Infrared absorbing material microparticle dispersion liquid and infrared absorbing material microparticle dispersion

Abstract

Provided are a dispersion liquid and a dispersion of microparticles of an infrared absorbing material, which have high permeability to light in the visible light region, have absorbency in the near-infrared region, and can be adjusted to a neutral color between the blue system and the bronze system. A microparticle dispersion liquid or dispersion of an infrared-absorbing material, which contains microparticles of an infrared-absorbing material and microparticles of iron oxide (Fe2O3) in a liquid medium or a solid medium, and which is characterized in that the microparticles of the infrared-absorbing material are composed of a compound represented by general formula MYWOZ (wherein M element is an element selected from among Cs, Rb, K, Tl, In, and the like, W is tungsten, 0.001 < = Y < = 1.0, 0 < = Y < = 1.0, 0 < = Y < = 1.0, 0 < = Y < = 1.0, and 0 < = Y < = 1.0). 2.2 < = Z < = 3.0) and having a hexagonal crystal structure, and the mass ratio [iron oxide microparticles / composite tungsten oxide microparticles] of the iron oxide microparticles and the composite tungsten oxide microparticles contained in the liquid medium or the solid medium is from 0.01 to 0.1 (inclusive).

Description

Technical Field

[0001] The present invention relates to an improvement in an infrared absorption material fine particle dispersion liquid and an infrared absorption material fine particle dispersion body that have high light transmittance in the visible light region, have absorbency in the near-infrared region, and can be adjusted to a neutral color between blue and bronze. Background Art

[0002] As a sunshade member used in window materials and the like, it is known that fine particles of a composite tungsten oxide represented by the general formula M Y WO Z are dispersed in a medium to form an infrared absorption material fine particle dispersion body in the form of a plate, film, thin film, etc. (Patent Document 1).

[0003] The above-mentioned composite tungsten oxide fine particles have light transmittance in the visible light region and absorbency in the near-infrared region. Therefore, the above-mentioned infrared absorption material fine particle dispersion body is suitable for window materials and the like having a function of shielding solar radiation.

[0004] However, the transmission color tone of the composite tungsten oxide fine particles is mostly in the blue system, and the window material using the composite tungsten oxide fine particles also has a dark blue system color tone. However, from the viewpoints of appearance and practicality, a black system or bronze system color tone with low chroma is mostly preferred.

[0005] Therefore, Patent Document 2 discloses a solar radiation shielding body for a vehicle window in which composite tungsten oxide fine particles, titanium nitride fine particles, and iron oxide fine particles are mixed and dispersed in a solid medium (see Examples 11 and 23). By containing iron oxide fine particles in the above-mentioned solar radiation shielding body, a* and b* in the L*a*b* color system are on the positive side, and the color tone of the solar radiation shielding body for a vehicle window can be adjusted to the bronze side (see Paragraph 0035).

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent No. 4096205 Gazette.

[0009] Patent Document 2: International Publication No. 2009 / 054051. Summary of the Invention

[0010] Problems to be Solved by the Invention

[0011] However, although adjusted to bronze, there is a problem that the visible light transmittance of the solar radiation shielding body for a vehicle window described in Patent Document 2 is significantly reduced to 10.1% (Example 22) to 31.9% (Example 25).

[0012] Furthermore, due to the diversity of users' preferred colors, there is also a widespread demand for window materials in neutral colors (e.g., light blue, yellowish green) between the blue series and the bronze series that are not bronze-colored, and there are problems that cannot be addressed by the method described in Patent Document 2.

[0013] The present invention was completed in view of such problems, and its object is to provide an infrared absorption material particle dispersion liquid and an infrared absorption material particle dispersion that have high light transmittance in the visible light region, have absorbability in the near-infrared region, and can be adjusted to a neutral color between the blue series and the bronze series.

[0014] Means for Solving the Problem

[0015] To solve the above problems, the inventors of the present invention selected a combination of composite tungsten oxide particles represented by the general formula M Y WO Z and iron oxide (Fe2O3) particles, dispersed these particles in a medium to prepare an infrared absorption material particle dispersion liquid and an infrared absorption material particle dispersion, and while changing the mass ratio of iron oxide (Fe2O3) particles to composite tungsten oxide particles [i.e., iron oxide (Fe2O3) particles / composite tungsten oxide particles], measured the respective transmittances [UV-A (315 - 400 nm) average, visible light, ST (solar radiation)] of the infrared absorption material particle dispersion liquid and the infrared absorption material particle dispersion, and evaluated the transmitted color based on the L*a*b* color system. As a result, it was found that when the above mass ratio [iron oxide (Fe2O3) particles / composite tungsten oxide particles] was set to 0.01 or more and 0.1 or less, the a* of the transmitted color in the infrared absorption material particle dispersion liquid evaluated by the L*a*b* color system was -20 or more and 0 or less, and the b* was -3.5 or more and 15 or less. The infrared absorption material particle dispersion obtained using this infrared absorption material particle dispersion liquid has high light transmittance in the visible light region, has absorbability in the near-infrared region, and the a* of the transmitted color evaluated by the L*a*b* color system is -20 or more and 0 or less, and the b* is -3.0 or more and 15 or less, and can be adjusted to a neutral color between the blue series and the bronze series.

[0016] The present invention was completed through the above-described technical analysis and discovery.

[0017] That is, the first invention of the present invention is an infrared absorption material particle dispersion liquid that contains infrared absorption material particles and iron oxide (Fe2O3) particles in a liquid medium, and is characterized in that

[0018] the above infrared absorption material particles are represented by the general formula M Y WO Z(wherein, the M element is one or more elements selected from H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, 0.001 ≤ Y ≤ 1.0, and 2.2 ≤ Z ≤ 3.0), and is composed of composite tungsten oxide particles having a hexagonal crystal structure.

[0019] The mass ratio of the iron oxide (Fe2O3) particles to the composite tungsten oxide particles in the above liquid medium [iron oxide (Fe2O3) particles / composite tungsten oxide particles] is 0.01 or more and 0.1 or less.

[0020] In addition, the second invention of the present invention is characterized in that in the infrared absorption material particle dispersion liquid described in the first invention.

[0021] The particle size of the above composite tungsten oxide particles is 1 nm or more and 200 nm or less.

[0022] The third invention is characterized in that in the infrared absorption material particle dispersion liquid described in the first invention.

[0023] The particle size of the above iron oxide (Fe2O3) particles is 1 nm or more and 200 nm or less.

[0024] The fourth invention is characterized in that in the infrared absorption material particle dispersion liquid described in the first invention.

[0025] The above liquid medium is one or a mixture of two or more selected from water, organic solvents, vegetable oils, compounds derived from vegetable oils, petroleum solvents, oils and fats, liquid resins, and plasticizers for liquid plastics.

[0026] The fifth invention is characterized in that in the infrared absorption material particle dispersion liquid described in any one of the first to fourth inventions.

[0027] When evaluating the infrared absorption material particle dispersion liquid by the L*a*b* color system, a* is -20 or more and 0 or less, and b* is -3.5 or more and 15 or less.

[0028] Then, the sixth invention of the present invention is an infrared absorption material particle dispersion, which is an infrared absorption material particle dispersion containing infrared absorption material particles and iron oxide (Fe2O3) particles in a solid medium, and is characterized in that.

[0029] The above-mentioned infrared absorption material particles are composed of composite tungsten oxide particles represented by the general formula M Y WO Z (wherein, the M element is one or more elements selected from H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, W is tungsten, O is oxygen, 0.001 ≤ Y ≤ 1.0, 2.2 ≤ Z ≤ 3.0) and having a hexagonal crystal structure,

[0030] The mass ratio of iron oxide (Fe2O3) particles to composite tungsten oxide particles in the above solid medium [iron oxide (Fe2O3) particles / composite tungsten oxide particles] is 0.01 or more and 0.1 or less.

[0031] Furthermore, the seventh invention of the present invention is characterized in that in the infrared absorption material particle dispersion described in the sixth invention,

[0032] The particle size of the above-mentioned composite tungsten oxide particles is 1 nm or more and 200 nm or less.

[0033] The eighth invention is characterized in that in the infrared absorption material particle dispersion described in the sixth invention,

[0034] The particle size of the above-mentioned iron oxide (Fe2O3) particles is 1 nm or more and 200 nm or less.

[0035] The ninth invention is characterized in that in the infrared absorption material particle dispersion described in the sixth invention,

[0036] The above solid medium is a resin or a metal alkoxide.

[0037] The tenth invention is characterized in that in the infrared absorption material particle dispersion according to any one of the sixth to ninth inventions,

[0038] When evaluating the infrared absorption material particle dispersion by the L*a*b* color system, a* is -20 or more and 0 or less, and b* is -3.0 or more and 15 or less.

[0039] Effects of the Invention

[0040] According to the present invention, the mass ratio of iron oxide (Fe2O3) particles to composite tungsten oxide particles in the medium [iron oxide (Fe2O3) particles / composite tungsten oxide particles] is set to be 0.01 or more and 0.1 or less. Therefore, it is possible to provide an infrared absorption material particle dispersion liquid and an infrared absorption material particle dispersion that have high transmittance to light in the visible light region, have absorbency in the near-infrared region, and are adjusted to a neutral color between blue and bronze. Detailed Embodiments

[0041] Hereinafter, the embodiments of the present invention will be specifically described.

[0042] 1. Infrared absorption material particle dispersion liquid

[0043] The infrared absorption material particle dispersion liquid of the present embodiment includes infrared absorption material particles composed of composite tungsten oxide particles represented by the general formula M Y WO Z and having a hexagonal crystal structure, iron oxide (Fe2O3) particles, a liquid medium, and additives added as needed. It is formed by dispersing the above infrared absorption material particles and iron oxide (Fe2O3) particles in the liquid medium. Hereinafter, each component will be described.

[0044] (1) Infrared absorption material particles

[0045] (1-1) The infrared absorption material particles of the present embodiment are particles composed of composite tungsten oxide particles represented by the general formula M Y WO Z (wherein, the M element is one or more elements selected from H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, W is tungsten, O is oxygen, 0.001 ≤ Y ≤ 1.0, 2.2 ≤ Z ≤ 3.0). As preferred M elements, one or more selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn can be exemplified. When applied to various window materials, etc., it effectively functions as an infrared absorption component.

[0046] The addition amount Y of the above-mentioned M element needs to be 0.001 or more and 1.0 or less, preferably around 0.33. This is because the Y value calculated theoretically based on the crystal structure of the hexagonal crystal is 0.33, and preferable optical properties can be obtained with an addition amount around it. As a typical example, Cs 0.33 WO3, Rb 0.33 WO3, K 0.33 WO3, Ba 0.33 WO3, etc. However, as long as Y and Z are within the above ranges, useful infrared absorption characteristics can be obtained.

