to the tungsten oxide. ..
  • the sunlight tunable photo-insulating material is irradiated with sunlight, the ultraviolet rays in the light rays are absorbed by the tungsten oxide to generate excited electrons and holes, and the amount of pentavalent tungsten is significantly increased due to a small amount of ultraviolet rays.
  • the coloring reaction is increased to accelerate the coloring reaction, and the coloring density is increased accordingly.
  • the pentavalent tungsten is rapidly oxidized to hexavalent and the decoloring reaction is enhanced.
  • the sunlight-modulated light capable of blocking the near-infrared rays of sunlight by exhibiting rapid coloring and decoloring reaction to sunlight and having an absorption peak at a wavelength of 1250 nm in the near-infrared region at the time of coloring. It has been proposed that an insulating material be obtained.
  • Patent Document 6 tungsten hexachloride is dissolved in alcohol and the medium is evaporated as it is, or after the medium is refluxed by heating, the medium is evaporated and then heated at 100° C. to 500° C. , Tungsten trioxide or a hydrate thereof, or a mixture of the two, to obtain a tungsten oxide fine particle powder. Then, it was disclosed that an electrochromic device can be obtained by using the tungsten oxide fine particles, that the optical characteristics of the film can be changed when a multilayer laminate is formed and protons are introduced into the film. ..
  • Patent Document 8 an infrared shielding material fine particle dispersion in which infrared shielding material fine particles are dispersed in a medium, optical characteristics, conductivity, and a manufacturing method of the infrared shielding material fine particle dispersion.
  • the infrared shielding material fine particles are fine particles of tungsten oxide represented by the general formula WyOz (where W is tungsten, O is oxygen, 2.2 ⁇ z/y ⁇ 2.999), and/or the general formula MxWyOz.
  • M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au. , Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be.
  • the particle diameter of the infrared shielding material fine particles is 1 nm or more and 800 nm or less.
  • the inventors of the present invention have used the infrared shielding material fine particle dispersion according to Patent Document 8 for vehicle-mounted or building materials, and shield the near-infrared region light while sufficiently incorporating visible light in sunlight. Then, we aimed to suppress the temperature rise in the room while maintaining the brightness.
  • an infrared absorbing material fine particle dispersion liquid in which infrared absorbing material fine particles are dispersed in a solvent is prepared, and a resin or the like is added to the infrared absorbing material fine particle dispersion liquid. May be dissolved into a coating solution, and the coating solution may be applied to a substrate or sprayed and then dried.
  • an optical member transparent base material, film, resin sheet, etc.
  • tungsten oxide fine particles and/or composite tungsten oxide fine particles may be air-conditioned depending on the use situation and method. It was found that the water vapor and water contained therein gradually penetrate into the coating layer and solid resin of the optical member. Then, when water vapor or water penetrates into the coating layer or the solid resin, the surface of the tungsten oxide fine particles and/or the composite tungsten oxide fine particles is decomposed, and the transmittance of light having a wavelength of 200 to 2600 nm changes with time. It has been found that there is a problem that the infrared absorption characteristics of the optical member gradually deteriorates.
  • the “coating layer” is a medium film that is solid at room temperature and has a predetermined film thickness formed on a base material by, for example, a method utilizing coating or spraying.
  • Patent Document 9 the inventors of the present invention have disclosed in Patent Document 9 that the tungsten oxide represented by the general formula WyOz and/or the general formula WyOz is used as the infrared shielding fine particles having excellent water resistance and excellent infrared shielding properties.
  • An infrared shielding fine particle coated with an organometallic compound and a method for producing the same have been disclosed.
  • the tungsten oxide fine particles and/or the composite tungsten oxide fine particles according to Patent Document 9 described above were excellent in moisture resistance.
  • infrared ray absorbing materials used for vehicles and building materials are used for a long period of time under various environments including high humidity and high temperature environments.
  • the infrared shielding fine particles disclosed in Patent Document 9 are required to have improved wet heat resistance.
  • the coating liquid described above does not contain an organic solvent having a high environmental load, and preferably has a main solvent of water. Has been. That is, an infrared absorbing fine particle dispersion liquid dispersed in a solvent containing water has been demanded.
  • the present invention has been made under the above-mentioned circumstances, and the problem is that surface-treated infrared absorbing fine particle dispersion liquid in which surface-treated infrared absorbing fine particles having excellent wet heat resistance are dispersed in a solvent containing water. , And a method for manufacturing the same.
  • the present inventors have used infrared absorbing fine particles having excellent optical characteristics, and the infrared absorbing fine particles are capable of improving chemical stability even in high humidity and high temperature environments. Researched. As a result, the compound having excellent affinity with the surface of the infrared absorbing fine particles, and uniformly adsorbed to the individual particle surface of the infrared absorbing fine particles to form a strong coating film, We have realized that it is important to coat the surface of the infrared absorbing fine particles.
  • the present inventors further researched, and conceived a metal chelate compound or a metal cyclic oligomer compound as a compound having excellent affinity for the above infrared absorbing fine particles and forming a coating film. Then, as a result of further research, the hydrolysis products of these compounds, which are produced when the metal chelate compound or the metal cyclic oligomer compound is hydrolyzed, or the polymerization products of the hydrolysis products are infrared absorbing fine particles. It was discovered that the compound is a compound that uniformly adsorbs to the surface of each particle and forms a strong coating film.
  • the surface of the infrared absorbing fine particles, the hydrolysis product of the metal chelate compound, the polymer of the hydrolysis product of the metal chelate compound, the hydrolysis product of the metal cyclic oligomer compound, the hydrolysis product of the metal cyclic oligomer compound Infrared absorbing fine particles (in some cases referred to as “surface-treated infrared absorbing fine particles” in the present invention) which are uniformly and firmly coated with a coating film containing one or more selected from polymers. It was done. It was also found that the surface-treated infrared absorbing fine particles maintained their infrared absorbing properties even when exposed to a high humidity and high temperature environment.
  • the present inventors further researched, and arrived at the present invention by conceiving a surface-treated infrared absorption fine particle dispersion liquid in which the surface-treated infrared absorption fine particles are dispersed in a solvent containing water.
  • a surface-treated infrared absorption fine particle dispersion in which surface-treated infrared absorption fine particles are dispersed in a solvent containing water In the surface-treated infrared absorbing fine particles, the surface of the infrared absorbing fine particles has a metal chelate compound hydrolysis product, a metal chelate compound hydrolysis product polymer, a metal cyclic oligomer compound hydrolysis product, and a metal cyclic oligomer compound.
  • the surface-treated infrared absorption fine particle dispersion liquid has a dispersed particle diameter of 20 nm or more and 400 nm or less.
  • the method for producing a surface-treated infrared-absorbing fine particle dispersion liquid comprising:
  • FIG. 3 is a schematic plan view of a crystal structure in a composite tungsten oxide having a hexagonal crystal structure.
  • the surface-treated infrared absorbing fine particle dispersion liquid according to the present invention is obtained by dispersing surface-treated infrared absorbing fine particles in a solvent containing water.
  • the surface-treated infrared absorbing fine particles according to the present invention the surface of the infrared absorbing fine particles is a hydrolysis product of the metal chelate compound, a polymer of the hydrolysis product of the metal chelate compound, a hydrolysis product of the metal cyclic oligomer compound.
  • a surface-treated infrared absorbing fine particle uniformly and firmly coated with a coating film containing at least one selected from the group consisting of polymers of hydrolysis products of metal cyclic oligomer compounds.
  • the dispersed particle diameter in the dispersion is 20 nm or more and 400 nm or less.
  • the infrared absorption fine particles are preferably tungsten oxide fine particles and/or composite tungsten oxide fine particles.
