TW201617490A - Heat-ray shielding fine particles, heat-ray shielding fine particles dispersion liquid, heat-ray shielding film, heat-ray shielding glass, heat-ray shielding fine particles dispersion body and heat-ray shielding laminated transparent base material - Google Patents

Abstract

Provided are: heat-ray-shielding microparticles for enabling use of a communication device, imaging device, sensor, or the like which uses near-infrared light in a corresponding wavelength region through a structure, a heat-ray-shielding film or heat-ray-shielding glass, a dispersion, or a laminated transparent substrate, while exhibiting heat-ray-shielding characteristics; a heat-ray-shielding microparticle liquid dispersion containing the heat-ray-shielding microparticles; a heat-ray-shielding film or heat-ray-shielding glass; a heat-ray-shielding dispersion; and a heat-ray-shielding laminated transparent substrate. Provided are: composite tungsten oxide microparticles having a hexagonal crystal structure represented by the general formula AaMbWcOd, element A being one or more species of elements selected from Mo, Ru, Cr, Ni, V, Co, Fe, Mn, Ti, Ge, Sn, Ga, Pb, Bi, In, Sb, Pd, and Tl, M being one or more species of elements selected from alkali metals and alkaline earth metals, W being tungsten, O being oxygen, 0.001 ≤ a/b ≤ 0.1, and 0.20 ≤ b/(a + c) ≤ 0.61, and 2.2 ≤ d/(a + c) ≤ 3.0; and a heat-ray-shielding microparticle liquid dispersion which uses the heat-ray-shielding microparticles.

Description

Heat ray shielding microparticles, heat ray shielding microparticle dispersion, heat ray shielding film, heat ray shielding glass, heat ray shielding microparticle dispersion, and heat ray shielding interlayer transparent substrate

The present invention relates to a heat ray shielding microparticle, a heat ray shielding microparticle dispersion, a heat ray shielding film, a heat ray shielding glass which has good visible light transmittance and excellent heat ray shielding function, and transmits near-infrared light having a predetermined wavelength. The heat ray shielding fine particle dispersion and the interlayer transparent substrate for heat ray shielding.

As a heat ray shielding technique which has good visible light transmittance and maintains transparency and reduces solar transmittance, various techniques have been proposed so far. Among them, the heat ray shielding technique using the conductive fine particles, the dispersion of the conductive fine particles, and the interlayer transparent substrate has the advantages of excellent heat ray shielding characteristics, low cost, radio wave permeability, and weather resistance. Higher.

For example, Patent Document 1 proposes an infrared absorbing synthetic resin molded article which is formed by laminating a transparent resin containing a fine powder of tin oxide in a dispersed state on a transparent synthetic resin substrate or transparently containing fine powder of tin oxide in a dispersed state. The synthetic resin is formed into a sheet or a film.

Patent Document 2 proposes a laminated glass in which an intermediate layer is interposed between at least two opposing plate glasses, in which Sn, Ti, Si, Zn, Zr, Fe, Al, and the like are dispersed. a metal of Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, Mo, an oxide of the metal, a nitride of the metal, a sulfide of the metal, and a metal A dopant of Sb or F, or a mixture of such.

In addition, the applicant discloses a coating liquid for a selective permeable membrane or a selective permeable membrane in which at least one of titanium nitride fine particles and lanthanum boride fine particles are dispersed.

However, in the heat ray shielding structure, the heat ray shielding fine particle dispersion, or the interlayer transparent substrate such as the infrared absorbing synthetic resin molded article disclosed in Patent Documents 1 to 3, heat rays having a high visible light transmittance are required. The problem of insufficient shielding performance. For example, as an example of the specific numerical value of the heat ray shielding performance of the heat ray shielding structure disclosed in Patent Documents 1 to 3, the visible light transmittance calculated based on JIS R 3106 (may be described only in the present invention as When the "visible light transmittance" is 70%, the solar radiation transmittance (which may be simply described as "insolation transmittance" in the present invention) calculated based on JIS R 3106 is more than 50%.

Therefore, the applicant disclosed in Patent Document 4 that a heat ray shielding fine particle dispersion is a dispersion of infrared ray shielding material fine particles in which infrared ray shielding material fine particles are dispersed in a medium, characterized in that the infrared ray shielding material fine particles are contained. General formula M _x W _y O _z (wherein element M is selected from the group consisting of 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 One or more elements of Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, and 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0) The composite tungsten oxide fine particles include any one or more of fine crystals having a hexagonal crystal, a tetragonal crystal, or a cubic crystal structure, and the fine particles of the infrared shielding material have a particle diameter of 1 nm or more and 800 nm or less.

As disclosed in Patent Document 4, the heat ray shielding fine particle dispersion using the composite tungsten oxide fine particles represented by the above formula M _x W _y O _z exhibits high heat ray shielding performance, and the visible light transmittance is 70%. The solar transmittance is improved to less than 50%. In particular, a heat ray-shielding fine particle dispersion using at least one selected from a specific element such as Cs or Rb, Tl as the element M and a crystal structure having hexagonal crystals as a composite tungsten oxide fine particle exhibits excellent heat ray shielding. The solar radiation transmittance at a visible light transmittance of 70% was improved to less than 37%.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2-136230

[Patent Document 2] Japanese Patent Laid-Open No. Hei 8-259279

[Patent Document 3] Japanese Patent Laid-Open No. Hei 11-181336

[Patent Document 4] International Publication No. WO2005/037932

However, the composite tungsten oxide fine particles represented by the above formula M _x W _y O _z or the heat ray shielding fine particle dispersion, the heat ray shielding film, the heat ray shielding glass, the heat ray shielding fine particle dispersion or the interlayer transparent layer using the same The use of substrates in the market has expanded and new problems have been discovered. This problem is caused by the composite tungsten oxide fine particles described in the above formula M _x W _y O _z , the heat ray shielding film or the heat ray shielding glass containing the composite tungsten oxide fine particles, and the composite tungsten oxide fine particles. When the dispersion transparent substrate for a dispersion or heat ray shielding is applied to a structure such as a window material, the transmittance of near-infrared light having a wavelength of 700 to 1200 nm is also greatly reduced in light passing through the window member or the like. The near-infrared light in this wavelength region is almost invisible to the human eye, and can be oscillated by a light source such as a low-cost near-infrared LED. Therefore, it is widely used for communication using near-infrared light, a camera, a sensor, and the like. However, a structure such as a window material containing a composite tungsten oxide fine particle represented by the above formula M _x W _y O _z , a heat ray shielding body, a heat ray shielding substrate, a dispersion, or an interlayer transparent substrate may also be used. The near-infrared light in this wavelength region is strongly absorbed together with the heat rays. As a result, it is necessary to abandon the use of a structure such as a window material containing a composite tungsten oxide fine particle represented by the above formula M _x W _y O _z , a heat ray shielding film or a heat ray shielding glass, a dispersion or an interlayer transparent substrate. The use of near-infrared light communication, cameras, sensors, and the like.

For example, when the heat ray shielding film containing the composite tungsten oxide fine particles described in Patent Document 4 is attached to a window of a general house, it includes an infrared oscillating machine placed indoors and an infrared receiver placed outdoors. Near-infrared light communication between the detecting devices is disturbed, causing the device to fail to operate normally.

In spite of the above problems, a structure such as a heat ray shielding film or a window material containing a composite tungsten oxide fine particle or the like, a dispersion, or an interlayer transparent substrate for heat ray shielding is high in the ability to cut off heat rays more, and Expanded use in the market area where heat ray shielding is expected. However, when such a heat ray shielding film or a structure such as a window material is used, wireless communication using a near-infrared light, a camera, a sensor, or the like cannot be used.

The present invention has been completed in view of the above problems. Further, the problem to be solved by the present invention is to provide a heat ray shielding fine particle, a heat ray shielding fine particle dispersion containing the heat ray shielding fine particle, a heat ray shielding film or a heat ray shielding glass, a heat ray shielding fine particle dispersion, and heat. The intercalation transparent substrate for ray shielding, which exhibits heat ray shielding characteristics and has a transmittance of near-infrared light having a wavelength of 700 to 1200 nm, even when applied to a structure such as a window material. A communication device, a camera, a sensor, or the like using the near-infrared light in the wavelength region of the structure, the heat ray shielding film or the heat ray shielding glass, the dispersion or the interlayer transparent substrate may be used.

The inventors of the present invention conducted various studies in order to solve the above problems. For example, it is also considered that if only the transmittance of near-infrared light in a region of a wavelength of 700 to 1200 nm is increased, the concentration of the composite tungsten oxide fine particles, the composite tungsten oxide in the heat ray shielding film or the heat ray shielding glass are appropriately reduced. The concentration of the fine particles, the heat ray shielding fine particle dispersion, or the concentration of the composite tungsten oxide fine particles in the interlayer transparent substrate for heat ray shielding may be sufficient. However, in the case of reducing the concentration in the film of the composite tungsten oxide fine particles, the heat ray absorbing ability at the bottom of the region having a wavelength of 1200 to 1800 nm is also lowered, and the heat ray shielding effect is lowered. Here, the inventors of the present invention have repeatedly conducted research to obtain an epoch-making insight by replacing one of the tungsten atoms with a selected one from the composite tungsten oxide fine particles represented by the above formula M _x W _y O _z . One or more metal atoms of Ru, Cr, Ni, V, Co, Fe, Mn, Ti, Ge, Sn, Ga, Pb, Bi, In, Sb, Pd, and Tl (described in the present invention) The "element A") is a heat ray shielding fine particle which can improve the transmittance of near-infrared light in a region of a wavelength of 700 to 1200 nm in a state in which the heat ray absorbing ability at the bottom of the wavelength of 1200 to 1800 nm is ensured.

However, it is also considered that the heat ray shielding fine particles having a transmittance of near-infrared light in a region having a wavelength of 700 to 1200 nm are used as an index for evaluating the heat ray shielding performance previously used as a composite tungsten oxide fine particle or a dispersion thereof, for example, The evaluation of the solar transmittance of the visible light transmittance evaluated in accordance with JIS R 3106 is inferior to the conventional composite tungsten oxide which does not contain the element A. Therefore, from this point of view, further studies have been conducted on the heat ray shielding fine particles having a transmittance of near-infrared light in a region of a wavelength of 700 to 1200 nm, and as a result, it is understood that the heat ray shielding fine particles and the conventional formula M _x W _y The composite tungsten oxide fine particles represented by O _z are not inferior in performance as heat ray shielding fine particles.

The reason is considered to be that the absorbance of human skin is small under near-infrared light having a wavelength of 700 to 1200 nm, but on the other hand, it is large under heat rays having a wavelength of 1500 to 2100 nm. Moreover, it is said that the reason why the sun gives the skin a hot feeling of heat (so-called hot feeling) is that the heat ray having a wavelength of 1500 to 2100 nm has a large influence (for example, referring to the end of the first class, the automotive technology society will pre-print the academic lecture). Set No. 33-99, 13 (1999)). That is, it is understood that by using the heat ray shielding microparticles of the present invention, even if the transmittance of near-infrared light having a wavelength of 700 to 1200 nm is improved, the transmission of heat rays having a wavelength of 1500 to 2100 nm can be suppressed, thereby reducing the viewpoint of the hot sensation. In other words, the characteristics of the heat ray shielding material, the heat ray shielding film or the heat ray shielding glass, the heat ray shielding fine particle dispersion or the interlayer transparent substrate are also equivalent to the conventional tungsten represented by the general formula M _x W _y O _z The oxide fine particles, the heat ray shielding film or the heat ray shielding glass using the composite tungsten oxide fine particles, the dispersion obtained by dispersing the composite tungsten oxide fine particles in various media, or the interlayer transparent substrate containing the fine particles. In other words, it has been found that a heat ray shielding film or a heat ray shielding glass containing the fine particles, a dispersion in which the fine particles are dispersed in various media, or an interlayer transparent substrate containing the fine particles is used to maintain the conventional general formula M _x The heat ray shielding film or the heat ray shielding glass which improves the transmittance of near-infrared light having a wavelength of 700 to 1200 nm in a state in which the composite tungsten oxide represented by W _y O _z has a high heat shielding property, thereby completing the present invention .

The heat ray shielding fine particles of the present invention are specifically represented by the general formula A _a M _b W _c O _d . The element A is one or more selected from the group consisting of Mo, Ru, Cr, Ni, V, Co, Fe, Mn, Ti, Ge, Sn, Ga, Pb, Bi, In, Sb, Pd, and Tl, and replaces tungsten. An element of one part of an atom. The element M is one or more elements selected from the group consisting of alkali metals and alkaline earth metals. W is tungsten and O is oxygen. Further, it is a composite tungsten oxide fine particle having a hexagonal crystal structure represented by 0.001 ≦ a/b ≦ 0.1, 0.20 ≦ b / (a + c) ≦ 0.61, 2.2 ≦ d / (a + c) ≦ 3.0, Further, it is ensured that the transmittance of near-infrared light in a region having a wavelength of 700 to 1200 nm is improved in a state in which the heat ray absorbing ability at the bottom of the wavelength of 1200 to 1800 nm is improved.

Here, the element A which replaces a part of the tungsten atom is solid-dissolved in the hexagonal crystal structure of the composite tungsten oxide, not only the physical mixture of the composite tungsten oxide and the compound containing the element A. Therefore, the element A or the compound containing the element A is not in the form of segregation such as grain boundary of the composite tungsten oxide. However, in the element A, a component other than the hexagonal crystal structure which is solid-dissolved in the composite tungsten oxide is used as a compound which inevitably contains the element A in engineering, and is segregated to a crystal or a grain boundary in a small amount.