[0047] In addition, in the above-mentioned composite tungsten oxide, a part of oxygen can also be replaced by other elements. As other elements, for example, nitrogen, sulfur, halogen, etc. can be cited.

[0048] (1-2) The particle size of the composite tungsten oxide constituting the infrared absorption material particles of the present embodiment can be appropriately selected according to the use purpose of the composite tungsten oxide particles and the infrared absorption material particle dispersion manufactured using the same, and is preferably 1 nm or more and 200 nm or less. This is because if the particle size is 200 nm or less, the powerful near-infrared absorption ability brought by the composite tungsten oxide particles can be exerted. In addition, if the particle size is 1 nm or more, industrial manufacturing is easy. It should be noted that if the particle size is larger than 200 nm and too large, the infrared absorption ability of the composite tungsten oxide particles themselves will decay, so it is not preferable.

[0049] Here, the particle size refers to the diameter of each non-aggregated composite tungsten oxide particle, that is, the average value of the primary particle size, and is the average particle size of the composite tungsten oxide particles contained in the infrared absorption material particle dispersion described later, and does not include the diameter of the aggregate of the composite tungsten oxide particles, which is different from the dispersion particle size described below.

[0050] It should be noted that the particle size is the average particle size measured and calculated from the electron microscope image, and even if the particles are processed into a particle dispersion film, a particle dispersion tablet, or a laminated glass sheet, the particle size will not change.

[0051] In addition, when the infrared absorption material particle dispersion is used for applications requiring transparency, it is preferable that the above-mentioned composite tungsten oxide particles have a dispersion particle size of 40 nm or less. This is because if the composite tungsten oxide particles have a dispersion particle size of 40 nm or less, the scattering of light based on Mie scattering and Rayleigh scattering of the particles is suppressed, and the visual recognition in the visible light wavelength region can be maintained, and transparency can be efficiently maintained at the same time. In the case of applications requiring transparency, such as the windshield of an automobile, in order to further suppress scattering, the dispersion particle size of the composite tungsten oxide particles is set to 30 nm or less, preferably 25 nm or less.

[0052] It should be noted that the dispersed particle size of the composite tungsten oxide particles refers to the particle size of the single particles of the composite tungsten oxide particles dispersed in the infrared absorption material particle dispersion and the agglomerated particles formed by the aggregation of the composite tungsten oxide particles.

[0053] (1 - 3) Method for manufacturing infrared absorption material particles

[0054] Hereinafter, a method for manufacturing composite tungsten oxide particles (infrared absorption material particles) represented by the general formula M Y WO Z will be described.

[0055] After weighing a specified amount of the starting material of the composite tungsten oxide and mixing them, heat treatment is performed in an inert gas atmosphere or a reducing gas atmosphere, whereby composite tungsten oxide particles can be obtained. In addition, the starting material of the composite tungsten oxide is a tungsten compound and an element M-containing simple substance or compound. However, in order to manufacture a tungsten compound as a starting material in which each component is uniformly mixed at the molecular level, it is preferable to mix each raw material with a solution, and the tungsten compound containing element M is preferably a substance that can be dissolved in a solvent such as water or an organic solvent.

[0056] The above-mentioned tungsten compound is preferably any one or more selected from tungsten trioxide powder, tungsten dioxide powder, hydrate of tungsten oxide, tungsten hexachloride powder, ammonium tungstate powder, hydrate powder of tungsten oxide obtained by dissolving tungsten hexachloride in alcohol and then drying, hydrate powder of tungsten oxide obtained by dissolving tungsten hexachloride in alcohol, adding water to precipitate it, and then drying, tungsten compound powder obtained by drying an ammonium tungstate aqueous solution, and metallic tungsten powder.

[0057] Here, when manufacturing composite tungsten oxide particles, if the starting material is a solution, from the viewpoint that each element can be easily and uniformly mixed, it is further preferable to use an ammonium tungstate aqueous solution or a tungsten hexachloride solution.

[0058] On the other hand, as the element M-containing simple substance or compound, there can be mentioned tungstenates, chloride salts, nitrate salts, sulfate salts, oxalate salts, oxides, carbonate salts, hydroxide salts, etc. containing element M, but not limited thereto, and as long as it is a substance in a solution state, it is preferable.

[0059] The raw materials for manufacturing composite tungsten oxide particles will be described in detail again.

[0060] In order to obtain the composite tungsten oxide represented by the general formula M Y WO ZAs the starting material for the composite tungsten oxide particles represented, it is possible to use a powder obtained by mixing any one or more powders selected from tungsten trioxide powder, tungsten dioxide powder, hydrates of tungsten oxides, tungsten hexachloride powder, ammonium tungstate powder, hydrate powder of tungsten oxide obtained by dissolving tungsten hexachloride in alcohol and then drying, hydrate powder of tungsten oxide obtained by dissolving tungsten hexachloride in alcohol, adding water to precipitate it, and then drying, tungsten compound powder obtained by drying an ammonium tungstate aqueous solution, and metallic tungsten powder, with a powder of an element or compound containing the M element.

[0061] Furthermore, if the tungsten compound as the starting material for obtaining the composite tungsten oxide particles is a solution or dispersion, each element can be easily and uniformly mixed. From this viewpoint, the starting material for the composite tungsten oxide particles is further preferably a powder obtained by mixing an alcohol solution of tungsten hexachloride or an ammonium tungstate aqueous solution with a compound solution containing the M element and then drying.

[0062] Similarly, the starting material for the composite tungsten oxide particles is also preferably a powder obtained by mixing a dispersion obtained by dissolving tungsten hexachloride in alcohol, adding water to form a precipitate, with a powder of an element or compound containing the M element or a compound solution containing the M element and then drying.

[0063] Examples of the compound containing the M element include tungstates, chloride salts, nitrates, sulfates, oxalates, oxides, carbonates, hydroxides, etc. of the M element, but are not limited thereto, as long as it is a substance that forms a solution state. Further, in the case of industrially manufacturing the composite tungsten oxide particles, if a hydrate powder of tungsten oxide or tungsten trioxide, and a carbonate or hydroxide of the M element are used, no harmful gases, etc. will be generated in the heat treatment stage, which is a preferred manufacturing method.

[0064] Here, as the heat treatment conditions of the composite tungsten oxide particles in an inert environment, it is preferably 650 °C or higher. The starting material heat-treated at 650 °C or higher has sufficient infrared absorption ability, and as particles having an infrared absorption function, the efficiency is good. As the inert gas, it is preferable to use inert gases such as Ar and N2. In addition, as the heat treatment conditions in a reducing environment, preferably, first, the starting material is heat-treated in a reducing gas environment at 100 °C or higher and 850 °C or lower, and then heat-treated in an inert gas environment at 650 °C or higher and 1200 °C or lower. The reducing gas at this time is not particularly limited, and H2 is preferred. In addition, when H2 is used as the reducing gas, as the composition of the reducing environment, H2 is preferably 0.1% or more by volume, and more preferably 2% or more. If H2 is 0.1% or more by volume, reduction can be carried out efficiently.

[0065] (2)Iron oxide (Fe2O3) particles

[0066] (2-1) The infrared absorption material particle dispersion liquid and the infrared absorption material particle dispersion of the present embodiment contain infrared absorption material particles (composite tungsten oxide particles) and iron oxide (Fe2O3) particles. Iron oxide (Fe2O3) particles are known as inorganic ultraviolet absorbers that absorb long-wave ultraviolet rays (UVA, wavelength 315 - 400 nm). The UVA contained in sunlight basically passes through the ozone layer of the earth and reaches the earth's surface, causing the skin of the human body to turn black through sun exposure. Moreover, it reaches the dermis of the skin and also affects skin aging.

[0067] The infrared absorption material particle dispersion obtained by using the infrared absorption material particle dispersion liquid of the present embodiment has high light transmittance in the visible light region, has absorbency in the near-infrared region, and also absorbs and shields the UVA contained in sunlight. Further, it contains iron oxide (Fe2O3) particles so as to be able to be adjusted to a neutral color (desired hue) between blue and bronze.

[0068] (2-2) In addition, the particle size of the iron oxide (Fe2O3) particles is preferably 1 nm or more and 200 nm or less. This is because iron oxide (Fe2O3) particles with a particle size of 1 nm or more can be obtained industrially, and when Fe2O3 particles with a particle size greater than 200 nm are used, the same adverse conditions as those of the composite tungsten oxide particles with a particle size greater than 200 nm will occur.

[0069] Here, the particle size of the iron oxide (Fe2O3) particles refers to the average value of the diameters of the non-aggregated iron oxide (Fe2O3) particles, that is, the primary particle size, and is the average particle size of the iron oxide (Fe2O3) particles contained in the infrared absorption material particle dispersion described later.

[0070] (3) Infrared absorption material particle dispersion liquid

[0071] The infrared absorption material particle dispersion liquid of the present embodiment can be produced by dispersing fine particles of an infrared absorption material (complex tungsten oxide fine particles) and iron oxide (Fe2O3) fine particles in a liquid medium at a specified ratio. In this case, a complex tungsten oxide fine particle dispersion liquid in which complex tungsten oxide fine particles (infrared absorption material fine particles) are dispersed in a liquid medium and an iron oxide (Fe2O3) fine particle dispersion liquid in which iron oxide (Fe2O3) fine particles are dispersed in a liquid medium can be prepared in advance, and these complex tungsten oxide fine particle dispersion liquid and iron oxide (Fe2O3) fine particle dispersion liquid can be mixed to produce the infrared absorption material particle dispersion liquid. Since the methods of pulverizing and dispersing the above-mentioned complex tungsten oxide fine particles and iron oxide (Fe2O3) fine particles in the liquid medium are different, it is preferable to separately produce the complex tungsten oxide fine particle dispersion liquid and the iron oxide (Fe2O3) fine particle dispersion liquid in advance.

[0072] It should be noted that in the present embodiment, the substance obtained by mixing the complex tungsten oxide fine particle dispersion liquid and the iron oxide (Fe2O3) fine particle dispersion liquid is sometimes simply referred to as "particle dispersion liquid".

[0073] (3-1) Complex tungsten oxide fine particle dispersion liquid and iron oxide (Fe2O3) fine particle dispersion liquid

[0074] By adding the above-mentioned complex tungsten oxide fine particles (infrared absorption material fine particles) and, as required, an appropriate amount of dispersant, coupling agent, surfactant, etc. to a liquid medium and performing a dispersion treatment, the complex tungsten oxide fine particle dispersion liquid of the present embodiment can be obtained.