  • the surface-treated infrared absorbing fine particle dispersion liquid according to the present invention [1] infrared absorbing fine particles, [2] infrared absorbing fine particle surface treating agent, [3] infrared absorbing fine particle surface treating method, [4] dispersion solvent, [5] The surface-treated infrared absorbing fine particle dispersion according to the present invention will be described in detail in this order.
  • the coating film formed by using at least one selected from the hydrolysis product of 1. and the polymerization product of the hydrolysis product of the metal cyclic oligomer compound may be simply referred to as the “coating film”.
  • Infrared absorbing fine particles used in the surface-treated infrared absorbing fine particle dispersion liquid according to the present invention have the general formula WyOz (where W is tungsten, O is oxygen, and 2.2 ⁇ z/y ⁇ 2.999).
  • MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb,
  • M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb,
  • W is tungsten
  • O oxygen
  • the infrared absorbing fine particles will be described below by taking the tungsten oxide fine particles and the composite tungsten oxide fine particles as examples. It is generally known that a material containing free electrons exhibits a reflection absorption response to an electromagnetic wave around a region of a sun ray having a wavelength of 200 nm to 2600 nm due to plasma vibration. It is known that when powder of such a substance is made into particles smaller than the wavelength of light, geometric scattering in the visible light region (wavelength 380 nm to 780 nm) is reduced and transparency in the visible light region is obtained. In the present invention, the term “transparency" is used to mean "the light in the visible light region has little scattering and high transparency".
  • the present inventors have found that, in a specific portion of the composition range of tungsten and oxygen, there is a particularly effective range as infrared absorbing fine particles, and tungsten oxide that is transparent in the visible light region and has absorption in the infrared region.
  • Invented fine particles of fine particles and fine particles of composite tungsten oxide are particularly effective range as infrared absorbing fine particles, and tungsten oxide that is transparent in the visible light region and has absorption in the infrared region.
  • Invented fine particles of fine particles and fine particles of composite tungsten oxide are particularly effective range as infrared absorbing fine particles, and tungsten oxide that is transparent in the visible light region and has absorption in the infrared region.
  • Invented fine particles of fine particles and fine particles of composite tungsten oxide are particularly effective range as infrared absorbing fine particles, and tungsten oxide that is transparent in the visible light region and has absorption in the infrared region.
  • Tungsten Oxide Fine Particles are fine particles of tungsten oxide represented by the general formula WyOz (where W is tungsten, O is oxygen, and 2.2 ⁇ z/y ⁇ 2.999). ..
  • the composition range of the tungsten and oxygen is such that the composition ratio of oxygen to tungsten is less than 3, and further, when the infrared absorbing fine particles are described as WyOz, 2. It is preferable that 2 ⁇ z/y ⁇ 2.999.
  • the value of z/y is 2.2 or more, it is possible to avoid the appearance of a crystal phase of WO 2 other than the purpose in the tungsten oxide, and the chemical stability as a material. Since it can be obtained, it becomes an effective infrared absorbing fine particle.
  • the value of z/y is 2.999 or less, the required amount of free electrons are generated, and the infrared absorbing fine particles are efficient.
  • MxWyOz (where M is the M element, W is tungsten, and O is oxygen). , 0.001 ⁇ x/y ⁇ 1, and 2.0 ⁇ z/y ⁇ 3 are desirable.
  • the element M in the composite tungsten oxide is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, At least one selected from Mo, Ta, Re, Be, Hf, Os, Bi, I, and Yb is preferable.
  • the element M is an alkali metal, an alkaline earth metal, a rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, More preferably, it is at least one element selected from Nb, V, Mo, Ta, and Re.
  • the element M further belongs to an alkali metal, an alkaline earth metal element, a transition metal element, a 4B group element, and a 5B group element. preferable.
  • the value of x/y indicating the added amount of the element M
  • a sufficient amount of free electrons are generated in the composite tungsten oxide to obtain the desired infrared absorption characteristics.
  • the composite tungsten oxide fine particles have a hexagonal crystal structure
  • the transmission of the fine particles in the visible light region is improved, and the absorption in the infrared region is improved.
  • FIG. 1 is a schematic plan view of the crystal structure of this hexagonal crystal.
  • six octahedrons formed by the WO 6 unit shown by reference numeral 11 are aggregated to form a hexagonal void
  • the element M shown by the reference numeral 12 is arranged in the void to form one hexagonal void.
  • a unit is formed, and a large number of this one unit are assembled to form a hexagonal crystal structure.
  • the composite tungsten oxide fine particles contain the unit structure described with reference to FIG.
  • the composite tungsten oxide fine particles may be crystalline or amorphous.
  • the addition amount of the element M is preferably 0.2 or more and 0.5 or less, more preferably 0. 33.
  • the value of x/y is 0.33, it is considered that the element M described above is arranged in all the hexagonal voids.
  • the cations of the element M are present in the hexagonal voids, the light transmission in the visible light region is improved, and the light absorption in the infrared region is improved.
  • the element M having a large ionic radius is added, the hexagonal crystal is likely to be formed.
  • one or more elements selected from Cs, K, Rb, Tl, In, Ba, Li, Ca, Sr, Fe and Sn, more preferably Cs, K, Rb, Tl and In. , Ba are likely to form hexagonal crystals when one or more elements selected from Ba are added.
  • Typical examples are Cs 0.33 WO z , Cs 0.03 Rb 0.30 WO z , Rb 0.33 WO z , K 0.33 WO z , Ba 0.33 WO z (2.0 ⁇ z ⁇ 3.0) can be preferably mentioned.
  • other elements may be used as long as the above-mentioned element M exists in the hexagonal void formed by the WO 6 unit, and the elements are not limited to the above-mentioned elements.
  • the addition amount of the element M is preferably 0.2 or more and 0.5 or less, more preferably 0. 33.
  • the value of x/y is 0.33, it is considered that the element M described above is arranged in all the hexagonal voids.
  • tetragonal and cubic composite tungsten oxides are also effective as infrared absorbing fine particles.
  • the absorption position in the infrared region tends to change, and the absorption position tends to move to the longer wavelength side in the order of cubic crystal ⁇ tetragonal crystal ⁇ hexagonal crystal.
  • incidental small absorption in the visible light region is in the order of hexagonal crystal, tetragonal crystal, and cubic crystal. Therefore, it is preferable to use the hexagonal composite tungsten oxide for the purpose of transmitting light in the visible light region and absorbing light in the infrared light region.
  • the tendency of the optical characteristics described here is only a rough tendency and changes depending on the type of the added element, the added amount, and the oxygen amount, and the present invention is not limited to this.
  • the infrared absorption fine particles preferably contain the above-mentioned tungsten oxide fine particles and/or composite tungsten oxide fine particles.
  • the infrared-absorbing fine particles according to the present invention largely absorb light in the near-infrared region, particularly in the vicinity of a wavelength of 1000 nm, the transmission color tone thereof is often from blue to green.
  • the crystallite diameter of the infrared absorption fine particles is preferably 1 nm or more and 200 nm or less, more preferably 1 nm or more and 100 nm or less, and further preferably 10 nm or more and 70 nm or less.
  • measurement of an X-ray diffraction pattern by a powder X-ray diffraction method ( ⁇ -2 ⁇ method) and analysis by the Rietveld method are used.
  • the X-ray diffraction pattern can be measured using, for example, a powder X-ray diffractometer "X'Pert-PRO/MPD" manufactured by Spectris PANalytical.
  • the dispersed particle size of the infrared absorbing fine particles can be selected depending on the purpose of use.
  • the dispersed particle size is a concept including the particle size of the aggregate unlike the crystallite size of the infrared absorbing fine particles.
  • the infrared-absorbing fine particles have a dispersed particle diameter of 800 nm or less. This is because particles having a dispersed particle size of less than 800 nm do not completely block light due to scattering, and can maintain visibility in the visible light region and at the same time efficiently retain transparency. .. Particularly when importance is attached to the transparency in the visible light region, it is preferable to further consider scattering by particles.
