WO2019093524A1 - 表面処理赤外線吸収微粒子、表面処理赤外線吸収微粒子粉末、当該表面処理赤外線吸収微粒子を用いた赤外線吸収微粒子分散液、赤外線吸収微粒子分散体およびそれらの製造方法 - Google Patents
表面処理赤外線吸収微粒子、表面処理赤外線吸収微粒子粉末、当該表面処理赤外線吸収微粒子を用いた赤外線吸収微粒子分散液、赤外線吸収微粒子分散体およびそれらの製造方法 Download PDFInfo
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- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
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- C08K5/527—Cyclic esters
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- C08K9/00—Use of pretreated ingredients
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/063—Coating
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- C09K3/00—Materials not provided for elsewhere
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/003—Light absorbing elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G02B5/24—Liquid filters
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2258—Oxides; Hydroxides of metals of tungsten
Definitions
- the present invention is an infrared-absorbing fine particle which transmits light in the visible light region and absorbs light in the infrared light region, wherein the surface of the fine particle is coated with a predetermined coating film, and the surface-treated infrared-absorbing fine particle
- the present invention relates to a surface-treated infrared-absorbing fine particle powder containing surface-treated infrared-absorbing fine particles, an infrared-absorbing fine particle dispersion using the surface-treated infrared-absorbing fine particles, an infrared-absorbing fine particle dispersion, and methods for producing them.
- the light shielding member for example, as a light shielding member used for a window material etc., inorganic pigments such as carbon black and titanium black having absorption characteristics from visible light region to near infrared region, and only visible light region Further, a light shielding film containing a black pigment containing an organic pigment such as aniline black having strong absorption characteristics, and a half mirror type light shielding member on which a metal such as aluminum is vapor-deposited are proposed.
- Patent Document 1 at least one selected from the group consisting of a group IIIa, a group IVa, a group Vb, a group VIb and a group VIIb of the periodic table as a first layer on the transparent glass substrate from the substrate side.
- a composite tungsten oxide film containing metal ions is provided, a transparent dielectric film is provided as a second layer on the first layer, and a group IIIa, IVa, Vb of the periodic table is provided on the second layer as a third layer.
- a composite tungsten oxide film containing at least one metal ion selected from the group consisting of group VIb and group VIIb, and the refractive index of the transparent dielectric film of the second layer being the first layer and the first layer By lowering the refractive index of the composite tungsten oxide film of the third layer, it is possible to preferably use an infrared ray shielding material which can be suitably used in a portion where high visible light transmittance and good infrared ray shielding performance are required. Vinegar has been proposed.
- Patent Document 2 a first dielectric film is provided as a first layer on a transparent glass substrate from the substrate side by the same method as Patent Document 1, and tungsten oxide is provided as a second layer on the first layer.
- An infrared blocking glass has been proposed in which a film is provided and a second dielectric film is provided as a third layer on the second layer.
- Patent Document 3 a composite tungsten oxide film containing the same metal element as in Patent Document 1 is provided as a first layer from the substrate side on a transparent substrate by the same method as in Patent Document 1, and the first layer A heat ray blocking glass having a transparent dielectric film provided thereon as a second layer has been proposed.
- Patent Document 4 tungsten trioxide (WO 3 ), molybdenum trioxide (MoO 3 ), niobium pentoxide (Nb 2 O 5 ), tantalum pentoxide containing an additive element such as hydrogen, lithium, sodium or potassium, etc.
- a metal oxide film selected from one or more of (Ta 2 O 5 ), vanadium pentoxide (V 2 O 5 ) and vanadium dioxide (VO 2 ) is coated by a CVD method or a spray method and is thermally heated at about 250 ° C.
- a solar control glass sheet having a solar light shielding property formed by being decomposed has been proposed.
- Patent Document 5 proposes a solar light-modulating light insulation material using tungsten oxide obtained by hydrolyzing tungstic acid, and adding an organic polymer having a specific structure of polyvinyl pyrrolidone to the tungsten oxide. ing.
- the solar light is irradiated with sunlight, the ultraviolet light in the light is absorbed by tungsten oxide to generate excited electrons and holes, and the amount of appearance of pentavalent tungsten is remarkable with a small amount of ultraviolet light.
- the color reaction is accelerated to increase, and the color density increases accordingly.
- pentavalent tungsten is extremely rapidly oxidized to hexavalent to accelerate the decoloring reaction.
- the coloration and decoloring reaction to sunlight is fast, an absorption peak appears at a wavelength of 1250 nm in the near-infrared region at the time of coloring, and it is possible to block the near-infrared light of sunlight It has been proposed that a thermal insulation material be obtained.
- Patent Document 6 the present inventors dissolve tungsten hexachloride in alcohol and evaporate the medium as it is or heat it to reflux, then evaporate the medium and then heat it at 100 ° C to 500 ° C. It has been disclosed to obtain a tungsten oxide fine particle powder comprising tungsten trioxide or its hydrate or a mixture of both. The present inventors have also disclosed that an electrochromic device can be obtained by using the tungsten oxide fine particles, that the optical characteristics of the film can be changed when a multilayer laminate is formed and protons are introduced into the film.
- Patent Document 7 uses ammonium meta-tungstate and various water-soluble metal salts as raw materials, heats the dried product of the mixed aqueous solution at a heating temperature of about 300 to 700 ° C., and is inactive to this heating MxWO 3 (M; metal element such as alkali, alkaline earth, rare earth, etc.) by supplying hydrogen gas added with gas (additional amount: about 50 vol% or more) or steam (additional amount: about 15 vol% or less)
- MxWO 3 M
- a method has been proposed for producing various tungsten bronzes represented by ⁇ x ⁇ 1).
- methods for producing various tungsten bronze-coated composites by performing the same operation on a support are proposed, and use as an electrode catalyst material for fuel cells and the like is proposed.
- the inventors of the present invention are directed to an infrared shielding material fine particle dispersion in which infrared shielding material fine particles are dispersed in a medium, and excellent optical properties, conductivity and manufacturing method of the infrared shielding material fine particle dispersion in Patent Document 8. Disclosed. Among other things, the infrared shielding properties were superior to conventional shielding materials.
- the infrared shielding material fine particle is a fine particle of tungsten oxide represented by a general formula WyOz (wherein W is tungsten, O is oxygen, 2.2 ⁇ z / y ⁇ 2.999), and / or a general formula MxWyOz (Where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au) , Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be , Hf, Os, Bi, I, W is tungsten, O is oxygen, 0.001 ⁇ x / y ⁇ 1, 2.2 ⁇ z / y ⁇ 3.0) Particles of the complex tungsten oxide represented by Particle diameter
- JP-A-8-59300 Unexamined-Japanese-Patent No. 8-12378 Japanese Patent Application Laid-Open No. 8-283044 Japanese Patent Laid-Open No. 2000-119045 JP-A-9-127559 JP 2003-121884 JP-A-8-73223 WO 2005/37932 International Publication No. 2010/55570
- a solid resin is a polymer medium that is solid at room temperature, and includes polymer media other than those three-dimensionally cross-linked (sometimes referred to as "matrix resin" in the present invention).
- Patent Document 9 a tungsten oxide represented by the general formula WyOz or / and a general formula as infrared shielding fine particles having excellent water resistance and excellent infrared shielding properties.
- the infrared absorbing material is basically used outdoors because of its nature, and high weatherability is often required. And, as market demand increases year by year, further improvement of water resistance and moisture and heat resistance is required for the infrared shielding fine particles disclosed in Patent Document 9.
- the present invention has been made under the above-mentioned circumstances, and the subject of the present invention is a surface-treated infrared-absorbing fine particle having excellent moisture-heat resistance and excellent infrared-absorbing characteristics, and the surface-treated infrared-absorbing fine particle A surface-treated infrared-absorbing fine particle powder, an infrared-absorbing fine particle dispersion liquid and an infrared-absorbing fine particle dispersion using the surface-treated infrared-absorbing fine particle, and a method for producing them.
- the present inventors set the tungsten oxide microparticles and / or composite tungsten oxide microparticles having excellent optical properties as infrared absorbing microparticles, and the heat and humidity resistance and chemical stability of the infrared absorbing microparticles.
- the individual infrared ray absorbing of the individual It was considered important to coat the surface of the particles.
- the present inventors have further studied, and have conceived metal chelate compounds and metal cyclic oligomer compounds as compounds forming the coating film, which are excellent in affinity in the above-mentioned infrared absorbing fine particles. And, as a result of further research, hydrolysis products of these compounds or polymers of the hydrolysis products, which are formed when the metal chelate compound and the metal cyclic oligomer compound are hydrolyzed, are individual infrared absorptions. It was conceived to be a compound that adsorbs uniformly on the surface of fine particles and forms a strong coating film.
- the surface of tungsten oxide fine particles and / or composite tungsten oxide fine particles is a hydrolysis product of a metal chelate compound, a polymer of a hydrolysis product of a metal chelate compound, a hydrolysis product of a metal cyclic oligomer compound, a metal Infrared absorbing fine particles coated with a coating film containing one or more selected from a hydrolysis product of a cyclic oligomer compound (in the present invention, it may be described as “surface-treated infrared absorbing fine particles”). The idea is to And, it has been found that the surface-treated infrared-absorbing fine particles have excellent moisture and heat resistance.
- the surface-treated infrared-absorbing fine particles, the surface-treated infrared-absorbing fine particle powder containing the surface-treated infrared-absorbing fine particles, and the infrared-absorbing fine particle dispersion prepared by dispersing the surface-treated infrared-absorbing fine particles in an appropriate medium It has been found that the fine absorbent particle dispersion and the like are excellent in heat and humidity resistance and have excellent infrared absorption characteristics, and the present invention has been made.
- the surface of the infrared absorbing particles is 1 type selected from hydrolysis products of metal chelate compounds, polymers of hydrolysis products of metal chelate compounds, products of hydrolysis of metal cyclic oligomer compounds, polymers of hydrolysis products of metal cyclic oligomer compounds.
- the surface-treated infrared-absorbing fine particles are coated with a coating film including the above.
- the second invention is It is a surface-treated infrared-absorbing fine particle according to the first invention, wherein the film thickness of the coating film is 0.5 nm or more.
- the third invention is The surface treatment according to the first or second invention, wherein the metal chelate compound or the metal cyclic oligomer compound contains one or more metal elements selected from Al, Zr, Ti, Si and Zn. Infrared absorbing fine particles.
- the fourth invention is The metal chelate compound or the metal cyclic oligomer compound according to any one of the first to third inventions characterized in having at least one selected from an ether bond, an ester bond, an alkoxy group and an acetyl group. Surface-treated infrared absorbing fine particles.
- the fifth invention is The infrared absorbing fine particles have a general formula WyOz (wherein W is tungsten, O is oxygen, 2.2 ⁇ z / y ⁇ 2.999), or / and a general formula MxWyOz (where M is 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, Mo, Ta, Re, Be, Hf, Os, Bi, I, Yb W is tungsten, O is oxygen, and infrared absorbing fine particles represented by 0.001 ⁇ x / y ⁇ 1, 2.0 ⁇ z / y ⁇ 3.0)
- the sixth invention is A surface-treated infrared-absorbing fine particle powder comprising the surface-treated infrared-absorbing fine particle according to any of the first to fifth inventions.
- the seventh invention is It is a surface-treated infrared-absorbing fine particle powder according to the sixth invention, wherein the carbon concentration is 0.2% by mass or more and 5.0% by mass or less.
- the eighth invention is A surface-treated infrared-absorbing fine particle according to any one of the first to fifth inventions is dispersed in a predetermined liquid medium.
- the ninth invention is The infrared light according to the eighth invention, wherein the liquid medium is at least one liquid medium selected from organic solvents, fats and oils, liquid plasticizers, compounds polymerized by curing, and water. It is an absorbing particle dispersion.
- the tenth invention is A surface-treated infrared-absorbing fine particle according to any one of the first to fifth inventions is dispersed in a predetermined solid resin, and the dispersion is an infrared-absorbing fine particle dispersion.
- the eleventh invention is The solid resin is at least one resin selected from fluorocarbon resin, PET resin, acrylic resin, polyamide resin, vinyl chloride resin, polycarbonate resin, olefin resin, epoxy resin, and polyimide resin. It is an infrared rays absorption particulate dispersion given in the 10th invention.
- the twelfth invention is The infrared-absorbing fine particle dispersion according to the eighth or ninth invention, which is a dried solidified product of the infrared-absorbing fine particle dispersion according to the eighth invention.
- the thirteenth invention is Mixing infrared radiation-absorbing fine particles and water, and performing dispersion treatment to obtain a dispersion for forming a coating film using water as a medium; Adding the metal chelate compound and / or the metal cyclic oligomer compound while stirring the dispersion for forming a coating film using the water as a medium; The stirring is continued even after the addition, and the surface of the infrared absorbing fine particles is treated with a hydrolysis product of a metal chelate compound, a polymer of a hydrolysis product of a metal chelate compound, a hydrolysis product of a metal cyclic oligomer compound, Coating with at least one selected from polymers of hydrolysis products of metal cyclic oligomer compounds, and obtaining an infrare
- the fourteenth invention is Mixing the infrared absorbing fine particles and the organic solvent and performing dispersion treatment to obtain a dispersion for forming a coating film using the organic solvent as a medium; Adding the metal chelate compound or / and the metal cyclic oligomer compound and water simultaneously and in parallel while stirring the dispersion for forming a coating film using the organic solvent as a medium; The stirring is continued even after the addition, and the surface of the infrared absorbing fine particles is treated with a hydrolysis product of a metal chelate compound, a polymer of a hydrolysis product of a metal chelate compound, a hydrolysis product of a metal cyclic oligomer compound, Coating with at least one selected from polymers of hydrolysis products of metal cyclic oligomer compounds, and obtaining an organic solvent dispersion liquid of infrared absorbing fine particles; surface-treated infrared absorbing fine particles It is a manufacturing method.
- the fifteenth invention is The surface according to the thirteenth or fourteenth invention, wherein the metal chelate compound or / and the metal cyclic oligomer compound contain one or more kinds of metal elements selected from Al, Zr, Ti, Si and Zn. It is a manufacturing method of processing infrared rays absorption particulates.
- the sixteenth invention is The infrared absorbing fine particles have a general formula WyOz (wherein W is tungsten, O is oxygen, 2.2 ⁇ z / y ⁇ 2.999), or / and a general formula MxWyOz (where M is 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, Mo, Ta, Re, Be, Hf, Os, Bi, I, Yb W is tungsten, O is oxygen, and infrared absorbing fine particles represented by 0.001 ⁇ x / y ⁇ 1, 2.0 ⁇ z / y ⁇ 3.0) Described in any of the thirteenth to fifteen
- the seventeenth invention is The dispersion for forming a coating film using water as a medium according to the thirteenth, fifteenth, or sixteenth invention, or the coating film using the organic solvent according to any of the fourteenth to sixteenth inventions as a medium Removing the medium from the dispersion liquid for formation to obtain a surface-treated infrared-absorbing fine particle powder containing surface-treated infrared-absorbing fine particles, which is a method for producing a surface-treated infrared-absorbing fine particle powder.
- the eighteenth invention is The method for producing surface-treated infrared-absorbing fine particle powder according to the seventeenth invention, wherein the carbon concentration contained in the surface-treated infrared-absorbing fine particle powder is 0.2% by mass to 5.0% by mass. It is.
- the nineteenth invention is A process of adding the surface-treated infrared-absorbing fine particle powder according to the seventeenth or eighteenth invention to a predetermined medium, and dispersing the mixture.
- the twentieth invention is The dispersion for forming a coating film using water as a medium according to the thirteenth, fifteenth, or sixteenth invention, or the coating film using the organic solvent according to any of the fourteenth to sixteenth inventions as a medium And a step of replacing the medium of the forming dispersion with a predetermined medium, and a method of producing the infrared-absorbing fine particle dispersion.
- the twenty-first invention is The dispersion for forming a coating film using water as a medium according to the thirteenth, fifteenth, or sixteenth invention, or the coating film using the organic solvent according to any of the fourteenth to sixteenth inventions as a medium
- a dispersion for forming a coating film, which uses the organic solvent according to any one of the inventions 14 to 16 as a medium, is used as a dispersion of infrared absorbing fine particles, which is a method for producing an infrared absorbing fine particle dispersion.
- the twenty-second invention is An infrared-absorbing fine particle dispersion obtained by the method for producing an infrared-absorbing fine particle dispersion according to any one of the nineteenth to twenty-first inventions is coated on a predetermined substrate and dried to obtain an infrared-absorbing fine particle dispersion. It is a manufacturing method of the infrared rays absorption fine particle dispersion characterized by having a process to obtain.