[0075] In addition, by adding iron oxide (Fe2O3) fine particles and, as required, an appropriate amount of dispersant, coupling agent, surfactant, etc. to a liquid medium and performing a dispersion treatment, the iron oxide (Fe2O3) fine particle dispersion liquid of the present embodiment can be obtained.

[0076] Regarding the liquid mediums of the above-mentioned complex tungsten oxide fine particle dispersion liquid and iron oxide (Fe2O3) fine particle dispersion liquid respectively, a function for maintaining the dispersibility of the complex tungsten oxide fine particles (infrared absorption material fine particles) and iron oxide (Fe2O3) fine particles and a function for not causing coating defects when coating the infrared absorption material particle dispersion liquid (dispersion liquid in which complex tungsten oxide fine particles and Fe2O3 fine particles are dispersed in a liquid medium) are required. In addition, as the liquid mediums respectively used for the complex tungsten oxide fine particle dispersion liquid and the iron oxide (Fe2O3) fine particle dispersion liquid, the same solvent or solvents having compatibility are preferably used.

[0077] (3-1-1) Liquid medium

[0078] As the above-mentioned liquid medium, water, organic solvents, vegetable oils, compounds derived from vegetable oils, petroleum solvents, oils and fats, liquid resins, liquid plasticizers, or mixtures thereof can be selected.

[0079] Moreover, as the organic solvents that meet the above requirements, various organic solvents such as alcohol-based, ketone-based, hydrocarbon-based, ethylene glycol-based, and water-based organic solvents can be selected. Specifically, alcohol-based solvents such as methanol, ethanol, 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol, and diacetone alcohol can be cited; ketone-based solvents such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; ester-based solvents such as 3-methyl-methoxy-propionate; glycol derivatives such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, and propylene glycol ethyl ether acetate; amides such as formamide, N-methylformamide, dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as vinyl chloride and chlorobenzene, etc. Among them, organic solvents with low polarity are preferred, and in particular, isopropanol, ethanol, 1-methoxy-2-propanol, dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether acetate, and n-butyl acetate are more preferred. These solvents can be used alone or in combination of two or more.

[0080] As the above-mentioned vegetable oil, linseed oil, sunflower oil, tung oil, sesame oil, cottonseed oil, rapeseed oil, soybean oil, rice bran oil, olive oil, coconut oil, palm oil, dehydrated castor oil, etc. are preferred.

[0081] As the compound derived from vegetable oil, fatty acid monoesters, ethers, etc. obtained by directly performing an ester reaction between the fatty acid of vegetable oil and a monohydric alcohol are preferred.

[0082] As the petroleum solvent, Isopar E, Exxsol hexane, Exxsol heptane, Exxsol E, Exxsol D30, Exxsol D40, Exxsol D60, Exxsol D80, Exxsol D95, Exxsol D110, Exxsol D130 (the above are manufactured by Exxon Mobil Corporation), etc. are preferred.

[0083] As the liquid resin, methyl methacrylate, etc. are preferred. In addition, as the liquid plasticizer for plastics, plasticizers such as compounds of monohydric alcohol and organic acid esters, ester-based plasticizers such as polyhydric alcohol organic acid ester compounds, and phosphoric acid-based plasticizers such as organic phosphoric acid-based plasticizers are preferably cited. Among them, triethylene glycol bis-2-ethylhexanoate, triethylene glycol bis-2-ethylbutyrate, and tetraethylene glycol bis-2-ethylhexanoate have low hydrolyzability, so they are more preferred.

[0084] (3-1-2) Dispersant, coupling agent, surfactant

[0085] The above-mentioned dispersant, coupling agent, and surfactant can be selected according to the use, but preferably have a group containing an amine, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group. These functional groups adsorb on the surface of the composite tungsten oxide particles, prevent the aggregation of the composite tungsten oxide particles and iron oxide (Fe2O3) particles, and have the effect of uniformly dispersing the infrared absorption material particles and iron oxide (Fe2O3) particles in the infrared absorption material particle dispersion (particle dispersion film) of the present embodiment.

[0086] Examples of dispersants that can be preferably used include phosphate compounds, polymer dispersants, silane coupling agents, titanate coupling agents, aluminum coupling agents, etc., but are not limited to these. As polymer dispersants, there are acrylic polymer dispersants, urethane polymer dispersants, acrylic block copolymer polymer dispersants, polyether dispersants, polyester polymer dispersants, etc.

[0087] In addition, for the addition amount of the dispersant, it is preferably in the range of 10 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the composite tungsten oxide particles, preferably in the range of 10 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the iron oxide (Fe2O3) particles, and more preferably in the range of 20 parts by mass to 200 parts by mass with respect to 100 parts by mass of each particle. If the addition amount of the dispersant is within the above range, the composite tungsten oxide particles (infrared absorption material particles) and iron oxide (Fe2O3) particles will not aggregate in the liquid medium and maintain dispersion stability.

[0088] For the dispersion treatment method, as long as it is a method of uniformly dispersing the composite tungsten oxide particles (infrared absorption material particles) and iron oxide (Fe2O3) particles in a liquid medium, it can be arbitrarily selected from known methods. For example, methods such as bead mills, ball mills, sand mills, and ultrasonic dispersion can be used.

[0089] In addition, in order to obtain a uniform composite tungsten oxide particle dispersion liquid and iron oxide (Fe2O3) particle dispersion liquid, various additives can also be added or the pH can be adjusted.

[0090] (3-1-3) Content of each particle

[0091] The content of each of the microparticles in the above-mentioned composite tungsten oxide microparticle dispersion liquid and iron oxide (Fe2O3) microparticle dispersion liquid is preferably 0.01% by mass to 75% by mass, more preferably 1% by mass or more and 35% by mass or less. This is because if the content of each microparticle is 0.01% by mass or more, it can be applied to the production of coatings, plastic molded articles (a form of the infrared absorption material microparticle dispersion of the present invention), etc., and if it is 75% by mass or less, industrial production is easy.

[0092] (3-2) Method for producing infrared absorption material microparticle dispersion liquid

[0093] The infrared absorption material microparticle dispersion liquid of the present embodiment can be produced by mixing the composite tungsten oxide microparticle dispersion liquid and the iron oxide (Fe2O3) microparticle dispersion liquid in such a way that the infrared absorption material microparticles (composite tungsten oxide microparticles) and the iron oxide (Fe2O3) microparticles have the following mass ratio.

[0094] Moreover, the mass ratio of iron oxide (Fe2O3) microparticles to composite tungsten oxide microparticles in the liquid medium [iron oxide (Fe2O3) microparticles / composite tungsten oxide microparticles] is 0.01 or more and 0.1 or less, preferably 0.01 or more and less than 0.1, and more preferably 0.01 or more and 0.07 or less.

[0095] (3-2-1) When the above mass ratio [iron oxide (Fe2O3) microparticles / composite tungsten oxide microparticles] is greater than 0.1, when the hue of the infrared absorption material microparticle dispersion liquid of the present embodiment or the infrared absorption material microparticle dispersion of the present embodiment obtained from the dispersion liquid is evaluated by the L*a*b* color system, there is a problem that both a* and b* are on the "positive" side and the hue becomes a reddish hue. In particular, if the above a* is 5 or more, the infrared absorption material microparticle dispersion liquid and the infrared absorption material microparticle dispersion of the present embodiment become a hue like bronze, and the color matching is not preferable.

[0096] In addition, when the mass ratio [iron oxide (Fe2O3) microparticles / composite tungsten oxide microparticles] is less than 0.01, the hue of the infrared absorption material microparticle dispersion liquid and the infrared absorption material microparticle dispersion of the present embodiment becomes a bluish hue emitted by the composite tungsten oxide microparticles, and the color matching is not preferable.

[0097] (3-2-2) On the other hand, when the above mass ratio [iron oxide (Fe2O3) particles / composite tungsten oxide particles] is set to be 0.01 or more and 0.1 or less, when the hue of the infrared absorption material particle dispersion obtained from the infrared absorption material particle dispersion liquid is evaluated by the L*a*b* color system, a* is in the range of -20 or more and 0 or less, and b* is in the range of -3.0 or more and 15 or less. Therefore, it is possible to adjust to a hue that is not reddish and a neutral color (e.g., light blue, yellowish green) between the blue system and the bronze system that is not bronze. In addition, for the above hue, if the chroma c* = [(a*) 2 +(b*) 2 1 / 2 in the L*a*b* color system is also considered, the chroma c* is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. It should be noted that the chroma c* in the L*a*b* color system is an index indicating the degree of inclusion of the a* and b* components. Non-color is 0, and the smaller the chroma c*, the more neutral the hue.

[0098] (3-2-3) Moreover, for the infrared absorption material particle dispersion having an excellent neutral hue, a* is in the range of -20 or more and -3.5 or less, b* is in the range of -3.0 or more and 10 or less, and c* is in the range of 10 or less. In addition, in order to obtain an infrared absorption material particle dispersion having an excellent neutral color, it is achieved by setting the mass ratio [iron oxide (Fe2O3) particles / composite tungsten oxide particles] of iron oxide (Fe2O3) particles and composite tungsten oxide particles in the liquid medium to be less than 0.1, and further to be 0.07 or less.

[0099] 2. Infrared absorption material particle dispersion

[0100] (1) Infrared absorption material particle dispersion

[0101] The infrared absorption material particle dispersion of the present embodiment is composed of infrared absorption material particles composed of composite tungsten oxide particles represented by the general formula M Y WO Z and having a hexagonal crystal structure, iron oxide (Fe2O3) particles, and additives added as needed, dispersed in a solid medium, and can be obtained by dispersing the infrared absorption material particle dispersion liquid of the present embodiment in the solid medium. It should be noted that when the infrared absorption material particle dispersion liquid of the present embodiment is processed into the above infrared absorption material particle dispersion, a part or all of the liquid medium contained in the infrared absorption material particle dispersion liquid is removed by volatilization or the like.

[0102] ​(1-1) Mass ratio of iron oxide (Fe2O3) particles to composite tungsten oxide particles

[0103] Moreover, for the infrared absorption material particle dispersion of the present embodiment, the mass ratio of the above-mentioned iron oxide (Fe2O3) particles to composite tungsten oxide particles [iron oxide (Fe2O3) particles / composite tungsten oxide particles] needs to be 0.01 or more and 0.1 or less as described above.

[0104] This is because when the above mass ratio is set to be 0.01 or more and 0.1 or less, when the hue of the infrared absorption material particle dispersion is evaluated by the L*a*b* color system, a* is in the range of -20 or more and 0 or less, and b* is in the range of -3.0 or more and 15 or less. Therefore, it can be adjusted to a neutral color between the blue system and the bronze system.