  • the dispersed particle size is 200 nm or less, preferably 100 nm or less.
  • the reason for this is that if the dispersed particle size of the particles is small, the scattering of light in the visible light region of wavelength 400 nm to 780 nm due to geometrical scattering or Mie scattering is reduced, and as a result, the infrared absorbing film becomes frosted glass. It is possible to avoid the loss of clear transparency. That is, when the dispersed particle diameter is 200 nm or less, the above-mentioned geometrical scattering or Mie scattering is reduced, and it becomes a Rayleigh scattering region.
  • the scattered light is proportional to the sixth power of the particle diameter, so that the scattering is reduced and the transparency is improved as the dispersed particle diameter is decreased. Further, when the dispersed particle diameter is 100 nm or less, scattered light becomes very small, which is preferable. From the viewpoint of avoiding light scattering, it is preferable that the dispersed particle diameter is small, and if the dispersed particle diameter is 1 nm or more, industrial production is easy.
  • the haze value of the infrared absorbing fine particle dispersion in which the infrared absorbing fine particles are dispersed in the medium can be set to a visible light transmittance of 85% or less and a haze of 30% or less.
  • the dispersed particle size of the infrared-absorbing fine particles can be measured using ELS-8000 manufactured by Otsuka Electronics Co., Ltd. based on the principle of the dynamic light scattering method.
  • the dispersed particle diameter of the infrared absorbing fine particles is different from the dispersed particle diameter of the surface-treated infrared absorbing fine particles according to the present invention. Specifically, the dispersed particle diameter of the infrared absorbing fine particles is measured before the surface treatment (surface coating), and the dispersed particle diameter of the surface treated infrared absorbing fine particles is measured after the surface treatment. ..
  • the so-called “Magnelli phase” having a composition ratio represented by 2.45 ⁇ z/y ⁇ 2.999 is chemically stable, and is in the infrared region. Since it has good absorption characteristics, it is preferable as an infrared absorbing fine particle.
  • the surface treatment agent used for coating the surface of the infrared absorption fine particles is a hydrolysis product of a metal chelate compound, a polymer of a hydrolysis product of a metal chelate compound, or a hydrolysis product of a metal cyclic oligomer compound.
  • a metal chelate compound a polymer of a hydrolysis product of a metal chelate compound, or a hydrolysis product of a metal cyclic oligomer compound.
  • One or more selected from decomposition products and polymers of hydrolysis products of metal cyclic oligomer compounds are metal alkoxides, metal acetylacetonates, and metal carboxylates, one or more selected from ether bonds, ester bonds, alkoxy groups, and acetyl groups.
  • the surface treatment agent (1) a metal chelate compound, (2) a metal cyclic oligomer compound, (3) a hydrolysis product of a metal chelate compound or a metal cyclic oligomer compound, and a polymer thereof, (4) The amount of surface treatment agent added will be described in this order.
  • the metal chelate compound used in the present invention is preferably one or more selected from Al-based, Zr-based, Ti-based, Si-based and Ti-based chelate compounds containing an alkoxy group.
  • Examples of the aluminum-based chelate compound include aluminum ethylate, aluminum isopropylate, aluminum sec-butyrate, mono-sec-butoxyaluminum diisopropylate, and other aluminum alcoholates or their polymers, ethyl acetoacetate aluminum diisopropylate, aluminum tris.
  • ethyl acetoacetate aluminum isopropylate
  • aluminum sec-butyrate aluminum sec-butyrate
  • mono-sec-butoxyaluminum diisopropylate aluminum alcoholates or their polymers
  • ethyl acetoacetate aluminum diisopropylate aluminum tris.
  • octyl acetoacetate aluminum diisoproplate stearyl acetoaluminum diisopropylate
  • aluminum tris(acetylacetonate) etc.
  • These compounds are prepared by dissolving aluminum alcoholate in an aprotic solvent, a petroleum solvent, a hydrocarbon solvent, an ester solvent, a ketone solvent, an ether solvent, an amide solvent, etc.
  • An alkoxy group-containing aluminum chelate compound obtained by adding a diketone, a ⁇ -keto ester, a monohydric or polyhydric alcohol, a fatty acid and the like, heating and refluxing, and performing a ligand substitution reaction.
  • zirconium-based chelate compounds include zirconium ethylate, zirconium butyrate and other zirconium alcoholates or polymers thereof, zirconium tributoxystearate, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium dibutoxybis(acetyl). Acetonate), zirconium tributoxyethyl acetoacetate, zirconium butoxyacetylacetonate bis(ethyl acetoacetate), and the like.
  • Titanium-based chelate compounds include titanium alcoholates such as methyl titanate, ethyl titanate, isopropyl titanate, butyl titanate, 2-ethylhexyl titanate and their polymers, titanium acetylacetonate, titanium tetraacetylacetonate, titanium octylene glycolate. , Titanium ethyl acetoacetate, titanium lactate, titanium triethanolaminate, and the like.
  • a tetrafunctional silane compound represented by the general formula: Si(OR) 4 (wherein R is the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms) or its partial hydrolysis is used.
  • Degradation products can be used.
  • Specific examples of the tetrafunctional silane compound include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.
  • silane monomers or oligomers
  • silanol (Si-OH) groups silanol
  • a partial hydrolysis product of a tetrafunctional silane compound (there is no appropriate terminology indicating the entire intermediate of the tetrafunctional silane compound), part or all of the alkoxy group is hydrolyzed,
  • examples thereof include silanol (Si—OH) group-based silane monomers, 4- to 5-mer oligomers, and polymers (silicone resins) having a weight average molecular weight (Mw) of about 800 to 8000.
  • Mw weight average molecular weight
  • Examples of the zinc-based chelate compounds include zinc octylate, zinc laurate, zinc stearates and other organic carboxylic acid zinc salts, acetylacetone zinc chelates, benzoylacetone zinc chelates, dibenzoylmethane zinc chelates, ethyl acetoacetate zinc chelates, and the like. It can be illustrated.
  • Metal cyclic oligomer compound is preferably one or more selected from Al-based, Zr-based, Ti-based, Si-based, and Zn-based cyclic oligomer compounds.
  • cyclic aluminum oligomer compounds such as cyclic aluminum oxide octylate can be preferably exemplified.
  • the coating film may contain undecomposed metal chelate compound and/or metal cyclic oligomer compound.
  • the coating film that coats the surface of the infrared absorbing fine particles has a hydroxyl group or a carboxyl group by partially or completely hydrolyzing an alkoxy group, an ether bond, or an ester bond in the above-described metal chelate compound or metal cyclic oligomer compound. It is preferable that the resulting hydrolysis product is a polymer that is self-condensed through the hydrolysis reaction.
  • the addition amount of the above-mentioned metal chelate compound or metal cyclic oligomer compound is 0.05 parts by weight or more and 1000 parts by weight or less in terms of metal element with respect to 100 parts by weight of infrared absorbing fine particles. Preferably. It is more preferably 5 parts by weight or more and 500 parts by weight or less, and most preferably 50 parts by weight or more and 250 parts by weight or less.
  • the addition amount of the metal chelate compound or the metal cyclic oligomer compound is preferably 1000 parts by weight or less.
  • [3] Surface Treatment Method of Infrared Absorption Fine Particles There are a plurality of treatment methods in the surface treatment method of infrared absorption fine particles (surface coating method), but (A) a surface treatment agent is added to an aqueous dispersion for forming a coating film. There will be described two treatment methods, that is, the treatment method (B) and the treatment method (B) of adding the surface treatment agent and water to the water-soluble organic solvent dispersion liquid.
  • the infrared absorbing fine particles are mixed with a solvent.