The reason why the heat ray shielding fine particles of the present invention improve the transmittance of near-infrared light in a region having a wavelength of 700 to 1200 nm in a state in which the heat ray absorbing ability at the bottom of the wavelength of 1200 to 1800 nm is ensured is not clearly explained. However, the inventors believe that the reason is that the electronic structure of the composite tungsten oxide fine particles and the electricity are derived from electricity. The light absorption mechanism of the substructure.

That is, it is considered that the broad absorption of the composite tungsten oxide fine particles in the near-infrared region includes a combination of two kinds of absorption mechanisms of local surface plasmon absorption caused by free electrons and small polarons caused by local electrons ( See, for example, J. Appl. Phys. 112, 074308 (2012)). Further, it is considered that the absorption of near-infrared light in the wavelength region of the wavelength of 700 to 1200 nm is absorbed by the small polaron. Furthermore, the transition energy of the small polaron is 1.5 eV (wavelength 826 nm). On the other hand, an absorption of a larger heat ray having a wavelength of 1200 to 1800 nm as a bottom utilizes absorption of local surface plasmon resonance caused by free electrons. Furthermore, the center of the energy of the local surface plasmon resonance is considered to be 0.83 eV (wavelength 1494 nm).

Investigation that, in the composite tungsten oxide fine particles, by using the element A substitution of tungsten atoms (W ⁵⁺⁾ and to ensure that the wavelength region of 700 to 1200 ~ 1800nm ~ 1200nm wavelength of improving the state of the bottom of the heat-ray absorption capacity of the The reason for the transmittance of near-infrared light is that the element A is inserted into the crystal structure of the composite tungsten oxide, the tungsten element is replaced, and the electron structure is changed. The element A becomes an electron absorption source in the crystal, and the W ^{5 is} reduced. The amount of ⁺ , thereby attenuating the absorption caused by the small polarons.

The present inventors have learned that the dispersion obtained by dispersing the heat ray shielding fine particles of the present invention in any liquid medium can be used for the production of a film or glass in the same manner as the dispersion of the conventional composite tungsten oxide fine particles. Raw materials for coatings, film or sheet and plate resins, masterbatches and other diverse heat ray shielding compositions. Further, the inventors of the present invention have thought of providing a coating layer on at least one side of a transparent substrate selected from a transparent film substrate or a transparent glass substrate, and containing the above-mentioned heat ray shielding fine particles in the coating layer. The adhesive can be manufactured to improve the near red color of the wavelength of 700 to 1200 nm while maintaining the high heat shielding property of the conventional composite tungsten oxide. A heat ray shielding film or a heat ray shielding glass having a transmittance of external light. Further, the inventors of the present invention have found that the organic solvent dispersion can be obtained by dispersing the heat ray shielding fine particles described above and a dispersing agent together in an organic solvent, and then removing the organic solvent to obtain a heat ray. The heat ray shielding fine particle dispersion in which the fine particles are dispersed in the dispersing agent in the form of a powder (which may be referred to as "dispersion powder" in the present invention). Further, it has been found that a liquid-like heat ray shielding fine particle dispersion can be obtained by dispersing the heat ray shielding fine particles or the dispersion powder in a plasticizer or a resin (in the present invention, it is sometimes referred to as "plasticizer dispersion liquid"). Or a granular heat ray shielding fine particle dispersion (may be described as "masterbatch" in the present invention). Further, it is understood that by uniformly mixing the dispersion powder or the plasticizer dispersion and the master batch into the transparent resin, it is possible to manufacture the wavelength 700 by maintaining the high heat shielding property of the conventional composite tungsten oxide. A heat ray shielding sheet or a heat ray shielding film having a transmittance of near-infrared light in a region of ~1200 nm. Further, it is also known that by allowing the heat ray shielding sheet or the heat ray shielding film to exist between a plurality of transparent substrates, it is possible to maintain the high heat shielding property of the conventional composite tungsten oxide. The present invention has been completed in a state in which a sandwich transparent substrate for heat ray shielding having a transmittance of near-infrared light having a wavelength of 700 to 1200 nm is used.

That is, to solve the above problems of the first line INVENTION A heat ray shielding fine particles, which based formula _{A a} M _b W _c O _d represents the fine particles of the composite tungsten oxide, and the element A is selected from Mo, Ru, Cr, Ni One or more elements of V, Co, Fe, Mn, Ti, Ge, Sn, Ga, Pb, Bi, In, Sb, Pd, and Tl, and M is one or more selected from the group consisting of alkali metals and alkaline earth metals. The element, W is tungsten, O is oxygen, and 0.001 ≦ a / b ≦ 0.1, 0.20 ≦ b / (a + c) ≦ 0.61, 2.2 ≦ d / (a + c) ≦ 3.0, and has hexagonal crystal structure.

The heat ray shielding fine particles according to the first aspect of the invention, wherein the heat ray shielding fine particles have a particle diameter of 1 nm or more and 800 nm or less.

According to a third aspect of the invention, the heat ray shielding fine particle dispersion liquid obtained by dispersing the heat ray shielding fine particles according to the first or second invention in a liquid medium to obtain a dispersion liquid, and the liquid medium It is selected from the group consisting of water, organic solvents, greases, liquid resins, plasticizers for liquid plastics, or mixtures thereof.

The heat ray shielding fine particle dispersion liquid according to the third aspect of the invention, wherein the content of the heat ray shielding fine particles contained in the liquid medium is 0.01% by mass or more and 50% by mass or less.

The heat ray shielding fine particle dispersion liquid according to the third aspect of the present invention, wherein the visible light transmittance is 85% when only the light absorption by the heat ray shielding fine particles is calculated. The transmittance of light having a wavelength of 850 nm is 23% or more and 45% or less, and the minimum value of transmittance in the range of 1200 to 1800 nm is 15% or less.

A sixth aspect of the invention is a heat ray shielding film or a heat ray shielding glass, characterized in that a coating layer is provided on at least one side of a transparent substrate selected from a transparent film substrate or a transparent glass substrate, wherein the coating layer contains heat rays The binder resin for shielding fine particles, the heat ray shielding microparticles are composite tungsten oxide microparticles represented by the following formula: _a composite tungsten oxide represented by the formula A _a M _b W _c O _d , and the A system is selected from the group consisting of Mo and Ru. One or more elements of Cr, Ni, V, Co, Fe, Mn, Ti, Ge, Sn, Ga, Pb, Bi, In, Sb, Pd, and Tl, and M is selected from alkali metals and alkaline earth metals. One or more elements, W is tungsten, O is oxygen, and 0.001 ≦ a / b ≦ 0.1, 0.20 ≦ b / (a + c) ≦ 0.61, 2.2 ≦ d / (a + c) ≦ 3.0, and The composite tungsten oxide fine particle system has a hexagonal crystal structure.

According to a seventh aspect of the invention, the heat ray shielding film or the heat ray shielding glass is characterized in that the composite tungsten oxide fine particles have a diameter of 1 nm or more and 800 nm or less.

According to a eighth aspect of the invention, the heat ray shielding film or the heat ray shielding glass is characterized in that the binder resin is a UV curable resin binder.

A ninth invention is a heat ray shielding film or a heat ray shielding glass, wherein the coating layer has a thickness of 10 μm or less.

A tenth invention is a heat ray shielding film characterized in that the transparent film substrate is a polyester film.

The eleventh aspect of the invention is the heat ray shielding film or the heat ray shielding glass, wherein the content of the heat ray shielding fine particles contained in the coating layer per unit projected area is 0.1 g/m ² or more and 5.0 g/m ² or less. .

According to a twelfth aspect of the invention, a heat ray shielding film or a heat ray shielding glass is characterized in that: when the visible light transmittance of the transparent substrate is 70%, the wavelength is 850 nm. The transmittance is 23% or more and 45% or less, and the minimum value of the transmittance in the range of 1200 to 1800 nm is 15% or less.

According to a thirteenth aspect of the invention, there is provided a heat ray shielding fine particle dispersion comprising at least a heat ray shielding fine particle and a thermoplastic resin, wherein the heat ray shielding fine particle is a composite tungsten oxide fine particle represented by the following formula: AaMbWcOd, and A is selected from the group consisting of Mo, Ru, Cr, Ni, V, Co, Fe, Mn, Ti, Ge, Sn, Ga, Pb, Bi, In, Sb, Pd, and Tl. One or more elements from alkali metals and alkaline earth metals, W is tungsten, O is oxygen, 0.001 ≦a/b ≦ 0.1, 0.20 ≦ b / (a + c) ≦ 0.61, 2.2 ≦ d / (a + c ) ≦ 3.0 and has a hexagonal crystal structure.

A fourteenth aspect of the invention is the heat ray shielding fine particle dispersion, characterized in that the thermoplastic resin is any one selected from the group consisting of polyethylene terephthalate resin, polycarbonate resin, acrylic resin, and benzene. Vinyl resin, polyamide resin, polyethylene resin, vinyl chloride resin, olefin resin, epoxy resin, polyimine resin, fluororesin, ethylene. a resin of a vinyl acetate copolymer, a resin group of polyvinyl acetal resin; or a mixture of two or more resins selected from the group of the above resins; or 2 selected from the group of resins described above A copolymer of the above resins.

According to a fifteenth aspect of the invention, in the heat ray shielding fine particle dispersion, the composite tungsten oxide fine particles have a diameter of 1 nm or more and 800 nm or less.

According to a sixteenth aspect of the invention, in the heat ray shielding fine particle dispersion, the composite tungsten oxide fine particles of 0.5% by mass or more and 80.0% by mass or less are contained.

The seventeenth invention is a heat ray shielding fine particle dispersion characterized by: The heat ray shielding fine particle dispersion is in the form of a sheet, a plate, or a film.

According to a thirteenth aspect, the heat ray shielding fine particle dispersion is characterized in that the content of the heat ray shielding fine particles per unit projection area included in the heat ray shielding fine particle dispersion is 0.1 g/m ² or more and 5.0 g/m. ^2.

According to a nineteenth aspect of the invention, in the heat ray shielding fine particle dispersion, the transmittance of the near-infrared light having a wavelength of 850 nm is 23% or more and 45% or less when the visible light transmittance of the thermoplastic resin is 70%, and The minimum value of the transmittance of the heat ray having a wavelength of 1200 to 1800 nm is 15% or less.

According to a twentieth aspect of the invention, there is provided a heat ray shielding fine particle dispersion according to any one of the present invention, characterized in that the heat ray shielding interlayer transparent substrate is provided between the plurality of transparent substrates.

According to a twenty-first aspect of the present invention, there is provided a sandwich transparent substrate for heat ray shielding, characterized in that a transmittance of near-infrared light having a wavelength of 850 nm is 23% or more and 45% or less, and a transmittance of a heat ray having a wavelength of 1200 to 1800 nm is minimum. It is 15% or less.

According to the first to fifth aspects of the present invention, it is possible to obtain heat ray shielding fine particles which exhibit heat ray shielding characteristics and have a transmittance to near-infrared light having a wavelength of 700 to 1200 nm, and to disperse the heat ray shielding fine particles in a liquid medium. The heat ray that is formed in the film shields the fine particle dispersion. Further, according to the sixth to twelfth inventions, the following heat ray shielding film or heat ray shielding glass can be obtained which is compared with a heat ray shielding film or a heat ray shielding glass using a composite tungsten oxide of the prior art. In a state in which the heat ray shielding property at the bottom of the heat ray region having a wavelength of 1200 to 1800 nm is maintained, the transmittance of the near-infrared light having a wavelength of 700 to 1200 nm is higher. Its knot As a result, it is possible to provide a heat ray shielding film or heat ray shielding which exhibits heat ray shielding characteristics and can use a communication device, a camera, a sensor, or the like using near-infrared light via a heat ray shielding film or a heat ray shielding glass. glass. Further, according to the invention of the thirteenth to twenty-firstth invention, the following heat ray shielding fine particle dispersion or interlayer transparent substrate which is a heat ray shielding fine particle dispersion or a sandwich transparent base using a conventional tungsten oxide of a conventional technique can be obtained. The transmittance of the near-infrared light having a wavelength of 700 to 1200 nm is higher in a state in which the heat ray shielding property of the heat ray region having a wavelength of 1200 to 1800 nm is maintained as compared with the material. As a result, it is possible to provide a heat ray shielding fine particle dispersion that exhibits heat ray shielding characteristics and can use a near-infrared light communication device, a camera, a sensor, or the like that shields the fine particle dispersion or the interlayer transparent substrate via heat rays. And a laminated transparent substrate for heat ray shielding.

Figure 1 is a graph showing the transmittance distribution of each wavelength of the heat ray shielding film of the present invention.

Hereinafter, in the embodiment of the present invention, the method of manufacturing [a] heat ray shielding fine particles, [b] heat ray shielding fine particles, and [c] heat ray shielding fine particle containing heat ray shielding fine particle dispersion, [d] A dispersion liquid containing heat ray shielding fine particles which is preferable for producing a heat ray shielding film and a heat ray shielding glass, a method for producing the same, [e] a method for producing a heat ray shielding film and a heat ray shielding glass, [f] A method for producing a heat ray shielding fine particle dispersion, and [g] a method for producing a heat shielding ray shielding interlayer transparent substrate will be described. Further, with respect to the method for producing the [f] heat ray shielding fine particle dispersion, (1) a method of manufacturing a fine particle-shaped heat ray shielding fine particle dispersion, and (2) a heat ray of a sheet shape or a film shape. Shading of microparticle dispersion The method is further explained.