[0105] (1-2) Content of composite tungsten oxide particles (infrared absorption material particles)

[0106] In addition, the content of composite tungsten oxide particles (infrared absorption material particles) per unit projected area contained in the infrared absorption material particle dispersion of the present embodiment is preferably 0.1 g / m 2 or more and 5.0 g / m 2 or less. This is because if the content of composite tungsten oxide particles per unit projected area contained in the infrared absorption material particle dispersion is within the above range, visible light transmittance and solar radiation shielding property (infrared shielding property) can be achieved.

[0107] It should be noted that the above "content per unit projected area" means the mass (g) of composite tungsten oxide particles (infrared absorption material particles) contained in the thickness direction per unit area (m 2 ) through which light passes in the infrared absorption material particle dispersion of the present embodiment.

[0108] (1-3) Solid medium

[0109] As the above solid medium for dispersing composite tungsten oxide particles (infrared absorption material particles) and iron oxide (Fe2O3) particles, for example, UV curable resin, thermosetting resin, electron beam curable resin, room temperature curable resin, thermoplastic resin, etc. can be selected according to the purpose. Specifically, polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, ethylene vinyl acetate copolymer, polyester resin, polyethylene terephthalate resin, fluororesin, polycarbonate resin, acrylic resin, polyvinyl butyral resin can be cited. These resins can be used alone or in combination.

[0110] In addition, a binder using metal alkoxide can also be used. As the above-mentioned metal alkoxide, alkoxides of Si, Ti, Al, Zr, etc. are representative. The binder using these metal alkoxides can be hydrolyzed and polycondensed by heating or the like to form an oxide coating film as a solid medium.

[0111] Moreover, when obtaining the infrared absorption material particle dispersion, the infrared absorption material particle dispersion liquid of the present embodiment can be processed into a dispersion powder, masterbatch, film, plastic molded body, etc.

[0112] (1-4) Additive

[0113] In order to further endow the infrared absorption material particle dispersion of the present embodiment with the function of shielding ultraviolet rays, at least one or more of inorganic titanium oxide, zinc oxide, cerium oxide particles, organic benzophenone, benzotriazole, etc. can be added.

[0114] In addition, in order to improve the visible light transmittance of the infrared absorption material particle dispersion of the present embodiment, transparent particles such as antimony tin oxide (ATO), indium tin oxide (ITO), zinc oxide added with aluminum, indium tin composite oxide, etc. can be further mixed into the solid medium. By adding these transparent particles to the solid medium, the transmittance near 750 nm in wavelength increases, while infrared light with a wavelength longer than 1200 nm is shielded. Therefore, an infrared absorption material particle dispersion having high transmittance to light in the visible light region and absorbency in the near-infrared region can be obtained.

[0115] (2) Embodiments of the infrared absorption material particle dispersion

[0116] Using the infrared absorption material particle dispersion liquid of the present embodiment, infrared absorption material particle dispersions in various forms shown below can be obtained.

[0117] (2-1) Particle dispersion film composed of a substrate and a coating film

[0118] The infrared absorption material particle dispersion liquid is mixed with a plastic or a monomer to prepare a particle coating liquid, and the obtained particle coating liquid is coated on a substrate by a known method to form a coating film, thereby enabling the production of a particle dispersion film.

[0119] Examples of the above-mentioned substrate include a film, a plate as required, etc., and the shape is not limited. In addition, as a transparent substrate material, PET (polyethylene terephthalate), acrylic acid, urethane, polycarbonate, polyethylene, ethylene vinyl acetate copolymer, vinyl chloride, fluororesin, etc. can be used for various purposes. In addition to resins, glass can also be used.

[0120] (2-2) Powdery particulate dispersion

[0121] By removing the volatile components from the infrared absorption material particulate dispersion liquid of the present embodiment, a powdery particulate dispersion (dispersion powder, plasticizer dispersion liquid) can be produced.

[0122] It should be noted that the "dispersion powder" refers to a dispersion in which infrared absorption material particles are highly dispersed in the resin and / or the dispersant from the infrared absorption material particulate dispersion liquid (including a resin component and a plasticizer) by removing the volatile components. In addition, the above-mentioned "plasticizer dispersion liquid" refers to a dispersion liquid in which infrared absorption material particles are highly dispersed in the plasticizer by removing the volatile components.

[0123] As a method for removing the volatile components from the infrared absorption material particulate dispersion liquid, it is preferable to subject the particulate dispersion liquid to reduced-pressure drying. Specifically, while stirring the infrared absorption material particulate dispersion liquid, reduced-pressure drying is performed to separate the composition of the infrared absorption material particles and iron oxide (Fe2O3) particles from the volatile components. As a device for reduced-pressure drying, a vacuum stirring type dryer can be cited, but any device having the above functions can be used, and there is no particular limitation. In addition, the pressure value during the reduced pressure in the drying process is appropriately selected.

[0124] By using this reduced-pressure drying method, the removal efficiency of the volatile components from the infrared absorption material particulate dispersion liquid is improved, and the above-mentioned "dispersion powder" and "plasticizer dispersion liquid" are not exposed to high temperatures for a long time. Therefore, the infrared absorption material particles and iron oxide (Fe2O3) particles dispersed in the "dispersion powder" and "plasticizer dispersion liquid" do not aggregate, which is preferable. Further, the productivity of the above-mentioned "dispersion powder" and "plasticizer dispersion liquid" is also improved, and it is also easy to recover the evaporated volatile components. Therefore, it is also preferable from an environmental aspect.

[0125] In the "dispersion powder" and "plasticizer dispersion liquid" of the present embodiment, the residual volatile components are preferably 5% by mass or less. This is because if the residual volatile components are 5% by mass or less, no bubbles will be generated when the "dispersion powder" and "plasticizer dispersion liquid" are processed into the "interlayer transparent substrate" described later, and the appearance and optical properties are maintained well.

[0126] In addition, after uniformly mixing the "dispersion powder" or "plasticizer dispersion liquid" of this embodiment, the powder or granules of the thermoplastic resin, and other additives as needed, they are kneaded with a vented single-screw extruder or twin-screw extruder and processed into granules by the method of cutting the molten extruded strands in a usual manner, thereby obtaining the masterbatch of this embodiment. In this case, as its shape, cylindrical shape, prismatic shape can be cited. In addition, the so-called hot cutting method of directly cutting the molten extrudate can also be adopted. In this case, a shape close to spherical shape is usually adopted.

[0127] As the transparent thermoplastic resin, it is possible to preferably select a resin from a resin group such as polyethylene terephthalate resin, polycarbonate resin, acrylic resin, styrene resin, polyamide resin, polyethylene resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluororesin, ethylene-vinyl acetate copolymer, a mixture of two or more resins selected from this resin group, and a copolymer of two or more resins selected from this resin group.

[0128] (2-3) Fine particle dispersion tablets, fine particle dispersion films

[0129] By uniformly mixing the above-mentioned "dispersion powder" or "plasticizer dispersion liquid" or masterbatch into the transparent resin, it is possible to manufacture sheet-like fine particle dispersion tablets or film-like fine particle dispersion films in which fine particles of an infrared absorption material and iron oxide (Fe2O3) particles are dispersed in the transparent resin.

[0130] When manufacturing the fine particle dispersion tablets and fine particle dispersion films of this embodiment, various thermoplastic resins can be used as the resin constituting the sheet or film. And considering that the fine particle dispersion tablets and fine particle dispersion films of this embodiment are applicable to various window materials, a thermoplastic resin with sufficient transparency is preferred.

[0131] Specifically, it is possible to preferably select a resin from a resin group such as polyethylene terephthalate resin, polycarbonate resin, acrylic resin, styrene resin, polyamide resin, polyethylene resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluororesin, ethylene-vinyl acetate copolymer, a mixture of two or more resins selected from this resin group, and a copolymer of two or more resins selected from this resin group.

[0132] In addition, when directly using the fine particle dispersion tablets of this embodiment as plate-like window materials, considering high transparency and general properties required for window materials such as rigidity, light weight, long-term durability, cost, etc., polyethylene terephthalate resin, polycarbonate resin, acrylic resin are preferred, and polycarbonate resin is further preferred.

[0133] On the other hand, when the fine particle dispersion tablets or fine particle dispersion films of the present embodiment are used as the intermediate layer of the "interlayer transparent substrate" described later, from the viewpoints of adhesion to the transparent substrate, weather resistance, penetration resistance, etc., polyvinyl acetal resins and ethylene-vinyl acetate copolymers are preferred, and polyvinyl butyral resin is more preferred.

[0134] In addition, when the fine particle dispersion tablets or fine particle dispersion films are used as the intermediate layer, when the thermoplastic resin constituting the tablets or films does not have sufficient flexibility and adhesion to the transparent substrate (for example, the thermoplastic resin is a polyvinyl acetal resin) when used alone, it is preferable to further add a plasticizer.

[0135] As the above-mentioned plasticizer, a substance that can be used as a plasticizer for the thermoplastic resin of the present embodiment can be used. As, for example, a plasticizer for a fine particle dispersion film composed of a polyvinyl acetal resin, plasticizers such as compounds of a monohydric alcohol and an organic acid ester, ester-based plasticizers such as polyhydric alcohol organic acid ester compounds, and phosphoric acid-based plasticizers such as organic phosphoric acid-based plasticizers can be cited. All plasticizers are preferably liquid at room temperature. Among them, plasticizers that are ester compounds synthesized from polyhydric alcohols and fatty acids are preferred.

[0136] After kneading the above-mentioned "dispersion powder" or "plasticizer dispersion liquid" or masterbatch with the thermoplastic resin and, if necessary, a plasticizer and other additives, the kneaded product is formed into a flat or curved sheet by a known method such as an extrusion molding method or an injection molding method, thereby enabling the production of fine particle dispersion tablets.

[0137] As a method for forming the above-mentioned fine particle dispersion tablets or fine particle dispersion films, known methods can be used. For example, a calender roll method, an extrusion method, a casting method, a blow molding method, etc. can be used.

[0138] (2-4) Interlayer transparent substrate

[0139] An "interlayer transparent substrate" in which the fine particle dispersion tablets or fine particle dispersion films of the present embodiment as the intermediate layer are sandwiched between a plurality of transparent substrates made of plate glass or plastic will be described.

[0140] This "interlayer transparent substrate" is formed by sandwiching the intermediate layer between transparent substrates on both sides. As the transparent substrate, plate glass or plate-shaped plastic or film-shaped plastic that is transparent in the visible light region is used. The material of the plastic is not particularly limited and can be selected according to the use. For example, in the case of being used for transportation equipment such as automobiles, from the viewpoint of ensuring the perspective of the driver and passengers of the transportation equipment, transparent resins such as polycarbonate resin, acrylic resin, and polyethylene terephthalate resin are preferred. In addition, PET resin, polyamide resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluororesin, etc. can be used.