- the twenty-third invention is A surface-treated infrared-absorbing fine particle powder obtained by the method of producing a surface-treated infrared-absorbing fine particle powder according to the seventeenth or eighteenth invention, or a method of manufacturing the infrared-absorbing fine particle dispersion according to any of the nineteenth to twenty-first inventions
- an infrared-absorbing fine particle dispersion having high moisture and heat resistance and excellent infrared absorption characteristics can be produced.
- FIG. 7 is a 300,000 times transmission electron micrograph of the surface-treated infrared-absorbing fine particles according to Example 1.
- the surface of the tungsten oxide fine particles and / or the composite tungsten oxide fine particles, which are infrared-absorbing fine particles is a hydrolysis product of a metal chelate compound or a hydrolysis product of a metal chelate compound
- coating films to impart moisture and heat resistance to infrared absorbing fine particles, hydrolysis product of metal chelate compound, polymer of hydrolysis product of metal chelate compound, metal cyclic oligomer compound to the surface of the fine particle.
- the coating film formed using at least one selected from the hydrolysis products of and the polymers of the hydrolysis products of metal cyclic oligomer compounds may be simply referred to as "coating films”.
- Infrared absorbing fine particles Generally, it is known that a material containing free electrons shows a reflection and absorption response to electromagnetic waves around a region of sunlight with a wavelength of 200 nm to 2600 nm by plasma vibration. It is known that when the powder of such a substance is made into particles smaller than the wavelength of light, geometric scattering in the visible light region (wavelength 380 nm to 780 nm) is reduced and transparency in the visible light region is obtained. In the present invention, “transparency” is used in the meaning of "little scattering and high transparency to light in the visible light region".
- tungsten oxide does not have effective free electrons, so it has low absorption and reflection characteristics in the infrared region, and is not effective as infrared absorbing fine particles.
- WO 3 having oxygen deficiency and a composite tungsten oxide obtained by adding a positive element such as Na to WO 3 are conductive materials and known to have free electrons. Then, analysis of single crystals or the like of materials having these free electrons suggests that free electrons respond to light in the infrared region.
- the present inventors have found that in a specific part of the composition range of tungsten and oxygen, there is a particularly effective range as infrared absorbing fine particles, and it is transparent in the visible light region and tungsten oxide having absorption in the infrared region. It was thought to be fine particles and composite tungsten oxide fine particles.
- the tungsten oxide particles and / or the composite tungsten oxide particles which are infrared absorbing particles according to the present invention (1) tungsten oxide particles, (2) composite tungsten oxide particles, (3) tungsten oxide particles And composite tungsten oxide fine particles will be described in this order.
- Tungsten oxide fine particles Tungsten oxide fine particles according to the present invention have a tungsten oxide represented by the general formula WyOz (where W is tungsten, O is oxygen, 2.2 ⁇ z / y ⁇ 2.999) Fine particles of
- the composition range of tungsten and oxygen is such that the composition ratio of oxygen to tungsten is less than 3 and the infrared absorbing fine particles are described as WyOz. It is preferable that 2 ⁇ z / y ⁇ 2.999. If the value of the z / y is 2.2 or more, it is possible to avoid the appearance of the crystal phase of WO 2 other than the purpose in the tungsten oxide, and the chemical stability as a material. As it is possible to obtain effective infrared absorbing fine particles. On the other hand, if the value of z / y is 2.999 or less, the required amount of free electrons is generated, resulting in efficient infrared-absorbing fine particles.
- the value of x / y indicating the amount of addition of the element M will be described. If the value of x / y is greater than 0.001, a sufficient amount of free electrons are generated in the composite tungsten oxide, and the desired infrared absorption effect can be obtained. Then, as the addition amount of the element M is larger, the supply amount of free electrons increases and the infrared absorption efficiency also increases, but the effect is also saturated when the value of x / y is about 1. In addition, it is preferable that the value of x / y is smaller than 1 because generation of an impurity phase in the infrared absorbing fine particles can be avoided.
- the element M is H, He, an alkali metal, an alkaline earth metal, a rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au , Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be It is preferable that it is one or more types selected from Hf, Os, Bi, I, and Yb.
- the element M is an alkali metal, an alkaline earth metal, a rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir , Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti It is more preferable that it is one or more types of elements selected from among Nb, V, Mo, Ta, and Re. And, from the viewpoint of improving the optical characteristics as infrared absorbing fine particles and weatherability, the element M is more preferably an alkaline earth metal element, a transition metal element, a 4B group element and a 5B group element.
- FIG. 1 is a schematic plan view of this hexagonal crystal structure.
- a hexagonal air gap is formed by collecting six octahedrons formed of WO 6 units indicated by reference numeral 11, and the element M indicated by reference numeral 12 is disposed in the space to form one piece.
- a unit is formed, and a large number of units of one unit are assembled to form a hexagonal crystal structure.
- the composite tungsten oxide fine particles include the unit structure described with reference to FIG.
- the composite tungsten oxide fine particles may be crystalline or amorphous.
- the present invention is not limited to the above-described elements.
- the addition amount of the additional element M is preferably 0.2 or more and 0.5 or less, more preferably 0 in the value of x / y. .33.
- the value of x / y is 0.33, it is considered that the above-described element M is disposed in all of the hexagonal voids.
- tetragonal and cubic complex tungsten oxides other than hexagonal crystals are also effective as infrared absorbing fine particles.
- the absorption position in the infrared region tends to change, and the absorption position tends to move to the long wavelength side in the order of cubic crystal ⁇ tetragonal crystal ⁇ hexagonal crystal.
- it is hexagonal, tetragonal and cubic in order of less absorption in the visible light region. Therefore, it is preferable to use a hexagonal composite tungsten oxide for applications that transmit light in the more visible light region and shield light in the more infrared region.
- the tendency of the optical characteristics described here is a rough tendency, and changes with the type of the additive element, the addition amount, and the oxygen amount, and the present invention is not limited to this.
- Tungsten Oxide Fine Particles and Composite Tungsten Oxide Fine Particles The infrared absorbing fine particles containing tungsten oxide fine particles or composite tungsten oxide fine particles according to the present invention largely absorb light in the near infrared region, particularly around a wavelength of 1000 nm. Therefore, there are many things that the transmission color tone becomes from blue to green.
- the dispersed particle diameter of the tungsten oxide fine particles or the composite tungsten oxide fine particles in the infrared absorbing fine particles can be respectively selected depending on the purpose of use.
- a particle diameter of 800 nm or less it is preferable to have a particle diameter of 800 nm or less. This is because particles smaller than 800 nm do not completely block light by scattering, and can maintain visibility in the visible light region and at the same time, can efficiently maintain transparency.
- the dispersed particle size is preferably 200 nm or less, preferably 100 nm or less.
- the reason for this is that if the dispersed particle size of the particles is small, scattering of light in the visible light region with a wavelength of 400 nm to 780 nm due to geometric or Mie scattering is reduced, resulting in an infrared absorbing film like frosted glass, It is possible to avoid losing clear transparency. That is, when the dispersed particle size is 200 nm or less, the geometric scattering or Mie scattering is reduced to be a Rayleigh scattering region.
- the scattered light is reduced in proportion to the sixth power of the particle diameter, so that the scattering is reduced as the dispersed particle diameter is reduced, and the transparency is improved. Further, when the dispersed particle size is 100 nm or less, the scattered light is extremely reduced, which is preferable. From the viewpoint of avoiding light scattering, it is preferable that the dispersed particle size is smaller, and industrial production is easy if the dispersed particle size is 1 nm or more.
- the haze value of the infrared-absorbing fine particle dispersion in which the infrared-absorbing fine particles according to the present invention are dispersed in a medium has a visible light transmittance of 85% or less and a haze of 30% or less be able to. If the haze is more than 30%, it looks like frosted glass and sharp transparency can not be obtained.
- the dispersed particle diameter of the infrared absorbing fine particles can be measured using ELS-8000 or the like manufactured by Otsuka Electronics Co., Ltd. based on the dynamic light scattering method.
- the so-called "Magnellie phase” having a composition ratio represented by 2.45 z z / y 2.99 2.999 is chemically stable, and in the infrared region.
- the absorption characteristics are also good, they are preferable as infrared absorbing fine particles.
- the crystallite diameter of the infrared absorbing fine particles is preferably 1 nm to 200 nm, more preferably 1 nm to 100 nm, and still more preferably 10 nm to 70 nm, from the viewpoint of exhibiting excellent infrared absorption characteristics.
- X-ray diffraction pattern For measurement of the crystallite diameter, measurement of an X-ray diffraction pattern by powder X-ray diffraction method ( ⁇ -2 ⁇ method) and analysis by Rietveld method are used.
- the measurement of the X-ray diffraction pattern can be performed, for example, using a powder X-ray diffractometer "X'Pert-PRO / MPD" manufactured by Spectrum S Corporation PANalytical.
- the surface treating agent used for surface coating of infrared absorbing fine particles is a polymerization product of a metal chelate compound and a polymerization product of a metal chelate compound hydrolysis product And at least one selected from the group consisting of hydrolysis products of metal cyclic oligomer compounds and polymers of hydrolysis products of metal cyclic oligomer compounds.
- the metal chelate compound and the metal cyclic oligomer compound are at least one selected from an ether bond, an ester bond, an alkoxy group, and an acetyl group from the viewpoint of being preferably a metal alkoxide, metal acetylacetonate and metal carboxylate. It is preferable to have
- (1) metal chelate compound, (2) metal cyclic oligomer compound, (3) hydrolysis product and polymer of metal chelate compound or metal cyclic oligomer compound, (4) The addition amount of the surface treatment agent will be described in order.
- the metal chelate compound used in the present invention is preferably one or more selected from Al-based, Zr-based, Ti-based, Si-based, and Zn-based chelate compounds containing an alkoxy group. .
- aluminum alcoholates such as aluminum ethylate, aluminum isopropylate, aluminum sec-butylate, mono-sec-butoxyaluminum diisopropylate or the like, or polymers thereof, ethylacetoacetate aluminum diisopropylate, aluminum tris (Ethyl acetoacetate), octyl acetoacetate aluminum diisopropyl plate, stearyl acetoaluminum diisopropiolate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetonate), etc. can be exemplified.
- These compounds dissolve aluminum alcoholate in aprotic solvents, petroleum solvents, hydrocarbon solvents, ester solvents, ketone solvents, ether solvents, amide solvents, etc., and Diketones, ⁇ -ketoesters, monohydric or polyhydric alcohols, fatty acids and the like are added, and the mixture is heated under reflux to be an alkoxy group-containing aluminum chelate compound obtained by a substitution reaction of a ligand.
- Zirconium-based chelate compounds such as zirconium ethylate, zirconium alcoholate such as zirconium butyrate or polymers thereof, zirconium tributoxystearate, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium dibutoxybis (acetyl) Examples include acetonate), zirconium tributoxyethylacetoacetate, zirconium butoxyacetylacetonate bis (ethylacetoacetate) and the like.
- titanium-based chelate compounds include titanium alcoholates such as methyl titanate, ethyl titanate, isopropyl titanate, butyl titanate and 2-ethylhexyl titanate, and polymers thereof, titanium acetylacetonate, titanium tetraacetylacetonate, titanium octylene glycolate And titanium ethyl acetoacetate, titanium lactate, titanium triethanol aminate, and the like.
- a tetrafunctional silane compound represented by the general formula: Si (OR) 4 (wherein R is the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms) or a hydrolysis thereof The product can be used.
- Specific examples of the tetrafunctional silane compound include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like.
- silane monomer or an oligomer in which a part or the whole of the alkoxy group of these alkoxysilane monomers is hydrolyzed to give a silanol (Si-OH) group, and a polymer self-condensed through a hydrolysis reaction Is also possible.
- a part or the whole of an alkoxy group is hydrolyzed to give a silanol
- examples thereof include silane monomers converted to (Si-OH) groups, oligomers of 4- to 5-mers, and polymers (silicone resins) having a weight average molecular weight (Mw) of about 800 to 8000.
- the alkoxysilyl group (Si-OR) in the alkoxysilane monomer is not all hydrolyzed into silanol (Si-OH) in the course of the hydrolysis reaction.
- Examples of zinc-based chelate compounds include zinc salts of organic carboxylic acids such as zinc octylate, zinc laurate and zinc stearate, zinc acetylacetonate chelates, benzoylacetone zinc chelates, dibenzoylmethane zinc chelates, ethyl acetoacetate zinc chelates, etc. It can be preferably exemplified.
- the metal cyclic oligomer compound according to the present invention is preferably at least one selected from Al-, Zr-, Ti-, Si-, and Zn-based cyclic oligomer compounds.
- cyclic aluminum oligomer compounds such as cyclic aluminum oxide octylate can be preferably exemplified.
- the type and concentration of the organic solvent are generally present even if water necessary and sufficient for the stoichiometric composition is present in the system.
- the alkoxy group, ether bond or ester bond of the metal chelate compound or metal cyclic oligomer compound to be the starting material is hydrolyzed. Therefore, depending on the conditions of the surface coating method described later, even after hydrolysis, it may be in an amorphous state in which carbon C is incorporated in its molecule.
- the coating film may contain an undecomposed metal chelate compound or / and a metal cyclic oligomer compound, but there is no particular problem if it is a trace amount.
- the addition amount of the metal chelate compound and the metal cyclic oligomer compound described above is 0.1 parts by mass or more and 1000 parts by mass or less in terms of metal element with respect to 100 parts by mass of infrared absorbing fine particles. Is preferred. More preferably, it is in the range of 1 part by mass or more and 500 parts by mass or less. More preferably, it is in the range of 10 parts by mass or more and 150 parts by mass or less.
- the metal chelate compound or the metal cyclic oligomer compound is 0.1 parts by mass or more, the hydrolysis product of those compounds and the polymer of the hydrolysis product cover the surface of the infrared absorbing fine particles The heat and humidity resistance is improved.
- the amount of the metal chelate compound or the metal cyclic oligomer compound is 1000 parts by mass or less, it can be avoided that the adsorption amount with respect to the infrared absorbing fine particles becomes excessive. Further, the improvement of the heat and moisture resistance by the surface coating is not saturated, and the improvement of the coating effect can be expected.
- the addition amount of the metal chelate compound or the metal cyclic oligomer compound is preferably 1000 parts by mass or less also from the industrial viewpoint.
- the surface of the infrared absorbing fine particle is a hydrolysis product of a metal chelate compound, a polymer of a hydrolysis product of a metal chelate compound, a hydrolysis product of a metal cyclic oligomer compound, a hydrolysis product of a metal cyclic oligomer compound It is coated with a coating film containing one or more selected from polymers.
- tungsten oxide or / and composite tungsten oxide which is infrared absorbing fine particles is finely pulverized in advance, It is preferable to disperse in a medium and keep it in a monodispersed state. Then, it is important to secure the dispersed state in the pulverization and dispersion treatment steps and to prevent the fine particles from aggregating each other.
- the surface treatment agent according to the present invention when added by subjecting the dispersion for forming a coating film according to the present invention to a pulverization / dispersion treatment, the surface treatment agent is applied to each infrared absorbing fine particle.
- the product of hydrolysis and the polymer of the product of hydrolysis can be uniformly and strongly coated.
- the grinding * dispersion processing method using apparatuses such as a bead mill, a ball mill, a sand mill, a paint shaker, an ultrasonic homogenizer, is mentioned, for example.
- a medium stirring mill such as a bead mill, a ball mill, a sand mill, a paint shaker, etc.
- medium media such as beads, balls, and Ottawa sand. It is preferable from that.
- the hydrolysis reaction of the surface treatment agent necessarily precedes the polymerization reaction of the generated hydrolysis product.
- the carbon C remaining amount in the surface treatment agent molecule present in the coating film can be reduced as compared with the case where water is not used as the medium.
- a high-density coating film could be formed by reducing the amount of carbon C remaining in the surface treatment agent molecules present in the coating film.
- dispersion liquid for forming a coating film using water as a medium a metal chelate compound, a metal cyclic oligomer compound, a hydrolysis product thereof, and a polymer of the hydrolysis product are metal immediately after the start of the addition. It may be decomposed into ions, but in such a case, the decomposition of the metal ion soot is completed when it becomes a saturated aqueous solution.
- the dispersion concentration of the tungsten oxide and / or the composite tungsten oxide in the dispersion for forming a coating film is 0.01% by mass to 80% by mass in the dispersion for forming a coating film using the water as a medium.
- the dispersion concentration is in this range, the pH can be 8 or less, and the infrared absorbing fine particles according to the present invention maintain the dispersion by electrostatic repulsion.
- the surface of all infrared absorbing fine particles is a hydrolysis product of a metal chelate compound, a polymer of a hydrolysis product of a metal chelate compound, a hydrolysis product of a metal cyclic oligomer compound, and a hydrolysis of a metal cyclic oligomer compound It is considered that the surface-treated infrared-absorbing fine particles according to the present invention are formed by being coated with a coating film containing one or more selected from polymer of the product.