[a]Heat ray shielding particles

The heat ray shielding fine particles of the present invention are composite tungsten oxide fine particles represented by the general formula A _a M _b W _c O _d . The element A is one or more elements selected from the group consisting of Mo, Ru, Cr, Ni, V, Co, Fe, Mn, Ti, Ge, Sn, Ga, Pb, Bi, In, Sb, Pd, and Tl. M is one or more elements selected from the group consisting of an alkali metal and an alkali metal, W is tungsten, and O is oxygen. Further, it is a composite tungsten oxide fine particle having a hexagonal crystal structure of 0.001 ≦ a/b ≦ 0.1, 0.20 ≦ b / (a + c) ≦ 0.61, 2.2 ≦ d / (a + c) ≦ 3.0.

The molar addition amount of the element M to the total of tungsten and the element A: b/(a+c) is preferably 0.2 or more and 0.61 or less, more preferably 0.30 or more and 0.45 or less. The reason for this is that if the value of b/(a+c) is 0.2 or more, the heat ray absorbing effect is sufficiently exhibited, and if it is 0.61 or less, the precipitation of the compound of the element A including Cs can be avoided, resulting in heat ray absorption. The effect is reduced.

Further, the ratio of addition of the element A to the element M: a/b is preferably 0.001 or more and 0.1 or less, more preferably 0.04 or more and 0.1 or less. The reason for this is that when the value of a/b is 0.001 or more, the effect of increasing the transmittance of near-infrared light having a wavelength of 700 to 1200 nm can be obtained, and if it is 0.1 or less, the heat ray absorbing effect at a wavelength of 1200 to 1800 nm can be secured.

Further, the value of d is preferably 2.2 ≦ d / (a + c) ≦ 3.0. The reason for this is that when oxygen is less than the stoichiometric ratio with respect to tungsten oxide and element A: d / (a + c) < 3.0, there is also supply of free electrons by adding the above element M. The reason is that by using the supply of free electrons, it is manifested that the local surface electricity caused by the free electrons is utilized. The near-infrared absorption of the strong resonance of the slurry. However, from the viewpoint of optical characteristics, it is more preferably 2.80 ≦d / (a + c) ≦ 3.00. Further, one part of oxygen in the composite tungsten oxide may be replaced with other elements. Examples of the other element include nitrogen, sulfur, halogen, and the like.

Composite tungsten oxide microparticles in the above general formula _{A a} M _b W _c O _d of the represented, as those of the embodiment having a plus features _{include: Mo 0.02 Cs 0.33 W 0.98 O} 3, Pb 0.02 Cs 0.33 W 0.98 O _{3, Sb 0.02 Cs 0.33 W 0.98} O 3, Bi 0.03 Cs 0.33 W 0.97 O 3, Sn 0.02 Cs 0.33 W 0.98 O 3, Mo 0.02 Sn 0.01 Cs 0.33 W 0.97 O 3 and the like. However, if the values of a, b, c, and d converge within the above range, the useful heat ray shielding characteristics of the present invention described above can be obtained.

The particle size of the heat ray shielding fine particles of the present invention can be appropriately selected according to the purpose of use of the heat ray shielding film/heat ray shielding substrate produced by using the heat ray shielding fine particles or the heat ray shielding fine particle dispersion liquid, and the particle diameter is preferably 1 nm or more and 800 nm or less. The reason for this is that when the particle diameter is 800 nm or less, the strong near-infrared absorption by the heat ray shielding fine particles of the present invention can be exhibited, and if the particle diameter is 1 nm or more, industrial production is easy.

When the heat ray shielding film is used for applications requiring transparency, it is preferred that the heat ray shielding fine particles have a dispersed particle diameter of 40 nm or less. The reason for this is that if the heat ray shielding fine particles have a dispersed particle diameter of less than 40 nm, scattering of light due to Mie scattering and Rayleigh scattering of the fine particles can be sufficiently suppressed, and the visibility in the visible light wavelength region can be maintained while being high. Maintain transparency efficiently. When it is used for applications such as a windshield for automobiles, in particular, in order to further suppress the scattering, it is preferable to set the dispersed particle diameter of the composite tungsten oxide to 30 nm or less, preferably 25 nm or less.

[b]Method for manufacturing heat ray shielding microparticles

The heat ray shielding fine particles represented by the general formula A _a M _b W _c O _{d of} the present invention can be obtained by heat-treating a tungsten compound starting material in an inert gas atmosphere or a reducing gas atmosphere.

First, the tungsten compound starting material will be described. The tungsten compound starting material of the present invention contains a simple substance or a mixture of compounds of each of tungsten, element A, and element M. As the tungsten raw material, it is preferably selected from the group consisting of tungstic acid powder, tungsten trioxide powder, tungsten dioxide powder, tungsten oxide hydrate powder, tungsten hexachloride powder, ammonium tungstate powder, or dissolved tungsten hexachloride powder. a hydrate powder of tungsten oxide obtained by drying in an alcohol, or a hydrate powder of tungsten oxide obtained by dissolving tungsten hexachloride in an alcohol, adding water to precipitate and drying it, or making tungsten Any one or more of the tungsten compound powder and the metal tungsten powder obtained by drying the aqueous solution of ammonium acid. As a raw material of the element A or the element M, a simple substance of the element A or M, a chloride salt of an element A or M, a nitrate, a sulfate, an oxalate, an oxide, a carbonate, a tungstate, or a hydroxide can be cited. Things, etc., but are not limited to these.

The above tungsten compound starting material was weighed to prepare and mix and mix in an amount of 0.001 ≦a/b ≦ 0.1, 0.20 ≦ b / (a + c) ≦ 0.61. In this case, it is preferred to uniformly mix the raw materials of tungsten, element A, and element M as uniformly as possible, and if possible, at a molecular level. Therefore, it is preferred that each of the above raw materials is mixed as a solution, and it is preferred that each raw material be dissolved in a solvent such as water or an organic solvent. When each raw material is soluble in a solvent such as water or an organic solvent, the tungsten compound starting material of the present invention can be produced by sufficiently mixing each raw material with a solvent and then volatilizing the solvent. However, even if there is no solvent which is soluble in the raw material, the raw material of the tungsten compound of the present invention can be produced by sufficiently uniformly mixing the respective raw materials by a known means such as a ball mill.

Next, the heat treatment in an inert gas atmosphere or a reducing gas atmosphere will be described. First, as a heat treatment condition in an inert gas atmosphere, it is preferably 400 ° C or more and 1000 ° C or less. The starting material which is heat-treated at 400 ° C or higher has sufficient heat ray absorbing power, and is effective as a heat ray shielding fine particle. As the inert gas, an inert gas such as Ar or N _{2 is} preferably used.

Further, as the heat treatment conditions in the reducing atmosphere, it is preferred to heat-treat the starting material at 300 ° C or higher and 900 ° C or lower. When it is 300 ° C or more, the formation reaction of the composite tungsten oxide having a hexagonal crystal structure of the present invention is carried out, and if it is 900 ° C or less, it is difficult to form composite tungsten oxide fine particles or metal tungsten having a structure other than hexagonal crystal. Unintended side reactants are preferred.

The reducing gas at this time is not particularly limited, and is preferably H ₂ . In the case where H _{2 is} used as the reducing gas, it is preferable to mix H ₂ in a volume ratio of 0.1% or more in an inert gas such as Ar or N ₂ as a composition of the reducing atmosphere. For mixing more than 0.2%. When H ₂ is 0.1% by volume or more, the reduction can be performed efficiently. The conditions of the reduction temperature and the reduction time, the kind and concentration of the reducing gas, and the like are preferably such that the oxygen in the structure of the composite tungsten oxide as the product is 2.2 ≦d/(a+c) with respect to the molar ratio of the element M and the tungsten. ) ≦ 3.0 is the appropriate choice. It may also be subjected to a heat treatment in an inert gas atmosphere after being subjected to a reduction treatment in a reducing gas atmosphere. The heat treatment in the inert gas atmosphere in this case is preferably carried out at a temperature of 400 ° C or more and 1200 ° C or less.

In view of improving the weather resistance, the heat ray shielding fine particles of the present invention are preferably subjected to surface treatment, and are coated with a compound containing at least one selected from the group consisting of Si, Ti, Zr, and Al, preferably an oxide. When the surface treatment is carried out, the organic compound containing one or more selected from the group consisting of Si, Ti, Zr, and Al is used. Know the surface treatment. For example, the heat ray shielding fine particles of the present invention may be mixed with an organic hydrazine compound and subjected to hydrolysis treatment.

[c]Heat ray shielding microparticle dispersion

The heat ray shielding fine particle dispersion of the present invention can be produced by dispersing the heat ray shielding fine particles of the present invention in a liquid medium. The heat ray-shielding fine particle dispersion can be used in various fields of the conventional strong absorption of near-infrared rays, such as the composite tungsten oxide disclosed in Patent Document 4, in the same manner as the conventional dispersion of the composite tungsten oxide fine particles. .

Hereinafter, the use examples of the [1] heat ray shielding fine particle dispersion liquid and the [2] heat ray shielding fine particle dispersion liquid will be described in order. Further, in the present invention, the heat ray shielding fine particle dispersion may be simply referred to as a "dispersion liquid".

[1] Method for producing heat ray shielding fine particle dispersion

The heat ray shielding fine particle dispersion of the present invention can be obtained by adding the heat ray shielding fine particles of the present invention and an appropriate amount of a dispersing agent, a coupling agent, a surfactant, and the like to a liquid medium and performing dispersion treatment. The medium for the heat ray shielding fine particle dispersion is required to maintain the dispersibility of the heat ray shielding fine particles and to prevent coating defects from being generated when the heat ray shielding the fine particle dispersion.

As the medium, a heat ray shielding dispersion can be produced by selecting water, an organic solvent, a grease, a liquid resin, a plasticizer for a liquid plastic, or a mixture thereof. As the organic solvent satisfying the above requirements, various types such as an alcohol system, a ketone system, a hydrocarbon system, a glycol system, and a water system can be selected. Specific examples thereof include alcohol solvents such as methanol, ethanol, 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol, and diacetone; acetone, methyl ethyl ketone, and methyl alcohol a ketone solvent such as propyl ketone, methyl isobutyl ketone, cyclohexanone or isophorone; an ester solvent such as 3-methyl-methoxy-propionate; ethylene glycol monomethyl ether, ethylene a glycol derivative such as alcohol monoethyl ether, ethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate; formamide, N-methylformamide, Indoleamines such as dimethylformamide, dimethylacetonitrile, N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene and xylene; 1,2-dichloroethane and chlorobenzene Halogenated hydrocarbons, etc. Among these, an organic solvent having a relatively low polarity is preferred, and more preferably isopropanol, ethanol, 1-methoxy-2-propanol, dimethyl ketone, methyl ethyl ketone, methyl iso Butyl ketone, toluene, propylene glycol monomethyl ether acetate, n-butyl acetate, and the like. These solvents can be used alone or in combination of two or more.

As the liquid resin, methyl methacrylate or the like is preferable. Preferred examples of the plasticizer for liquid plastics include a plasticizer as a compound of a monohydric alcohol and an organic acid ester, or a polyhydric alcohol organic acid ester compound, such as an ester-based plasticizer or an organic phosphate-based plasticizer. Phosphate-based plasticizers, etc. Among them, triethylene glycol di(2-ethylhexanoate), triethylene glycol bis(2-ethylbutyrate), tetraethylene glycol di(2-ethylhexanoate) are more hydrolyzable. Low, so better.

The dispersing agent, the coupling agent, and the surfactant may be selected depending on the use, and preferably have an amine group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group. These functional groups have an effect of adsorbing on the surface of the composite tungsten oxide fine particles, preventing aggregation of the composite tungsten oxide fine particles, and uniformly dispersing the heat ray shielding fine particles of the present invention in the heat ray shielding film.

Examples of the dispersing agent which can be suitably used include a phosphate compound, a polymer dispersant, a decane coupling agent, a titanate coupling agent, and an aluminum coupling agent, but are not limited thereto. Examples of the polymer-based dispersant include an acrylic polymer. Dispersant, urethane polymer dispersant, acrylic acid. The block copolymer is a polymer dispersant, a polyether dispersant, a polyester polymer dispersant, and the like.

The amount of the dispersant added is preferably in the range of 10 parts by weight to 1000 parts by weight, more preferably 20 parts by weight to 200 parts by weight, per 100 parts by weight of the heat ray shielding fine particles. When the amount of the dispersant added is within the above range, the heat ray shielding fine particles do not aggregate in the liquid, and the dispersion stability is maintained.

The method of dispersing the treatment may be arbitrarily selected from known methods in order to uniformly disperse the heat ray shielding fine particles in the liquid medium. For example, a bead mill, a ball mill, a sand mill, or ultrasonic dispersion may be used. . In order to obtain a uniform heat ray shielding microparticle dispersion, various additives or dispersing agents may be added or the pH may be adjusted.

The content of the heat ray shielding fine particles in the heat ray shielding fine particle dispersion is preferably from 0.01% by mass to 50% by mass. When it is 0.01% by mass or more, it can be suitably used for the production of the following coating film or plastic molded body, and if it is 50 mass% or less, industrial production is easy. Further, it is preferably 1% by mass or more and 35% by mass or less.

The heat ray shielding fine particle dispersion of the present invention obtained by dispersing such heat ray shielding fine particles in a liquid medium can be placed in a suitable transparent container, and the transmittance of light can be measured as a function of wavelength using a spectrophotometer. When the visible light transmittance of the heat ray shielding fine particle dispersion of the present invention is only 85% when the light absorption of the heat ray shielding fine particles is calculated, the transmittance of near-infrared light at a wavelength of 850 nm is 23% or more and 45% or less. The minimum value of the transmittance of the heat rays existing in the range of 1200 to 1800 nm is 15% or less. Further, in the measurement, the visible light transmittance of the heat ray shielding fine particle dispersion was adjusted to 85% by using the dispersion solution thereof. The agent or the appropriate solvent having compatibility with the dispersion solvent is diluted and easily carried out.