  • An infrared absorbing fine particle water dispersion for forming a coating film dispersed in water (sometimes referred to as "water dispersion for forming coating film” in the present invention) is prepared.
  • the surface treating agent is added to the prepared aqueous dispersion for forming a coating film, followed by mixing and stirring.
  • the surface of the infrared absorbing fine particles shows that the hydrolysis product of the metal chelate compound, the polymerization product of the hydrolysis product of the metal chelate compound, the hydrolysis product of the metal cyclic oligomer compound, and the hydrolysis product of the metal cyclic oligomer compound. It is coated with a coating film containing at least one selected from polymers.
  • a treatment method of adding a surface treatment agent to an aqueous dispersion for forming a coating film (1) preparation of an aqueous dispersion for forming a coating film, (2) infrared rays using the aqueous dispersion for forming a coating film
  • the surface treatment method of the absorbing fine particles and (3) treatment after mixing and stirring in the coating film forming aqueous dispersion will be described in this order.
  • Aqueous Dispersion for Forming Coating Film In order to coat the surface of the infrared-absorbing fine particles to produce surface-treated infrared-absorbing fine particles, first, the infrared-absorbing fine particles are dispersed in water to prepare an appropriate concentration range, In addition, an aqueous dispersion for forming a coating film having a pH in an appropriate range is prepared. Then, the surface treatment agent (see the section "[2] Surface treatment agent for infrared absorbing fine particles”) is added to the aqueous dispersion for coating film formation having the concentration and pH while mixing and stirring.
  • the surface of the fine particles is a hydrolysis product of the metal chelate compound, a polymer of the hydrolysis product of the metal chelate compound, or a metal. It is coated with a coating film containing one or more selected from a hydrolysis product of a cyclic oligomer compound and a polymerization product of a hydrolysis product of a metal cyclic oligomer compound.
  • infrared absorbing fine particles for example, tungsten oxide or/and composite tungsten oxide are previously finely pulverized and dispersed in water to obtain a monodispersed state. It is preferable to keep it.
  • the concentration range of the tungsten oxide and/or the composite tungsten oxide to be dispersed is preferably 0.01% by mass or more and 80% by mass or less. Within this concentration range, the liquid stability of the dispersion is excellent. Moreover, when an appropriate liquid medium, dispersant, coupling agent, or surfactant is selected, gelation of the dispersion liquid or sedimentation of particles will occur for 6 months or longer even when placed in a constant temperature bath at a temperature of 40°C. Instead, the dispersed particle size can be maintained in the range of 1 to 800 nm.
  • the concentration range is more preferably 3% by mass or more and 80% by mass or less. This is because the pH of the aqueous dispersion for forming a coating film can be set to 8 or less, and when the surface treatment agent is added later, the dispersibility of the infrared absorbing fine particles is maintained by the electrostatic repulsion action of the fine particles. Because it will be. However, even if the concentration range is 0.01% by mass or more and less than 3% by mass, the solvent replacement treatment or the solvent replacement treatment described in the section of "[5] Surface-treated infrared absorbing fine particle dispersion liquid (ii) other production method" is performed.
  • the drying treatment By performing the drying treatment, it is possible to obtain a surface-treated infrared absorbing fine particle dispersion liquid having good dispersibility. Then, it is important that the dispersed state is ensured and the fine particles are not aggregated during the pulverization and dispersion treatment process.
  • the pulverization/dispersion treatment include a pulverization/dispersion treatment method using a bead mill, a ball mill, a sand mill, a paint shaker, an ultrasonic homogenizer, or the like.
  • beads, balls, using Ottawa sand media media, crushing with a media stirring mill such as a beads mill, ball mill, sand mill, paint shaker, etc. is required to reach the desired dispersed particle diameter It is preferable because the time is short.
  • the pH range of the coating film forming aqueous dispersion is preferably 8 or less. This is because the dispersibility of the infrared absorbing fine particles is maintained by the electrostatic repulsion action of the surface-treated infrared absorbing fine particles.
  • the pH of the coating film forming aqueous dispersion is slightly shifted to the alkaline side.
  • the pH of the coating film-forming aqueous dispersion exceeds 8
  • the surface-treated infrared-absorbing fine particles agglomerate and the dispersion stability is not ensured.
  • the tungsten oxide and/or the composite tungsten oxide is slightly dissolved in water, the pH in the aqueous dispersion for forming a coating film before the addition of the surface treatment agent is oscillated toward the acid side.
  • the concentration range of the tungsten oxide and/or the composite tungsten oxide before the addition of the surface treatment agent is 80% by mass or less, the aggregation due to the interparticle interaction does not occur, and the infrared absorbing fine particles are dispersed by the electrostatic repulsion action. Sex is maintained.
  • the concentration range of the tungsten oxide and/or the composite tungsten oxide before the surface treatment agent is added is 3% by mass or more and 80% by mass or less.
  • the hydrolysis reaction of the surface treatment agent always precedes, and thereafter the polymerization reaction of the generated hydrolysis product occurs.
  • By reducing the amount of carbon C remaining in the molecules of the surface treatment agent present in the coating film it is considered possible to form a coating film that densely covers the surface of each infrared absorbing fine particle. ..
  • the coating film forming aqueous dispersion is water, or an appropriate amount containing water. It is also desirable to dilute to an appropriate concentration with an organic solvent.
  • the dispersion concentration of the tungsten oxide or/and the composite tungsten oxide as the infrared absorbing fine particles is diluted to 3% by mass or more and 30% by mass or less, more preferably 5% by mass or more and 20% by mass or less, This is because everything is uniformly surface-coated, the pH of the dispersion liquid can be set to 8 or less, and the dispersibility of the infrared absorbing fine particles is maintained by the electrostatic repulsion action of the fine particles.
  • the surface treatment agent When the surface treatment agent is added dropwise, in order to uniformly coat the infrared absorbing fine particles, the surface treatment agent itself diluted with an appropriate solvent is added dropwise to adjust the amount of the surface treatment agent added per hour. It is also preferable to
  • the solvent used for dilution is preferably one that does not react with the surface treatment agent and has high compatibility with water that is the medium of the coating film forming aqueous dispersion. Specifically, solvents such as alcohols, ketones and glycols can be preferably used.
  • the dilution ratio of the surface treatment agent is not particularly limited. However, from the viewpoint of ensuring productivity, the dilution ratio is preferably 100 times or less.
  • a metal chelate compound, a metal cyclic oligomer compound, a hydrolysis product of these, and a polymer of the hydrolysis product are decomposed into metal ions immediately after addition.
  • the decomposition up to the metal ion is completed. That is, after the decomposition up to the metal ions is completed, the added surface treatment agent becomes a hydrolysis product or a polymer thereof and becomes a coating film for coating the surface of the infrared absorbing fine particles.
  • the infrared absorbing fine particles maintain dispersion due to electrostatic repulsion.
  • the surface of all the infrared absorbing fine particles was hydrolyzed with a metal chelate compound, a polymer of the hydrolyzed product of the metal chelate compound, a hydrolysis product of the metal cyclic oligomer compound, and a hydrolysis product of the metal cyclic oligomer compound.
  • the surface-treated infrared absorbing fine particles according to the present invention are produced by being coated with a coating film containing at least one selected from the polymer of the products.
  • the surface-treated infrared-absorbing fine particles according to the present invention obtained by the surface-treating method described above are used as a raw material for an infrared-absorbing fine-particle dispersion or an infrared-absorbing substrate. It can be used in the form of fine particles, or dispersed in a liquid medium or a solid medium.
  • the generated surface-treated infrared absorbing fine particles do not need to be further heat-treated to increase the density and chemical stability of the coating film. This is because the density and adhesiveness of the coating film are sufficiently increased so that the desired moist heat resistance can be obtained without the heat treatment.