- the film thickness of the coating film of the surface treatment infrared rays absorption microparticle which concerns on this invention is 0.5 nm or more. This is because if the film thickness of the coating film is 0.5 nm or more, it is considered that the surface-treated infrared-absorbing fine particles exhibit sufficient wet heat resistance and chemical stability. On the other hand, it is considered that the film thickness of the coating film is preferably 100 nm or less from the viewpoint that the surface-treated infrared-absorbing fine particles secure predetermined optical properties. The film thickness is preferably 0.5 nm or more and 20 nm or less, more preferably 1 nm or more and 10 nm or less. The film thickness of the coating film can be measured by a transmission electron microscope, and a portion without the lattice of the infrared absorbing fine particles (arrangement of atoms in the crystal) corresponds to the coating film.
- the surface treatment agent according to the present invention and the pure water are dropped in parallel while stirring and mixing the dispersion for forming a coating film using an organic solvent as a medium.
- the medium temperature that affects the reaction rate, and the dropping rate of the surface treatment agent and the pure water are appropriately controlled.
- an organic solvent what is necessary is just a solvent which melt
- the surface-treated infrared-absorbing fine particles according to the present invention obtained in the step of preparing the dispersion for forming a coating film described above are an infrared-absorbing fine particle dispersion or As a raw material of an infrared rays absorption base material, it can be used in the state disperse
- the dispersion for forming a coating film or the surface-treated infrared absorbing fine particle according to the purpose of obtaining the powder of the surface-treated infrared absorbing fine particle from the dispersion for forming a coating film, the purpose of drying the obtained surface-treated infrared absorbing fine particle powder, etc. It is possible to heat treat the powder.
- the heat treatment temperature does not exceed the temperature at which the surface-treated infrared-absorbing fine particles strongly aggregate to form strong aggregates. This is because the surface-treated infrared-absorbing fine particle according to the present invention is required to have transparency in many cases from the use thereof in the infrared-absorbing fine particle dispersion and the infrared-absorbing base material to be finally used.
- an infrared-absorbing fine particle dispersion or an infrared-absorbing substrate is produced by using an aggregate as the infrared-absorbing material, one having a high haze (haze) will be obtained.
- heat treatment is carried out above the temperature at which strong aggregates are formed, the strong aggregates are crushed dry or / and wet in order to ensure the transparency of the infrared absorbing fine particle dispersion or the infrared absorbing substrate. Will be redispersed.
- the coating film on the surface of the surface-treated infrared-absorbing fine particles may be scratched, and in some cases, part of the coating film may be exfoliated, and the surface of the fine particles may be exposed during the disintegration and redispersion. Conceivable.
- the surface-treated infrared-absorbing fine particles according to the present invention do not require heat treatment after the treatment after mixing and stirring, and thus do not cause strong aggregation, and thus dispersion treatment for breaking up strong aggregation is It is unnecessary or it can be done in a short time.
- the coating film of the surface-treated infrared-absorbing fine particles according to the present invention remains coated with the individual infrared-absorbing fine particles without being damaged.
- the infrared rays absorption fine particle dispersion and infrared rays absorption base material which are manufactured using the surface treatment infrared rays absorption microparticles show moisture heat resistance superior to those obtained by the conventional method.
- a high density coating film can be formed by reducing the amount of carbon C remaining in the surface treatment agent molecules present in the coating film.
- the carbon concentration to be contained is preferably 0.2% by mass or more and 5.0% by mass or less. More preferably, it is 0.5 mass% or more and 3.0 mass% or less.
- the infrared absorbing fine particle dispersion according to the present invention is one in which the surface-treated infrared absorbing fine particle according to the present invention is dispersed in a liquid medium.
- a liquid medium one or more liquid mediums selected from organic solvents, fats and oils, liquid plasticizers, compounds polymerized by curing, water, and the like can be used.
- the infrared absorbing fine particle dispersion according to the present invention (i) production method, (ii) organic solvent used, (iii) oil used, (iv) liquid plasticizer used, (v) polymerizing by curing used The compound to be used, (vi) the dispersant to be used, and (vii) the method of using the infrared-absorbing fine particle dispersion will be described in this order.
- the above-mentioned dispersion for forming a coating film is heated, dried, or under the condition that strong aggregation of the surface treated infrared absorbing fine particles can be avoided.
- it is dried by vacuum flow drying at room temperature, spray drying or the like to obtain a surface-treated infrared-absorbing fine particle powder according to the present invention.
- the surface-treated infrared-absorbing fine particle powder may be added to the liquid medium described above and re-dispersed.
- the dispersion for forming a coating film is separated into the surface-treated infrared absorbing fine particles and the medium, and the medium of the dispersion for forming a coating film is replaced with the medium of the infrared-absorbing fine particle dispersion (so-called solvent substitution). It is also preferable to produce an infrared absorbing fine particle dispersion.
- the medium of the coating film-forming dispersion and the medium of the infrared absorbing fine particle dispersion are made to correspond in advance, and the coating film-forming dispersion after surface treatment is used as it is as the infrared absorbing fine particle dispersion. Is also a preferred configuration.
- Alcohols, ketones, hydrocarbons, glycols, water systems, etc. can be used.
- alcohol solvents such as methanol, ethanol, 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol and diacetone alcohol
- Ketone solvents such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone
- Ester 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, propylene glycol monomethyl ether, ethylene glycol isopropyl ether, propylene glycol monomethyl ether,
- organic solvents particularly, dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether acetate, n-butyl acetate and the like can be preferably used.
- Fats and oils used as fats and oils used for the infrared rays absorption fine particle dispersion concerning the present invention vegetable fats and oils or vegetable origin fats and oils are preferred.
- vegetable oils include dry oils such as linseed oil, sunflower oil, soy sauce and eno oil, sesame oil, cottonseed oil, rapeseed oil, semi-dry oil such as soybean oil, rice bran oil and poppy seed oil, olive oil, palm oil, palm oil and dehydrated castor oil Non-drying oil, etc. can be used.
- fatty acid monoesters obtained by direct ester reaction of fatty acid of vegetable oil and monoalcohol, ethers, etc. can be used.
- commercially available petroleum solvents can also be used as fats and oils.
- Isopar (registered trademark) E, Exol (registered trademark) Hexane, Hexane, E, D30, D40, D60, D80, D95, D110, D130 (all manufactured by Exxon Mobil), etc. are used. I can do it.
- liquid plasticizer used for the infrared absorbing fine particle dispersion for example, a plasticizer which is a compound of a monohydric alcohol and an organic acid ester, a polyhydric alcohol organic acid ester compound It is possible to use ester-based plasticizers, phosphoric acid-based plasticizers such as organic phosphoric acid-based plasticizers, and the like. In addition, what is liquid at all at room temperature is preferable. Among them, plasticizers which are ester compounds synthesized from polyhydric alcohols and fatty acids can be preferably used.
- the ester compound synthesized from the polyhydric alcohol and the fatty acid is not particularly limited, and examples thereof include glycols such as triethylene glycol, tetraethylene glycol and tripropylene glycol, butyric acid, isobutyric acid, caproic acid and 2-ethyl butyric acid Using glycol-based ester compounds, etc. obtained by reaction with monobasic organic acids such as heptyl acid, n-octyl acid, 2-ethylhexyl acid, pelargonic acid (n-nonyl acid), decyl acid and the like It can.
- ester compounds of tetraethylene glycol and tripropylene glycol with the monobasic organic compounds and the like can also be mentioned.
- fatty acid esters of triethylene glycol such as triethylene glycol dihexanate, triethylene glycol di-2-ethyl butyrate, triethylene glycol di-octanate, triethylene glycol di-2-ethyl hexanonate, etc. It can be used. Furthermore, fatty acid esters of triethylene glycol can also be preferably used.
- (V) Compound which is polymerized by curing which is used is a monomer or oligomer which forms a polymer by polymerization etc. is there. Specifically, a methyl methacrylate monomer, an acrylate monomer, a styrene resin monomer, etc. can be used.
- liquid media described above can be used in combination of two or more. Furthermore, if necessary, an acid or an alkali may be added to these liquid media to adjust the pH.
- (Vi) Dispersant used in the dispersion liquid of the infrared absorbing fine particle according to the present invention in order to further improve the dispersion stability of the surface treated infrared absorbing fine particle and to avoid the coarsening of the dispersed particle diameter due to reaggregation, various kinds The addition of dispersants, surfactants, coupling agents, etc. is also preferred.
- the said dispersing agent, a coupling agent, and surfactant can be selected according to a use, it is what has an amine-containing group, a hydroxyl group, a carboxyl group, a sulfo group, or an epoxy group as a functional group. preferable.
- These functional groups are adsorbed on the surface of the surface-treated infrared absorbing fine particle to prevent aggregation and have an effect of uniformly dispersing. Polymeric dispersants having any of these functional groups in the molecule are more preferred.
- an acrylic-styrene copolymer based dispersant having a functional group is also mentioned as a preferred dispersant.
- acrylic-styrene copolymer-based dispersants having a carboxyl group as a functional group and acrylic dispersants having an amine-containing group as a functional group are mentioned as more preferable examples.
- the dispersant having a functional group containing an amine is preferably one having a molecular weight of Mw 2000 to 200,000 and an amine value of 5 to 100 mg KOH / g.
- a dispersant having a carboxyl group one having a molecular weight of Mw 2000 to 200,000 and an acid value of 1 to 50 mg KOH / g is preferable.
- SOLSPERSE registered trademark
- 3000 5000, 9000, 11200, 12000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000 by Nippon Lubrisol Corporation.
- Addispur (registered trademark) (same as the following) PB-711, PB-821, PB-822, etc .; Company-made Disparon (registered trademark) 1751N, 1831, 1850, 1860, 1934, DA-400N, DA-703-50, DA-325, DA-375, DA-550, DA-705, DA-725 , DA-1401, DA-7301, DN-900, NS-5210, NVI-8514L, etc .; Alphon (registered trademark) manufactured by Toagosei Co., Ltd.
- the infrared absorbing fine particle dispersion according to the present invention manufactured as described above is applied to the surface of a suitable substrate, and a dispersion film is formed there to obtain infrared absorption. It can be used as a base material. That is, the dispersion film is a kind of the dried and solidified material of the infrared absorbing fine particle dispersion.
- the infrared absorbing fine particle dispersion can be dried and pulverized to obtain a powdery infrared absorbing fine particle dispersion according to the present invention (sometimes referred to as "dispersed powder" in the present invention). .
- the said dispersed powder is 1 type of the dry solidified thing of an infrared rays absorption microparticle dispersion liquid.
- the dispersed powder is a powdery dispersion in which surface-treated infrared-absorbing fine particles are dispersed in a solid medium (dispersant etc.), and is distinguished from the above-mentioned surface-treated infrared-absorbing fine particle powder. Since the dispersed powder contains a dispersant, it is possible to easily re-disperse the surface-treated infrared-absorbing fine particles in the medium by mixing with a suitable medium.
- the dispersed powder can be used as a raw material for adding surface-treated infrared absorbing fine particles to an infrared absorbing product in a dispersed state. That is, the dispersed powder in which the surface-treated infrared absorbing fine particles according to the present invention are dispersed in a solid medium may be dispersed again in a liquid medium and used as a dispersion for an infrared absorbing product, which will be described later. As such, the dispersed powder may be kneaded into a resin and used.
- the infrared absorbing fine particle dispersion in which the surface-treated infrared absorbing fine particles according to the present invention are mixed and dispersed in a liquid medium is used for various applications utilizing photothermal conversion.
- surface-treated infrared-absorbing fine particles are added to uncured thermosetting resin, or after surface-treated infrared-absorbing fine particles according to the present invention are dispersed in an appropriate solvent, uncured thermosetting resin is added.
- a curable ink composition can be obtained.
- the curable ink composition is provided on a predetermined base material, and when cured by being irradiated with an infrared ray such as an infrared ray, the curable ink composition has excellent adhesion to the base material.
- the curable ink composition is applied in a predetermined amount, irradiated with an electromagnetic wave such as infrared rays to be cured, piled up, and then formed into a three-dimensional object.
- Curing ink composition most suitable for
- the infrared absorbing fine particle dispersion according to the present invention is one in which the surface-treated infrared absorbing fine particles according to the present invention are dispersed in a solid medium.
- solid media such as resin and glass, can be used as the said solid media.
- the infrared absorbing fine particle dispersion according to the present invention will be described in the order of (i) production method and (ii) moisture and heat resistance.
- the surface-treated infrared-absorbing fine particles according to the present invention are kneaded into a resin, they are mixed by heating and mixing at a temperature (about 200 to 300 ° C.) around the melting point of the resin.
- a temperature about 200 to 300 ° C.
- it can be formed by an extrusion molding method, an inflation molding method, a solution casting method, a casting method or the like.
- the thickness of the film or board at this time may be appropriately set according to the purpose of use, and the amount of filler to the resin (that is, the amount of the surface treated infrared absorbing fine particles according to the present invention) Depending on the optical properties and mechanical properties, but generally 50% by weight or less based on the resin is preferable. When the amount of the filler with respect to the resin is 50% by mass or less, fine particles in the solid resin can avoid granulation, so that good transparency can be maintained. In addition, the amount of surface-treated infrared-absorbing fine particles according to the present invention can be controlled, which is advantageous in cost.
- the infrared absorbing fine particle dispersion in which the surface treated infrared absorbing fine particles according to the present invention are dispersed in a solid medium can be used even in a state of being further pulverized into powder.
- the surface-treated infrared-absorbing fine particles according to the present invention are already sufficiently dispersed in the solid medium. Therefore, the powdery infrared-absorbing fine particle dispersion is dissolved as a so-called master batch in an appropriate liquid medium or kneaded with resin pellets or the like to easily produce a liquid or solid infrared-absorbing fine particle dispersion. You can do it.
- the resin used as the matrix of the film or board mentioned above is not specifically limited, It can select according to a use.
- a low cost, highly transparent and versatile resin PET resin, acrylic resin, polyamide resin, vinyl chloride resin, polycarbonate resin, olefin resin, epoxy resin, polyimide resin, etc. can be used.
- a fluorine resin can also be used in consideration of the weather resistance.
- the infrared-absorbing fine particle dispersion according to the present invention is exposed when the dispersion having a visible light transmittance of about 80% is exposed to a moist heat atmosphere at 85 ° C. and 90% for 9 days.
- the amount of change in visible light transmittance before and after is 2.0% or less, and has excellent heat and humidity resistance.
- the infrared-absorbing base material according to the present invention is one in which a dispersion film containing surface-treated infrared-absorbing fine particles according to the present invention is formed on the surface of a predetermined base material.
- a dispersion film containing the surface-treated infrared absorbing fine particles according to the present invention is formed on a predetermined substrate surface.
- the infrared absorbing substrate according to the present invention is excellent in moisture heat resistance and chemical stability, and infrared It can be suitably used as an absorbent material.
- the infrared absorbing base material according to the present invention will be described in the order of (i) production method and (ii) moisture and heat resistance.
- a liquid medium such as an organic solvent such as alcohol or water, a resin binder, and optionally a dispersant
- the liquid medium may be removed or hardened to obtain an infrared ray absorbing base material in which the infrared absorbing fine particle dispersion is directly laminated on the base material surface.
- the resin binder component can be selected according to the application, and examples thereof include an ultraviolet curable resin, a thermosetting resin, a room temperature curing resin, a thermoplastic resin, and the like.
- the infrared absorbing fine particle dispersion containing no resin binder component may be laminated on the surface of the substrate, and after the lamination, the infrared absorbing fine particle dispersion containing a binder medium is contained in the liquid medium. It may be applied on the layer of
- liquid infrared absorption in which the surface-treated infrared-absorbing fine particles are dispersed in one or more liquid media selected from organic solvents, organic solvents in which resin is dissolved, organic solvents in which resin is dispersed, and water.
- An infrared-absorbing substrate obtained by applying the fine particle dispersion to the surface of the substrate and solidifying the obtained coating film by an appropriate method may be mentioned.
- the infrared rays absorption base material which apply
- a liquid infrared-absorbing fine particle dispersion obtained by mixing an infrared-absorbing fine particle dispersion in which surface-treated infrared-absorbing fine particles are dispersed in a powdery solid medium in a predetermined medium is applied to the substrate surface.
- an infrared-absorbing substrate obtained by curing the coating film by an appropriate method there may also be mentioned an infrared-absorbing substrate obtained by curing the coating film by an appropriate method.
- an infrared-absorbing substrate obtained by applying an infrared-absorbing fine particle dispersion obtained by mixing two or more of the various liquid infrared-absorbing fine particle dispersions onto the surface of the substrate and solidifying the obtained coating film by an appropriate method is also mentioned.
- the material of the substrate described above is not particularly limited as long as it is a transparent body, but glass, a resin board, a resin sheet, and a resin film are preferably used.