The light transmittance distribution of the heat ray shielding fine particle dispersion of the present invention described above is generally combined with the use of a composite tungsten oxide having a composition equivalent to the heat ray shielding fine particles of the present invention except that tungsten is not substituted with the element A. Compared with the distribution of light in the case of the fine particles, the minimum transmittance of the solar radiation present in the range of 1200 to 1800 nm is not greatly increased, and the width of the visible light transmission band is widened on the long wavelength side, and has a wavelength of 700 to 1200 nm. The range of near-infrared light transmittance.

[2] Use case of heat ray shielding fine particle dispersion

By dispersing the heat ray shielding fine particles or the heat ray shielding fine particle dispersion liquid of the present invention in a solid medium, a dispersion powder or a master batch, a heat ray shielding film, a heat ray shielding plastic molded body, or the like can be produced.

A method of producing a heat ray shielding film using the heat ray shielding fine particle dispersion of the present invention will be described as an example of a general method of use. The heat ray shielding film can be produced by mixing the heat ray shielding fine particle dispersion with a plastic or a monomer to prepare a coating liquid, and forming a coating film on the substrate by a known method.

The medium of the coating film can be selected, for example, from a UV curable resin, a thermosetting resin, an electron beam curing resin, a room temperature curing resin, a thermoplastic resin, or the like, depending on the purpose. Specific examples thereof include polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, and ethylene. Vinyl acetate copolymer, polyester resin, polyethylene terephthalate resin, fluororesin, polycarbonate resin, acrylic resin, polyvinyl butyral resin. These resins may be used singly or in combination. Further, a binder using a metal alkoxide can also be used. As the above metal alkoxide, alkoxylation of Si, Ti, Al, Zr, etc. is representative Things. The binder using these metal alkoxides can be hydrolyzed and polycondensed by heating or the like to form an oxide film.

The substrate may be a film as described above, and may be a plate as needed, and the shape is not limited. As a transparent substrate material, PET, acrylic resin, urethane, polycarbonate, polyethylene, ethylene can be used according to various purposes. Vinyl acetate copolymer, vinyl chloride, fluororesin, and the like. Further, glass may be used in addition to the resin.

[d] a dispersion containing heat ray shielding fine particles which is preferable for producing a heat ray shielding film and a heat ray shielding glass, and a method for producing the same

The heat ray shielding fine particle dispersion liquid is obtained by dispersing heat ray shielding fine particles in a liquid medium. The heat ray shielding fine particle dispersion liquid can be obtained by adding the composite tungsten oxide fine particles of the present invention, an appropriate amount of a dispersing agent, a coupling agent, a surfactant, and the like to a liquid medium, and performing dispersion treatment. The fine particles are dispersed in a liquid medium to prepare a dispersion.

For the medium of the heat ray shielding fine particle dispersion, a function for maintaining the dispersibility of the fine particles and a function for not applying a coating defect when the dispersion liquid is applied are required. Specifically, water, an organic solvent, a liquid plastic monomer or a plasticizer for plastics, or a mixture thereof may be selected. However, in order to form a coating on the film or on the glass, it is preferred to select a low boiling organic solvent as the medium. The reason for this is that if the medium is a low-boiling organic solvent, it can be easily removed in the drying step after coating, without impairing the properties of the coating film, such as hardness or transparency.

As the organic solvent satisfying the above requirements, various types such as an alcohol system, a ketone system, a hydrocarbon system, a glycol system, and a water system can be selected. Specifically, methanol, ethanol, and Alcohol solvent such as 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol or diacetone; acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone Ketone solvent such as isophorone; ester solvent such as 3-methyl-methoxy-propionate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, propylene glycol monomethyl ether a diol derivative such as propylene glycol monoethyl ether, propylene glycol methyl ether acetate or propylene glycol diethyl ether acetate; formamide, N-methylformamide, dimethylformamide, dimethylacetamide, N - amides such as methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene. However, among these, an organic solvent having a relatively low polarity is preferred, and more preferably isopropanol, ethanol, 1-methoxy-2-propanol, dimethyl ketone, methyl ethyl ketone, or Isobutyl ketone, toluene, propylene glycol monomethyl ether acetate, n-butyl acetate, and the like. These solvents can be used alone or in combination of two or more.

The dispersing agent, the coupling agent, and the surfactant may be selected depending on the use, and preferably have an amine group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group. The functional groups exert an effect of preventing the agglomeration of the heat ray shielding particles by being adsorbed on the surface of the fine particles by the heat ray shielding, and are formed on a transparent substrate selected from the following transparent film substrates or transparent glass substrates. In the coating layer, the heat ray shielding fine particles are uniformly dispersed. Examples of the dispersing agent which can be suitably used include a phosphate compound, a polymer dispersant, a decane coupling agent, a titanate coupling agent, and an aluminum coupling agent, but are not limited thereto. Examples of the polymer-based dispersant include an acrylic polymer dispersant, an urethane polymer dispersant, and acrylic acid. The block copolymer is a polymer dispersant, a polyether dispersant, a polyester polymer dispersant, and the like.

The amount of the dispersant to be added is preferably in the range of 10 parts by weight to 1000 parts by weight, more preferably 20 parts by weight to 200 parts by weight, per 100 parts by weight of the composite tungsten oxide fine particles. If the amount of dispersant added is within the above range, then The tungsten oxide does not agglomerate in the liquid while maintaining dispersion stability.

The method of the dispersion treatment can be arbitrarily selected from known methods as long as the fine particles are uniformly dispersed in the liquid medium. For example, a bead mill, a ball mill, a sand mill, or ultrasonic dispersion can be used. In order to obtain a uniform heat ray shielding microparticle dispersion, various additives or dispersing agents may be added or the pH may be adjusted.

The content of the heat ray shielding fine particles in the organic solvent dispersion is preferably from 0.01% by mass to 50% by mass. When the content of the heat ray shielding fine particles is 0.01% by mass or more, a heat ray suitable for producing a coating layer or a plastic molded body selected from a transparent film substrate or a transparent glass substrate described below can be obtained. Mask the microparticle dispersion. On the other hand, if the content of the heat ray shielding fine particles is 50% by mass or less, industrial production of the heat ray shielding fine particle dispersion is easy. In this regard, the content of the heat ray shielding fine particles in the organic solvent dispersion liquid is preferably 1% by mass or more and 35% by mass or less.

Moreover, it is preferable that the heat ray shielding fine particles in the organic solvent dispersion liquid are dispersed with an average dispersed particle diameter of 40 nm or less. When the average dispersed particle diameter of the heat ray shielding fine particles is 40 nm or less, the optical characteristics such as the haze of the heat ray shielding film produced by using the heat ray shielding fine particle dispersion of the present invention are more preferably improved.

[e] Heat ray shielding film and method for manufacturing heat ray shielding glass

The heat ray shielding film or the heat ray shielding glass can be produced by forming the coating containing the heat ray shielding fine particles on the transparent substrate selected from the substrate film or the substrate glass by using the heat ray shielding fine particle dispersion.

By masking the above-mentioned heat ray shielding microparticle dispersion with plastic or monomer A coating liquid is prepared by mixing, and a coating film is formed on a transparent substrate by a known method, whereby a heat ray shielding film or a heat ray shielding glass can be produced. For example, a heat ray shielding film can be produced as follows. A dielectric resin is added to the heat ray shielding fine particle dispersion to obtain a coating liquid. After the coating liquid is applied onto the surface of the film substrate, the solvent is evaporated and the resin is cured by a predetermined method, whereby the coating film in which the heat ray shielding fine particles are dispersed in the medium can be formed.

As the dielectric resin of the coating film, for example, a UV curing resin, a thermosetting resin, an electron beam curing resin, a room temperature curing resin, a thermoplastic resin, or the like can be selected depending on the purpose. Specific examples thereof include polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, ethylene-vinyl acetate copolymer, polyester resin, and poly Ethylene terephthalate resin, fluororesin, polycarbonate resin, acrylic resin, polyvinyl butyral resin. These resins may be used singly or in combination. However, in the medium for coating, it is particularly preferable to use a UV curable resin binder from the viewpoints of productivity, equipment cost, and the like.

Further, a binder using a metal alkoxide can also be used. The metal alkoxide is typically an alkoxide such as Si, Ti, Al or Zr. The binder using these metal alkoxides can be hydrolyzed and polycondensed by heating or the like to form a coating layer containing an oxide film.

Further, the film substrate is not limited to the film shape, and may be, for example, a plate shape or a sheet shape. As the film substrate material, PET, acrylic, urethane, polycarbonate, polyethylene, ethylene can be used according to various purposes. Vinyl acetate copolymer, vinyl chloride, fluororesin, and the like. However, as the heat ray shielding film, a polyester film is preferable, and a PET film is more preferable. Further, in order to achieve easy adhesion of the surface of the film substrate, surface treatment is preferably performed. Also, in order to improve the glass The adhesion of the glass substrate or the film substrate to the coating layer, the formation of an intermediate layer on the glass substrate or the film substrate, and the formation of a coating layer on the intermediate layer are also preferable. The configuration of the intermediate layer is not particularly limited, and examples thereof include a polymer film, a metal layer, an inorganic layer (for example, an inorganic oxide layer such as cerium oxide, titanium oxide, or zirconium oxide), an organic/inorganic composite layer, and the like.

The method of providing a coating on the substrate film or the substrate glass is not particularly limited as long as it is a method in which the dispersion containing the heat ray shielding fine particles can be uniformly applied to the surface of the substrate. For example, a bar coating method, a gravure coating method, a spray coating method, a dip coating method, and the like can be mentioned. For example, according to the bar coating method using a UV-curable resin, a bar coater which can meet the purpose of satisfying the thickness of the coating film and the content of the above-mentioned heat ray shielding fine particles can be used to have a moderate flow rate. The coating liquid of the liquid concentration and the additive is appropriately adjusted to form a coating film on the substrate film or the substrate glass. Then, the organic solvent contained in the coating liquid is removed by drying, and then irradiated with ultraviolet rays to be cured, whereby a coating layer can be formed on the substrate film or the substrate glass. In this case, the drying conditions of the coating film vary depending on the respective components, the type of the solvent, or the ratio of use, and are usually from 60 ° C to 140 ° C for about 20 seconds to 10 minutes. The irradiation of the ultraviolet rays is not particularly limited, and for example, a UV exposure machine such as an ultrahigh pressure mercury lamp can be suitably used. Further, the adhesion between the substrate and the coating, the smoothness of the coating film at the time of coating, the drying property of the organic solvent, and the like can be handled by the steps before and after the coating is formed. Examples of the above-described steps include a surface treatment step of a substrate, a prebaking (preheating of the substrate) step, a post-baking (post-substrate heating) step, and the like, and can be appropriately selected. The heating temperature in the prebaking step and/or the post-baking step is preferably from 80 ° C to 200 ° C, and the heating time is preferably from 30 seconds to 240 seconds.

The thickness of the coating on the substrate film or on the substrate glass is not particularly limited. Preferably, it is preferably 10 μm or less, more preferably 6 μm or less. The reason for this is that if the thickness of the coating layer is 10 μm or less, sufficient pencil hardness can be exhibited to have abrasion resistance, and in addition, when the solvent is volatilized in the coating layer and the adhesive is hardened, the substrate film can be prevented from being generated. The steps such as warping are abnormal.

The content of the heat ray shielding fine particles contained in the coating layer is not particularly limited, and the content per unit projected area of the film/glass/coating layer is preferably 0.1 g/m ² or more and 5.0 g/m ² or less. The reason is that when the content is 0.1 g/m ² or more, the heat ray shielding characteristics can be remarkably exhibited as compared with the case where the heat ray shielding fine particles are not contained, and if the content is 5.0 g/m ² or less, the heat ray shielding is performed. The film/glass/coating sufficiently maintains visible light transmission.

The optical characteristics of the heat ray shielding film or the heat ray shielding glass to be produced are such that when the visible light transmittance of the transparent substrate is 70%, the transmittance at a wavelength of 850 nm is 23% or more and 45% or less. The minimum value of the transmittance in the range of 1200 to 1800 nm is 15% or less. Further, adjusting the visible light transmittance to 70% is easily performed by adjusting the concentration of the fine particles in the coating liquid or by adjusting the film thickness of the coating layer.

The limit value of the above-described transmittance distribution is generally not significantly increased as compared with the case of using a composite tungsten oxide fine particle having a conventional technique other than the element A. The minimum transmittance of the range from 1200 to 1800 nm, the width of the visible light transmission band is widened on the long wavelength side, and has a higher transmittance in the range of 700 to 1200 nm. It should be noted that the above-mentioned transmittance distribution is limited to a certain width by using composite tungsten oxide fine particles having the same composition and concentration, and may be based on the size or shape of the fine particles, the state of aggregation, and inclusion. The refractive index of the dispersing agent By.

Further, in order to impart an ultraviolet shielding function to the heat ray shielding film or the heat ray shielding glass of the present invention, inorganic titanium oxide, particles such as zinc oxide or cerium oxide, organic benzophenone or benzotriene may be added. At least one of azole and the like.

Further, in order to increase the visible light transmittance of the heat ray shielding film or the heat ray shielding glass of the present invention, particles such as ATO, ITO, or aluminum-added zinc oxide or indium tin composite oxide may be further mixed in the coating layer. By adding the transparent particles to the coating layer, the transmittance near the wavelength of 750 nm is increased, and on the other hand, the infrared light having a wavelength longer than 1200 nm is shielded, so that the transmittance of the near-infrared light is high and the heat ray shielding is obtained. A heat ray shield with a high characteristic.