  • (B) Treatment Method of Adding Surface Treatment Agent and Water to Water-Soluble Organic Solvent Dispersion In the treatment method of adding the surface treatment agent and water to the water-soluble organic solvent dispersion fluid, Infrared absorbing fine particles are dispersed in the organic solvent to prepare a dispersion liquid. Then, the surface treatment agent and water are added in parallel to the prepared dispersion liquid and mixed and stirred. As a result, the surface of the infrared absorbing fine particles has a metal chelate compound hydrolysis product, a metal chelate compound hydrolysis product polymer, a metal cyclic oligomer compound hydrolysis product, and a metal cyclic oligomer compound hydrolysis product. And a coating film containing at least one polymer selected from the above.
  • the surface treatment agent and water are added in parallel.
  • water is excessively added first aggregation or deterioration of infrared absorption characteristics may occur depending on the infrared absorption fine particles. For example, when the infrared absorbing fine particles are cubic sodium tungsten bronze, they react with water to cause a decrease in infrared absorbing characteristics.
  • the surface-treated infrared absorbing fine particles according to the present invention do not cause agglomeration because it does not require a heat treatment after the treatment after mixing and stirring, and therefore a dispersion treatment for crushing the agglomeration. Unnecessary or in a short time.
  • the coating film of the surface-treated infrared absorbing fine particles according to the present invention uniformly and firmly coats the individual infrared absorbing fine particles without damaging them.
  • the infrared absorbing fine particle dispersion and the infrared absorbing base material produced by using the surface-treated infrared absorbing fine particles show better wet heat resistance than those obtained by the conventional method.
  • the dispersion solvent of the surface-treated infrared absorbing fine particle dispersion liquid according to the present invention is a solvent containing water, and is a solvent consisting essentially of water. That is, when the dispersion solvent contains a trace amount of an organic solvent resulting from the production process of the surface-treated infrared absorbing fine particle dispersion according to the present invention, and optionally contains one or more water-soluble organic substances. There is.
  • the organic solvent or water-soluble organic substance is alcohols, glycols, water-soluble resins, or the like, but it is preferable that they have low toxicity to the human body.
  • the surface-treated infrared absorbing fine particle dispersion liquid according to the present invention is obtained by dispersing the surface-treated infrared absorbing fine particle dispersion liquid according to the present invention in water as a dispersion solvent.
  • the surface-treated infrared absorbing fine particle dispersion according to the present invention will be described in the order of (1) surface-treated infrared absorbing fine particle dispersion, and (2) method for producing surface-treated infrared absorbing fine particle dispersion.
  • the pH value of the surface-treated infrared absorbing fine particle dispersion liquid according to the present invention is preferably 4 or more and 10 or less.
  • the concentration of the surface-treated infrared absorbing fine particles is preferably 0.01% by mass or more and 80% by mass or less. When the concentration is within this range, the surface-treated infrared absorbing fine particles can maintain dispersibility in water.
  • the surface-treated infrared absorbing fine particle dispersion liquid according to the present invention may further contain a dispersant in order to improve the dispersibility of the surface-treated infrared absorbing fine particles and avoid coarsening of the dispersed particle diameter due to re-aggregation.
  • a dispersant in order to improve the dispersibility of the surface-treated infrared absorbing fine particles and avoid coarsening of the dispersed particle diameter due to re-aggregation.
  • an additive can be used also when adjusting pH.
  • a water-soluble dispersant is preferable. Further, those having an acidic functional group and having an acid value of 10 mg/KOH or more are preferable.
  • An ammonium salt or acrylic polymer dispersant can be preferably used.
  • SOLSPERSE registered trademark
  • BYK Japan Japan's DISPERBYK (registered trademark) (the same applies hereinafter)-102, 180, 184, 185, 187, 190, 191, 192, 193, 194N, 2010, 2012, 2015, 2060, 2096, Anti- Terra® (registered trademark)-250 and the like; BASF Japan Ltd. JONCRYL (registered trademark) (hereinafter the same) 67, 678, 586, 611, 682, 683, 690 and the like;
  • two or more kinds of dispersants can be used in combination.
  • one kind uses a dispersant having an acidic functional group
  • the other kind uses a nonionic dispersant having no acidic and basic functional groups.
  • It may exhibit excellent dispersion stability.
  • a dispersant having all acidic functional groups is used as the dispersant, excellent dispersion stability may be exhibited in some cases.
  • the surface-treated infrared absorbing fine particle dispersion according to the present invention is obtained by dispersing the surface-treated infrared absorbing fine particle according to the present invention in water as a dispersion solvent.
  • the surface-treated infrared-absorbing fine particle dispersion obtained immediately after the surface treatment to the infrared-absorbing fine particles contains an organic solvent such as alcohol produced by the hydrolysis reaction of the surface-treating agent, or the surface treatment to be used. Depending on the type of agent, it may contain an organic solvent having a boiling point higher than that of water.
  • the content of the organic solvent can be reduced by an appropriate method such as solvent substitution treatment, washing treatment, or drying treatment.
  • the surface-treated infrared absorbing fine particle dispersion liquid is directly produced after the surface treatment of the surface-treated infrared absorbing fine particle according to the present invention (i) A production method of directly forming the dispersion liquid And (ii) other manufacturing method having a step of removing the organic solvent after the surface treatment of the surface-treated infrared absorbing fine particles according to the present invention.
  • the surface-treated infrared absorbing fine particle dispersion liquid according to the present invention is "[3] Surface treatment method of infrared absorbing fine particles
  • A Surface treatment to aqueous dispersion liquid for forming coating film.
  • Dispersion liquid containing surface-treated infrared absorbing fine particles and water when the method described in the section "(2) Surface treatment method of infrared absorbing fine particles using aqueous dispersion for forming coating film" is adopted. Since it can be obtained, it can be directly used as the surface-treated infrared absorbing fine particle dispersion liquid according to the present invention.
  • the organic component derived from the surface treatment agent is as small as possible. Therefore, it is preferable to use a low molecular weight surface treatment agent and use the surface treatment agent without diluting it with an organic solvent.
  • a dispersant or an additive may be added to the surface-treated infrared absorbing fine particle dispersion liquid, if necessary, to improve and stabilize the dispersibility of the surface-treated infrared absorbing fine particles.
  • the method for dispersing the surface-treated infrared-absorbing fine particles include the same methods as the above-described pulverizing/dispersing method.
  • a bead mill, a ball mill, a sand mill, a paint shaker, an ultrasonic homogenizer, or the like may be used.
  • the method used may be mentioned.
  • the time required for the dispersion treatment is extremely short.
  • the surface-treated infrared absorbing fine particle dispersion according to the present invention contains an organic solvent in the dispersion immediately after the surface treatment of the infrared absorbing fine particles according to the present invention by the manufacturing method.
  • the method described in the section “[3] Surface treatment method of infrared absorbing fine particles (B) Treatment method of adding surface treatment agent and water to water-soluble organic solvent dispersion” is adopted, surface treatment is carried out.
  • aluminum ethyl acetoacetate diisopropylate is used as the agent, the following are mentioned.
  • the hydrolysis reaction leaves ethyl acetoacetate having a boiling point of 181° C., which is contained in the dispersion liquid immediately after the surface treatment. Since these solvents have a boiling point higher than that of water, it is extremely difficult to evaporate and remove only the solvent while leaving water by the heat treatment.
  • the method for producing the surface-treated infrared absorption fine particle dispersion according to the present invention by removing the organic solvent from the dispersion immediately after the surface treatment of the infrared absorption fine particles ⁇ 1>
  • Surface treatment infrared absorption by solvent substitution treatment A method for producing a fine particle dispersion, ⁇ 2> a method for producing a surface-treated infrared absorbing fine particle dispersion by a washing treatment, and ⁇ 3> a method for producing a surface treated infrared absorbing fine particle dispersion by a drying treatment will be described in this order.