- the resin used for the resin board, the resin sheet, and the resin film is not particularly limited as long as it does not cause a defect in the surface condition and the durability of the required board, sheet, and film.
- polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose, polycarbonate-based polymers, acrylic polymers such as polymethyl methacrylate, and polystyrenes such as polystyrene and acrylonitrile-styrene copolymer -Based polymer, polyethylene, polypropylene, polyolefin having cyclic or norbornene structure, olefin-based polymer such as ethylene-propylene copolymer, vinyl chloride-based polymer, amide-based polymer such as aromatic polyamide, imide-based polymer, sulfone-based polymer, poly Ether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol poly -, Vinylidene chloride polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene
- polyester-based biaxially oriented films such as polyethylene terephthalate, polybutylene terephthalate or polyethylene-2,6-naphthalate are preferable in view of mechanical properties, optical properties, heat resistance and economy.
- the polyester-based biaxially oriented film may be a copolyester-based.
- the infrared-absorbing fine particle dispersion or the infrared-absorbing article such as a film or a board which is an infrared-absorbing substrate according to the present invention And excellent in chemical stability. Therefore, for example, in various buildings and vehicles, these infrared absorbing articles are intended to shield light in the infrared region while sufficiently incorporating visible light, and to suppress the temperature rise in the room while maintaining the brightness. It can be suitably used as a window material, etc., which is used in a PDP (plasma display panel), etc., and which filters infrared rays emitted forward from the PDP.
- PDP plasma display panel
- the surface treated infrared absorbing fine particles according to the present invention have absorption in the infrared region, when the printing surface containing the surface treated infrared absorbing fine particles is irradiated with an infrared laser, it absorbs infrared rays having a specific wavelength. Therefore, the forgery prevention printed matter obtained by printing the forgery prevention ink containing the surface-treated infrared absorbing fine particles on one side or both sides of the printing substrate is irradiated with an infrared ray having a specific wavelength, and its reflection or transmission is read. The authenticity of the printed matter can be determined from the difference in the amount of reflection or the amount of transmission.
- the said forgery prevention printed matter is an example of the infrared rays absorption particulate dispersion concerning the present invention.
- the infrared absorbing fine particle dispersion according to the present invention and the binder component are mixed to produce an ink, the ink is applied on a substrate, the applied ink is dried, and then the dried ink is cured.
- the light-to-heat conversion layer can be formed.
- the light-to-heat conversion layer can generate heat only at a desired place with high accuracy by irradiation of electromagnetic waves such as infrared rays, and can be applied to a wide range of fields such as electronics, medicine, agriculture, machinery, etc. It is.
- the said photothermal conversion layer is an example of the infrared rays absorption particulate dispersion concerning the present invention.
- the surface-treated infrared-absorbing fine particles according to the present invention are dispersed in an appropriate medium, and the dispersion is contained in the surface and / or the inside of the fiber to obtain an infrared-absorbing fiber.
- the infrared rays absorption fiber absorbs near infrared rays etc. from sunlight etc. efficiently by containing surface treatment infrared rays absorption microparticles, and becomes an infrared rays absorption fiber excellent in heat retention, and at the same time light in the visible light range Since it transmits, it becomes an infrared absorbing fiber excellent in design.
- the said infrared rays absorption fiber is an example of the infrared rays absorption particulate dispersion concerning the present invention.
- the film-like or board-like infrared-absorbing fine particle dispersion according to the present invention can be applied to a material used for a roof or an outer wall material of an agricultural and horticultural house. And while allowing visible light to pass through and securing the light necessary for photosynthesis of plants in the house for agriculture and horticulture, heat insulation is achieved by efficiently absorbing light such as near-infrared light contained in other sunlight. It can be used as a heat insulation material for agricultural and horticultural facilities with the property.
- the said heat insulation material for agricultural and horticultural facilities is an example of the infrared rays absorption particulate dispersion concerning the present invention.
- the dispersed particle diameter of the fine particles in the dispersion in Examples and Comparative Examples is indicated by an average value measured by a particle size measurement device (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.) based on the dynamic light scattering method.
- the crystallite diameter is measured by powder X-ray diffraction method ( ⁇ -2 ⁇ method) using a powder X-ray diffractometer (X'Pert-PRO / MPD manufactured by Spectris Co., Ltd. PANalytical), using Rietveld method. Calculated.
- the film thickness of the coating film of the surface-treated infrared-absorbing fine particles is determined by using a 300,000-fold photographic data obtained by using a transmission electron microscope (HF-2200 manufactured by Hitachi, Ltd.) where there is no plaid of the infrared-absorbing fine particles It was read as a coated film.
- the optical properties of the infrared absorbing sheet were measured using a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.), and the visible light transmittance and the solar radiation transmittance were calculated according to JIS R3106.
- the haze value of the infrared ray absorbing sheet was measured using a haze meter (HM-150 manufactured by Murakami Color Co., Ltd.), and calculated according to JIS K7105.
- the infrared ray absorbing sheet having a visible light transmittance of about 80% is exposed to a moist heat atmosphere at 85 ° C. and 90% for 9 days. And, for example, in the case of hexagonal cesium tungsten bronze, it is judged that the change in solar radiation transmittance is 2.0% or less before and after the exposure is considered to be good in heat and moisture resistance, and the change is more than 2.0% It was judged that heat and humidity resistance was insufficient.
- the optical characteristic value (visible light transmittance, haze value) of the infrared rays absorption sheet is a value including the optical characteristic value of the resin sheet which is a base material.
- a mixed solution obtained by mixing 25% by mass and 75% by mass of pure water is loaded into a paint shaker containing 0.3 mm ⁇ ZrO 2 beads, pulverized and dispersed for 10 hours, Cs according to Example 1
- a dispersion of 0.33 WO z fine particles was obtained.
- the dispersed particle size of the Cs 0.33 WO z fine particles in the obtained dispersion was measured to be 100 nm.
- the particle refractive index was set to 1.81, and the particle shape was non-spherical.
- the background was measured using pure water, and the solvent refractive index was 1.33.
- the crystallite diameter was measured to be 32 nm.
- the obtained dispersion of Cs 0.33 WO z fine particles and pure water are mixed to obtain a dispersion A for forming a coating film according to Example 1 in which the concentration of Cs 0.33 WO z fine particles is 2% by mass.
- the obtained coating film-forming dispersion A 890 g was placed in a beaker, and while being vigorously stirred by a bladed stirrer, 360 g of a surface treating agent diluted solution was added dropwise over 3 hours. After dropwise addition of the surface treatment agent dilution liquid a, stirring was further performed at a temperature of 20 ° C. for 24 hours to prepare a ripening liquid according to Example 1. Next, the medium was evaporated from the ripening solution by vacuum flow drying to obtain a powder (surface-treated infrared-absorbing fine particle powder) including the surface-treated infrared-absorbing fine particles according to Example 1.
- Example 1 8% by mass of the surface-treated infrared-absorbing fine particle powder according to Example 1 was mixed with 24% by mass of the polyacrylate dispersant and 68% by mass of toluene.
- the obtained mixed solution was loaded on a paint shaker containing 0.3 mm ⁇ ZrO 2 beads, ground and dispersed for 1 hour, and an infrared-absorbing fine particle dispersion liquid according to Example 1 was obtained.
- the medium was evaporated from the infrared absorbing fine particle dispersion by vacuum flow drying to obtain an infrared absorbing fine particle dispersed powder according to Example 1.
- the infrared ray absorbing fine particle dispersed powder according to Example 1 and the polycarbonate resin were dry blended so that the visible light transmittance of the infrared ray absorbing sheet to be obtained later becomes around 80% (in this example, the concentration of the surface treated infrared ray absorbing fine particles Were blended to give 0.06 wt%).
- the obtained blend was kneaded at 290 ° C. using a twin-screw extruder, extruded from a T-die, and made into a sheet material of 0.75 mm thickness by a calender roll method, to obtain an infrared-absorbing sheet according to Example 1 .
- the infrared absorbing sheet is an example of the infrared absorbing particle dispersion according to the present invention.
- the visible light transmittance was 79.6%
- the solar radiation transmittance was 48.6%
- the haze was 0.9%.
- the obtained infrared absorption sheet according to Example 1 was exposed to a moist heat atmosphere at 85 ° C. and 90% for 9 days, and the optical characteristics were measured.
- the visible light transmittance was 80.2%, and the solar radiation transmittance was 49.5 %, The haze was 0.9%. It was found that the change in visible light transmittance due to exposure to a moist heat atmosphere was 0.6%, the change in solar radiation transmittance was as small as 0.9%, and the haze did not change.
- the manufacturing conditions are shown in Table 1 and the evaluation results are shown in Table 3.
- Example 2 and 3 Surface-treated infrared-absorbing fine particle powder and infrared-absorbing fine particle according to Examples 2 and 3 by performing the same operation as in Example 1 except that the amount of surface treatment agent dilution liquid a and the dropping addition time thereof are changed The dispersion, the infrared ray absorbing fine particle dispersed powder, and the infrared ray absorbing sheet were obtained, and the same evaluation as in Example 1 was carried out.
- the manufacturing conditions are shown in Table 1 and the evaluation results are shown in Table 3.
- Example 4 The ripening solution according to Example 1 was allowed to stand for 1 hour to separate the surface-treated infrared-absorbing fine particles from the medium by solid-liquid separation. Then, only the medium which is the supernatant was removed to obtain an infrared absorbing fine particle slurry. Isopropyl alcohol was added to the obtained infrared-absorbing fine particle slurry and stirred for 1 hour, and then allowed to stand for 1 hour, and solid-liquid separation of the surface-treated infrared-absorbing fine particles and the medium was performed again. Next, only the supernatant medium was removed to obtain an infrared absorbing fine particle slurry again.
- Example 4 An infrared-absorbing fine particle dispersed powder and an infrared-absorbing sheet according to Example 4 are obtained by performing the same operation as in Example 1 except that the infrared-absorbing fine particle dispersion according to Example 4 is used, Example 1 The same evaluation was performed. The manufacturing conditions are shown in Table 1 and the evaluation results are shown in Table 3. Note * 1 in Table 1 indicates that the surface-treated infrared-absorbing fine particles and the medium were separated into solid and liquid.
- Example 5 A surface treatment agent diluted solution b according to Example 5 was obtained by mixing 2.4% by mass of zirconium tributoxyacetylacetonate and 97.6% by mass of isopropyl alcohol.
- the surface-treated infrared-absorbing fine particle powder and the infrared-absorbing fine particle dispersion according to Example 5 are operated in the same manner as in Example 1 except that the surface treatment agent dilution liquid b is used instead of the surface treatment agent dilution liquid a.
- a liquid, infrared ray absorbing fine particle dispersed powder, and an infrared ray absorbing sheet were obtained, and the same evaluation as in Example 1 was carried out.
- the manufacturing conditions are shown in Table 1 and the evaluation results are shown in Table 3.
- Example 6 2.6 mass% of diisopropoxytitanium bisethylacetoacetate and 97.4 mass% of isopropyl alcohol were mixed to obtain a surface treatment agent diluted solution c according to Example 6.
- the surface-treated infrared-absorbing fine particle powder and the infrared-absorbing fine particle dispersion according to Example 6 are operated in the same manner as in Example 1 except that the surface treatment agent dilution liquid c is used instead of the surface treatment agent dilution liquid a.
- a liquid, infrared ray absorbing fine particle dispersed powder, and an infrared ray absorbing sheet were obtained, and the same evaluation as in Example 1 was carried out.
- the manufacturing conditions are shown in Table 1 and the evaluation results are shown in Table 3.
- Example 7 Surface-treated infrared-absorbing fine particle powder and infrared-absorbing fine particle dispersion according to Example 7 by performing the same operation as in Example 1 except that polymethyl methacrylate resin is used instead of polycarbonate resin as the solid resin
- the infrared ray absorbing fine particle dispersed powder and the infrared ray absorbing sheet were obtained, and the same evaluation as in Example 1 was carried out.
- the manufacturing conditions are shown in Table 1 and the evaluation results are shown in Table 3.
- a dispersion B for forming a coating film was prepared by mixing a dispersion of Na 0.33 WO z fine particles according to Example 8 with isopropyl alcohol and having a concentration of infrared absorbing fine particles (cubic sodium tungsten bronze fine particles) of 2%. Obtained.
- the obtained dispersion B for forming a coating film B is placed in a beaker, and while the solution is vigorously stirred by a bladed stirrer, 360 g of a surface treatment agent diluent a and 100 g of pure water as a diluent d are paralleled over 3 hours It was added dropwise. After the dropwise addition, the mixture was stirred for 24 hours at a temperature of 20 ° C. to prepare a ripening solution according to Example 8. Next, the medium was evaporated from the ripening solution by vacuum flow drying to obtain a surface-treated infrared-absorbing fine particle powder according to Example 8.
- the infrared ray according to Example 8 is carried out in the same manner as in Example 1 except that the surface-treated infrared absorption fine particle powder according to Example 8 is used instead of the surface-treated infrared absorption fine particle powder according to Example 1.
- An absorbing particle dispersion, an infrared absorbing particle dispersion powder, and an infrared absorbing sheet were obtained, and the same evaluation as in Example 1 was performed.
- the manufacturing conditions are shown in Table 1 and the evaluation results are shown in Table 3.
- Note * 2 in Table 1 indicates that the diluent d is pure water
- Note * 5 indicates that the dropping amount of a is 360 g
- the dropping amount of d is 100 g
- Note * 7 indicates , A, d are shown to be dropped in parallel.
- the dispersed particle size and the crystallite size of the infrared absorbing fine particles are measured in the same manner as in Example 1 except that tungsten bronze powder (Example 10) or W 18 O 49 (Example 11) of the magneli phase is used. Furthermore, dispersions C to E for forming a coating film were obtained.
- the surface-treated infrared rays according to Examples 9 to 11 are carried out in the same manner as in Example 1 except that the dispersions C to E for forming a coating film are used instead of the dispersion A for forming a coating film.
- Absorbent fine particle powder, infrared ray absorbing fine particle dispersion, infrared ray absorbing fine particle dispersed powder, and an infrared ray absorbing sheet were obtained, and the same evaluation as in Example 1 was carried out.
- the manufacturing conditions are shown in Table 1 and the evaluation results are shown in Table 3.
- the mixed solution thus obtained is loaded on a paint shaker containing 0.3 mm ⁇ ZrO 2 beads and subjected to a grinding and dispersing treatment for 6 hours (Example 12) or 4 hours (Example 13).
- a dispersion of such Cs 0.33 WO z fine particles was obtained.
- the dispersed particle sizes of the Cs 0.33 WO z fine particles in the obtained dispersions according to Examples 12 and 13 were 140 nm and 120 nm, respectively.
- the particle refractive index was set to 1.81, and the particle shape was non-spherical.
- the background was measured using pure water, and the solvent refractive index was 1.33.
- the crystallite sizes of the Cs 0.33 WO z fine particles according to Examples 12 and 13 were measured, and were 50 nm and 42 nm, respectively.
- the surface treatment according to Examples 12 and 13 is carried out in the same manner as in Example 2 except that the coating film-forming dispersions F and G are used instead of the coating film-forming dispersion A.
- An infrared-absorbing fine particle powder, an infrared-absorbing fine particle dispersion, an infrared-absorbing fine particle dispersed powder, and an infrared-absorbing sheet were obtained, and the same evaluation as in Example 1 was carried out.
- the manufacturing conditions are shown in Table 1 and the evaluation results are shown in Table 3.
- Example 14 By using 309 g of tetraethoxysilane as the surface treatment agent e, using the surface treatment agent e instead of the surface treatment agent dilution liquid a, and not adding isopropyl alcohol, the same operation as in Example 1 is performed, The surface-treated infrared-absorbing fine particle powder, the infrared-absorbing fine particle dispersion, the infrared-absorbing fine particle dispersed powder, and the infrared-absorbing sheet according to Example 14 were obtained and evaluated in the same manner as in Example 1. The manufacturing conditions are shown in Table 1 and the evaluation results are shown in Table 3.
- Example 15 A surface treatment agent diluted solution f according to Example 15 was obtained by mixing 4.4% by mass of zinc acetylacetonate and 95.6% by mass of isopropyl alcohol.
- the surface-treated infrared-absorbing fine particle powder and the infrared-absorbing fine particle dispersion according to Example 15 are carried out in the same manner as in Example 1 except that the surface treatment agent dilution liquid f is used instead of the surface treatment agent dilution liquid a.
- a liquid, infrared ray absorbing fine particle dispersed powder, and an infrared ray absorbing sheet were obtained, and the same evaluation as in Example 1 was carried out.
- the manufacturing conditions are shown in Table 1 and the evaluation results are shown in Table 3.