[f] Method for producing heat ray shielding fine particle dispersion

For the method for producing a heat ray-shielding fine particle dispersion, (1) a method for producing a powder-like heat ray shielding fine particle dispersion, and (2) a sheet shape or a film shape heat ray shielding fine particle dispersion (heat) A method of producing a radiation shielding film or a heat ray shielding sheet will be described.

(1) Method for producing heat ray shielding fine particle dispersion in powder form

The heat ray shielding fine particles are dispersed together with a dispersing agent, a coupling agent, and/or a surfactant in an organic solvent to obtain an organic solvent dispersion. Thereafter, by removing the organic solvent from the organic solvent dispersion, the dispersion powder of the present invention in which the heat ray shielding fine particles are dispersed in the dispersant can be obtained. The method of dispersing the heat ray shielding fine particles in an organic solvent is arbitrarily selected as long as the fine particles are uniformly dispersed in an organic solvent. Choose. As an example, a bead mill, a ball mill, a sand mill, ultrasonic dispersion or the like can be used.

As the organic solvent, various types such as an alcohol system, a ketone system, a hydrocarbon system, a glycol system, and a water system can be selected. Specific examples thereof include alcohol solvents such as methanol, ethanol, 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol, and diacetone; acetone, methyl ethyl ketone, and methyl propyl ketone; a ketone solvent such as methyl isobutyl ketone, cyclohexanone or isophorone; an ester solvent such as 3-methyl-methoxy-propionate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Glycol derivatives such as ethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate; formamide, N-methylformamide, dimethylformate Amidoxime such as guanamine, dimethylacetamide or N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene Wait. However, among these, an organic solvent having a relatively low polarity is preferred, and more preferably isopropanol, ethanol, 1-methoxy-2-propanol, dimethyl ketone, methyl ethyl ketone, or Isobutyl ketone, toluene, propylene glycol monomethyl ether acetate, n-butyl acetate, and the like. These solvents can be used alone or in combination of two or more.

The dispersing agent, the coupling agent, and the surfactant may be selected depending on the use, and preferably have an amine group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group. These functional groups have an effect of preventing the aggregation of the heat ray shielding fine particles by being adsorbed on the surface of the fine particles by the heat ray shielding, and uniformly dispersing the heat ray shielding fine particles in the heat ray shielding fine particle dispersion. Examples of the dispersing agent which can be suitably used include a phosphate compound, a polymer dispersant, a decane coupling agent, a titanate coupling agent, and an aluminum coupling agent, but are not limited thereto. Examples of the polymer-based dispersant include an acrylic polymer dispersant, an urethane polymer dispersant, and acrylic acid. Block copolymer polymer dispersant, polyether dispersant, polyester polymer dispersant Wait.

Further, the concentration of the heat ray shielding fine particles in the organic solvent dispersion liquid to the organic solvent is preferably 1% by mass or more and 50% by mass or less. When the concentration of the heat ray shielding fine particles with respect to the organic solvent is 1% by mass or more, it is possible to prevent the amount of the organic solvent to be removed from becoming excessive and the manufacturing cost to be high. On the other hand, when the concentration of the heat ray shielding fine particles with respect to the organic solvent is 50% by mass or less, it is possible to avoid the occurrence of aggregation of fine particles, which makes it difficult to disperse the fine particles, or the viscosity of the liquid is remarkably increased to cause operation. It becomes a difficult situation.

Further, the heat ray shielding fine particles in the organic solvent dispersion are preferably dispersed at an average dispersed particle diameter of 40 nm or less. When the average dispersed particle diameter of the heat ray shielding fine particles is 40 nm or less, the optical characteristics such as the haze of the heat ray shielding film produced by using the heat ray shielding fine particle dispersion of the present invention are more preferably improved.

The dispersion powder or the plasticizer dispersion of the present invention can be obtained by removing the organic solvent from the organic solvent dispersion. As a method of removing the organic solvent from the organic solvent dispersion, it is preferred to dry the organic solvent dispersion under reduced pressure. Specifically, the organic solvent dispersion liquid is stirred while being dried under reduced pressure, and the composition containing the heat ray shielding fine particles is separated from the organic solvent component. The apparatus for the vacuum drying is not particularly limited as long as it is a device having the above functions. Further, the pressure value at the time of pressure reduction in the drying step is appropriately selected.

By using the vacuum drying method, the efficiency of removing the organic solvent from the organic solvent dispersion is improved, and the dispersion powder or the plasticizer dispersion of the present invention is not exposed to a high temperature for a long period of time, and thus does not cause dispersion in the dispersion powder or It is preferred that the heat ray in the plasticizer dispersion shields the agglomeration of the fine particles. Further, the dispersion powder or the plasticizer is dispersed The productivity of the liquid is also improved, and it is also easy to recover the evaporated organic solvent, which is also preferable in terms of environmental protection.

In the dispersion powder or the plasticizer dispersion of the present invention obtained after the drying step, the residual organic solvent is preferably 5% by mass or less. The reason for this is that when the residual organic solvent is 5% by mass or less, the dispersion powder or the plasticizer dispersion liquid is processed into a heat-ray shielding interlayer transparent substrate without generating bubbles, and the appearance or optical characteristics are favorably maintained. Further, the master batch of the present invention can be obtained by dispersing heat ray shielding fine particles or dispersion powder in a resin and granulating the resin.

Further, the master batch may be obtained by uniformly mixing the heat ray shielding fine particles or the above dispersed powder, the powder or granules of the thermoplastic resin, and other additives as needed, and using the vented single shaft or double The shaft extruder is kneaded and processed into pellets by generally cutting the melt extruded strands. In this case, as the shape, a columnar shape or a prismatic shape may be mentioned. Further, a so-called thermal cutting method in which the melt extrudate is directly cut can also be used. In this case, a shape close to a sphere is generally adopted.

(2) Method for producing sheet-like or film-like heat ray shielding fine particle dispersion

The sheet-like or film-like heat ray-shielding fine particle dispersion of the present invention can be produced by uniformly mixing the dispersion powder, the plasticizer dispersion, or the master batch of the present invention into a transparent resin. According to the sheet-like or film-like heat ray shielding fine particle dispersion, it is possible to manufacture heat ray shielding which ensures the heat ray shielding property of the conventional composite tungsten oxide and the transmittance of near-infrared light having a wavelength of 700 to 1200 nm. Sheet or heat ray shielding film.

For manufacturing the heat ray shielding sheet or the heat ray shielding film of the present invention In the case of the resin constituting the sheet or film, a variety of thermoplastic resins can be used. Further, in consideration of application of the heat ray shielding sheet or the heat ray shielding film of the present invention to various window materials, a thermoplastic resin having sufficient transparency is preferable. Specifically, a preferred resin can be selected from the group consisting of polyethylene terephthalate resin, polycarbonate resin, acrylic resin, styrene resin, polyamide resin, polyethylene resin, vinyl chloride. Resin, olefin resin, epoxy resin, polyimine resin, fluororesin, ethylene. A resin in the resin group of the vinyl acetate copolymer, a mixture of two or more resins selected from the group of resins, or a copolymer of two or more resins selected from the group of resins.

Further, when the heat ray shielding sheet of the present invention is used as a sheet-like window material as it is, it is considered that the transparency is high and the general characteristics required for the window material, that is, rigidity, light weight, long-term durability, In terms of cost and the like, a polyethylene terephthalate resin, a polycarbonate resin, an acrylic resin is preferable, and a polycarbonate resin is further preferable. On the other hand, when the heat ray shielding sheet or the heat ray shielding film of the present invention is used as the intermediate layer of the laminated glass for heat ray shielding described below, the adhesion to the transparent substrate, weather resistance, and penetration resistance are obtained. From the viewpoint of sex, etc., it is preferably polyvinyl acetal resin or ethylene. The vinyl acetate copolymer is further preferably a polyvinyl butyral resin.

Further, when a heat ray shielding sheet or a heat ray shielding film is used as an intermediate layer and the thermoplastic resin constituting the sheet or film alone does not sufficiently have flexibility or adhesion to a transparent substrate, for example, When the thermoplastic resin is a polyvinyl acetal resin, it is preferred to further add a plasticizer. As the plasticizer, a substance which can be used as a plasticizer for the thermoplastic resin of the present invention can be used. For example, as a plasticizer used for a heat ray shielding film containing a polyvinyl acetal resin, it can be listed. A plasticizer which is a compound of a monohydric alcohol and an organic acid ester, a polyhydric alcohol organic acid ester compound, or the like is used as an ester-based plasticizer, an organic phosphate-based plasticizer, or the like as a phosphate-based plasticizer. Any of the plasticizers is preferably liquid at room temperature. Among them, a plasticizer which is an ester compound synthesized from a polyol and a fatty acid is preferred.

The heat ray shielding sheet can be produced by kneading a dispersion powder or a plasticizer dispersion or a master batch, a thermoplastic resin, and optionally a plasticizer and other additives, and then performing extrusion molding and injection molding. The kneaded material is formed into a sheet such as a flat or curved surface by a known method such as a method. A well-known method can be used for the formation of a heat ray shielding sheet or a heat ray shielding film. For example, a calender roll method, an extrusion method, a casting method, an inflation method, or the like can be used.

[g] Method for producing interlayer transparent substrate for heat ray shielding

The heat ray shielding sheet or the heat ray shielding film of the present invention will be described as an interlayer transparent layer for heat ray shielding in which an intermediate layer is interposed between a plurality of transparent substrates including a plate glass or a plastic material. The interlayer transparent layer for heat ray shielding is obtained by sandwiching an intermediate layer from both sides thereof using a transparent substrate. As the transparent substrate, a plate glass which is transparent to a visible light region, a plate-shaped plastic, or a film-like plastic can be used. The material of the plastic is not particularly limited and may be selected according to the use. For example, in the case of a conveyor such as a car, it is preferably polycarbonate in terms of ensuring the perspective of the driver or the rider of the conveyor. a transparent resin such as an ester resin, an acrylic resin, or a polyethylene terephthalate resin, or a PET resin, a polyamide resin, a vinyl chloride resin, an olefin resin, an epoxy resin, or a polyimide resin. Fluororesin, etc.

The interlayer transparent substrate for heat ray shielding of the present invention can also be obtained by sandwiching the heat ray shielding sheet or the heat ray shielding film of the present invention. The plurality of inorganic glasses opposed thereto are bonded and integrated by a known method. The obtained interlayer inorganic glass for heat ray shielding can be mainly used as a window for inorganic glass or a building for a car.

The concentration of the heat ray shielding fine particles contained in the heat ray shielding sheet, the heat ray shielding film, and the heat ray shielding interlayer transparent substrate is not particularly limited, and the content per unit projected area of the sheet/film is preferably 0.1 g/m ² or more and 5.0 g/m ² or less. The reason is that when it is 0.1 g/m ² or more, the heat ray shielding property can be remarkably exhibited as compared with the case where the heat ray shielding fine particles are not contained, and if it is 5.0 g/m ² or less, the heat ray shielding sheet is used. / The film does not completely lose the visible light transmission.

The optical characteristics of the heat ray shielding sheet, the heat ray shielding film, or the heat ray shielding sandwich structure of the present invention, when the visible light transmittance of the thermoplastic resin is 70%, the transmittance of near-infrared light having a wavelength of 850 nm The minimum value of the transmittance of the heat rays of 23% or more and 45% or less and the wavelength of 1200 to 1800 nm is 15% or less. Here, the visible light transmittance of the thermoplastic resin is adjusted to 70% by adjusting the concentration of the heat ray shielding fine particles contained in the organic solvent dispersion, the dispersion powder, the plasticizer dispersion or the master batch, and preparing the resin. In the case of the composition, the heat ray shielding fine particles, the dispersion powder, the amount of the plasticizer dispersion or the master batch, and the film thickness of the film or sheet are easily carried out.

The form of the transmittance distribution of the heat ray shielding fine particles of the present invention described above is as follows: if compared with the transmission distribution in the case of using a composite tungsten oxide fine particle having a conventional technique other than the element A, which has an equivalent composition, Then you know that you have the following specialties.

1. The heat ray shielding fine particle of the present invention is a region of a visible light transmission band which is widened in a region of a wavelength of 700 to 1200 nm which is a region of near-infrared light and has a larger area in the region. High transmittance.

2. The heat ray shielding fine particles of the present invention hardly change the value of the minimum value of the transmittance existing in the region of the wavelength of 1200 to 1800 nm.

[Examples]

Hereinafter, the present invention will be more specifically described with reference to the embodiments. Here, Examples 1 to 19 and Comparative Examples 1 to 3 relate to heat ray shielding fine particle dispersion liquid containing heat ray shielding fine particles, and Examples 20 to 39 and Comparative Examples 4 to 6 relate to heat ray shielding film or heat ray shielding. Glass, Examples 40 to 60 and Comparative Examples 7 to 9 are sheet-shaped heat ray shielding fine particle dispersions or heat ray shielding interlayer transparent substrates. However, the invention is not limited to the following examples.

In Examples 1 to 19 and Comparative Examples 1 to 3, the transmittance of the heat ray shielding fine particle dispersion liquid for light having a wavelength of 300 to 2100 nm is to maintain the dispersion liquid in a unit for a spectrophotometer (manufactured by GL Science Co., Ltd., model number) :S10-SQ-1, material: Synthetic quartz, optical path length: 1 mm) was measured using a spectrophotometer U-4100 manufactured by Hitachi, Ltd. At the time of the measurement, the transmittance was measured in a state in which the solvent (methyl isobutyl ketone) was filled in the above-mentioned unit, and the reference line for the transmittance measurement was determined. As a result, the light transmittance and the visible light transmittance of Examples 1 to 19 and Comparative Examples 1 to 3 described below were excluded from light reflection by the surface of the unit for the spectrophotometer or light absorption by the solvent. Contribute, and only calculate the light absorption of the heat ray shielding particles. The visible light transmittance is calculated based on JIS R 3106 based on the transmittance of light having a wavelength of 380 to 780 nm. The average dispersed particle diameter of the heat ray shielding fine particles was measured using a Microtrac particle size distribution meter manufactured by Nikkiso Co., Ltd.