  • ⁇ 1> Method for Producing Surface-treated Infrared Absorbing Fine Particle Dispersion by Solvent Substitution Treatment first, the surface-treated infrared absorbing fine particle dispersion immediately after the surface treatment is dispersed. The liquid is solid-liquid separated. In order to perform the solid-liquid separation, the dispersion concentration of the infrared absorbing fine particles in the coating film forming aqueous dispersion before the surface treatment is set to less than 3% by mass, or the surface treated infrared absorbing fine particles are dispersed immediately after the surface treatment.
  • a pH adjustor may be added to the liquid to adjust the pH value to 9 or more.
  • the organic solvent can be reduced.
  • the content of the organic solvent can be infinitely reduced as the number of decantations and the addition of pure water is increased, but the content can be reduced to a practical content by repeating three times or more.
  • the atmosphere for the drying treatment is preferably a reduced pressure atmosphere from the viewpoint of being able to remove all the solvent at a lower temperature.
  • the atmosphere for the drying treatment is preferably a reduced pressure inert gas atmosphere or a vacuum atmosphere.
  • the surface-treated infrared-absorbing fine particles are dried so as not to exceed the temperature at which strong aggregates are formed, and the obtained surface-treated infrared-absorbing fine particle powder is dried and/or wet-processed.
  • the crushing/redispersion treatment include the same methods as the crushing/dispersion treatment method described above.For example, a method using an apparatus such as a bead mill, a ball mill, a sand mill, a paint shaker, or an ultrasonic homogenizer may be used. Can be mentioned.
  • the surface-treated infrared absorbing fine particle dispersion according to the present invention produced as described above is applied to the surface of an appropriate substrate and cured to form an infrared absorbing group. It can be used as a material. Further, since the infrared absorbing fine particles have a function of absorbing infrared rays and converting them into heat, the formed cured film can be used as a photothermal conversion layer. At this time, since the surface-treated infrared ray absorbing fine particle dispersion liquid according to the present invention contains almost no organic solvent component, the coating process can be performed without impairing the health of the worker in the process.
  • the surface-treated infrared absorbing fine particle dispersion liquid contains a dispersant
  • it is dried and pulverized to obtain a powdery surface-treated infrared absorbing fine particle dispersion (in the present invention, "surface-treated infrared absorbing fine particles”). It may be described as “dispersed powder”.), and it can also be used as a raw material to be added to an infrared absorbing product or a photothermal conversion product.
  • the surface-treated infrared absorption fine particles according to the present invention is a powdery dispersion dispersed in a solid medium, the surface-treated infrared absorption fine particles dispersion powder, again, the liquid It may be dispersed in a medium and used as a dispersion for infrared absorbing products, or may be kneaded into a resin and used as described later.
  • the surface-treated infrared ray absorbing fine particle dispersion liquid according to the present invention contains almost no organic solvent component, the drying treatment can be performed without impairing the health of the worker in the process.
  • the surface-treated infrared absorbing fine particle dispersion powder obtained by the drying treatment contains almost no organic component as a residual solvent, crushing treatment, dispersing treatment, and resin kneading treatment are performed without impairing the health of workers in the process. You can
  • the surface-treated infrared absorbing fine particles in the surface-treated infrared absorbing fine particle dispersion liquid according to the present invention produced as described above are dispersed according to the usage method. desirable. In terms of the dispersed particle size of the surface-treated infrared absorbing fine particles, it is desirable that the particle size is 20 nm or more and 400 nm or less.
  • the dispersed particle size of the fine particles in the dispersions in Examples and Comparative Examples is shown as an average value measured by a particle size measuring device (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.) based on the dynamic light scattering method.
  • the crystallite diameter is measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method) using a powder X-ray diffractometer (X'Pert-PRO/MPD manufactured by Spectris Co., Ltd. PANalytical), and the Rietveld method is used. Calculated.
  • the optical characteristics of the surface-treated infrared-absorbing fine particle dispersion were measured by diluting with pure water so that the visible light transmittance was 80% in a measuring glass cell of a spectrophotometer, and then using a spectrophotometer (U manufactured by Hitachi, Ltd. -4100) in the wavelength range of 200 nm to 2600 nm at 5 nm intervals, and the visible light transmittance and the solar radiation transmittance were calculated according to JIS R3106.
  • the surface-treated infrared absorption fine particle dispersion is exposed to an air atmosphere at 85° C. for 24 hours. Then, for example, when hexagonal cesium tungsten bronze fine particles are used as the infrared absorbing fine particles, it is determined that the amount of change in solar radiation transmittance before and after the exposure is 4.0% or less is considered to have good wet heat resistance, and the amount of change is Moisture and heat resistance was judged to be insufficient if it exceeded 4.0%.
  • Cs/W (molar ratio) 0.33 hexagonal cesium tungsten bronze (Cs 0.33 WO z , 2.2 ⁇ z ⁇ 3.0) powder (YM-01 manufactured by Sumitomo Metal Mining Co., Ltd.) 25% by mass Cs 0.33 WO z according to Example 1 was loaded into a paint shaker containing 0.3 mm ⁇ ZrO 2 beads and pulverized and dispersed for 10 hours. A fine particle dispersion was obtained. When the dispersed particle size of the Cs 0.33 WO z fine particles in the obtained dispersion was measured, it was 100 nm. The particle refractive index was 1.81 and the particle shape was non-spherical as settings for particle size measurement. The background was measured using pure water, and the solvent refractive index was 1.33. Then, the crystallite diameter of the Cs 0.33 WO z fine particles obtained after removing the solvent from the obtained dispersion was 32 nm.
  • the obtained dispersion liquid of Cs 0.33 WO z fine particles was mixed with pure water to obtain an aqueous dispersion liquid A for forming a coating film according to Example 1 in which the concentration of Cs 0.33 WO z fine particles was 2% by mass. Obtained.
  • 2.5% by mass of aluminum ethyl acetoacetate diisopropylate as an aluminum-based chelate compound and 97.5% by mass of isopropyl alcohol (IPA) were mixed to obtain a surface treatment agent dilution liquid a.
  • aqueous dispersion A for coating film formation 890 g of the obtained aqueous dispersion A for coating film formation was placed in a beaker, and 360 g of the surface treatment agent dilution liquid a was added dropwise thereto over 3 hours while stirring strongly with a stirrer with a blade. After the dropwise addition of the surface treatment agent dilution liquid a, stirring was further performed at a temperature of 20° C. for 24 hours to prepare an aging liquid according to Example 1. Then, a powder containing the surface-treated infrared-absorbing fine particles according to Example 1 (surface-treated infrared-absorbing fine-particle powder) is obtained by performing a drying treatment at a temperature of 120° C. for 24 hours using vacuum fluidized drying to evaporate the medium from the aging liquid. ) Got.
  • Example 1 10% by mass of the surface-treated infrared absorbing fine particle powder according to Example 1 and 90% by mass of pure water were mixed.
  • the obtained mixed liquid was loaded into a paint shaker containing 0.3 mm ⁇ ZrO 2 beads and crushed for 1 hour to obtain a surface-treated infrared absorbing fine particle dispersion liquid according to Example 1.
  • the dispersion particle diameter of the obtained surface-treated infrared absorbing fine particle dispersion liquid according to Example 1 was 180 nm.
  • the particle refractive index was 1.81 and the particle shape was non-spherical as settings for particle size measurement.
  • the background was measured using pure water, and the solvent refractive index was 1.33.
  • the visible light transmittance was 79.6% and the solar radiation transmittance was 56.6%.
  • the surface-treated infrared absorbing fine particle dispersion liquid obtained in Example 1 was exposed to an air atmosphere of 85° C. for 24 hours, and its optical characteristics were measured.