- Example 16 The medium was evaporated from the aging solution according to Example 1 by spray drying instead of vacuum flow drying to obtain a powder (surface treated infrared absorption fine particle powder) containing surface-treated infrared-absorbing fine particles according to Example 16. The same operation as in Example 1 was carried out except for that, to obtain an infrared-absorbing fine particle dispersion, an infrared-absorbing fine particle dispersed powder, and an infrared-absorbing sheet according to Example 16, and the same evaluation as in Example 1 was carried out. The manufacturing conditions are shown in Table 1 and the evaluation results are shown in Table 3.
- Comparative Example 1 7% by mass of hexagonal cesium tungsten bronze powder, 24% by mass of polyacrylate dispersant and 69% by mass of toluene were mixed, and the obtained mixture was loaded on a paint shaker containing 0.3 mm ⁇ ZrO 2 beads for 4 hours.
- the dispersion was subjected to pulverization / dispersion treatment to obtain a coating film-forming dispersion H according to Comparative Example 1.
- the diameter of the dispersed particles of the infrared absorbing fine particles in the obtained coating film-forming dispersion liquid H was 100 nm.
- the particle refractive index was set to 1.81, and the particle shape was non-spherical.
- the background was measured using toluene, and the solvent refractive index was 1.50.
- the crystallite diameter was measured to be 32 nm.
- the infrared absorbing fine particle dispersion liquid according to Comparative Example 1 was used as it is without adding a surface treatment agent to the coating film formation dispersion H.
- the medium was evaporated from the infrared-absorbing fine particle dispersion liquid according to Comparative Example 1 by vacuum flow drying to obtain an infrared-absorbing fine particle dispersion powder according to Comparative Example 1.
- the infrared-absorbing fine particle dispersed powder according to Comparative Example 1 and the polycarbonate resin were dry-blended so that the concentration of the infrared-absorbing fine particles was 0.075 wt%.
- the obtained blend was kneaded at 290 ° C. using a twin-screw extruder, extruded from a T-die, and made into a sheet material of 0.75 mm thickness by a calendar roll method, to obtain an infrared ray absorbing sheet according to Comparative Example 1 .
- the obtained infrared absorption sheet according to Comparative Example 1 was exposed to a moist heat atmosphere at 85 ° C. and 90% for 9 days, and the optical characteristics were measured.
- the visible light transmittance was 81.2% and the solar radiation transmittance was 52.6 %,
- the haze was 1.2%.
- the change in visible light transmittance due to exposure to a moist heat atmosphere was 2.0%, and the change in solar radiation transmittance was 4.2%, which was found to be large compared to the examples.
- the rate of change of the haze was 0.2%.
- the production conditions are shown in Table 2 and the evaluation results are shown in Table 4.
- Comparative Example 2 An infrared-absorbing fine particle dispersion, infrared-absorbing fine particle dispersed powder according to Comparative Example 2 by performing the same operation as Comparative Example 1 except that polymethyl methacrylate resin is used instead of polycarbonate resin as the solid resin An infrared absorption sheet was obtained, and the same evaluation as in Example 1 was performed. The production conditions are shown in Table 2 and the evaluation results are shown in Table 4.
- the dispersed particle size of the Cs 0.33 WO z fine particles in the obtained dispersion was measured to be 100 nm.
- the particle refractive index was set to 1.81, and the particle shape was non-spherical.
- the background was measured using isopropyl alcohol, and the solvent refractive index was 1.38.
- the crystallite diameter was measured to be 32 nm.
- Dispersion liquid for forming a coating film wherein the dispersion of Cs 0.33 WO z fine particles according to Comparative Example 7 and isopropyl alcohol are mixed, and the concentration of the infrared light absorbing fine particles (hexagonal cesium tungsten bronze fine particles) is 3.5% I got 21 g of aluminum ethyl acetoacetate diisopropylate was added to the obtained coating film forming dispersion I 733 g, mixed and stirred, and then dispersed using an ultrasonic homogenizer.
- the dispersion-treated product was placed in a beaker, and 100 g of pure water was added dropwise as a diluent d over 1 hour while vigorously stirring with a bladed stirrer. Furthermore, 140 g of tetraethoxysilane was added dropwise over 2 hours as a surface treatment agent e 'while stirring, and then stirring was performed at 20 ° C for 15 hours, and this solution was heated and aged at 70 ° C for 2 hours. Next, the medium was evaporated from the ripening solution by vacuum flow drying, and heat treated at a temperature of 200 ° C. for 1 hour in a nitrogen atmosphere to obtain a surface-treated infrared-absorbing fine particle powder of Comparative Example 7.
- the infrared absorption according to Comparative Example 7 is performed by the same operation as in Example 1 except that the infrared absorption fine particle dispersion according to Comparative Example 7 is used instead of the infrared absorption fine particle dispersion according to Example 1.
- the fine particle dispersed powder and the infrared absorbing sheet were obtained, and the same evaluation as in Example 1 was carried out.
- the production conditions are shown in Table 2 and the evaluation results are shown in Table 4.
- Note * 3 in Table 2 indicates that Diluent d is pure water
- Note * 4 indicates that 21 g of aluminum ethyl acetoacetate diisopropylate was added prior to the addition of water / tetraethoxysilane.
- Note * 6 indicates that the dropping amount of water is 100 g, that of tetraethoxysilane is 140 g, and note * 8 indicates that the dropping time of water is 1 h and the dropping time of tetraethoxysilane is 2 h Is shown.
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Abstract
Description
さらに、当該表面処理赤外線吸収微粒子や、当該表面処理赤外線吸収微粒子を含む表面処理赤外線吸収微粒子粉末、当該表面処理赤外線吸収微粒子が適宜な媒質中に分散した赤外線吸収微粒子分散液を用いて製造した赤外線吸収微粒子分散体等が、耐湿熱性に優れ、且つ、優れた赤外線吸収特性を有することを知見し、本発明に至った。
赤外線吸収微粒子の表面が、
金属キレート化合物の加水分解生成物、金属キレート化合物の加水分解生成物の重合物、金属環状オリゴマー化合物の加水分解生成物、金属環状オリゴマー化合物の加水分解生成物の重合物、から選択される1種以上を含む被覆膜で被覆されていることを特徴とする表面処理赤外線吸収微粒子である。
第2の発明は、
前記被覆膜の膜厚が0.5nm以上であることを特徴とする第1の発明に記載の表面処理赤外線吸収微粒子である。
第3の発明は、
前記金属キレート化合物または前記金属環状オリゴマー化合物が、Al、Zr、Ti、Si、Znから選択される1種類以上の金属元素を含むことを特徴とする第1または第2の発明に記載の表面処理赤外線吸収微粒子である。
第4の発明は、
前記金属キレート化合物または前記金属環状オリゴマー化合物が、エーテル結合、エステル結合、アルコキシ基、アセチル基から選択される1種以上を有することを特徴とする第1から第3の発明のいずれかに記載の表面処理赤外線吸収微粒子である。
第5の発明は、
前記赤外線吸収微粒子が、一般式WyOz(但し、Wはタングステン、Oは酸素、2.2≦z/y≦2.999)、または/および、一般式MxWyOz(但し、Mは、H、He、アルカリ金属、アルカリ土類金属、希土類元素、Mg、Zr、Cr、Mn、Fe、Ru、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl、Si、Ge、Sn、Pb、Sb、B、F、P、S、Se、Br、Te、Ti、Nb、V、Mo、Ta、Re、Be、Hf、Os、Bi、I、Ybのうちから選択される1種類以上の元素、Wはタングステン、Oは酸素、0.001≦x/y≦1、2.0≦z/y≦3.0)で表記される赤外線吸収微粒子であることを特徴とする、第1から第4の発明いずれかに記載の表面処理赤外線吸収微粒子である。
第6の発明は、
第1から第5の発明のいずれかに記載の表面処理赤外線吸収微粒子を含むことを特徴とする表面処理赤外線吸収微粒子粉末である。
第7の発明は、
炭素濃度が、0.2質量%以上5.0質量%以下であることを特徴とする第6の発明に記載の表面処理赤外線吸収微粒子粉末である。
第8の発明は、
第1から第5の発明のいずれかに記載の表面処理赤外線吸収微粒子が、所定の液体媒質中に分散していることを特徴とする赤外線吸収微粒子分散液である。
第9の発明は、
前記液体媒質が、有機溶剤、油脂、液状可塑剤、硬化により高分子化される化合物、水、から選択される1種以上の液体媒質であることを特徴とする第8の発明に記載の赤外線吸収微粒子分散液である。
第10の発明は、
第1から第5の発明のいずれかに記載の表面処理赤外線吸収微粒子が、所定の固体状樹脂中に分散していることを特徴とする赤外線吸収微粒子分散体である。
第11の発明は、
前記固体状樹脂が、フッ素樹脂、PET樹脂、アクリル樹脂、ポリアミド樹脂、塩化ビニル樹脂、ポリカーボネート樹脂、オレフィン樹脂、エポキシ樹脂、ポリイミド樹脂、から選択される1種以上の樹脂であることを特徴とする第10の発明に記載の赤外線吸収微粒子分散体である。
第12の発明は、
第8または第9の発明に記載の赤外線吸収微粒子分散液の乾燥固化物であることを特徴とする赤外線吸収微粒子分散体である。
第13の発明は、
赤外線吸収微粒子と水とを混合し、分散処理を行って水を媒質とする被覆膜形成用分散液を得る工程と、
前記水を媒質とする被覆膜形成用分散液を撹拌しながら、金属キレート化合物または/および金属環状オリゴマー化合物を添加する工程と、
前記添加後も前記攪拌を継続して、前記赤外線吸収微粒子の表面を、金属キレート化合物の加水分解生成物、金属キレート化合物の加水分解生成物の重合物、金属環状オリゴマー化合物の加水分解生成物、金属環状オリゴマー化合物の加水分解生成物の重合物、から選択される1種以上で被覆し、赤外線吸収微粒子分散液を得る工程と、を有することを特徴とする表面処理赤外線吸収微粒子の製造方法である。
第14の発明は、
赤外線吸収微粒子と有機溶剤とを混合し、分散処理を行って有機溶剤を媒質とする被覆膜形成用分散液を得る工程と、
前記有機溶剤を媒質とする被覆膜形成用分散液を撹拌しながら、金属キレート化合物または/および金属環状オリゴマー化合物と、水とを、同時に並行して添加する工程と、