[0141] In addition, the "interlayer transparent substrate" of the present embodiment can also be obtained by laminating and integrating a plurality of inorganic glasses sandwiching the above-mentioned fine particle dispersion tablets or fine particle dispersion films using a known method. The obtained "interlayer transparent substrate" can mainly be used as an inorganic glass for a windshield of an automobile or a window of a building.

[0142] The concentration of the infrared absorption material fine particles (composite tungsten oxide fine particles) contained in the above-mentioned fine particle dispersion tablets, fine particle dispersion films, and "interlayer transparent substrate" is not particularly limited, and the content of the composite tungsten oxide fine particles (infrared absorption material fine particles) per unit projected area of the tablet / membrane is preferably 0.1 g / m 2 or more and 5.0 g / m 2 or less. This is because if the above content is 0.1 g / m 2 or more, the infrared absorption characteristics can be significantly exhibited as compared with the case where no infrared absorption material fine particles are contained, and if the content is 5.0 g / m 2 or less, the visible light transmittance in the fine particle dispersion tablet / membrane can be maintained.

[0143] Examples

[0144] Hereinafter, comparative examples are also listed to specifically illustrate the examples of the present invention, but the present invention is not limited by the following examples.

[0145] (1) Transmittance of infrared absorption material fine particle dispersion liquid and infrared absorption material fine particle dispersion

[0146] Regarding the transmittance of the infrared absorption material fine particle dispersion liquid of the examples and comparative examples to light with wavelengths of 300 to 2100 nm, the above dispersion liquid was held in a cuvette for a spectrophotometer (manufactured by GL Sciences Inc., model: S10-SQ-1, material: synthetic quartz, optical path length: 1 mm), and measured using a spectrophotometer U-4100 manufactured by Hitachi, Ltd. At the time of this measurement, the transmittance was measured in a state where the solvent (methyl isobutyl ketone: abbreviated as MIBK) of the above dispersion liquid filled the cuvette, and the measurement baseline of the transmittance was obtained. As a result, for the spectral transmittance and visible light transmittance described below, the influence caused by the light reflection on the surface of the cuvette for the spectrophotometer and the light absorption of the solvent was excluded, and only the light absorption of the fine particles was calculated.

[0147] In addition, the transmittance of the infrared absorption material fine particle dispersions (fine particle dispersion films, fine particle dispersion tablets, laminated glass sheets) of the examples and comparative examples to light with wavelengths of 300 to 2100 nm was also measured using a spectrophotometer U-4100 manufactured by Hitachi, Ltd. Based on the transmittance of light with wavelengths of 380 to 780 nm, the visible light transmittance was calculated based on JIS A5759.

[0148] (2) Particle size of infrared absorption material particles and iron oxide particles

[0149] The average dispersed particle size (average value of dispersed particle sizes) of the infrared absorption material particles and iron oxide (Fe2O3) particles in the examples and comparative examples was measured using a Microtrac particle size distribution meter manufactured by Nikkiso Co., Ltd. In addition, the particle size was calculated by observing the powder obtained by removing the solvent from each dispersion liquid with a transmission electron microscope (TEM).

[0150] (3) Hue of infrared absorption material particle dispersion liquid and infrared absorption material particle dispersion

[0151] For the hues of the infrared absorption material particle dispersion liquid and infrared absorption material particle dispersions (particle dispersion film, particle dispersion tablet, laminated glass sheet) in the examples and comparative examples, the values of a* and b* were measured using the L*a*b* color system (D65 light source / 10-degree field of view) based on JIS Z8701. Also, the chroma c* = [(a*) 2 +(b*) 2 1 / 2 .

[0152] (4) Particle dispersion film

[0153] The "particle dispersion film" in the examples and comparative examples (refer to Table 1-1, Table 1-2, Table 1-3) refers to an infrared absorption material particle dispersion composed of a base material (PET film) and a coating film formed on the base material [an infrared absorption coating film in which infrared absorption material particles and iron oxide particles (iron oxide particles are not included in Comparative Example 2) are dispersed].

[0154] (5) Particle dispersion tablet

[0155] The "particle dispersion tablet" in the examples and comparative examples (refer to Table 1-1, Table 1-2, Table 1-3) refers to an infrared absorption material particle dispersion composed of a polycarbonate tablet in which infrared absorption material particles and iron oxide particles (iron oxide particles are not included in Comparative Example 2) are dispersed.

[0156] (6) Laminated glass sheet

[0157] The "laminated glass sheet" in the examples and comparative examples (refer to Table 1-1, Table 1-2, Table 1-3) refers to an infrared absorption material particle dispersion composed of two glass sheets and an infrared absorption film [a polyvinyl butyral film in which infrared absorption material particles and iron oxide particles (iron oxide particles are not included in Comparative Example 2) are dispersed] sandwiched between the glass sheets.

[0158] [Example 1]

[0159] ​(1) Infrared Absorbing Material Particle Dispersion Liquid

[0160] (1-1) Composite Tungsten Oxide (Cs 0.33 WO3) Particles

[0161] Weigh the powders of tungstic acid (H2WO4) and cesium hydroxide (CsOH) in a ratio equivalent to Cs / W (molar ratio) = 0.33 / 1.00, and thoroughly mix them with an agate mortar to form a mixed powder. While supplying 5% H2 gas with N2 gas as the carrier, heat the above-mentioned mixed powder, perform a reduction treatment at a temperature of 600°C for 1 hour, and then sinter at 800°C for 30 minutes in an N2 gas environment to obtain the composite tungsten oxide (Cs 0.33 WO3) particles of Example 1 (hereinafter, simply referred to as "Powder A").

[0162] Measure Powder A using X-ray diffraction method, and judge that Powder A is a hexagonal single phase.

[0163] (1-2) Composite Tungsten Oxide Particle Dispersion Liquid

[0164] Weigh 20% by mass of the above-mentioned Powder A, 10% by mass of an acrylic polymer dispersant having an amine-containing group as a functional group (acrylic dispersant with an amine value of 48 mgKOH / g and a decomposition temperature of 250°C: hereinafter, simply referred to as "Dispersant a"), and 70% by mass of methyl isobutyl ketone (MIBK). Load them into a paint shaker equipped with beads, and perform a pulverization and dispersion treatment for 15 hours to obtain a composite tungsten oxide particle dispersion liquid (hereinafter, simply referred to as "Dispersion Liquid A"). Here, measure the average dispersion particle size of the infrared absorbing material particles (composite tungsten oxide particles) in Dispersion Liquid A, and the result is 26 nm, and the particle size obtained from the TEM image is 19 nm.

[0165] (1-3) Fe2O3 Particle Dispersion Liquid

[0166] Weigh 15% by mass of Fe2O3 particles, 80% by mass of MIBK, and 5% by mass of the above-mentioned Dispersant a. Load them into a paint shaker equipped with beads, and perform a pulverization and dispersion treatment for 10 hours to obtain an Fe2O3 particle dispersion liquid (hereinafter, simply referred to as "Dispersion Liquid a"). Here, measure the average dispersion particle size of the Fe2O3 particles in Dispersion Liquid a, and the result is 25 nm, and the particle size obtained from the TEM image is 48 nm.

[0167] (1-4) Manufacture of Infrared Absorbing Material Particle Dispersion Liquid

[0168] The above dispersion A and dispersion a were mixed such that the mass ratio of Fe2O3 fine particles to composite tungsten oxide fine particles became [Fe2O3 fine particles / composite tungsten oxide fine particles] = 0.1, and the infrared absorption material fine particle dispersion of Example 1 (hereinafter simply referred to as "fine particle dispersion A") was produced.

[0169] (1-5) Optical properties of the infrared absorption material fine particle dispersion

[0170] Then, the above fine particle dispersion A was appropriately diluted with MIBK and placed in a rectangular container with a thickness of 10 mm, and the spectral transmittance was measured.

[0171] According to the transmittance curve of fine particle dispersion A measured by adjusting the dilution rate such that the transmittance under the condition of a wavelength of 1000 nm became less than 10%, the average value of the transmittance under the condition of UV-A (wavelength 315 - 400 nm) was 21.5%, the visible light transmittance was 70.8%, the solar radiation (ST) transmittance was 36.3%, the a* value in the CIE1976L*a*b* color space was -3.5, the b* value was 14.9, and the c* value was 15.3.

[0172] The measurement results of the fine particle dispersion A of Example 1 were recorded in Tables 1-1, 1-2, and 1-3.

[0173] (2) Fine particle dispersion film

[0174] (2-1) Production of the fine particle dispersion film

[0175] 50 parts by mass of "Aronix UV-3701" (hereinafter referred to as UV-3701) manufactured by Toagosei Co., Ltd., which is a UV curable resin for hard coat, was mixed into 100 parts by mass of the above fine particle dispersion A to prepare a fine particle coating solution. This fine particle coating solution was coated on a PET film (HPE-50 manufactured by Teijin Limited) using a bar coater to form a coating film.

[0176] It should be noted that the same PET film was also used in other examples and comparative examples.

[0177] Then, the PET film provided with the coating film was dried at 80°C for 60 seconds to evaporate the solvent, and then cured with a high-pressure mercury lamp to produce the fine particle dispersion film of Example 1 (hereinafter simply referred to as "fine particle dispersion film A") provided with a coating film containing infrared absorption material fine particles (composite tungsten oxide fine particles) and Fe2O3 fine particles.

[0178] (2-2) Optical properties of the fine particle dispersion film

[0179] In the fine particle dispersion film A of Example 1, the fine particle concentration of the above-mentioned fine particle coating liquid and the film thickness of the coating film were adjusted. According to the transmittance curve of the fine particle dispersion film A of Example 1 measured in such a manner that the transmittance at a wavelength of 1000 nm was less than 10%, the average value of the transmittance under the condition of UV-A (wavelength 315 - 400 nm) was 17.2%, the visible light transmittance was 63.1%, the solar radiation (ST) transmittance was 32.4%, the a* value in the CIE1976L*a*b* color space was -3.4, the b* value was 15.0, and the c* value was 15.3.

[0180] The measurement results of the fine particle dispersion film A of Example 1 are shown in Table 1-1, Table 1-2, and Table 1-3.