  • the visible light transmittance was 80.2% and the solar radiation transmittance was 58. It was 0.5%. It was also found that the change in visible light transmittance before and after exposure to the atmosphere at 85° C. was 0.6%, and the change in solar radiation transmittance was 1.9%, which were both small.
  • Examples 2 and 3 By performing the same operation as in Example 1 except that the amount of the surface treatment agent diluting liquid a and the dropping addition time thereof were changed, the surface-treated infrared absorbing fine particle dispersion liquids according to Examples 2 and 3 were obtained. The same evaluation as in Example 1 was performed. The manufacturing conditions and evaluation results are shown in Tables 1 to 3.
  • Example 4 The ripening solution according to Example 1 was allowed to stand for 1 hour to perform solid-liquid separation of the surface-treated infrared absorbing fine particles and the medium. Then, only the supernatant medium was removed by decantation using pure water to obtain an infrared absorbing fine particle slurry. Pure water was added to the obtained infrared absorbing fine particle slurry, and 0.5% by mass of cesium carbonate was further added as a pH adjusting agent, and the mixture was stirred for 1 hour and then allowed to stand for 1 hour, and then surface treated infrared absorption again. The fine particles and the medium were solid-liquid separated.
  • Example 4 The decantation and the addition of pure water were repeated twice more (three times of decantation and pure water addition were carried out) to obtain the surface-treated infrared absorbing fine particle dispersion liquid of Example 4. With respect to the surface-treated infrared absorbing fine particle dispersion liquid according to Example 4, the same evaluation as in Example 1 was performed. The manufacturing conditions and evaluation results are shown in Tables 1 to 3.
  • Example 5 The dispersion liquid of Cs 0.33 WO z fine particles according to Example 1 is mixed with pure water, and the concentration of the Cs 0.33 WO z fine particles is 6% by mass. I got -6. 890 g of the obtained aqueous dispersion A-6 for forming a coating film was placed in a beaker and stirred vigorously with a stirrer equipped with a blade, to which an aluminum chelate compound such as aluminum ethyl acetoacetate diisopropylpropionate was added as a surface treatment agent. A rate of 133.5 g was added dropwise over 1 hour. After the dropwise addition of the surface treatment agent, stirring was carried out at a temperature of 20° C.
  • Example 5 For the surface-treated infrared absorbing fine particle dispersion liquid according to Example 5, the same evaluation as in Example 1 was performed. The manufacturing conditions and evaluation results are shown in Tables 1 to 3.
  • Example 6 2.4% by mass of zirconium tributoxyacetylacetonate and 97.6% by mass of isopropyl alcohol were mixed to obtain a surface treating agent dilution liquid b according to Example 6.
  • a surface-treated infrared absorbing fine particle dispersion liquid according to Example 6 was produced by performing the same operation as in Example 1 except that the surface treatment agent dilution liquid b was used instead of the surface treatment agent dilution liquid a.
  • the same evaluation as in Example 1 was performed for the surface-treated infrared absorbing fine particle dispersion liquid according to Example 6, the same evaluation as in Example 1 was performed. The manufacturing conditions and evaluation results are shown in Tables 1 to 3.
  • Example 7 2.6% by mass of diisopropoxytitanium bisethylacetoacetate and 97.4% by mass of isopropyl alcohol were mixed to obtain a surface treating agent dilution liquid c according to Example 7.
  • a surface-treated infrared absorbing fine particle dispersion liquid according to Example 7 was prepared by performing the same operation as in Example 1 except that the surface treatment agent dilution liquid c was used instead of the surface treatment agent dilution liquid a.
  • the same evaluation as in Example 1 was performed for the surface-treated infrared absorbing fine particle dispersion liquid according to Example 7, the same evaluation as in Example 1 was performed. The manufacturing conditions and evaluation results are shown in Tables 1 to 3.
  • the mixture was loaded into a paint shaker containing 2 beads and pulverized and dispersed for 10 hours to obtain a dispersion liquid of Na 0.33 WO z fine particles according to Example 8.
  • the dispersed particle diameter of Na 0.33 WO z fine particles in the obtained dispersion was measured, it was 100 nm.
  • the particle refractive index was 1.81 and the particle shape was non-spherical as settings for particle size measurement.
  • the background was measured using isopropyl alcohol and the solvent refractive index was 1.38. After removing the solvent of the obtained dispersion liquid, the crystallite size was measured and found to be 32 nm.
  • a dispersion of Na 0.33 WO z fine particles according to Example 8 was mixed with isopropyl alcohol to obtain an aqueous dispersion B for forming a coating film in which the concentration of infrared absorbing fine particles (cubic sodium tungsten bronze fine particles) was 2%. Obtained. 520 g of the obtained coating film forming aqueous dispersion B was placed in a beaker, and while being strongly stirred by a stirrer with a blade, 360 g of the surface treatment agent diluting liquid a and 100 g of pure water as the diluting agent d were concurrently added over 3 hours. It was added dropwise. After the dropwise addition, stirring was carried out at a temperature of 20° C. for 24 hours to prepare an aging liquid according to Example 8. Next, the medium was evaporated from this aged liquid by vacuum fluidization drying at a temperature of 120° C. for 24 hours to obtain a surface-treated infrared absorbing fine particle powder according to Example 8.
  • Example 8 By performing the same operation as in Example 1 except that the surface-treated infrared absorption fine particle powder according to Example 8 was used in place of the surface-treated infrared absorption fine particle powder according to Example 1, the surface according to Example 8 was obtained. A treated infrared absorbing fine particle dispersion was prepared. With respect to the surface-treated infrared absorbing fine particle dispersion liquid according to Example 8, the same evaluation as in Example 1 was performed. The manufacturing conditions and evaluation results are shown in Tables 1 to 3.
  • an aqueous dispersion C for forming a coating film according to Example 9 an aqueous dispersion D for forming a coating film according to Example 10, and an aqueous dispersion E for forming a coating film according to Example 11 were obtained.
  • Example 9 By performing the same operation as in Example 1 except that the coating film forming aqueous dispersions C to E were used instead of the coating film forming aqueous dispersion A, the surface-treated infrared rays according to Examples 9 to 11 were obtained. An absorption particle dispersion liquid was prepared. Then, the same evaluations as in Example 1 were performed on the surface-treated infrared absorbing fine particle dispersion liquids according to Examples 9 to 11. The manufacturing conditions and evaluation results are shown in Tables 1 to 3.
  • the resulting mixed liquid was loaded into a paint shaker containing 0.3 mm ⁇ ZrO 2 beads, and pulverization/dispersion treatment was performed for 4 hours (Example 12) or 6 hours (Example 13).
  • a dispersion liquid of Cs 0.33 WO z fine particles according to When the dispersed particle size of Cs 0.33 WO z fine particles in the obtained dispersion was measured, it was 140 nm in Example 12 and 120 nm in Example 13.
  • the particle refractive index was 1.81 and the particle shape was non-spherical as settings for particle size measurement.
  • the background was measured using pure water, and the solvent refractive index was 1.33.
  • Example 12 was 42 nm
  • Example 13 was 50 nm.
  • Example 12 The coating according to Example 12 in which the obtained dispersion liquid of Cs 0.33 WO z fine particles according to Examples 12 and 13 was mixed with pure water, and the concentration of Cs 0.33 WO z fine particles was 2% by mass.
  • An aqueous dispersion F for forming a film and an aqueous dispersion G for forming a coating film according to Example 13 were obtained.
  • the surface-treated infrared absorbing fine particle dispersion liquids according to Examples 12 and 13 were prepared. Then, the same evaluations as in Example 1 were performed on the surface-treated infrared absorbing fine particle dispersion liquids according to Examples 12 and 13.
  • the manufacturing conditions and evaluation results are shown in Tables 1 to 3.