前記添加後も前記攪拌を継続して、前記赤外線吸収微粒子の表面を、金属キレート化合物の加水分解生成物、金属キレート化合物の加水分解生成物の重合物、金属環状オリゴマー化合物の加水分解生成物、金属環状オリゴマー化合物の加水分解生成物の重合物、から選択される1種以上で被覆し、赤外線吸収微粒子の有機溶剤分散液を得る工程と、を有することを特徴とする表面処理赤外線吸収微粒子の製造方法である。
第15の発明は、
前記金属キレート化合物または/および金属環状オリゴマー化合物が、Al、Zr、Ti、Si、Znから選択される1種類以上の金属元素を含むことを特徴とする第13または第14の発明に記載の表面処理赤外線吸収微粒子の製造方法である。
第16の発明は、
前記赤外線吸収微粒子が、一般式WyOz(但し、Wはタングステン、Oは酸素、2.2≦z/y≦2.999)、または/および、一般式MxWyOz(但し、Mは、H、He、アルカリ金属、アルカリ土類金属、希土類元素、Mg、Zr、Cr、Mn、Fe、Ru、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl、Si、Ge、Sn、Pb、Sb、B、F、P、S、Se、Br、Te、Ti、Nb、V、Mo、Ta、Re、Be、Hf、Os、Bi、I、Ybのうちから選択される1種類以上の元素、Wはタングステン、Oは酸素、0.001≦x/y≦1、2.0≦z/y≦3.0)で表記される赤外線吸収微粒子であることを特徴とする、第13から第15の発明のいずれかに記載の表面処理赤外線吸収微粒子の製造方法である。
第17の発明は、
第13、第15または第16の発明に記載の水を媒質とする被覆膜形成用分散液、または、第14から第16の発明のいずれかに記載の有機溶剤を媒質とする被覆膜形成用分散液から媒質を除去して、表面処理赤外線吸収微粒子を含む表面処理赤外線吸収微粒子粉末を得る工程、を有することを特徴とする表面処理赤外線吸収微粒子粉末の製造方法である。
第18の発明は、
前記表面処理赤外線吸収微粒子粉末に含まれる炭素濃度が、0.2質量%以上5.0質量%以下であることを特徴とする、第17の発明に記載の表面処理赤外線吸収微粒子粉末の製造方法である。
第19の発明は、
第17または第18の発明に記載の表面処理赤外線吸収微粒子粉末を所定の媒質に加え、分散させる工程、を有することを特徴とする赤外線吸収微粒子分散液の製造方法である。
第20の発明は、
第13、第15または第16の発明に記載の水を媒質とする被覆膜形成用分散液、または、第14から第16の発明のいずれかに記載の有機溶剤を媒質とする被覆膜形成用分散液の媒質を、所定の媒質に溶媒置換する工程、を有することを特徴とする赤外線吸収微粒子分散液の製造方法である。
第21の発明は、
第13、第15または第16の発明に記載の水を媒質とする被覆膜形成用分散液、または、第14から第16の発明のいずれかに記載の有機溶剤を媒質とする被覆膜形成用分散液の媒質を、予め、所定の媒質としておくことにより、得られた第13、第15または第16の発明に記載の水を媒質とする被覆膜形成用分散液、または、第14から第16の発明のいずれかに記載の有機溶剤を媒質とする被覆膜形成用分散液を、赤外線吸収微粒子分散液とすることを特徴とする赤外線吸収微粒子分散液の製造方法である。
第22の発明は、
第19から第21の発明のいずれかに記載の赤外線吸収微粒子分散液の製造方法で得られた赤外線吸収微粒子分散液を、所定の基材上に塗布して乾燥し、赤外線吸収微粒子分散体を得る工程を有することを特徴とする赤外線吸収微粒子分散体の製造方法である。
第23の発明は、
第17または第18の発明に記載の表面処理赤外線吸収微粒子粉末の製造方法で得られた表面処理赤外線吸収微粒子粉末、第19から第21の発明のいずれかに記載の赤外線吸収微粒子分散液の製造方法で得られた赤外線吸収微粒子分散液、のいずれかを、所定の固体状樹脂中に分散させる工程を有することを特徴とする赤外線吸収微粒子分散体の製造方法である。
尚、本発明において、「赤外線吸収微粒子へ耐湿熱性を付与する為に、当該微粒子の表面へ、金属キレート化合物の加水分解生成物、金属キレート化合物の加水分解生成物の重合物、金属環状オリゴマー化合物の加水分解生成物、金属環状オリゴマー化合物の加水分解生成物の重合物、から選択される1種以上を用いて形成した被覆膜」を、単に「被覆膜」と記載する場合がある。
一般に、自由電子を含む材料は、プラズマ振動によって波長200nmから2600nmの太陽光線の領域周辺の電磁波に反射吸収応答を示すことが知られている。このような物質の粉末を、光の波長より小さい粒子にすると、可視光領域(波長380nmから780nm)の幾何学散乱が低減されて可視光領域の透明性が得られることが知られている。
尚、本発明において「透明性」とは、「可視光領域の光に対して散乱が少なく透過性が高い。」という意味で用いている。
一方、酸素欠損を持つWO3や、WO3にNa等の陽性元素を添加した複合タングステン酸化物は、導電性材料であり、自由電子を持つ材料であることが知られている。そして、これらの自由電子を持つ材料の単結晶等の分析により、赤外線領域の光に対する自由電子の応答が示唆されている。
本発明者等は、当該タングステンと酸素との組成範囲の特定部分において、赤外線吸収微粒子として特に有効な範囲があることを見出し、可視光領域においては透明で、赤外線領域においては吸収を持つタングステン酸化物微粒子、複合タングステン酸化物微粒子に想到した。
ここで、本発明に係る赤外線吸収微粒子であるタングステン酸化物微粒子または/および複合タングステン酸化物微粒子について、(1)タングステン酸化物微粒子、(2)複合タングステン酸化物微粒子、(3)タングステン酸化物微粒子および複合タングステン酸化物微粒子、の順で説明する。
本発明に係るタングステン酸化物微粒子は、一般式WyOz(但し、Wはタングステン、Oは酸素、2.2≦z/y≦2.999)で表記されるタングステン酸化物の微粒子である。
当該z/yの値が2.2以上であれば、当該タングステン酸化物中に目的以外であるWO2の結晶相が現れるのを回避することが出来ると伴に、材料としての化学的安定性を得ることが出来るので有効な赤外線吸収微粒子となる。一方、当該z/yの値が2.999以下であれば、必要とされる量の自由電子が生成され効率よい赤外線吸収微粒子となる。
上述したWO3へ、後述する元素Mを添加し複合タングステン酸化物とすることで、当該WO3中に自由電子が生成され、特に近赤外線領域に自由電子由来の強い吸収特性が発現し、1000nm付近の近赤外線吸収微粒子として有効となる。
即ち、当該WO3に対し、酸素量の制御と、自由電子を生成する元素Mの添加とを併用することで、より効率の良い赤外線吸収微粒子を得ることが出来る。この酸素量の制御と、自由電子を生成する元素Mの添加とを併用した赤外線吸収微粒子の一般式をMxWyOz(但し、Mは、前記M元素、Wはタングステン、Oは酸素)と記載したとき、0.001≦x/y≦1、2.0≦z/y≦3の関係を満たす赤外線吸収微粒子が望ましい。
x/yの値が0.001より大きければ、複合タングステン酸化物において十分な量の自由電子が生成され目的とする赤外線吸収効果を得ることが出来る。そして、元素Mの添加量が多いほど、自由電子の供給量が増加し、赤外線吸収効率も上昇するが、x/yの値が1程度で当該効果も飽和する。また、x/yの値が1より小さければ、当該赤外線吸収微粒子中に不純物相が生成されるのを回避できるので好ましい。
図1において、符号11で示すWO6単位にて形成される8面体が6個集合して六角形の空隙が構成され、当該空隙中に、符号12で示す元素Mが配置して1箇の単位を構成し、この1箇の単位が多数集合して六方晶の結晶構造を構成する。
そして、可視光領域における光の透過を向上させ、赤外領域における光の吸収を向上させる効果を得る為には、複合タングステン酸化物微粒子中に、図1を用いて説明した単位構造が含まれていれば良く、当該複合タングステン酸化物微粒子が結晶質であっても非晶質であっても構わない。
本発明に係る、タングステン酸化物微粒子や複合タングステン酸化物微粒子を含有する赤外線吸収微粒子は、近赤外線領域、特に波長1000nm付近の光を大きく吸収するため、その透過色調は青色系から緑色系となる物が多い。
まず、透明性を保持したい応用に使用する場合は、800nm以下の粒子径を有していることが好ましい。これは、800nmよりも小さい粒子は、散乱により光を完全に遮蔽することが無く、可視光線領域の視認性を保持し、同時に効率良く透明性を保持することができるからである。特に可視光領域の透明性を重視する場合は、さらに粒子による散乱を考慮することが好ましい。
さらに分散粒子径が100nm以下になると、散乱光は非常に少なくなり好ましい。光の散乱を回避する観点からは、分散粒子径が小さい方が好ましく、分散粒子径が1nm以上あれば工業的な製造は容易である。
尚、赤外線吸収微粒子の分散粒子径は、動的光散乱法を原理とした大塚電子株式会社製ELS-8000等を用いて測定することができる。
また、優れた赤外線吸収特性を発揮させる観点から、赤外線吸収微粒子の結晶子径は1nm以上200nm以下であることが好ましく、より好ましくは1nm以上100nm以下、さらに好ましくは10nm以上70nm以下である。結晶子径の測定には、粉末X線回折法(θ―2θ法)によるX線回折パターンの測定と、リートベルト法による解析を用いる。X線回折パターンの測定には、例えばスペクトリス株式会社PANalytical製の粉末X線回折装置「X’Pert-PRO/MPD」などを用いて行うことができる。
本発明に係る赤外線吸収微粒子の表面被覆に用いる表面処理剤は、金属キレート化合物の加水分解生成物、金属キレート化合物の加水分解生成物の重合物、金属環状オリゴマー化合物の加水分解生成物、金属環状オリゴマー化合物の加水分解生成物の重合物、から選択される1種以上である。
そして、当該金属キレート化合物、金属環状オリゴマー化合物は、金属アルコキシド、金属アセチルアセトネート、金属カルボキシレートであることが好ましい観点から、エーテル結合、エステル結合、アルコキシ基、アセチル基から選択される1種以上を有することが好ましい。
ここで、本発明に係る表面処理剤について、(1)金属キレート化合物、(2)金属環状オリゴマー化合物、(3)金属キレート化合物や金属環状オリゴマー化合物の加水分解生成物および重合物、(4)表面処理剤の添加量、の順で説明する。
本発明に用いる金属キレート化合物は、アルコキシ基を含有するAl系、Zr系、Ti系、Si系、Zn系のキレート化合物から選ばれる一種又は二種以上であることが好ましい。
これらの化合物は、アルミニウムアルコレートを非プロトン性溶媒や、石油系溶剤、炭化水素系溶剤、エステル系溶剤、ケトン系溶剤、エーテル系溶剤、アミド系溶剤等に溶解し、この溶液に、β-ジケトン、β-ケトエステル、一価または多価アルコール、脂肪酸等を加えて、加熱還流し、リガンドの置換反応により得られた、アルコキシ基含有のアルミニウムキレート化合物である。
また、4官能性シラン化合物の加水分解生成物(4官能性シラン化合物の中間体全体を指示する適宜な術語が存在しない。)としては、アルコキシ基の一部あるいは全量が加水分解して、シラノール(Si-OH)基となったシランモノマー、4~5量体のオリゴマー、および、重量平均分子量(Mw)が800~8000程度の重合体(シリコーンレジン)が挙げられる。尚、アルコキシシランモノマー中のアルコキシシリル基(Si-OR)は、加水分解反応の過程において、その全てが加水分解してシラノール(Si-OH)になるわけではない。
本発明に係る金属環状オリゴマー化合物としては、Al系、Zr系、Ti系、Si系、Zn系の環状オリゴマー化合物から選ばれる1種以上であることが好ましい。中でも、環状アルミニウムオキサイドオクチレート等、の環状アルミニウムオリゴマー化合物を好ましく例示することができる。
本発明では、上述した金属キレート化合物や金属環状オリゴマー化合物における、アルコキシ基、エーテル結合、エステル結合の全量が加水分解し、ヒドロキシル基やカルボキシル基となった加水分解生成物、一部が加水分解した部分加水分解生成物、または/および、当該加水分解反応を経て自己縮合した重合物を、本発明に係る赤外線吸収微粒子の表面に被覆して被覆膜とし、本発明に係る表面処理赤外線吸収微粒子を得るものである。
即ち、本発明における加水分解生成物は、部分加水分解生成物を含む概念である。
その結果、被覆膜には、未分解の金属キレート化合物または/および金属環状オリゴマー化合物が含有される場合があるが、微量であれば特に問題は無い。
上述した金属キレート化合物や金属環状オリゴマー化合物の添加量は、赤外線吸収微粒子100質量部に対して、金属元素換算で0.1質量部以上、1000質量部以下であることが好適である。より好ましくは、1質量部以上、500質量部以下の範囲である。さらに好ましくは、10質量部以上、150質量部以下の範囲である。
また、金属キレート化合物または金属環状オリゴマー化合物が1000質量部以下であれば、赤外線吸収微粒子に対する吸着量が過剰になることを回避出来る。また、表面被覆による耐湿熱性の向上が飽和せず、被覆効果の向上が望める。
さらに、金属キレート化合物または金属環状オリゴマー化合物が1000質量部以下であることで、赤外線吸収微粒子に対する吸着量が過剰になり、媒質除去時に当該金属キレート化合物または金属環状オリゴマー化合物の加水分解生成物や、当該加水分解生成物の重合物を介して微粒子同士が造粒し易くなることを回避出来るからである。当該望まれない微粒子同士の造粒回避によって、良好な透明性を担保することが出来る。
加えて、金属キレート化合物または金属環状オリゴマー化合物の過剰による、添加量および処理時間の増加による生産コスト増加も回避出来る。よって工業的な観点からも金属キレート化合物や金属環状オリゴマー化合物の添加量は、1000質量部以下とすることが好ましい。
本発明に係る赤外線吸収微粒子の表面被覆方法においては、まず、赤外線吸収微粒子を適宜な媒質中に分散させた被覆膜形成用の赤外線吸収微粒子分散液(本発明において「被覆膜形成用分散液」と記載する場合がある。)を調製する。そして、調製された被覆膜形成用分散液中へ表面処理剤を添加して混合攪拌を行う。すると、赤外線吸収微粒子の表面が、金属キレート化合物の加水分解生成物、金属キレート化合物の加水分解生成物の重合物、金属環状オリゴマー化合物の加水分解生成物、金属環状オリゴマー化合物の加水分解生成物の重合物、から選択される1種以上を含む被覆膜で被覆される。
ここで、本発明に係る表面被覆方法について、(1)被覆膜形成用分散液の調製、(2)水を媒質とする被覆膜形成用分散液の調製、(3)添加水量を調整した被覆膜形成用分散液の調製、(4)被覆膜形成用分散液における混合攪拌後の処理、の順で説明する。
本発明に係る被覆膜形成用分散液においては、赤外線吸収微粒子であるタングステン酸化物または/および複合タングステン酸化物を予め細かく粉砕して、適宜な媒質中に分散させ、単分散の状態にしておくことが好ましい。そして、この粉砕、分散処理工程中において分散状態を担保し、微粒子同士を凝集させないことが肝要である。これは、赤外線吸収微粒子の表面処理の過程において、当該微粒子が凝集を起こし、当該微粒子が凝集体の状態で表面被覆され、ひいては、後述する赤外線吸収微粒子分散体中においても当該凝集体が残存し、後述する赤外線吸収微粒子分散体や赤外線吸収基材の透明性が低下する事態を回避する為である。
当該粉砕・分散処理の具体的方法としては、例えば、ビーズミル、ボールミル、サンドミル、ペイントシェーカー、超音波ホモジナイザーなどの装置を用いた粉砕・分散処理方法が挙げられる。その中でも、ビーズ、ボール、オタワサンドといった媒体メディアを用いた、ビーズミル、ボールミル、サンドミル、ペイントシェーカー等の媒体攪拌ミルで粉砕、分散処理を行うことは、所望の分散粒子径への到達時間が短いことから好ましい。
本発明者らは、上述した被覆膜形成用分散液の調製において、水を媒質とする被覆膜形成用分散液を攪拌混合しながら、ここへ、本発明に係る表面処理剤を添加し、さらに、添加された金属キレート化合物、金属環状オリゴマー化合物の加水分解反応を即座に完了させるのが好ましいことを知見した。本発明において「水を媒質とする被覆膜形成用分散液」と記載する場合がある。
これは、添加した本発明に係る表面処理剤の反応順序が影響していると考えられる。即ち、水を媒質とする被覆膜形成用分散液中においては、表面処理剤の加水分解反応が必ず先立ち、その後に、生成した加水分解生成物の重合反応が起こる。この結果、水を媒質としない場合に比較して、被覆膜中に存在する表面処理剤分子内の炭素C残存量を低減することが出来るからであると考えられる。当該被覆膜中に存在する表面処理剤分子内の炭素C残存量を低減することで、高密度な被覆膜を形成することが出来たと考えている。
一方、当該水を媒質とする被覆膜形成用分散液中において、被覆膜形成用分散液中におけるタングステン酸化物または/および複合タングステン酸化物の分散濃度が0.01質量%以上80質量%以下とすることが好ましい。分散濃度がこの範囲であれば、pHを8以下とすることができ、本発明に係る赤外線吸収微粒子は静電反発によって分散を保っている。
その結果、全ての赤外線吸収微粒子の表面は、金属キレート化合物の加水分解生成物、金属キレート化合物の加水分解生成物の重合物、金属環状オリゴマー化合物の加水分解生成物、金属環状オリゴマー化合物の加水分解生成物の重合物、から選択される1種以上を含む被覆膜で被覆され、本発明に係る表面処理赤外線吸収微粒子が生成すると考えられる。
被覆膜の膜厚は、透過型電子顕微鏡で測定することができ、赤外線吸収微粒子の格子縞(結晶中の原子の並び)のないところが被覆膜に相当する。
上述した水を媒質とする被覆膜形成用分散液の調製法の変形例として、被覆膜形成用分散液の媒質として有機溶剤を用い、添加水量を適宜な値に調整しながら上述した反応順序を実現する方法もある。本発明において「有機溶剤を媒質とする被覆膜形成用分散液」と記載する場合がある。
当該調製方法は、後工程の都合により被覆膜形成用分散液中に含まれる水分量を低減したい場合にも便宜である。
具体的には、有機溶剤を媒質とする被覆膜形成用分散液を攪拌混合しながら、本発明に係る表面処理剤と純水とを並行滴下するものである。このとき、反応速度に影響する媒質温度や、表面処理剤と純水との滴下速度を適宜に制御する。尚、有機溶剤としては、アルコール系、ケトン系、グリコール系等、の室温で水に溶解する溶剤であれば良く、種々のものを選択することが可能である。