[0181] (3) Fine particle dispersible tablets

[0182] (3-1) Manufacture of fine particle dispersible tablets

[0183] The above-mentioned dispersant a was further added to the fine particle dispersion liquid A, and after preparation in such a manner that the mass ratio of the dispersant a to the composite tungsten oxide fine particles became [dispersant a / composite tungsten oxide fine particles] = 3, MIBK was removed from the fine particle dispersion liquid A using a spray dryer to obtain a fine particle dispersion powder (hereinafter, simply referred to as "fine particle dispersion powder A").

[0184] Then, the above-mentioned fine particle dispersion powder A was added to a polycarbonate resin as a thermoplastic resin in such a manner that the transmittance of the manufactured fine particle dispersible tablet (2.0 mm thick) at a wavelength of 1000 nm was less than 10% to prepare a composition for manufacturing a fine particle dispersible tablet.

[0185] The composition for manufacturing a fine particle dispersible tablet prepared was kneaded at 280°C using a twin-screw extruder, extruded from a T-die, and formed into a 2.0 mm thick sheet by a calender roll method to obtain the fine particle dispersible tablet of Example 1 (hereinafter, simply referred to as "fine particle dispersible tablet A").

[0186] (3-2) Optical properties of fine particle dispersible tablets

[0187] According to the transmittance curve of the fine particle dispersible tablet A of Example 1, the average value of the transmittance under the condition of UV-A (wavelength 315 - 400 nm) was 17.0%, the visible light transmittance was 63.7%, the solar radiation (ST) transmittance was 32.5%, the a* value in the CIE1976L*a*b* color space was -3.4, the b* value was 14.9, and the c* value was 15.3.

[0188] The measurement results of the fine particle dispersible tablet A of Example 1 are shown in Table 1-1, Table 1-2, and Table 1-3.

[0189] (4) Laminated glass sheet

[0190] (4-1) Manufacture of infrared absorption film sandwiched between two glass sheets

[0191] Triethylene glycol di-2-ethylbutyrate as a plasticizer was added to polyvinyl butyral resin to prepare a mixture in such a manner that the mass ratio of polyvinyl butyral resin to plasticizer was [polyvinyl butyral resin / plasticizer] = 100 / 40.

[0192] A prescribed amount of the above-mentioned particulate dispersion powder A was added to the mixture to prepare a composition for manufacturing an infrared absorption film (a polyvinyl butyral film in which infrared absorption material particles and iron oxide particles are dispersed). It should be noted that the above-mentioned prescribed amount is an amount such that the transmittance of the manufactured laminated glass sheet is less than 10% under the condition of a wavelength of 1000 nm.

[0193] Then, the composition for manufacturing the infrared absorption film was kneaded and mixed at 70 °C for 30 minutes using a three-roll mixer to form a mixture. The mixture was heated to 180 °C using a die extruder, formed into a film with a thickness of about 1 mm, and wound around a roll to obtain an infrared absorption film (a polyvinyl butyral film in which infrared absorption material particles and iron oxide particles are dispersed).

[0194] (4-2) Manufacture of laminated glass sheet

[0195] The obtained infrared absorption film was cut into 10 cm × 10 cm and sandwiched between two inorganic transparent glass plates with the same size and a thickness of 3 mm to form a laminate.

[0196] Then, the laminate was placed in a rubber vacuum bag, the air inside the bag was evacuated, held at 90 °C for 30 minutes, returned to room temperature, and taken out of the bag.

[0197] Then, the laminate was placed in an autoclave device and pressurized and heated at a pressure of 12 kg / cm 2 and a temperature of 140 °C for 20 minutes to produce the laminated glass sheet of Example 1 (hereinafter, simply referred to as "laminated glass sheet A").

[0198] (4-3) Optical properties of laminated glass sheet

[0199] According to the transmittance curve of the laminated glass sheet A of Example 1, the average value of the transmittance under the condition of UV-A (wavelength 315 - 400 nm) was 15.2%, the visible light transmittance was 62.7%, the solar radiation (ST) transmittance was 30.9%, the a* value in the CIE1976L*a*b* color space was -4.7, the b* value was 15.0, and the c* value was 15.7.

[0200] The measurement results of the laminated glass sheet A of Example 1 are shown in Tables 1-1, 1-2, and 1-3.

[0201] [Example 2]

[0202] (1) Infrared absorption material particle dispersion liquid

[0203] (1-1) Preparation of infrared absorption material particle dispersion liquid

[0204] The above dispersion liquid A (the composite tungsten oxide particle dispersion liquid of Example 1, the same hereinafter) and dispersion liquid a (the Fe2O3 particle dispersion liquid of Example 1, the same hereinafter) were mixed so that the mass ratio of Fe2O3 particles to composite tungsten oxide particles was [Fe2O3 particles / composite tungsten oxide particles] = 0.03, and the infrared absorption material particle dispersion liquid of Example 2 (hereinafter, simply referred to as "particle dispersion liquid B") was prepared.

[0205] (1-2) Optical properties of infrared absorption material particle dispersion liquid

[0206] The particle dispersion liquid B of Example 2 was appropriately diluted with MIBK and placed in a rectangular container with a thickness of 10 mm, and the spectral transmittance was measured.

[0207] According to the transmittance curve of the particle dispersion liquid B measured by adjusting the dilution rate so that the transmittance at a wavelength of 1000 nm is less than 10%, the average value of the transmittance under the condition of UV-A (wavelength 315-400 nm) is 42.9%, the visible light transmittance is 78.1%, the solar radiation (ST) transmittance is 41.4%, the a* value in the CIE1976L*a*b* color space is -4.9, the b* value is 0.9, and the c* value is 5.0.

[0208] The measurement results of the particle dispersion liquid B of Example 2 are shown in Table 1-1, Table 1-2, and Table 1-3.

[0209] (2) Particle dispersion film

[0210] (2-1) Preparation of particle dispersion film

[0211] Except for using the above particle dispersion liquid B, the particle dispersion film of Example 2 (hereinafter, simply referred to as "particle dispersion film B") was prepared in the same manner as in Example 1.

[0212] (2-2) Optical properties of particle dispersion film

[0213] In the particulate dispersion film B of Example 2, the transmittance curve of the particulate dispersion film B of Example 2 measured by adjusting the particulate concentration of the particulate coating liquid and the film thickness of the coating film so that the transmittance at a wavelength of 1000 nm is less than 10% has an average transmittance of 34.5% under UV-A (wavelength 315 - 400 nm) conditions, a visible light transmittance of 69.7%, a solar radiation (ST) transmittance of 36.8%, an a* value of -4.8, a b* value of 1.5, and a c* value of 5.0 in the CIE1976L*a*b* color space.

[0214] The measurement results of the particulate dispersion film B of Example 2 are shown in Table 1-1, Table 1-2, and Table 1-3.

[0215] (3) Particulate dispersible tablets

[0216] (3-1) Manufacture of particulate dispersible tablets

[0217] Except for further adding the above dispersant a to the particulate dispersion liquid B, the particulate dispersion powder of Example 2 (hereinafter, simply referred to as "particulate dispersion powder B") was obtained in the same manner as in Example 1.

[0218] Then, the above particulate dispersion powder B was added to the polycarbonate resin so that the transmittance of the manufactured particulate dispersible tablet (2.0 mm thick) at a wavelength of 1000 nm was less than 10%. Otherwise, in the same manner as in Example 1, the particulate dispersible tablet of Example 2 (hereinafter, simply referred to as "particulate dispersible tablet B") was obtained.

[0219] (3-2) Optical properties of particulate dispersible tablets

[0220] According to the transmittance curve of the particulate dispersible tablet B of Example 2, the average transmittance under UV-A (wavelength 315 - 400 nm) conditions is 33.9%, the visible light transmittance is 70.3%, the solar radiation (ST) transmittance is 37.0%, the a* value in the CIE1976L*a*b* color space is -4.8, the b* value is 1.4, and the c* value is 5.0.

[0221] The measurement results of the particulate dispersible tablet B of Example 2 are shown in Table 1-1, Table 1-2, and Table 1-3.

[0222] (4) Laminated glass sheets

[0223] (4-1) Manufacture of laminated glass sheets

[0224] To the mixture of Example 1 prepared such that the mass ratio of polyvinyl butyral resin to plasticizer is [polyvinyl butyral resin / plasticizer]=100 / 40, the above-mentioned particulate dispersion powder B was added, and in other respects, an infrared absorption film (a polyvinyl butyral film in which infrared absorption material particles and iron oxide particles are dispersed) was produced in the same manner as in Example 1, and this infrared absorption film was used. In addition, a laminated glass sheet of Example 2 (hereinafter simply referred to as "laminated glass sheet B") was produced in the same manner as in Example 1.

[0225] (4-2) Optical properties of the laminated glass sheet

[0226] According to the transmittance curve of the laminated glass sheet B of Example 2, the average value of the transmittance under the condition of UV-A (wavelength 315 - 400 nm) is 30.2%, the visible light transmittance is 69.2%, the solar radiation (ST) transmittance is 35.2%, the a* value in the CIE1976L*a*b* color space is -6.2, the b* value is 1.9, and the c* value is 6.5.

[0227] The measurement results of the laminated glass sheet B of Example 2 are shown in Table 1-1, Table 1-2, and Table 1-3.

[0228] [Comparative Example 1]

[0229] (1) Infrared absorption material particle dispersion liquid

[0230] (1-1) Production of the infrared absorption material particle dispersion liquid

[0231] The above-mentioned dispersion liquid A and dispersion liquid a were mixed such that the mass ratio of Fe2O3 particles to composite tungsten oxide particles is [Fe2O3 particles / composite tungsten oxide particles]=0.2 to produce the infrared absorption material particle dispersion liquid of Comparative Example 1 (hereinafter simply referred to as "particle dispersion liquid C").

[0232] (1-2) Optical properties of the infrared absorption material particle dispersion liquid

[0233] The particle dispersion liquid C of Comparative Example 1 was appropriately diluted with MIBK and placed in a rectangular container with a thickness of 10 mm, and the spectral transmittance was measured.

[0234] According to the transmittance curve of the particle dispersion liquid C measured by adjusting the dilution rate such that the transmittance under the condition of a wavelength of 1000 nm is less than 10%, the average value of the transmittance under the condition of UV-A (wavelength 315 - 400 nm) is 5.3%, the visible light transmittance is 60.5%, the solar radiation (ST) transmittance is 30.9%, the a* value in the CIE1976L*a*b* color space is 2.1, the b* value is 37.1, and the c* value is 37.2.

[0235] The measurement results of the fine particle dispersion liquid C of Comparative Example 1 are shown in Tables 1-1, 1-2, and 1-3.