In Examples 20 to 60 and Comparative Examples 4 to 9, the heat in each of the examples The insolation transmittance of the radiation shielding film, the heat ray shielding glass, the heat ray shielding sheet, and the interlayer transparent substrate is 300 to 2100 nm measured according to the spectrophotometer U-4100 manufactured by Hitachi, Ltd. The transmittance of light in the region is calculated based on JIS R 3106:1998. When the transmittance was measured, unlike the measurement of the solvents in Examples 1 to 19 and Comparative Examples 1 to 3, the reference line for the transmittance measurement was determined using a normal atmosphere. As a result, the light transmittance, the visible light transmittance, and the solar radiation transmittance of Examples 20 to 60 and Comparative Examples 4 to 9 described below, in addition to the contribution of light absorption by the heat ray shielding fine particles, also included various sample surfaces. The light reflection, or the contribution of light absorption by a transparent substrate or a thermoplastic resin that acts as a binder. Further, the average particle diameter of the heat ray shielding fine particles was measured using a Microtrac particle size distribution meter manufactured by Nikkiso Co., Ltd.

[Example 1] (Mo _0.015 Cs _0.33 W _0.985 O ₃ MIBK dispersion)

Weighing each of tungstic acid (H ₂ WO ₄ ), barium hydroxide (CsOH), and molybdenum trioxide (MoO ₃ ) in a ratio equivalent to Mo/Cs/W (Morby)=0.015/0.33/0.985 After the powder, it was thoroughly mixed with an agate mortar to prepare a mixed powder. The mixed powder was heated under a supply of 5% hydrogen gas supported on a nitrogen gas to be subjected to a reduction treatment at a temperature of 600 ° C for 1 hour, and then calcined at 800 ° C for 30 minutes in a nitrogen atmosphere to obtain Mo _0.015 Cs of the claim 1 . The heat ray shielding fine particle powder (hereinafter referred to as "powder A") represented by _0.33 W _0.985 O ₃ . 20% by mass of powder A, an acrylic polymer dispersing agent having an amine group as a functional group (an amine value of 48 mg KOH/g, an acrylic dispersing agent having a decomposition temperature of 250 ° C) (hereinafter referred to as "dispersant a") 10% by mass and 70% by mass of methyl isobutyl ketone. Put these loads in 0.3mm In a ZrO ₂ bead paint shaker, pulverization and dispersion treatment were carried out for 10 hours to obtain a heat ray shielding fine particle dispersion (hereinafter referred to as "dispersion A"). Here, the average dispersed particle diameter of the heat ray shielding fine particles in the dispersion A was measured and found to be 19 nm.

The powder A was measured by an X-ray diffraction method, and as a result, it was pure hexagonal crystal, and no diffraction of molybdenum trioxide or molybdenum dioxide was observed. Further, observation by a transmission electron microscope revealed that segregation of a molybdenum compound or the like was not observed at the grain boundary of the heat ray shielding fine particles. Therefore, it was judged that the added molybdenum component was completely dissolved in the crystal of hexagonal germanium tungsten bronze.

The dispersion A was appropriately diluted with MIBK and placed in a rectangular container having a thickness of 1 mm to measure the spectral transmittance. The transmittance distribution when the dilution ratio is adjusted so that the visible light transmittance at the time of light absorption of the heat ray shielding fine particles is 85%, the transmittance at a wavelength of 850 nm is 37%, and the transmittance is the minimum at the wavelength. It becomes 10% at 1610nm. It was confirmed that the visible light transmission band was significantly wider than that of the undissolved molybdenum tantalum tungsten bronze shown in Comparative Example 1 below. The measurement results are shown in Table 1.

[Comparative Example 1] (Cs MIBK _0.33 WO ₃ of dispersion)

In the procedure of Example 1, except that molybdenum trioxide was not added as a raw material for addition, a powder of the composition represented by Cs _0.33 WO ₃ of Comparative Example 1 was obtained in exactly the same manner. This powder was mixed with a dispersing agent and a solvent using a paint shaker to prepare a dispersion, and as a result, the average dispersed particle diameter was 20 nm. In addition, the spectral transmittance at the time of measuring the dilution ratio so that the visible light transmittance at the time of light absorption of the heat ray shielding fine particles is 85% is measured, and the transmittance at a wavelength of 850 nm is 22% according to the transmittance distribution. The minimum value of the transmittance is 10% at a wavelength of 1515 nm. From the above, it was confirmed that the transmittance of near-infrared light at a wavelength of 850 nm was 15% lower than that of Example 1. The measurement results are shown in Table 1.

[Examples 2 to 19] (MICK dispersion of A _a Cs _b W _c O _d )

The amount of the tungsten compound starting material is adjusted and mixed as a, b, and c of the element A, the element M (Cs), and the tungsten ratio (mole ratio) as shown in Table 1. In the same manner as in Example 1, calcination was carried out to prepare the heat ray shielding fine particle powders of Examples 2 to 19. The calcination time was appropriately adjusted so that the oxygen in the structure of the composite tungsten oxide was a value shown in Table 1 with respect to the molar ratio d/(a+c) of the element M and tungsten. At this time, X-ray diffraction measurement and transmission electron microscope observation were performed on all the calcined powders, and it was confirmed that the element A was solid-dissolved in the hexagonal crystal of the tungsten bronze fine particle crystal. The prepared heat ray shielding fine particle powder, solvent, and dispersing agent were mixed and dispersed in a paint shaker to prepare heat ray shielding fine particle dispersion liquids of Examples 2 to 19.

The average dispersed particle diameter of the heat ray shielding fine particles of Examples 2 to 19 was measured and described in Table 1. Further, the dilution ratios of the heat ray shielding fine particle dispersions of Examples 2 to 19 were appropriately adjusted, and the transmittance was measured by a spectrophotometer, and the wavelength at which the visible light transmittance at the time of light absorption of the heat ray shielding fine particles was 85% was measured. The transmittance of near-infrared light at 850 nm and the minimum transmittance of heat rays at a wavelength of 1200 to 1800 nm. The measurement results are shown in Table 1.

[Comparative Example 2] (WO _2.72 of MIBK dispersion)

Performs tungsten trioxide (WO ₃₎ powder was supplied with nitrogen as the carrier of 3% of hydrogen under heating at 600 ℃ to the reduction treatment for 1 hour, to obtain the tungsten oxide WO _2.72 (hereinafter referred to as fine α).

The fine particles α 20% by mass, the dispersant a 10% by mass, and the methyl isobutyl ketone 70% by mass were weighed. Put these loads in 0.3mm In a ZrO ₂ bead paint shaker, pulverization and dispersion treatment were carried out for 13 hours to obtain a composite tungsten oxide fine particle dispersion (hereinafter referred to as dispersion α). Here, the average dispersed particle diameter of the composite tungsten oxide fine particles contained in the dispersion liquid α was measured and found to be 31 nm.

The dispersion liquid α was appropriately diluted with MIBK, and the optical characteristics when the visible light transmittance at the time of light absorption by the heat ray shielding fine particles was 85% were measured, and as a result, the transmittance of near-infrared light having a wavelength of 850 nm was 68%, and the wavelength was 1200. The minimum transmittance of the transmittance of heat rays at ~1800 nm is 58%. The measurement results are shown in Table 1.

[Comparative Example 3] (MIBK dispersion of LaB ₆ )

5% by mass of lanthanum hexaboride (LaB ₆ ) powder, 3% by mass of dispersant a, and 92% by mass of methyl isobutyl ketone were weighed. Put these loads in 0.3mm In a ZrO ₂ bead paint shaker, pulverization and dispersion treatment were carried out for 20 hours to obtain a lanthanum hexaboride fine particle dispersion (hereinafter referred to as dispersion β). Here, the average dispersed particle diameter of the lanthanum hexaboride microparticles contained in the dispersion liquid β was measured and found to be 34 nm.

The dispersion liquid β was appropriately diluted with MIBK, and the optical characteristics when the visible light transmittance at the time of light absorption by the heat ray shielding fine particles was 85% were measured. As a result, the transmittance of light of near-infrared light having a wavelength of 850 nm was 44%. However, the minimum value of the transmittance is in a wavelength region shorter than the wavelength of 1200 to 1800 nm, and the transmittance at a wavelength of 975 nm is 38%. The measurement results are shown in Table 1.

[Evaluation of Examples 1 to 19 and Comparative Examples 1 to 3]

The heat ray shielding fine particles of Examples 1 to 19 were compared with Comparative Example 1 which is a conventional composite tungsten oxide fine particle, and the visible light transmittance at the time of light absorption of only the heat ray shielding fine particles was 85%, and the wavelength was 850 nm. The transmittance of near-infrared light is high. As a result, it was found that the high thermal shielding property of the composite tungsten oxide was ensured, and a high transmittance was obtained for the near-infrared light having a wavelength of 700 to 1200 nm. On the other hand, in Comparative Examples 2 and 3 in which WO _2.72 or lanthanum hexaboride was used as the heat ray shielding fine particles, only the wavelength of 850 nm when the visible light transmittance at the time of light absorption of the heat ray shielding fine particles was 85% was calculated. The transmittance of infrared light is high, but the absorption of heat rays having a wavelength of 1200 to 1800 nm is not sufficient, so that the heat ray shielding characteristics as high as the heat ray shielding particles of the present invention are not obtained.

[Example 20] (using Mo _0.015 Cs _0.33 W _0.985 O ₃ of the heat ray shielding film)

Weighing each of tungstic acid (H ₂ WO ₄ ), barium hydroxide (CsOH), and molybdenum trioxide (MoO ₃ ) in a ratio equivalent to Mo/Cs/W (Morby)=0.015/0.33/0.985 After the powder, it was thoroughly mixed with an agate mortar to prepare a mixed powder. The mixed powder was heated at a temperature of 600 ° C for 1 hour under a supply of 5% hydrogen gas supported on a nitrogen gas to carry out a reduction treatment, and then calcined at 800 ° C for 30 minutes in a nitrogen atmosphere to obtain a composite tungsten oxide Mo _0.015 Cs. _0.33 W _0.985 O ₃ (hereinafter referred to as powder B). The powder B was measured by an X-ray diffraction method, and as a result, it was pure hexagonal crystal, and no diffraction of molybdenum trioxide or molybdenum dioxide was observed. Further, when the powder B was observed by a transmission electron microscope, the crystal grains of the hexagonal germanium tungsten bronze were observed, and no segregation of the molybdenum compound or the like was observed at the grain boundary of the multi-grain. From this, it was judged that the molybdenum component was completely dissolved in the crystal of hexagonal germanium tungsten bronze.

Weighing 20% by mass of powder B, an acrylic polymer dispersing agent having an amine group as a functional group (an acrylic value of 48 mg KOH/g, an acrylic dispersing agent having a decomposition temperature of 250 ° C) (hereinafter referred to as dispersant b) 10 mass %, and methyl isobutyl ketone 70% by mass. Put these loads in 0.3mm In a ZrO ₂ bead paint shaker, pulverization and dispersion treatment were carried out for 10 hours to obtain a composite tungsten oxide fine particle dispersion (hereinafter referred to as dispersion B). Here, the dispersed average particle diameter of the composite tungsten oxide fine particles in the dispersion B was measured and found to be 19 nm.

Mixing as ultraviolet light for hard coating with respect to 100 parts by weight of dispersion B 50 parts by weight of ARONIX UV-3701 (hereinafter referred to as UV-3701) manufactured by East Asia Synthetic of a cured resin, and formed into a heat ray shielding fine particle coating liquid, which was applied to a PET film using a bar coater. (HPE-50 manufactured by Teijin) was formed to form a coating film. Further, the same PET film was used in the other examples and comparative examples. The PET film provided with the coating film was dried at 80 ° C for 60 seconds to evaporate the solvent, and then cured by a high-pressure mercury lamp to prepare a heat ray shielding film provided with a coating film containing heat ray shielding fine particles.

In the production of the heat ray shielding film, the heat ray shielding fine particle concentration of the coating liquid or the film thickness of the coating film was adjusted, and the visible light transmittance including the transparent substrate was set to 70%. The optical characteristics of the heat ray shielding film were measured, and as a result, the transmittance at a wavelength of 850 nm was 38%, and the minimum value of the transmittance was 11% at a wavelength of 1610 nm. Further, the solar transmittance was measured to be 38%, and the haze was measured to be 0.9%. The results are shown in Table 2, and the transmittance distribution of each wavelength is indicated by a solid line in FIG.

[Comparative Example 4] (heat ray shielding film using Cs _0.33 WO ₃ )

So as to be corresponding to Cs / W (mole ratio) = 0.33 of the weighing tungstic acid (H ₂ WO _4), and cesium hydroxide (CsOH) 37.4g (corresponding to Cs / W (mole ratio) = 0.33) After each powder, it was thoroughly mixed by an agate mortar to prepare a mixed powder. After the mixed powder was heated under a nitrogen gas is supplied to the carrier of the 5% hydrogen reduction treatment for 1 hour at 600 ℃ at the, under a nitrogen atmosphere at 800 deg.] C baked for 30 minutes to obtain the composite tungsten oxide Cs _0.33 WO ₃ (hereinafter referred to as fine particles γ).