  • Example 14 to 18 10% by mass of the surface-treated infrared absorbing fine particle powder according to Example 2, 85% by mass of pure water, and dispersants ⁇ to ⁇ (however, ⁇ in Example 14, ⁇ in Example 15, ⁇ in Example 16, and Example 17).
  • Example 18 and ⁇ in Example 18 are mixed with 5% by mass, and the obtained mixed solution is loaded into a paint shaker containing 0.3 mm ⁇ ZrO 2 beads and crushed for 1 hour, Coating film forming aqueous dispersion A- ⁇ according to Example 14, coating film forming aqueous dispersion A- ⁇ according to Example 15, coating film forming aqueous dispersion A- ⁇ according to Example 16, Example A coating film forming aqueous dispersion A- ⁇ according to Example 17 and a coating film forming aqueous dispersion A- ⁇ according to Example 18 were obtained.
  • the dispersant ⁇ is a dispersant having a functional group of phosphoric acid, an acid value of 60 mgKOH/g, and a base value of 0 mgKOH/g.
  • the dispersant ⁇ is a dispersant having a functional group of a carboxylic acid, an acid value of 70 mgKOH/g, and a base value of 0 mgKOH/g.
  • the dispersant ⁇ is a dispersant having a carboxylic acid as a functional group, an acid value of 15 mgKOH/g, and a base value of 0 mgKOH/g.
  • the dispersant ⁇ is a dispersant having a carboxylic acid as a functional group, an acid value of 110 mgKOH/g, and a base value of 0 mgKOH/g.
  • the dispersant ⁇ is a dispersant containing phosphoric acid as a functional group and having an acid value of 85 mgKOH/g and a base value of 85 mgKOH/g.
  • the coating film forming aqueous dispersions A- ⁇ to A- ⁇ according to Examples 14 to 18 were used, and the dropping time of the surface treatment diluent was changed.
  • the surface-treated infrared absorbing fine particle dispersion liquids according to Examples 14 to 18 were produced.
  • the same evaluations as in Example 1 were performed on the surface-treated infrared absorbing fine particle dispersion liquids according to Examples 14 to 18.
  • the manufacturing conditions and evaluation results are shown in Tables 1 to 3.
  • Example 19 10% by mass of the surface-treated infrared absorbing fine particle powder according to Example 2, 80% by mass of pure water, 5% by mass of dispersant ⁇ and 5% by mass of dispersant ⁇ were mixed, and the resulting mixed solution was mixed with 0.3 mm ⁇ ZrO 2 beads. The paint shaker put in was put and crushed for 1 hour to obtain an aqueous dispersion A- ⁇ for forming a coating film according to Example 19.
  • the dispersant ⁇ is a nonionic dispersant having no acid and basic functional groups and an acid value of less than 1 mgKOH/g and a base value of less than 1 mgKOH/g.
  • Example 19 The same as Example 1 except that the coating film forming aqueous dispersion A- ⁇ according to Example 19 was used instead of the coating film forming aqueous dispersion A, and the dropping time of the surface treatment diluent was changed. By performing the operation, a surface-treated infrared absorbing fine particle dispersion liquid according to Example 19 was prepared. Then, the same evaluation as in Example 1 was performed on the surface-treated infrared absorbing fine particle dispersion liquid according to Example 19. The manufacturing conditions and evaluation results are shown in Tables 1 to 3.
  • Example 1 A hexagonal cesium tungsten bronze powder (10% by mass) was mixed with pure water (90% by mass), and the resulting mixed solution was loaded into a paint shaker containing 0.3 mm ⁇ ZrO 2 beads and pulverized/dispersed for 4 hours. An aqueous dispersion for forming a coating film according to No. 1 was obtained. When the dispersed particle diameter of the infrared absorbing fine particles in the obtained dispersion was measured in the same manner as in Example 1, it was 100 nm. The particle refractive index was 1.81 and the particle shape was non-spherical as settings for particle size measurement. The background was measured using water, and the solvent refractive index was 1.33.
  • the infrared absorbing fine particle dispersion liquid according to Comparative Example 1 was used as it was without adding the surface treatment diluent dropwise to the coating film forming aqueous dispersion liquid according to Comparative Example 1.
  • the infrared absorbing fine particle dispersion liquid according to Comparative Example 1 was evaluated in the same manner as in Example 1. The manufacturing conditions and evaluation results are shown in Tables 1 to 3.
  • the infrared absorbing fine particle dispersion liquid using the hexagonal cesium tungsten bronze set to the visible light transmittance of 80% according to Comparative Examples 1 to 6 using the infrared absorbing fine particles not subjected to the surface treatment was heated to 85° C.
  • the amount of change in solar radiation transmittance before and after the exposure was 7.4% or more, and it was revealed that the moisture and heat resistance was poor.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un liquide de dispersion de particules fines à absorption infrarouge traitées en surface qui est obtenu par dispersion de particules fines à absorption infrarouge traitées en surface dans un solvant qui contient de l'eau. Ledit liquide est configuré de telle sorte que: chacune des particules fines à absorption infrarouge traitées en surface est obtenue en recouvrant la surface d'une particule fine à absorption infrarouge avec un film de revêtement qui contient une ou plusieurs substances choisies parmi un produit d'hydrolyse d'un composé de chélate métallique, un produit de polymérisation d'un produit d'hydrolyse d'un composé chélaté métallique, un produit d'hydrolyse d'un composé oligomère cyclique métallique et un produit de polymérisation d'un produit d'hydrolyse d'un composé oligomère cyclique métallique; et le diamètre de particule dispersé des particules fines à absorption infrarouge traitées en surface est compris entre 20 nm à 400 nm (inclus).
PCT/JP2019/045630 2018-11-28 2019-11-21 Liquide de dispersion de particules fines à absorption infrarouge traitées en surface et son procédé de production WO2020110906A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005037932A1 (fr) * 2003-10-20 2005-04-28 Sumitomo Metal Mining Co., Ltd. Microparticules de matiere ecran anti-infrarouge, dispersion de telles microparticules, leur procede de production, et ecran ainsi realise
JP2008291109A (ja) * 2007-05-24 2008-12-04 Sumitomo Metal Mining Co Ltd 赤外線遮蔽微粒子およびその製造方法、赤外線遮蔽微粒子分散体、赤外線遮蔽体、ならびに赤外線遮蔽基材
WO2010055570A1 (fr) * 2008-11-13 2010-05-20 住友金属鉱山株式会社 Particules bloquant les infrarouges, leur procédé de fabrication, dispersion de particules bloquant les infrarouges les utilisant et base bloquant les infrarouges
WO2017217459A1 (fr) * 2016-06-15 2017-12-21 住友金属鉱山株式会社 Dispersion de microparticules de protection contre les rayons thermiques, base transparente stratifiée de protection contre les rayons thermiques, et procédés de production s'y rapportant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005037932A1 (fr) * 2003-10-20 2005-04-28 Sumitomo Metal Mining Co., Ltd. Microparticules de matiere ecran anti-infrarouge, dispersion de telles microparticules, leur procede de production, et ecran ainsi realise
JP2008291109A (ja) * 2007-05-24 2008-12-04 Sumitomo Metal Mining Co Ltd 赤外線遮蔽微粒子およびその製造方法、赤外線遮蔽微粒子分散体、赤外線遮蔽体、ならびに赤外線遮蔽基材
WO2010055570A1 (fr) * 2008-11-13 2010-05-20 住友金属鉱山株式会社 Particules bloquant les infrarouges, leur procédé de fabrication, dispersion de particules bloquant les infrarouges les utilisant et base bloquant les infrarouges
WO2017217459A1 (fr) * 2016-06-15 2017-12-21 住友金属鉱山株式会社 Dispersion de microparticules de protection contre les rayons thermiques, base transparente stratifiée de protection contre les rayons thermiques, et procédés de production s'y rapportant

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