[0236] (2) Fine particle dispersion film

[0237] (2-1) Production of fine particle dispersion film

[0238] Except for using the above-mentioned fine particle dispersion liquid C, in the same manner as in Example 1, a fine particle dispersion film of Comparative Example 1 (hereinafter, simply referred to as "fine particle dispersion film C") was produced.

[0239] (2-2) Optical properties of fine particle dispersion film

[0240] In the fine particle dispersion film C of Comparative Example 1, according to the transmittance curve of the fine particle dispersion film C of Comparative Example 1 measured by adjusting the fine particle concentration of the fine particle coating liquid and the film thickness of the coating film so that the transmittance at a wavelength of 1000 nm is less than 10%, the average value of the transmittance under the condition of UV-A (wavelength 315 - 400 nm) is 4.3%, the visible light transmittance is 54.0%, the solar radiation (ST) transmittance is 27.6%, the a* value in the CIE1976L*a*b* color space is 2.1, the b* value is 36.2, and the c* value is 36.3.

[0241] The measurement results of the fine particle dispersion film C of Comparative Example 1 are shown in Tables 1-1, 1-2, and 1-3.

[0242] (3) Fine particle dispersible tablets

[0243] (3-1) Production of fine particle dispersible tablets

[0244] Except for further adding the above-mentioned dispersant a to the fine particle dispersion liquid C, in the same manner as in Example 1, a fine particle dispersion powder of Comparative Example 1 (hereinafter, simply referred to as "fine particle dispersion powder C") was obtained.

[0245] Then, the above-mentioned fine particle dispersion powder C was added to the polycarbonate resin so that the transmittance of the produced fine particle dispersible tablets (2.0 mm thick) at a wavelength of 1000 nm was less than 10%. Except for this, in the same manner as in Example 1, a fine particle dispersible tablet of Comparative Example 1 (hereinafter, simply referred to as "fine particle dispersible tablet C") was obtained.

[0246] (3-2) Optical properties of fine particle dispersible tablets

[0247] According to the transmittance curve of the fine particle dispersible tablet C of Comparative Example 1, the average value of the transmittance under the condition of UV-A (wavelength 315 - 400 nm) is 4.2%, the visible light transmittance is 54.5%, the solar radiation (ST) transmittance is 27.7%, the a* value in the CIE1976L*a*b* color space is 2.1, the b* value is 36.2, and the c* value is 36.3.

[0248] The measurement results of the fine particle dispersible tablets C of Comparative Example 1 are shown in Tables 1-1, 1-2, and 1-3.

[0249] (4) Laminated glass sheet

[0250] (4-1) Manufacture of laminated glass sheet

[0251] The above fine particle dispersion powder C was added to the mixture of Example 1 prepared such that the mass ratio of polyvinyl butyral resin to plasticizer was [polyvinyl butyral resin / plasticizer] = 100 / 40. Except for this, an infrared absorption film (a polyvinyl butyral film in which infrared absorption material fine particles and iron oxide fine particles are dispersed) was manufactured in the same manner as in Example 1. And, using this infrared absorption film, except for this, in the same manner as in Example 1, a laminated glass sheet of Comparative Example 1 (hereinafter, simply referred to as "laminated glass sheet C") was produced.

[0252] (4-2) Optical properties of laminated glass sheet

[0253] According to the transmittance curve of the laminated glass sheet C of Comparative Example 1, the average value of the transmittance under the condition of UV-A (wavelength 315 - 400 nm) was 3.8%, the visible light transmittance was 53.6%, the solar radiation (ST) transmittance was 26.2%, the a* value in the CIE1976L*a*b* color space was 0.9, the b* value was 36.2, and the c* value was 36.2.

[0254] The measurement results of the laminated glass sheet C of Comparative Example 1 are shown in Tables 1-1, 1-2, and 1-3.

[0255] [Comparative Example 2]

[0256] (1) Infrared absorption material fine particle dispersion liquid

[0257] (1-1) Manufacture of infrared absorption material fine particle dispersion liquid

[0258] An infrared absorption material fine particle dispersion liquid of Comparative Example 2 (hereinafter, simply referred to as "fine particle dispersion liquid D") in which the mass ratio of Fe2O3 fine particles to composite tungsten oxide fine particles was [Fe2O3 fine particles / composite tungsten oxide fine particles] = 0.0, that is, composed only of dispersion liquid A without mixing dispersion liquid a, was manufactured.

[0259] (1-2) Optical properties of infrared absorption material fine particle dispersion liquid

[0260] The fine particle dispersion liquid D of Comparative Example 2 was appropriately diluted with MIBK and placed in a rectangular container with a thickness of 10 mm, and the spectral transmittance was measured.

[0261] The transmittance curve of the particulate dispersion D measured by adjusting the dilution rate so that the transmittance at a wavelength of 1000 nm is less than 10% has an average transmittance of 56.6% under UV-A (wavelength 315 - 400 nm) conditions, a visible light transmittance of 81.3%, a solar radiation (ST) transmittance of 44.1%, an a* value of -4.8, a b* value of -4.8, and a c* value of 6.8 in the CIE1976L*a*b* color space.

[0262] The measurement results of the particulate dispersion D of Comparative Example 2 are shown in Table 1-1, Table 1-2, and Table 1-3.

[0263] (2) Particulate dispersion film

[0264] (2-1) Fabrication of particulate dispersion film

[0265] Except for using the above particulate dispersion D, a particulate dispersion film of Comparative Example 2 (hereinafter simply referred to as "particulate dispersion film D") was fabricated in the same manner as in Example 1.

[0266] (2-2) Optical properties of particulate dispersion film

[0267] In the particulate dispersion film D of Comparative Example 2, the transmittance curve of the particulate dispersion film D of Comparative Example 2 measured by adjusting the particulate concentration of the particulate coating solution and the film thickness of the coating film so that the transmittance at a wavelength of 1000 nm becomes less than 10% has an average transmittance of 45.3% under UV-A (wavelength 315 - 400 nm) conditions, a visible light transmittance of 72.5%, a solar radiation (ST) transmittance of 39.1%, an a* value of -4.7, a b* value of -3.9, and a c* value of 6.1 in the CIE1976L*a*b* color space.

[0268] The measurement results of the particulate dispersion film D of Comparative Example 2 are shown in Table 1-1, Table 1-2, and Table 1-3.

[0269] (3) Particulate dispersible tablets

[0270] (3-1) Fabrication of particulate dispersible tablets

[0271] Except for further adding the above dispersant a to the particulate dispersion D, a particulate dispersion powder of Comparative Example 2 (hereinafter simply referred to as "particulate dispersion powder D") was obtained in the same manner as in Example 1.

[0272] Then, the above particulate dispersion powder D was added to the polycarbonate resin so that the transmittance of the fabricated particulate dispersible tablets (2.0 mm thick) at a wavelength of 1000 nm becomes less than 10%. Except for this, a particulate dispersible tablet of Comparative Example 2 (hereinafter simply referred to as "particulate dispersible tablet D") was obtained in the same manner as in Example 1.

[0273] (3-2) Optical properties of the particulate dispersible tablets

[0274] According to the transmittance curve of the particulate dispersible tablet D of Comparative Example 2, the average value of the transmittance under the condition of UV-A (wavelength 315 - 400 nm) is 44.5%, the visible light transmittance is 73.1%, the solar radiation (ST) transmittance is 39.3%, the a* value in the CIE1976L*a*b* color space is -4.8, the b* value is -4.0, and the c* value is 6.2.

[0275] The measurement results of the particulate dispersible tablet D of Comparative Example 2 are shown in Tables 1-1, 1-2, and 1-3.

[0276] (4) Laminated glass sheet

[0277] (4-1) Manufacture of the laminated glass sheet

[0278] To the mixture of Example 1 prepared such that the mass ratio of polyvinyl butyral resin to plasticizer is [polyvinyl butyral resin / plasticizer] = 100 / 40, the above-mentioned particulate dispersion powder D was added. Except for this, an infrared absorption film (a polyvinyl butyral film dispersed with infrared absorption material particles and containing no iron oxide particles) was manufactured in the same manner as in Example 1. And, using this infrared absorption film, a laminated glass sheet of Comparative Example 2 (hereinafter, simply referred to as "laminated glass sheet D") was produced in the same manner as in Example 1.

[0279] (4-2) Optical properties of the laminated glass sheet

[0280] According to the transmittance curve of the laminated glass sheet D of Comparative Example 2, the average value of the transmittance under the condition of UV-A (wavelength 315 - 400 nm) is 39.6%, the visible light transmittance is 72.1%, the solar radiation (ST) transmittance is 37.5%, the a* value in the CIE1976L*a*b* color space is -6.2, the b* value is -3.4, and the c* value is 7.1.

[0281] The measurement results of the laminated glass sheet D of Comparative Example 2 are shown in Tables 1-1, 1-2, and 1-3.

[0282] [Comparative Example 3]

[0283] (1) Infrared absorption material particle dispersion liquid

[0284] (1-1) Manufacture of the infrared absorption material particle dispersion liquid

[0285] The above dispersion A and dispersion a were mixed such that the mass ratio of Fe2O3 fine particles to composite tungsten oxide fine particles was [Fe2O3 fine particles / composite tungsten oxide fine particles] = 0.5 to produce the infrared absorption material fine particle dispersion of Comparative Example 3 (hereinafter simply referred to as "fine particle dispersion E").

[0286] (1-2) Optical properties of the infrared absorption material fine particle dispersion

[0287] The fine particle dispersion E of Comparative Example 3 was appropriately diluted with MIBK and placed in a rectangular container with a thickness of 10 mm, and the spectral transmittance was measured.

[0288] According to the transmittance curve of the fine particle dispersion E measured by adjusting the dilution rate such that the transmittance at a wavelength of 1000 nm was less than 10%, the average value of the transmittance under UV-A (wavelength 315 - 400 nm) conditions was 0.5%, the visible light transmittance was 48.6%, the solar radiation (ST) transmittance was 26.4%, the a* value in the CIE1976L*a*b* color space was 13.5, the b* value was 61.5, and the c* value was 63.0.

[0289] The measurement results of the fine particle dispersion E of Comparative Example 3 were recorded in Tables 1-1, 1-2, and 1-3.

[0290] (2) Fine particle dispersion film

[0291] (2-1) Fabrication of the fine particle dispersion film

[0292] Except for using the above fine particle dispersion E, a fine particle dispersion film of Comparative Example 3 (hereinafter simply referred to as "fine particle dispersion film E") was produced in the same manner as in Example 1.