上述した被覆膜形成用分散液の調製工程にて得られた本発明に係る表面処理赤外線吸収微粒子は、赤外線吸収微粒子分散体や赤外線吸収基材の原料として、微粒子状態、液体媒質または固体媒質に分散された状態で用いることが出来る。
即ち、生成した表面処理赤外線吸収微粒子は、さらに加熱処理を施して被覆膜の密度や化学的安定性を高めるといった操作は必要ない。当該加熱処理をせずとも既に所望の耐湿熱性を得られる程、当該被覆膜の密度や密着性は十分に高まっているからである。
これは、本発明に係る表面処理赤外線吸収微粒子には、最終的に用いられる赤外線吸収微粒子分散体や赤外線吸収基材において、それらの用途から、多くの場合は透明性が求められる為である。赤外線吸収材料として凝集体を用いて、赤外線吸収微粒子分散体や赤外線吸収基材を作製すると、曇り度(ヘイズ)の高いものが得られてしまうこととなる。もし強凝集体を形成する温度を超えて加熱処理した場合、赤外線吸収微粒子分散体や赤外線吸収基材の透明性を確保する為には、当該強凝集体を乾式または/および湿式で解砕して再分散させることとなる。しかし、当該解砕して再分散させる際、表面処理赤外線吸収微粒子の表面にある被覆膜が傷付き、場合によっては一部の被覆膜が剥離し、当該微粒子の表面が露出することも考えられる。
以下、本発明に係る表面処理赤外線吸収微粒子を用いて得られる赤外線吸収微粒子分散体、赤外線吸収基材、並びに物品について、(1)赤外線吸収微粒子分散液、(2)赤外線吸収微粒子分散体、(3)赤外線吸収基材、(4)赤外線吸収微粒子分散体や赤外線吸収基材を用いた物品、の順に説明する。
本発明に係る赤外線吸収微粒子分散液は、本発明に係る表面処理赤外線吸収微粒子が液体媒質中に分散しているものである。当該液体媒質としては、有機溶剤、油脂、液状可塑剤、硬化により高分子化される化合物、水、から選択される1種以上の液体媒質を用いることが出来る。
本発明に係る赤外線吸収微粒子分散液について(i)製造方法、(ii)使用する有機溶剤、(iii)使用する油脂、(iv)使用する液状可塑剤、(v)使用する硬化により高分子化される化合物、(vi)使用する分散剤、(vii)赤外線吸収微粒子分散液の使用方法、の順に説明する。
本発明に係る赤外線吸収微粒子分散液を製造するには、上述した被覆膜形成用分散液を、表面処理赤外線吸収微粒子の強凝集を回避出来る条件での加熱、乾燥、または、例えば室温下における真空流動乾燥、噴霧乾燥等によって乾燥し、本発明に係る表面処理赤外線吸収微粒子粉末を得る。そして、当該表面処理赤外線吸収微粒子粉末を、上述した液体媒質中に添加して再分散させればよい。また、被覆膜形成用分散液を、表面処理赤外線吸収微粒子と媒質とに分離し、被覆膜形成用分散液の媒質を赤外線吸収微粒子分散液の媒質へ置き換え(所謂、溶媒置換)て、赤外線吸収微粒子分散液を製造することも好ましい構成である。
本発明に係る赤外線吸収微粒子分散液に使用する有機溶剤としては、アルコール系、ケトン系、炭化水素系、グリコール系、水系、等を使用することが出来る。
具体的には、メタノール、エタノール、1-プロパノール、イソプロパノール、ブタノール、ペンタノール、ベンジルアルコール、ジアセトンアルコールなどのアルコール系溶剤;
アセトン、メチルエチルケトン、メチルプロピルケトン、メチルイソブチルケトン、シクロヘキサノン、イソホロンなどのケトン系溶剤;
3-メチル-メトキシ-プロピオネートなどのエステル系溶剤;
エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールイソプロピルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテートなどのグリコール誘導体;
フォルムアミド、N-メチルフォルムアミド、ジメチルホルムアミド、ジメチルアセトアミド、N-メチル-2-ピロリドンなどのアミド類;
トルエン、キシレンなどの芳香族炭化水素類;
エチレンクロライド、クロルベンゼン、等を使用することが出来る。
そして、これらの有機溶剤中でも、特に、ジメチルケトン、メチルエチルケトン、メチルイソブチルケトン、トルエン、プロピレングリコールモノメチルエーテルアセテート、酢酸n-ブチル、等を好ましく使用することが出来る。
本発明に係る赤外線吸収微粒子分散液に使用する油脂としては、植物油脂または植物由来油脂が好ましい。
植物油としては、アマニ油、ヒマワリ油、桐油、エノ油等の乾性油、ゴマ油、綿実油、菜種油、大豆油、米糠油、ケシ油等の半乾性油、オリーブ油、ヤシ油、パーム油、脱水ヒマシ油等の不乾性油、等を使用することが出来る。
植物油由来の化合物としては、植物油の脂肪酸とモノアルコールを直接エステル反応させた脂肪酸モノエステル、エーテル類、等を使用することが出来る。
また、市販の石油系溶剤も油脂として用いることが出来る。
市販の石油系溶剤として、アイソパー(登録商標)E、エクソール(登録商標)Hexane、Heptane、E、D30、D40、D60、D80、D95、D110、D130(以上、エクソンモービル製)、等を使用することが出来る。
本発明に係る赤外線吸収微粒子分散液に使用する液状可塑剤としては、例えば、一価アルコールと有機酸エステルとの化合物である可塑剤、多価アルコール有機酸エステル化合物等のエステル系である可塑剤、有機リン酸系可塑剤等のリン酸系である可塑剤、等を使用することが出来る。尚、いずれも室温で液状であるものが好ましい。
なかでも、多価アルコールと脂肪酸から合成されたエステル化合物である可塑剤を好ましく使用することが出来る。当該多価アルコールと脂肪酸とから合成されたエステル化合物は特に限定されないが、例えば、トリエチレングリコール、テトラエチレングリコール、トリプロピレングリコール等のグリコールと、酪酸、イソ酪酸、カプロン酸、2-エチル酪酸、ヘプチル酸、n-オクチル酸、2-エチルヘキシル酸、ペラルゴン酸(n-ノニル酸)、デシル酸等の一塩基性有機酸との反応によって得られた、グリコール系エステル化合物、等を使用することが出来る。
また、テトラエチレングリコール、トリプロピレングリコールと、前記一塩基性有機とのエステル化合物等も挙げられる。
なかでも、トリエチレングリコールジヘキサネート、トリエチレングリコールジ-2-エチルブチレート、トリエチレングリコールジ-オクタネート、トリエチレングリコールジ-2-エチルヘキサノネート等のトリエチレングリコールの脂肪酸エステル、等を使用することが出来る。さらに、トリエチレングリコールの脂肪酸エステルも好ましく使用することが出来る。
本発明に係る赤外線吸収微粒子分散液に使用する、硬化により高分子化される化合物は、重合等により高分子を形成する単量体やオリゴマーである。
具体的には、メチルメタクリレート単量体、アクレリート単量体、スチレン樹脂単量体、等を使用することが出来る。
本発明に係る赤外線吸収微粒子分散液中において、表面処理赤外線吸収微粒子の分散安定性を一層向上させ、再凝集による分散粒子径の粗大化を回避する為に、各種の分散剤、界面活性剤、カップリング剤などの添加も好ましい。
当該分散剤、カップリング剤、界面活性剤は用途に合わせて選定可能であるが、アミンを含有する基、水酸基、カルボキシル基、スルホ基、または、エポキシ基を官能基として有するものであることが好ましい。これらの官能基は、表面処理赤外線吸収微粒子の表面に吸着して凝集を防ぎ、均一に分散させる効果を持つ。これらの官能基のいずれかを分子中にもつ高分子系分散剤は、さらに好ましい。
上述のようにして製造された本発明に係る赤外線吸収微粒子分散液は、適宜な基材の表面に塗布し、ここに分散膜を形成して赤外線吸収基材として利用することが出来る。つまり、当該分散膜は、赤外線吸収微粒子分散液の乾燥固化物の一種である。
また、当該赤外線吸収微粒子分散液を乾燥し、粉砕処理して、本発明に係る粉末状の赤外線吸収微粒子分散体(本発明において「分散粉」と記載する場合もある。)とすることが出来る。つまり、当該分散粉は、赤外線吸収微粒子分散液の乾燥固化物の一種である。当該分散粉は表面処理赤外線吸収微粒子が固体媒質中(分散剤等)に分散された粉末状の分散体であり、上述の表面処理赤外線吸収微粒子粉末とは区別する。当該分散粉は分散剤を含んでいるため、適宜な媒質と混合することで表面処理赤外線吸収微粒子を媒質中へ容易に再分散させることが可能である。
例えば、表面処理赤外線吸収微粒子を未硬化の熱硬化性樹脂へ添加する、または、本発明に係る表面処理赤外線吸収微粒子を適宜な溶媒中に分散した後、未硬化の熱硬化性樹脂を添加することにより、硬化型インク組成物を得ることが出来る。当該硬化型インク組成物は、所定の基材上に設けられ、赤外線などの赤外線を照射されて硬化した際、当該基材への密着性に優れたものである。そして、当該硬化型インク組成物は、従来のインクとしての用途に加え、所定量を塗布し、ここへ赤外線などの電磁波を照射して硬化させて積み上げ、後3次元物体を造形する光造形法に最適な硬化型インク組成物となる。
本発明に係る赤外線吸収微粒子分散体は、本発明に係る表面処理赤外線吸収微粒子が固体媒質中に分散しているものである。尚、当該固体媒質としては、樹脂、ガラス、等の固体媒質を用いることが出来る。
本発明に係る赤外線吸収微粒子分散体について(i)製造方法、(ii)耐湿熱性、の順に説明する。
本発明に係る表面処理赤外線吸収微粒子を樹脂に練り込み、フィルムやボードに成形する場合、当該表面処理赤外線吸収微粒子を直接樹脂に練り込むことが可能である。また、前記赤外線吸収微粒子分散液と樹脂とを混合すること、または、当該表面処理赤外線吸収微粒子が固体媒質に分散された粉末状の分散体を液体媒質に添加しかつ樹脂と混合することも可能である。
固体媒質として樹脂を用いた場合、例えば、厚さ0.1μm~50mmのフィルムまたはボードを構成する形態であってもよい。
この場合、さらに、当該表面処理赤外線吸収微粒子を樹脂に混合してペレット化し、当該ペレットを各方式でフィルムやボードを形成することも可能である。例えば、押し出し成形法、インフレーション成形法、溶液流延法、キャスティング法等により形成可能である。この時のフィルムやボードの厚さは、使用目的によって適宜設定すればよく、樹脂に対するフィラー量(すなわち、本発明に係る表面処理赤外線吸収微粒子の配合量)は、基材の厚さや必要とされる光学特性、機械特性に応じて可変であるが、一般的に樹脂に対して50質量%以下が好ましい。
樹脂に対するフィラー量が50質量%以下であれば、固体状樹脂中での微粒子同士が造粒を回避出来るので、良好な透明性を保つことが出来る。また、本発明に係る表面処理赤外線吸収微粒子の使用量も制御出来るのでコスト的にも有利である。
本発明に係る赤外線吸収微粒子分散体は、可視光透過率80%前後に設定した当該分散体を、85℃90%の湿熱雰囲気中に9日間暴露を行ったとき、当該暴露前後における可視光透過率の変化量が2.0%以下であり、優れた耐湿熱性を有している。
本発明に係る赤外線吸収基材は、所定の基材表面に、本発明に係る表面処理赤外線吸収微粒子を含有する分散膜が形成されているものである。
所定の基材表面に、本発明に係る表面処理赤外線吸収微粒子を含有する分散膜が形成されていることにより、本発明に係る赤外線吸収基材は、耐湿熱性および化学安定性に優れ、且つ赤外線吸収材料として好適に利用出来るものである。
本発明に係る赤外線吸収基材について(i)製造方法、(ii)耐湿熱性、の順に説明する。
例えば、本発明に係る表面処理赤外線吸収微粒子を、アルコール等の有機溶剤や水等の液体媒質と、樹脂バインダーと、所望により分散剤とを混合した赤外線吸収微粒子分散液を、適宜な基材表面に塗布した後、液体媒質を除去したり、硬化させたりすることで、赤外線吸収微粒子分散体が基材表面に直接積層された赤外線吸収基材を得ることが出来る。
樹脂ボード、樹脂シート、樹脂フィルムに用いる樹脂としては、必要とするボード、シート、フィルムの表面状態や耐久性に不具合を生じないものであれば特に制限はない。例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系ポリマー、ジアセチルセルロース、トリアセチルセルロース等のセルロース系ポリマー、ポリカーボネート系ポリマー、ポリメチルメタクリレート等のアクリル系ポリマー、ポリスチレン、アクリロニトリル・スチレン共重合体等のスチレン系ポリマー、ポリエチレン、ポリプロピレン、環状ないしノルボルネン構造を有するポリオレフィン、エチレン・プロピレン共重合体等のオレフィン系ポリマー、塩化ビニル系ポリマー、芳香族ポリアミド等のアミド系ポリマー、イミド系ポリマー、スルホン系ポリマー、ポリエーテルスルホン系ポリマー、ポリエーテルエーテルケトン系ポリマー、ポリフェニレンスルフィド系ポリマー、ビニルアルコール系ポリマー、塩化ビニリデン系ポリマー、ビニルブチラール系ポリマー、アリレート系ポリマー、ポリオキシメチレン系ポリマー、エポキシ系ポリマーや、さらにこれらの二元系、三元系各種共重合体、グラフト共重合体、ブレンド物等の透明ポリマーからなるボード、シート、フィルムが挙げられる。特に、ポリエチレンテレフタレート、ポリブチレンテレフタレートあるいはポリエチレン-2,6-ナフタレート等のポリエステル系2軸配向フィルムが、機械的特性、光学特性、耐熱性および経済性の点より好適である。当該ポリエステル系2軸配向フィルムは共重合ポリエステル系であっても良い。
上記赤外線吸収基材においては、可視光透過率80%に設定した当該赤外線吸収基材へ、85℃90%の湿熱雰囲気中に9日間暴露を行ったとき、当該暴露前後における可視光透過率の変化量が2.0%以下であり、優れた耐湿熱性を有している。
上述したように、本発明に係る赤外線吸収微粒子分散体や赤外線吸収基材であるフィルムやボード等の赤外線吸収物品は、耐湿熱性および化学安定性に優れている。
そこで、これらの赤外線吸収物品は、例えば、各種建築物や車両において、可視光線を十分に取り入れながら赤外領域の光を遮蔽し、明るさを維持しつつ室内の温度上昇を抑制することを目的とした窓材等、PDP(プラズマディスプレイパネル)に使用され、当該PDPから前方に放射される赤外線を遮蔽するフィルター等、に好適に使用することができる。
実施例および比較例における分散液中の微粒子の分散粒子径は、動的光散乱法に基づく粒径測定装置(大塚電子株式会社製ELS-8000)により測定した平均値をもって示した。また、結晶子径は、粉末X線回折装置(スペクトリス株式会社PANalytical製X’Pert-PRO/MPD)を用いて粉末X線回折法(θ―2θ法)により測定し、リートベルト法を用いて算出した。
表面処理赤外線吸収微粒子の被覆膜の膜厚は、透過型電子顕微鏡(日立製作所株式会社社製 HF-2200)を用いて得た30万倍の写真データより赤外線吸収微粒子の格子縞のないところを被覆膜として読み取った。
赤外線吸収シートの光学特性は、分光光度計(日立製作所株式会社製 U-4100)を用いて測定し、可視光透過率と日射透過率とはJISR3106に従って算出した。当該赤外線吸収シートのヘイズ値は、ヘイズメーター(村上色彩株式会社製 HM-150)を用いて測定し、JISK7105に従って算出した。
赤外線吸収シートの耐湿熱性の評価方法は、可視光透過率80%前後の当該赤外線吸収シートを85℃90%の湿熱雰囲気中に9日間暴露する。そして、例えば六方晶セシウムタングステンブロンズの場合は、当該暴露前後における日射透過率の変化量が2.0%以下のものを耐湿熱性が良好と判断し、変化量が2.0%を超えるものは耐湿熱性が不足と判断した。
尚、ここでいう赤外線吸収シートの光学特性値(可視光透過率、ヘイズ値)は、基材である樹脂シートの光学特性値を含む値である。
Cs/W(モル比)=0.33の六方晶セシウムタングステンブロンズ(Cs0.33WOz、2.0≦z≦3.0)粉末CWO(登録商標)(住友金属鉱山株式会社製YM-01)25質量%と純水75質量%とを混合して得られた混合液を、0.3mmφZrO2ビーズを入れたペイントシェーカーに装填し10時間粉砕・分散処理し、実施例1に係るCs0.33WOz微粒子の分散液を得た。得られた分散液中のCs0.33WOz微粒子の分散粒子径を測定したところ、100nmであった。尚、粒径測定の設定として、粒子屈折率は1.81とし、粒子形状は非球形とした。また、バックグラウンドは純水を用いて測定し、溶媒屈折率は1.33とした。また、得られた分散液の溶媒を除去したあと、結晶子径を測定したところ32nmであった。得られたCs0.33WOz微粒子の分散液と純水を混合し、Cs0.33WOz微粒子の濃度が2質量%である実施例1に係る被覆膜形成用分散液Aを得た。
一方、アルミニウム系のキレート化合物としてアルミニウムエチルアセトアセテートジイソプロピレート2.5質量%と、イソプロピルアルコール(IPA)97.5質量%とを混合して表面処理剤希釈液aを得た。
ここで、実施例1に係る表面処理赤外線吸収微粒子の被覆膜の膜厚を、透過型電子顕微鏡により測定したところ2nmであることが判明した。尚、実施例1に係る表面処理赤外線吸収微粒子の30万倍の透過型電子顕微鏡写真を図2に示す。
表面処理剤希釈液aの量とその滴下添加時間とを変更したこと以外は、実施例1と同様の操作をすることで、実施例2および3に係る表面処理赤外線吸収微粒子粉末、赤外線吸収微粒子分散液、赤外線吸収微粒子分散粉、赤外線吸収シートを得て、実施例1と同様の評価を実施した。当該製造条件を表1、評価結果を表3に示す。
実施例1に係る熟成液を、1時間静置させ、表面処理赤外線吸収微粒子と媒質とを固液分離させた。次いで、上澄みである媒質のみを除去して赤外線吸収微粒子スラリーを得た。得られた赤外線吸収微粒子スラリーにイソプロピルアルコールを添加して1時間攪拌させた後、1時間静置させ、再び表面処理赤外線吸収微粒子と媒質とを固液分離させた。次いで、上澄みである媒質のみを除去し、再び赤外線吸収微粒子スラリーを得た。
ジルコニウムトリブトキシアセチルアセトネート2.4質量%とイソプロピルアルコール97.6質量%とを混合して実施例5に係る表面処理剤希釈液bを得た。表面処理剤希釈液aの代わりに表面処理剤希釈液bを用いたこと以外は、実施例1と同様の操作をすることで、実施例5に係る表面処理赤外線吸収微粒子粉末、赤外線吸収微粒子分散液、赤外線吸収微粒子分散粉、赤外線吸収シートを得て、実施例1と同様の評価を実施した。当該製造条件を表1、評価結果を表3に示す。