20% by mass of the fine particles γ, 10% by mass of the dispersing agent b, and 70% by mass of the methyl isobutyl ketone were weighed. Put these loads in 0.3mm In a ZrO ₂ bead paint shaker, pulverization and dispersion treatment were carried out for 10 hours to obtain a composite tungsten oxide fine particle dispersion (hereinafter referred to as dispersion γ). Here, the dispersed average particle diameter of the composite tungsten oxide fine particles in the dispersion γ was measured and found to be 20 nm.

50 parts by weight of UV-3701 was mixed with 100 parts by weight of the dispersion liquid to form a heat ray shielding fine particle coating liquid, and the coating liquid was applied onto a film by a bar coater to form a coating film. The coating film was dried at 80 ° C for 60 seconds to evaporate the solvent, and then cured by a high-pressure mercury lamp to prepare a film on which a coating film containing heat ray shielding fine particles was formed.

In the production of the heat ray shielding film, the heat ray shielding fine particle concentration of the coating liquid or the film thickness of the coating film was adjusted, and the visible light transmittance including the transparent substrate was set to 70%. The optical characteristics of the heat ray shielding film were measured, and as a result, the transmittance at a wavelength of 850 nm was measured to be 22%, the minimum value of the transmittance at a wavelength of 1200 to 1800 nm was measured to be 10%, and the solar transmittance was measured to be 34%, and the haze was measured as 0.9%. This result is shown in Table 2, and the transmittance distribution of each wavelength is shown by the broken line in FIG.

[Examples 21 to 38] (heat ray shielding film coated with A _a Cs _b W _c O _d )

The ratio of the ratio of the element A, the element M (Cs), the tungsten and the oxygen to the value shown in Table 2 was weighed in the same manner as in Example 20, and then sufficiently mixed with an agate mortar to prepare a mixed powder. Then, heat treatment was carried out in the same manner as in Example 20 to prepare composite tungsten oxide powders of Examples 21 to 38. Among them, in Example 36, a mixture of cerium and tin (corresponding to Bi:Sn (Mole ratio) = 1:1) was used as the element A. The X-ray diffraction measurement and the transmission electron microscope observation of all of the composite tungsten oxide powders of Examples 21 to 38 were carried out, and it was confirmed that the element A was solid-dissolved in the hexagonal crystal of the tungsten bronze fine particle crystal.

Appropriate adjustment of the coating film of the composite tungsten oxide fine particle dispersion film The transmittance was measured by a spectrophotometer, and the transmittance at a wavelength of 850 nm and the wavelength of 1200 to 1800 nm when the visible light transmittance including the transparent substrate was 70% in the same manner as in Example 20 was measured in the same manner as in Example 20. The minimum transmittance, the insolation transmittance, and the haze value. The measurement results are shown in Table 2.

[Comparative Example 5] (using the heat ray shielding film of WO _2.72 )

The tungsten trioxide (WO ₃ ) powder was heated under a supply of 3% hydrogen gas supported on a nitrogen gas, and subjected to a reduction treatment at a temperature of 600 ° C for 1 hour to obtain a tungsten oxide WO _2.72 (hereinafter referred to as fine particles δ).

The fine particles δ 20% by mass, the dispersant b 10% by mass, and the methyl isobutyl ketone 70% by mass were weighed. Put these loads in 0.3mm ZrO ₂ beads in a paint shaker, for 13 hours pulverization and dispersion treatment, to obtain the tungsten oxide particle dispersion liquid (hereinafter referred to as dispersion δ). Here, the dispersed average particle diameter of the tungsten oxide fine particles in the dispersion δ was measured and found to be 31 nm.

50 parts by weight of UV-3701 was mixed with respect to 100 parts by weight of the dispersion liquid to prepare a heat ray shielding fine particle coating liquid, and the coating liquid was applied onto a film by a bar coater to form a coating film. The coating film was dried at 80 ° C for 60 seconds to evaporate the solvent, and then cured by a high-pressure mercury lamp to prepare a film on which a coating film containing heat ray shielding fine particles was formed.

The coating film thickness of the tungsten oxide fine particle dispersed film was appropriately adjusted, and the transmittance was measured by a spectrophotometer. The same as in Example 20, the visible light transmittance of the transparent substrate was set to 70% in the same manner as in Example 20. The transmittance at a wavelength of 850 nm, the minimum transmittance at a wavelength of 1200 to 1800 nm, the solar transmittance, and the haze value. The transmittance at a wavelength of 850 nm was 48%, and the wavelength was 1200 to 1800. The minimum transmittance at nm was 38%, the solar transmittance was 56%, and the haze was 0.9%. The measurement results are shown in Table 2.

[Comparative Example 6] (heat ray shielding film using LaB ₆ )

5% by mass of lanthanum hexaboride (LaB ₆ ) powder, 3 % by mass of dispersant b, and 92% by mass of methyl isobutyl ketone were weighed. Put these loads in 0.3mm ZrO ₂ beads in a paint shaker for 20 hours pulverization and dispersion treatment, to obtain a dispersion of lanthanum hexaboride fine particles (hereinafter referred to as dispersion ε). Here, the dispersed average particle diameter of the ruthenium hexaboride particles in the dispersion ε was measured and found to be 31 nm.

50 parts by weight of UV-3701 was mixed with 100 parts by weight of the dispersion liquid to form a heat ray shielding fine particle coating liquid, and the coating liquid was applied onto a film by a bar coater to form a coating film. The coating film was dried at 80 ° C for 60 seconds to evaporate the solvent, and then cured by a high-pressure mercury lamp to prepare a film on which a coating film containing heat ray shielding fine particles was formed.

The coating film thickness of the lanthanum hexaboride microparticle-dispersed film was appropriately adjusted, and the transmittance was measured by a spectrophotometer. The same as in Example 20, the visible light transmittance including the transparent substrate was 70% as in the case of Example 20. The transmittance at a wavelength of 850 nm, the minimum transmittance at a wavelength of 1200 to 1800 nm, the solar transmittance, and the haze value showed a transmittance of 40% at a wavelength of 850 nm. The minimum transmittance is present in a wavelength region shorter than the wavelength of 1200 to 1800 nm, and the transmittance at a wavelength of 975 nm is 35%. Further, the solar transmittance was measured to be 49%, and the haze was measured to be 1.0%. The measurement results are shown in Table 2.

[Evaluation of Examples 20 to 38 and Comparative Examples 4 to 6]

With respect to Examples 20 to 38, it was found that the transmittance of light having a wavelength of 850 nm when the visible light transmittance of the transparent substrate was 70% was high, and the heat ray shielding property which is high as a composite tungsten oxide was obtained, and A near-infrared light having a wavelength of 700 to 1200 nm has a transmittance of a heat ray shielding film. On the other hand, regarding the heat ray shielding film of Comparative Example 4 using the composite tungsten oxide of the prior art, it was found that the transmittance of light having a wavelength of 850 nm when the visible light transmittance of the transparent substrate was 70% and Example 20~ 38 is lower. Further, it was confirmed from Fig. 1 that the heat ray shielding film of Example 20 containing molybdenum as the element A was broadened to the region of near-infrared light as compared with the heat ray shielding film of Comparative Example 4 containing no element A.

Further, the heat ray shielding film of Comparative Example 5 using WO _2.72 as a heat ray shielding fine particle or the heat ray shielding film of Comparative Example 6 using lanthanum hexaboride includes a transparent substrate having a visible light transmittance of 70%. The transmittance of light having a wavelength of 850 nm is high. However, the solar transmittances when the visible light transmittance of the transparent substrate was 70% were 56% and 49%, respectively. Namely, it was found that the heat ray shielding films of Comparative Examples 5 and 6 did not have high heat ray shielding characteristics as in the heat ray shielding film using the composite tungsten oxide of the present invention.

[Example 39] (Heat ray shielding glass using Mo _0.015 Cs _0.33 W _0.985 O ₃ )

Powder B was produced in the same manner as in Example 20, and the powder was dispersed and liquefied in a MIBK solvent. 50 parts by weight of ARONIX UV-3701 (hereinafter abbreviated as UV-3701) manufactured by East Asia Synthetic Co., Ltd., which is an ultraviolet curing resin for hard coating, was added to 100 parts by weight of the dispersion to prepare a heat ray shielding fine particle coating liquid, and a rod was used. The coating machine was applied onto an inorganic transparent glass of 10 cm × 10 cm × 2 mm to form a coating film. The coated film was dried at 80 ° C for 60 seconds to evaporate the solvent, and then hardened with a high pressure mercury lamp. Thereby, a heat ray shielding glass in which a coating film containing heat ray shielding fine particles is formed is produced.

When the heat ray shielding glass was produced, the heat ray shielding fine particle concentration of the coating liquid or the film thickness of the coating film was adjusted, and the visible light transmittance including the transparent substrate was set to 70%. The optical characteristics of the heat ray shielding glass were measured, and as a result, the transmittance at a wavelength of 850 nm was measured to be 36%, the minimum value of the transmittance at a wavelength of 1200 to 1800 nm was measured to be 9%, and the solar transmittance was measured to be 36%, and the haze was measured as 0.5%. According to the above results, in the same manner as in the embodiment 20, the light transmittance of the light having a wavelength of 850 nm when the visible light transmittance of the transparent substrate is 70% is high, and the higher heat for retaining the composite tungsten oxide is obtained. A heat ray shielding glass having a radiation shielding property and having a transmittance for near-infrared light having a wavelength of 700 to 1200 nm.

[Example 40] (Heat ray shielding sheet using Mo _0.015 Cs _0.33 W _0.985 O ₃ )

Weighing each of tungstic acid (H ₂ WO ₄ ), barium hydroxide (CsOH), and molybdenum trioxide (MoO ₃ ) in a ratio equivalent to Mo/Cs/W (Morby)=0.015/0.33/0.985 After the powder, it was thoroughly mixed with an agate mortar to prepare a mixed powder. The mixed powder was heated at a temperature of 600 ° C for 1 hour under a supply of 5% hydrogen gas supported on a nitrogen gas to carry out a reduction treatment, and then calcined at 800 ° C for 30 minutes in a nitrogen atmosphere to obtain a composite tungsten oxide Mo _0.015 Cs. _0.33 W _0.985 O ₃ (hereinafter referred to as powder C). The powder C was measured by an X-ray diffraction method, and as a result, it was pure hexagonal crystal, and no diffraction of molybdenum trioxide or molybdenum dioxide was observed. Further, when the powder C was observed by a transmission electron microscope, the crystal grains of the hexagonal germanium tungsten bronze were observed, and no segregation of the molybdenum compound or the like was observed at the grain boundary of the multi-grain. From this, it was judged that the molybdenum component was completely dissolved in the crystal of hexagonal germanium tungsten bronze.

Weighing 20% by mass of powder C, an acrylic polymer dispersing agent having an amine group as a functional group (an acrylic value of 48 mg KOH/g, an acrylic dispersing agent having a decomposition temperature of 250 ° C) (hereinafter referred to as dispersing agent c) 10 mass %, and methyl isobutyl ketone 70% by mass. Put these loads in 0.3mm In a ZrO ₂ bead paint shaker, pulverization and dispersion treatment were carried out for 10 hours to obtain a composite tungsten oxide fine particle dispersion (hereinafter referred to as dispersion C). Here, the dispersed average particle diameter of the composite tungsten oxide fine particles in the dispersion C was measured and found to be 19 nm.

Further, the dispersing agent c is further added to the dispersion C, and the mass ratio of the dispersing agent c to the composite tungsten oxide fine particles is determined to be [dispersant c/composite tungsten oxide fine particles]=3. Then, methyl isobutyl ketone is removed from the composite tungsten oxide fine particle dispersion C by using a spray dryer to obtain a composite tungsten oxide fine particle dispersion powder (hereinafter referred to as dispersion powder C).

In the polycarbonate resin which is a thermoplastic resin, a predetermined amount of the dispersion powder C is added so that the visible light transmittance of the thermoplastic ray-shielding sheet (thickness: 1.0 mm) to be made of the thermoplastic resin is 70%, and heat is prepared. A composition for producing a radiation shielding sheet.

The composition for heat-ray shielding sheet production was kneaded at 280 ° C using a twin-screw extruder, extruded from a T-die, and a sheet having a thickness of 1.0 mm was formed by a calender roll method to obtain an example. 40 heat ray shielding sheets. The optical characteristics of the obtained heat ray shielding sheet of Example 40 were measured, and as a result, the visible light transmittance of the thermoplastic resin was 70%, the transmittance at a wavelength of 850 nm was 39%, and the minimum transmittance was at a wavelength of 1610 nm. 13%. Further, the solar transmittance was measured to be 37%, and the haze was measured to be 0.5%.

[Comparative Example 7] (Heat ray shielding sheet using Cs _0.33 WO ₃ )

Tungstic acid (H ₂ WO ₄ ) and 37.4 g of cesium hydroxide (CsOH) (corresponding to Cs/W (Morby) = 0.33) were thoroughly mixed with an agate mortar to prepare a mixed powder. The mixed powder was heated under a supply of 5% hydrogen gas supported on a nitrogen gas, and then subjected to a reduction treatment at a temperature of 600 ° C for 1 hour, and then calcined at 800 ° C for 30 minutes in a nitrogen atmosphere to obtain a composite tungsten oxide Cs. _0.33 WO ₃ (hereinafter referred to as "fine particles").