[0293] (2-2) Optical properties of the fine particle dispersion film

[0294] In the fine particle dispersion film E of Comparative Example 3, according to the transmittance curve of the fine particle dispersion film E of Comparative Example 3 measured by adjusting the fine particle concentration of the fine particle coating liquid, the film thickness of the coating film, and making the transmittance at a wavelength of 1000 nm less than 10%, the average value of the transmittance under UV-A (wavelength 315 - 400 nm) conditions was 0.4%, the visible light transmittance was 43.4%, the solar radiation (ST) transmittance was 23.7%, the a* value in the CIE1976L*a*b* color space was 13.2, the b* value was 59.5, and the c* value was 61.0.

[0295] The measurement results of the fine particle dispersion film E of Comparative Example 3 were recorded in Tables 1-1, 1-2, and 1-3.

[0296] (3) Fine particle dispersible tablets

[0297] (3-1) Manufacture of particulate dispersible tablets

[0298] Except for further adding the above dispersant a to the particulate dispersion E, in the same manner as in Example 1, particulate dispersion powder of Comparative Example 3 (hereinafter, simply referred to as "particulate dispersion powder E") was obtained.

[0299] Then, to the polycarbonate resin, the above particulate dispersion powder E was added such that the transmittance of the manufactured particulate dispersible tablet (2.0 mm thick) at a wavelength of 1000 nm was less than 10%. Except for this, in the same manner as in Example 1, particulate dispersible tablets of Comparative Example 3 (hereinafter, simply referred to as "particulate dispersible tablets E") were obtained.

[0300] (3-2) Optical properties of particulate dispersible tablets

[0301] According to the transmittance curve of the particulate dispersible tablets E of Comparative Example 3, the average value of the transmittance under UV-A (wavelength 315 - 400 nm) conditions was 0.4%, the visible light transmittance was 43.8%, the solar radiation (ST) transmittance was 23.7%, the a* value in the CIE1976L*a*b* color space was 13.1, the b* value was 59.6, and the c* value was 61.1.

[0302] The measurement results of the particulate dispersible tablets E of Comparative Example 3 are shown in Tables 1-1, 1-2, and 1-3.

[0303] (4) Laminated glass sheet

[0304] (4-1) Manufacture of laminated glass sheet

[0305] To the mixture of Example 1 prepared such that the mass ratio of polyvinyl butyral resin to plasticizer was [polyvinyl butyral resin / plasticizer] = 100 / 40, the above particulate dispersion powder E was added. Except for this, in the same manner as in Example 1, an infrared absorption film (a polyvinyl butyral film in which infrared absorption material particles and iron oxide particles are dispersed) was manufactured, and using this infrared absorption film, in the same manner as in Example 1, laminated glass sheets of Comparative Example 3 (hereinafter, simply referred to as "laminated glass sheets E") were produced.

[0306] (4-2) Optical properties of laminated glass sheet

[0307] According to the transmittance curve of the laminated glass sheets E of Comparative Example 3, the average value of the transmittance under UV-A (wavelength 315 - 400 nm) conditions was 0.4%, the visible light transmittance was 43.0%, the solar radiation (ST) transmittance was 22.2%, the a* value in the CIE1976L*a*b* color space was 12.0, the b* value was 59.3, and the c* value was 60.5.

[0308] The measurement results of the laminated glass sheet E of Comparative Example 3 are shown in Tables 1-1, 1-2, and 1-3.

[0309] Table 1-1

[0310]

[0311] Table 1-2 Solar transmittance ((ST (film)): According to JIS A5759

[0312]

[0313] Table 1-3

[0314]

[0315] [Confirmation]

[0316] (1) Examples 1-2

[0317] (1-1) Visible light transmittance

[0318] The visible light transmittance of the infrared absorption material fine particle dispersions (fine particle dispersion films, fine particle dispersion tablets, laminated glass sheets) of Examples 1-2 was in the range of 62.7% (laminated glass sheet A of Example 1) to 70.3% (fine particle dispersion tablet B of Example 2), and it was confirmed that the infrared absorption material fine particle dispersions of Examples 1-2 had high light transmittance in the visible light region.

[0319] (1-2) Solar (ST) transmittance

[0320] The solar (ST) transmittance of the infrared absorption material fine particle dispersions (fine particle dispersion films, fine particle dispersion tablets, laminated glass sheets) of Examples 1-2 was in the range of 30.9% (laminated glass sheet A of Example 1) to 37.0% (fine particle dispersion tablet B of Example 2), and it was also confirmed that the infrared absorption material fine particle dispersions of Examples 1-2 had absorbency in the near-infrared region.

[0321] (1-3) a*, b*, and c* values in the CIE1976L*a*b* color space

[0322] When evaluating the hue of the infrared absorption material fine particle dispersions (fine particle dispersion films, fine particle dispersion tablets, laminated glass sheets) of Examples 1-2 by the L*a*b* color system, a* was in the range of -20 or more and 0 or less, and b* was in the range of -3.0 or more and 15 or less, and it was confirmed that the hue of the infrared absorption material fine particle dispersions of Examples 1-2 was adjusted to a neutral color between the blue system and the bronze system.

[0323] In particular, for the infrared absorption material particle dispersion (particle dispersion film, particle dispersion tablet, laminated glass sheet) of Example 2 in which the mass ratio of iron oxide (Fe2O3) particles to composite tungsten oxide particles [iron oxide (Fe2O3) particles / composite tungsten oxide particles] is set to less than 0.1, when evaluated by the L*a*b* color system, a* is in the range of -20 or more and -3.5 or less, b* is in the range of -3.0 or more and 10 or less, and c* is in the range of 10 or less. Therefore, it was confirmed that the color was adjusted to a neutral color with excellent chroma between the blue and bronze colors.

[0324] (2) Comparative Examples 1 to 3

[0325] (2-1) Visible light transmittance

[0326] The visible light transmittance of the infrared absorption material particle dispersions (particle dispersion films, particle dispersion tablets, laminated glass sheets) of Comparative Examples 1 to 3 was in the range of 43.0% (laminated glass sheet E of Comparative Example 3) to 73.1% (particle dispersion tablet D of Comparative Example 2). It was confirmed that the infrared absorption material particle dispersions of Comparative Examples 1 to 3 had substantially the same light transmittance in the visible light region as that of the Examples.

[0327] (2-2) Solar radiation (ST) transmittance

[0328] The solar radiation (ST) transmittance of the infrared absorption material particle dispersions (particle dispersion films, particle dispersion tablets, laminated glass sheets) of Comparative Examples 1 to 3 was in the range of 22.2% (laminated glass sheet E of Comparative Example 3) to 39.3% (particle dispersion tablet D of Comparative Example 2). It was also confirmed that the infrared absorption material particle dispersions of Comparative Examples 1 to 3 also had absorbability in the near-infrared region.

[0329] (2-3) a*, b*, and c* values in the CIE1976L*a*b* color space

[0330] (2-3-1) For the hues of the infrared absorption material particle dispersions (particle dispersion films, particle dispersion tablets, laminated glass sheets) of Comparative Examples 1 and 3, when evaluated by the L*a*b* color system, both a* and b* were on the "positive" side, showing a bronze color. It was confirmed that the color was not adjusted to a neutral color between the blue and bronze colors.

[0331] (2-3-2) For the hues of the infrared absorption material particle dispersions (particle dispersion films, particle dispersion tablets, laminated glass sheets) of Comparative Example 2, when evaluated by the L*a*b* color system, both a* and b* were on the "negative" side, showing the blue color brought by the composite tungsten oxide particles. It was confirmed that the color was not adjusted to a neutral color between the blue and bronze colors.

[0332] Industrial applicability

[0333] The infrared absorption material particle dispersion liquid and the infrared absorption material particle dispersion body according to the present invention have high light transmittance in the visible light region, absorption in the near-infrared region, and can be adjusted to a neutral color between blue and bronze, and thus have industrial applicability as window materials for automobiles, electric trains, buildings, etc.

Claims

1. An infrared absorption material particle dispersion liquid, which is an infrared absorption material particle dispersion liquid containing infrared absorption material particles and iron oxide Fe2O3 particles in a liquid medium, characterized in that The infrared absorption material particles are composed of composite tungsten oxide particles represented by the general formula M Y WO Z and having a hexagonal crystal structure, wherein the M element is one or more elements selected from H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, W is tungsten, O is oxygen, 0.001 ≤ Y ≤ 1.0, 2.2 ≤ Z ≤ 3.0, the mass ratio of iron oxide Fe2O3 particles to composite tungsten oxide particles in the liquid medium, that is, iron oxide Fe2O3 particles / composite tungsten oxide particles, is 0.01 or more and 0.1 or less.

2. The infrared absorption material particle dispersion liquid according to claim 1, wherein The particle size of the composite tungsten oxide particles is 1 nm or more and 200 nm or less.

3. The infrared absorption material particle dispersion liquid according to claim 1, characterized in that, The particle size of the iron oxide Fe2O3 particles is 1 nm or more and 200 nm or less.

4. The infrared absorption material particle dispersion liquid according to claim 1, wherein The liquid medium is one or a mixture of two or more selected from water, organic solvents, vegetable oils, compounds derived from vegetable oils, petroleum solvents, oils and fats, liquid resins, and plasticizers for liquid plastics.

5. The infrared absorption material particle dispersion liquid according to any one of claims 1 to 4, wherein When evaluating the infrared absorption material particle dispersion liquid by the L*a*b* color system, a* is -20 or more and 0 or less, and b* is -3.5 or more and 15 or less.

6. An infrared absorption material particle dispersion, which is an infrared absorption material particle dispersion containing infrared absorption material particles and iron oxide Fe2O3 particles in a solid medium, characterized in that The infrared absorption material particles are composed of composite tungsten oxide particles represented by the general formula M Y WO Z and having a hexagonal crystal structure, wherein the M element is one or more elements selected from H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, W is tungsten, O is oxygen, 0.001 ≤ Y ≤ 1.0, 2.2 ≤ Z ≤ 3.0, the mass ratio of iron oxide Fe2O3 particles to composite tungsten oxide particles in the solid medium, that is, iron oxide Fe2O3 particles / composite tungsten oxide particles, is 0.01 or more and 0.1 or less.

7. The infrared absorption material particle dispersion according to claim 6, characterized in that, The particle size of the composite tungsten oxide particles is 1 nm or more and 200 nm or less.

8. The infrared absorption material particle dispersion according to claim 6, characterized in that, The particle size of the iron oxide Fe2O3 particles is 1 nm or more and 200 nm or less.

9. The infrared absorption material particle dispersion according to claim 6, characterized in that, The solid medium is a resin or a metal alkoxide.

10. The infrared absorption material particle dispersion according to any one of claims 6 to 9, characterized in that When evaluating the infrared absorption material particle dispersion by the L*a*b* color system, a* is -20 or more and 0 or less, and b* is -3.0 or more and 15 or less.

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