ジイソプロポキシチタンビスエチルアセトアセテート2.6質量%とイソプロピルアルコール97.4質量%とを混合して実施例6に係る表面処理剤希釈液cを得た。表面処理剤希釈液aの代わりに表面処理剤希釈液cを用いたこと以外は、実施例1と同様の操作をすることで、実施例6に係る表面処理赤外線吸収微粒子粉末、赤外線吸収微粒子分散液、赤外線吸収微粒子分散粉、赤外線吸収シートを得て、実施例1と同様の評価を実施した。当該製造条件を表1、評価結果を表3に示す。
固体状樹脂としてポリカーボネート樹脂の代わりにポリメタクリル酸メチル樹脂を用いたこと以外は、実施例1と同様の操作をすることで、実施例7に係る表面処理赤外線吸収微粒子粉末、赤外線吸収微粒子分散液、赤外線吸収微粒子分散粉、赤外線吸収シートを得て、実施例1と同様の評価を実施した。当該製造条件を表1、評価結果を表3に示す。
Na/W(モル比)=0.33の立方晶ナトリウムタングステンブロンズ粉末(住友金属鉱山株式会社製)25質量%とイソプロピルアルコール75質量%とを混合し、得られた混合液を、0.3mmφZrO2ビーズを入れたペイントシェーカーに装填して10時間粉砕・分散処理し、実施例8に係るNa0.33WOz微粒子の分散液を得た。得られた分散液中のNa0.33WOz微粒子の分散粒子径を測定したところ、100nmであった。尚、粒径測定の設定として、粒子屈折率は1.81とし、粒子形状は非球形とした。また、バックグラウンドはイソプロピルアルコールを用いて測定し、溶媒屈折率は1.38とした。また、得られた分散液の溶媒を除去したあと、結晶子径を測定したところ32nmであった。
六方晶セシウムタングステンブロンズ粉末の代わりに、K/W(モル比)=0.33の六方晶カリウムタングステンブロンズ粉末(実施例9)や、Rb/W(モル比)=0.33の六方晶ルビジウムタングステンブロンズ粉末(実施例10)や、マグネリ相のW18O49(実施例11)を用いた以外は、実施例1と同様にして赤外線吸収微粒子の分散粒子径および結晶子径を測定し、更に被覆膜形成用分散液C~Eを得た。
被覆膜形成用分散液Aの代わりに被覆膜形成用分散液C~Eを用いたこと以外は、実施例1と同様の操作をすることで、実施例9~11に係る表面処理赤外線吸収微粒子粉末、赤外線吸収微粒子分散液、赤外線吸収微粒子分散粉、赤外線吸収シートを得て、実施例1と同様の評価を実施した。当該製造条件を表1、評価結果を表3に示す。
Cs/W(モル比)=0.33の六方晶セシウムタングステンブロンズ(Cs0.33WOz)粉末(住友金属鉱山株式会社製YM-01)25質量%と純水75質量%とを混合して得られた混合液を、0.3mmφZrO2ビーズを入れたペイントシェーカーに装填し6時間(実施例12)または4時間(実施例13)の粉砕・分散処理を行い、実施例12、13に係るCs0.33WOz微粒子の分散液を得た。
また、得られた分散液の溶媒を除去したあと、実施例12、13に係るCs0.33WOz微粒子の結晶子径を測定したところ、それぞれ50nm、42nmであった。
テトラエトキシシラン309gを表面処理剤eとし、表面処理剤希釈液aの代わりに表面処理剤eを用い、イソプロピルアルコールを添加しなかったこと以外は、実施例1と同様の操作をすることで、実施例14に係る表面処理赤外線吸収微粒子粉末、赤外線吸収微粒子分散液、赤外線吸収微粒子分散粉、赤外線吸収シートを得て、実施例1と同様の評価を実施した。当該製造条件を表1、評価結果を表3に示す。
亜鉛アセチルアセトナート4.4質量%とイソプロピルアルコール95.6質量%とを混合して実施例15に係る表面処理剤希釈液fを得た。表面処理剤希釈液aの代わりに表面処理剤希釈液fを用いたこと以外は、実施例1と同様の操作をすることで、実施例15に係る表面処理赤外線吸収微粒子粉末、赤外線吸収微粒子分散液、赤外線吸収微粒子分散粉、赤外線吸収シートを得て、実施例1と同様の評価を実施した。当該製造条件を表1、評価結果を表3に示す。
真空流動乾燥の代わりに噴霧乾燥によって、実施例1に係る熟成液から媒質を蒸発させて実施例16に係る表面処理赤外線吸収微粒子を含む粉末(表面処理赤外線吸収微粒子粉末)を得た。それ以外は実施例1と同様の操作をすることで、実施例16に係る赤外線吸収微粒子分散液、赤外線吸収微粒子分散粉、赤外線吸収シートを得て、実施例1と同様の評価を実施した。当該製造条件を表1、評価結果を表3に示す。
六方晶セシウムタングステンブロンズ粉末7質量%とポリアクリレート系分散剤24質量%とトルエン69質量%とを混合し、得られた混合液を、0.3mmφZrO2ビーズを入れたペイントシェーカーに装填し4時間粉砕・分散処理し、比較例1に係る被覆膜形成用分散液Hを得た。得られた被覆膜形成用分散液H中の赤外線吸収微粒子の分散粒子径を測定したところ、100nmであった。尚、粒径測定の設定として、粒子屈折率は1.81とし、粒子形状は非球形とした。また、バックグラウンドはトルエンを用いて測定し、溶媒屈折率は1.50とした。また、得られた分散液の溶媒を除去したあと、結晶子径を測定したところ32nmであった。
次いで、この被覆膜形成用分散液Hへ表面処理剤を加えることなく、このまま比較例1に係る赤外線吸収微粒子分散液とした。当該比較例1に係る赤外線吸収微粒子分散液から真空流動乾燥により媒質を蒸発させ、比較例1に係る赤外線吸収微粒子分散粉を得た。
固体状樹脂としてポリカーボネート樹脂の代わりにポリメタクリル酸メチル樹脂を用いたこと以外は、比較例1と同様の操作をすることで、比較例2に係る赤外線吸収微粒子分散液、赤外線吸収微粒子分散粉、赤外線吸収シートを得て、実施例1と同様の評価を実施した。当該製造条件を表2、評価結果を表4に示す。
六方晶セシウムタングステンブロンズ粉末の代わりに、Na/W(モル比)=0.33の立方晶ナトリウムタングステンブロンズ粉末(比較例3)や、K/W(モル比)=0.33の六方晶カリウムタングステンブロンズ粉末(比較例4)や、Rb/W(モル比)=0.33の六方晶ルビジウムタングステンブロンズ粉末(比較例5)や、マグネリ相のW18O49(比較例6)を用いたこと以外は、比較例1と同様の操作をすることで、比較例3~6に係る赤外線吸収微粒子分散液、赤外線吸収微粒子分散粉、赤外線吸収シートを得て、実施例1と同様の評価を実施した。当該製造条件を表2、評価結果を表4に示す。
Cs/W(モル比)=0.33の六方晶セシウムタングステンブロンズ粉末13質量%とイソプロピルアルコール87質量%とを混合し、得られた混合液を、0.3mmφZrO2ビーズを入れたペイントシェーカーに装填し5時間粉砕・分散処理し、比較例7に係るCs0.33WOz微粒子の分散液を得た。得られた分散液中のCs0.33WOz微粒子の分散粒子径を測定したところ、100nmであった。尚、粒径測定の設定として、粒子屈折率は1.81とし、粒子形状は非球形とした。また、バックグラウンドはイソプロピルアルコールを用いて測定し、溶媒屈折率は1.38とした。また、得られた分散液の溶媒を除去したあと、結晶子径を測定したところ32nmであった。
Claims (23)
- 赤外線吸収微粒子の表面が、
金属キレート化合物の加水分解生成物、金属キレート化合物の加水分解生成物の重合物、金属環状オリゴマー化合物の加水分解生成物、金属環状オリゴマー化合物の加水分解生成物の重合物、から選択される1種以上を含む被覆膜で被覆されていることを特徴とする表面処理赤外線吸収微粒子。 - 前記被覆膜の膜厚が0.5nm以上であることを特徴とする請求項1に記載の表面処理赤外線吸収微粒子。
- 前記金属キレート化合物または前記金属環状オリゴマー化合物が、Al、Zr、Ti、Si、Znから選択される1種類以上の金属元素を含むことを特徴とする請求項1または2に記載の表面処理赤外線吸収微粒子。
- 前記金属キレート化合物または前記金属環状オリゴマー化合物が、エーテル結合、エステル結合、アルコキシ基、アセチル基から選択される1種以上を有することを特徴とする請求項1から3のいずれかに記載の表面処理赤外線吸収微粒子。
- 前記赤外線吸収微粒子が、一般式WyOz(但し、Wはタングステン、Oは酸素、2.2≦z/y≦2.999)、または/および、一般式MxWyOz(但し、Mは、H、He、アルカリ金属、アルカリ土類金属、希土類元素、Mg、Zr、Cr、Mn、Fe、Ru、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl、Si、Ge、Sn、Pb、Sb、B、F、P、S、Se、Br、Te、Ti、Nb、V、Mo、Ta、Re、Be、Hf、Os、Bi、I、Ybのうちから選択される1種類以上の元素、Wはタングステン、Oは酸素、0.001≦x/y≦1、2.0≦z/y≦3.0)で表記される赤外線吸収微粒子であることを特徴とする、請求項1から4のいずれかに記載の表面処理赤外線吸収微粒子。
- 請求項1から5のいずれかに記載の表面処理赤外線吸収微粒子を含むことを特徴とする表面処理赤外線吸収微粒子粉末。
- 炭素濃度が、0.2質量%以上5.0質量%以下であることを特徴とする請求項6に記載の表面処理赤外線吸収微粒子粉末。
- 請求項1から5のいずれかに記載の表面処理赤外線吸収微粒子が、所定の液体媒質中に分散していることを特徴とする赤外線吸収微粒子分散液。
- 前記液体媒質が、有機溶剤、油脂、液状可塑剤、硬化により高分子化される化合物、水、から選択される1種以上の液体媒質であることを特徴とする請求項8に記載の赤外線吸収微粒子分散液。
- 請求項1から5のいずれかに記載の表面処理赤外線吸収微粒子が、所定の固体状樹脂中に分散していることを特徴とする赤外線吸収微粒子分散体。
- 前記固体状樹脂が、フッ素樹脂、PET樹脂、アクリル樹脂、ポリアミド樹脂、塩化ビニル樹脂、ポリカーボネート樹脂、オレフィン樹脂、エポキシ樹脂、ポリイミド樹脂、から選択される1種以上の樹脂であることを特徴とする請求項10に記載の赤外線吸収微粒子分散体。
- 請求項8または9に記載の赤外線吸収微粒子分散液の乾燥固化物であることを特徴とする赤外線吸収微粒子分散体。
- 赤外線吸収微粒子と水とを混合し分散処理を行って、水を媒質とする被覆膜形成用分散液を得る工程と、
前記水を媒質とする被覆膜形成用分散液を撹拌しながら、金属キレート化合物または/および金属環状オリゴマー化合物を添加する工程と、
前記添加後も前記攪拌を継続して、前記赤外線吸収微粒子の表面を、金属キレート化合物の加水分解生成物、金属キレート化合物の加水分解生成物の重合物、金属環状オリゴマー化合物の加水分解生成物、金属環状オリゴマー化合物の加水分解生成物の重合物、から選択される1種以上で被覆し、赤外線吸収微粒子分散液を得る工程と、を有することを特徴とする表面処理赤外線吸収微粒子の製造方法。 - 赤外線吸収微粒子と有機溶剤とを混合し分散処理を行って、有機溶剤を媒質とする被覆膜形成用分散液を得る工程と、
前記有機溶剤を媒質とする被覆膜形成用分散液を撹拌しながら、金属キレート化合物または/および金属環状オリゴマー化合物と、水とを、同時に並行して添加する工程と、
前記添加後も前記攪拌を継続して、前記赤外線吸収微粒子の表面を、金属キレート化合物の加水分解生成物、金属キレート化合物の加水分解生成物の重合物、金属環状オリゴマー化合物の加水分解生成物、金属環状オリゴマー化合物の加水分解生成物の重合物、から選択される1種以上で被覆し、赤外線吸収微粒子の有機溶剤分散液を得る工程と、を有することを特徴とする表面処理赤外線吸収微粒子の製造方法。 - 前記金属キレート化合物または/および金属環状オリゴマー化合物が、Al、Zr、Ti、Si、Znから選択される1種類以上の金属元素を含むことを特徴とする請求項13または14に記載の表面処理赤外線吸収微粒子の製造方法。
- 前記赤外線吸収微粒子が、一般式WyOz(但し、Wはタングステン、Oは酸素、2.2≦z/y≦2.999)、または/および、一般式MxWyOz(但し、Mは、H、He、アルカリ金属、アルカリ土類金属、希土類元素、Mg、Zr、Cr、Mn、Fe、Ru、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl、Si、Ge、Sn、Pb、Sb、B、F、P、S、Se、Br、Te、Ti、Nb、V、Mo、Ta、Re、Be、Hf、Os、Bi、I、Ybのうちから選択される1種類以上の元素、Wはタングステン、Oは酸素、0.001≦x/y≦1、2.0≦z/y≦3.0)で表記される赤外線吸収微粒子であることを特徴とする、請求項13から15のいずれかに記載の表面処理赤外線吸収微粒子の製造方法。
- 請求項13、15または16に記載の水を媒質とする被覆膜形成用分散液、または、請求項14から16のいずれかに記載の有機溶剤を媒質とする被覆膜形成用分散液から媒質を除去して、表面処理赤外線吸収微粒子を含む表面処理赤外線吸収微粒子粉末を得る工程、を有することを特徴とする表面処理赤外線吸収微粒子粉末の製造方法。
- 前記表面処理赤外線吸収微粒子粉末に含まれる炭素濃度が、0.2質量%以上5.0質量%以下であることを特徴とする、請求項17に記載の表面処理赤外線吸収微粒子粉末の製造方法。
- 請求項17または18に記載の表面処理赤外線吸収微粒子粉末を所定の媒質に加え、分散させる工程、を有することを特徴とする赤外線吸収微粒子分散液の製造方法。
- 請求項13、15または16に記載の水を媒質とする被覆膜形成用分散液、または、請求項14から16のいずれかに記載の有機溶剤を媒質とする被覆膜形成用分散液の媒質を、所定の媒質に溶媒置換する工程、を有することを特徴とする赤外線吸収微粒子分散液の製造方法。
- 請求項13、15または16に記載の水を媒質とする被覆膜形成用分散液、または、請求項14から16のいずれかに記載の有機溶剤を媒質とする被覆膜形成用分散液の媒質を、予め、所定の媒質としておくことにより、得られた請求項13、15または16に記載の水を媒質とする被覆膜形成用分散液、または、請求項14から16のいずれかに記載の有機溶剤を媒質とする被覆膜形成用分散液を、赤外線吸収微粒子分散液とすることを特徴とする赤外線吸収微粒子分散液の製造方法。
- 請求項19から21のいずれかに記載の赤外線吸収微粒子分散液の製造方法で得られた赤外線吸収微粒子分散液を、所定の基材上に塗布して乾燥し、赤外線吸収微粒子分散体を得る工程を有することを特徴とする赤外線吸収微粒子分散体の製造方法。
- 請求項17または18に記載の表面処理赤外線吸収微粒子粉末の製造方法で得られた表面処理赤外線吸収微粒子粉末、請求項19から21のいずれかに記載の赤外線吸収微粒子分散液の製造方法で得られた赤外線吸収微粒子分散液、のいずれかを、所定の固体状樹脂中に分散させる工程を有することを特徴とする赤外線吸収微粒子分散体の製造方法。
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US20210214273A1 (en) * | 2018-05-11 | 2021-07-15 | Sumitomo Metal Mining Co., Ltd. | Surface-treated infrared absorbing fine particle dispersion liquid and infrared absorbing transparent substrate |
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JP2021067842A (ja) * | 2019-10-24 | 2021-04-30 | 住友金属鉱山株式会社 | 近赤外線遮蔽材料の製造方法 |
JP7318483B2 (ja) | 2019-10-24 | 2023-08-01 | 住友金属鉱山株式会社 | 近赤外線遮蔽材料の製造方法 |
JP2021116212A (ja) * | 2020-01-28 | 2021-08-10 | 住友金属鉱山株式会社 | 赤外線吸収微粒子粉末、赤外線吸収微粒子粉末分散液、赤外線吸収微粒子分散体、および、それらの製造方法 |
WO2022085730A1 (ja) | 2020-10-23 | 2022-04-28 | 住友金属鉱山株式会社 | 表面処理赤外線吸収微粒子およびその製造方法、赤外線吸収微粒子分散液、並びに赤外線吸収微粒子分散体 |
KR20230092871A (ko) | 2020-10-23 | 2023-06-26 | 스미토모 긴조쿠 고잔 가부시키가이샤 | 표면 처리 적외선 흡수 미립자 및 그 제조 방법, 적외선 흡수 미립자 분산액, 그리고 적외선 흡수 미립자 분산체 |
WO2022270303A1 (ja) | 2021-06-22 | 2022-12-29 | 住友金属鉱山株式会社 | 赤外線吸収複合微粒子、赤外線吸収微粒子分散液、および、赤外線吸収微粒子分散体 |
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BR112020009258A2 (pt) | 2020-10-20 |
JP6769562B2 (ja) | 2020-10-14 |
JPWO2019093524A1 (ja) | 2020-10-01 |
AU2018365930B2 (en) | 2021-10-28 |
MY184955A (en) | 2021-04-30 |
AU2018365930A1 (en) | 2020-06-18 |
KR20200084323A (ko) | 2020-07-10 |
CN111373011B (zh) | 2023-04-21 |
EP3712223A4 (en) | 2021-07-21 |
EP3712223A1 (en) | 2020-09-23 |
TW201922622A (zh) | 2019-06-16 |
IL274587A (en) | 2020-06-30 |
CN111373011A (zh) | 2020-07-03 |
MX2021008815A (es) | 2021-08-24 |
KR102263303B1 (ko) | 2021-06-14 |
US11208563B2 (en) | 2021-12-28 |
TWI722334B (zh) | 2021-03-21 |
IL274587B (en) | 2022-08-01 |
BR112020009258B1 (pt) | 2021-02-23 |
US20210047518A1 (en) | 2021-02-18 |
MX2020004746A (es) | 2020-08-20 |
EP3712223B1 (en) | 2022-10-26 |
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