20% by mass of the fine particles 、, 10% by mass of the dispersing agent c, and 70% by mass of the methyl isobutyl ketone were weighed. Put these loads in 0.3mm In a ZrO ₂ bead paint shaker, pulverization and dispersion treatment were carried out for 10 hours to obtain a composite tungsten oxide fine particle dispersion (hereinafter referred to as a dispersion liquid). Here, the dispersed average particle diameter of the composite tungsten oxide fine particles in the dispersion crucible was measured and found to be 20 nm. Further, a dispersing agent c is further added to the dispersion liquid, and the weight ratio of the dispersing agent c to the composite tungsten oxide fine particles is [dispersant c/composite tungsten oxide fine particles]=3. Next, methyl isobutyl ketone is removed from the composite tungsten oxide fine particle dispersion liquid using a spray dryer to obtain a composite tungsten oxide fine particle dispersion powder (hereinafter referred to as a dispersed powder).

In the polycarbonate resin as the thermoplastic resin, a predetermined amount of the dispersed powder is added so that the visible light transmittance of the thermoplastic ray-shielding sheet (thickness: 1.0 mm) to be produced is 70%, and heat is prepared. A composition for producing a radiation shielding sheet.

The composition for heat ray-shielding sheet production was kneaded at 280 ° C using a twin-screw extruder, extruded from a T-die, and a sheet having a thickness of 1.0 mm was formed by a calender roll method to obtain Comparative Example 7. The heat ray shields the sheet. The optical characteristics of the heat ray shielding sheet were measured, and as a result, the visible light transmittance of the thermoplastic resin was 70%, the transmittance at a wavelength of 850 nm was measured to be 24%, and the minimum value of the transmittance at a wavelength of 1200 to 1800 nm was determined to be 10%. The solar transmittance was measured to be 33%, and the haze was determined to be 0.6%.

[Examples 41 to 58] (heat ray shielding sheets using A _a Cs _b W _c O _d )

In the same manner as in Example 40, the compound powder was weighed and heat-treated in the same manner as in Example 40, except that the ratio of the element A, the element M, the tungsten and the oxygen were the values shown in Table 3, and the examples 41 to 58 were produced. Composite tungsten oxide powder. Wherein, in Example 58, a mixture of bismuth and tin (corresponding to Bi:Sn (Mohr ratio)=1:1) was used. Element A. All of the composite tungsten oxide powders of Examples 41 to 58 were subjected to X-ray diffraction measurement and transmission electron microscope observation, and it was confirmed that the element A was solid-dissolved in the hexagonal crystal of the tungsten bronze fine particle crystal. The composite tungsten oxide powder, the solvent, and the dispersing agent c of Examples 41 to 58 were placed in a paint shaker, and stirred and mixed in the same manner as in Example 40 to prepare fine particles dispersed in Examples 41 to 58. liquid. Further, a dispersant c is further added to each of the fine particle dispersions of the examples 41 to 58 in such a manner that the mass ratio of the dispersant c to the composite tungsten oxide fine particles becomes [dispersant c/composite tungsten oxide fine particles]=3. Preparation was carried out. Next, the solvent was removed from the fine particle dispersion to prepare composite tungsten oxide fine particle dispersion powders of Examples 41 to 58. Using the composite tungsten oxide fine particle dispersion powders of the above Examples 41 to 58 and kneading into a polycarbonate resin in the same manner as in Example 40, the sheets of Examples 41 to 58 were produced. The transmittance of the sheets of Examples 41 to 58 was measured using a spectrophotometer, and the transmittance at a wavelength of 850 nm including the visible light transmittance of the thermoplastic resin was 70%, and the minimum transmittance at a wavelength of 1200 to 1800 nm was measured. , solar radiation transmittance, haze value. The measurement results are shown in Table 3.

[Comparative Example 8] (using the heat ray shielding sheet of WO _2.72 )

The tungsten trioxide (WO ₃ ) powder was heated under a supply of 3% hydrogen gas supported on a nitrogen gas, and subjected to a reduction treatment at a temperature of 600 ° C for 1 hour to obtain a tungsten oxide WO _2.72 (hereinafter referred to as fine particles η).

The fine particles η 20% by mass, the dispersant c 10% by mass, and the methyl isobutyl ketone 70% by mass were weighed. Put these loads in 0.3mm ZrO ₂ beads in a paint shaker, for 13 hours pulverization and dispersion treatment, to obtain the tungsten oxide particle dispersion liquid (hereinafter referred to as dispersion η). Here, the dispersed average particle diameter of the tungsten oxide fine particles in the dispersion η was measured and found to be 31 nm.

Further, the dispersing agent c is further added to the dispersion η, and the weight ratio of the dispersing agent c to the tungsten oxide fine particles is set to [dispersant c/tungsten oxide fine particles]=3. Next, methyl isobutyl ketone is removed from the tungsten oxide fine particle dispersion η using a spray dryer to obtain a tungsten oxide fine particle dispersion powder (hereinafter referred to as dispersion powder η).

In the polycarbonate resin as the thermoplastic resin, a predetermined amount of the dispersed powder η is added so that the visible light transmittance of the thermoplastic ray-shielding sheet (thickness: 1.0 mm) to be formed is 70%, and heat is prepared. A composition for producing a radiation shielding sheet.

The composition for heat-ray shielding sheet production was kneaded at 280 ° C using a twin-screw extruder, extruded from a T-die, and a sheet having a thickness of 1.0 mm was formed by a calender roll method to obtain Comparative Example 8. The heat ray shields the sheet. The optical characteristics of the heat ray shielding sheet were measured, and as a result, the visible light transmittance of the thermoplastic resin was 70%, the transmittance at a wavelength of 850 nm was 49%, and the minimum value of the transmittance at a wavelength of 1200 to 1800 nm was 39%. The solar transmittance was measured to be 55%, and the haze was measured to be 0.9%. The measurement results are shown in Table 3.

[Comparative Example 9] (heat ray shielding sheet using LaB ₆ )

5% by mass of lanthanum hexaboride (LaB ₆ ) powder, 3% by mass of dispersant c, and 92% by mass of methyl isobutyl ketone were weighed. Put these loads in 0.3mm In a ZrO ₂ bead paint shaker, pulverization and dispersion treatment were carried out for 20 hours to obtain a lanthanum hexaboride fine particle dispersion (hereinafter referred to as dispersion θ). Here, the dispersed average particle diameter of the ruthenium hexaboride particles in the dispersion θ was measured and found to be 31 nm.

Further, the dispersing agent c is further added to the dispersion θ, and the weight ratio of the dispersing agent c to the lanthanum hexaboride particles is [dispersant c / lanthanum hexaboride microparticles] = 3. Next, methyl isobutyl ketone is removed from the hexaboride hexaboride fine particle dispersion θ by a spray dryer to obtain a tungsten oxide fine particle dispersion powder (hereinafter referred to as a dispersion powder θ).

In the polycarbonate resin which is a thermoplastic resin, a predetermined amount of the dispersion powder θ is added so that the visible light transmittance of the thermoplastic ray-shielding sheet (thickness: 1.0 mm) to be produced is 70%. A composition for producing a heat ray shielding sheet.

The composition for heat-ray shielding sheet production was kneaded at 280 ° C using a twin-screw extruder, extruded from a T-die, and a sheet having a thickness of 1.0 mm was formed by a calender roll method to obtain Comparative Example 9. The heat ray shields the sheet. The optical characteristics of the heat ray shielding sheet were measured, and as a result, the visible light transmittance of the thermoplastic resin was 70%, and the transmittance at a wavelength of 850 nm was 41%. The minimum transmittance is present in a wavelength region shorter than the wavelength of 1200 to 1800 nm, and the transmittance at a wavelength of 975 nm is 36%. Further, the solar transmittance was measured to be 48%, and the haze was measured to be 1.0%. The measurement results are shown in Table 3.

[Evaluation of Examples 40 to 58 and Comparative Examples 7 to 9]

In Examples 40 to 58, it was found that the transmittance of light having a wavelength of 850 nm at a visible light transmittance of 70% is higher than that of Comparative Example 7 using a conventional heat-shielding sheet of a composite tungsten oxide. A heat ray shielding sheet having a high heat ray shielding property as a composite tungsten oxide and having a transmittance for near-infrared light having a wavelength of 700 to 1200 nm.

In Comparative Example 8 using WO _2.72 as a heat ray shielding fine particle or the heat ray shielding sheet of Comparative Example 9 using lanthanum hexaboride, the transmittance of light having a wavelength of 850 nm when the visible light transmittance was 70% was high. However, the solar transmittances at a visible light transmittance of 70% were 55% and 48%, respectively, which were significantly higher than the 34 to 38% of the heat ray shielding sheets of Examples 40 to 58 using the composite tungsten oxide, instead of It has a higher heat ray shielding property such as a heat ray shielding sheet using a composite tungsten oxide.

[Example 59] (Heat ray shielding masterbatch using Mo _0.015 Cs _0.33 W _0.985 O ₃ )

The dispersion powder C (the composite powder of the composite tungsten oxide Cs _0.33 Mo _0.015 W _0.985 O ₃ ) produced in Example 40 and the polycarbonate resin particles were mixed so that the concentration of the composite tungsten oxide became 2.0% by mass, and The mixture was prepared by uniformly mixing using a mixer. The mixture was melt-kneaded at 290 ° C using a twin-screw extruder, and the extruded strands were cut into pellets to obtain a masterbatch of Example 59 for heat ray shielding of a transparent resin molded body (hereinafter referred to as a mother). Material C). A heat-ray shielding sheet production composition of Example 59 was prepared by adding a predetermined amount of the master batch C to the polycarbonate resin pellets. In addition, the heat ray shielding sheet (thickness 1.0 mm) manufactured by the above-mentioned quantitative system includes the thermoplastic resin having a visible light transmittance of 70%.

The heat ray-shielding sheet-forming composition of Example 59 was kneaded at 280 ° C using a twin-screw extruder, extruded from a T-die, and a sheet having a thickness of 1.0 mm was formed by a calender roll method. The heat ray shielding sheet of Example 59 was obtained. The optical characteristics of the obtained heat ray shielding sheet of Example 59 were measured, and as a result, the visible light transmittance of the thermoplastic resin was 70%, the transmittance at a wavelength of 850 nm was 38%, and the minimum value of the transmittance was 1610 nm. 10%. The visible light transmittance of the thermoplastic resin was measured to be 70%, the solar transmittance was measured to be 37%, and the haze was measured to be 0.9%. From the above results, it was confirmed that, similarly to the dispersion powder of Example 40, A masterbatch suitable as a heat ray shielding fine particle dispersion which can be suitably used for the manufacture of a heat ray shielding sheet is produced.

[Example 60] (Heat ray shielding film using Mo _0.015 Cs _0.33 W _0.985 O ₃ and interlayer transparent substrate for heat ray shielding)

Adding a plasticizer of triethylene glycol bis(2-ethylbutyrate) to a polyvinyl butyral resin, and making a weight ratio of polyvinyl butyral resin to a plasticizer becomes [polyvinyl alcohol A mixture prepared from a butyral resin/plasticizer] = 100/40. A dispersion powder C (composite tungsten oxide Cs _0.33 Mo _0.015 W _0.985 O ₃ dispersion powder) prepared in Example 40 was added to the mixture to prepare a composition for producing a heat ray shielding film. In addition, the visible light transmittance of the transparent base material and the thermoplastic resin which are the heat-ray shielding interlayer transparent substrates manufactured by the above-mentioned quantitative system is 70%.

The composition for production was kneaded and mixed at 70 ° C for 30 minutes using a three-roll mixer to prepare a mixture. The mixture was heated to 180 ° C by a die extruder, thinned to a thickness of about 1 mm, and wound up into a roll, whereby the heat ray shielding film of Example 60 was produced. The heat ray shielding film of Example 60 was cut into 10 cm × 10 cm, and sandwiched between two sheets of inorganic transparent glass sheets having the same size and a thickness of 2 mm to form a laminate. Next, the laminated body was placed in a vacuum bag made of rubber, and the inside of the bag was degassed and kept at 90 ° C for 30 minutes, and then returned to normal temperature and taken out from the bag. Then, the laminated body was placed in an autoclave, and heated under pressure at a pressure of 12 kg/cm ² and a temperature of 140 ° C for 20 minutes to prepare a laminated glass sheet for heat ray shielding of Example 60. Here, for the purpose of comparison, the dispersing powder prepared in Comparative Example 7 (dispersion powder of composite tungsten oxide Cs _0.33 WO ₃ fine particles) was used instead of the dispersing powder C, and the laminated glass for heat ray shielding of Example 60 was produced. The heat-shielding film of the prior art and the interlayer transparent substrate for heat ray shielding are produced by the same process of the sheet.

The optical characteristics of the interlayer transparent substrate for heat ray shielding of Example 60 were measured. As a result, when the visible light transmittance of the transparent substrate and the thermoplastic resin was 70%, the transmittance at 850 nm was 35%, and the transmittance was the minimum. It became 7% at a wavelength of 1580 nm. On the other hand, on Cs for comparison of conventional production technologies _0.33 WO ₃ of a laminated heat ray shielding transparent substrate used, including visible light transmittance in a transparent substrate and a thermoplastic resin is 70% at a wavelength of 850nm The transmittance was 20%, and the minimum value of the transmittance was 6% at a wavelength of 1590 nm. From the above results, it was confirmed that the interlayer transparent layer for heat ray shielding of Example 60 in which molybdenum was added as the element A was kept in the heat ray shielding as compared with the conventional transparent layer for heat ray shielding without molybdenum. In the state of the characteristic, the near-infrared light is transmitted.

Claims (21)

A heat ray shielding microparticle, which is _a composite tungsten oxide microparticle represented by the general formula A _a M _b W _c O _d , and the element A is selected from the group consisting of Mo, Ru, Cr, Ni, V, Co, Fe, Mn, Ti, One or more elements selected from the group consisting of Ge, Sn, Ga, Pb, Bi, In, Sb, Pd, and Tl, and M is one or more selected from the group consisting of alkali metals and alkaline earth metals, W is tungsten, and O is oxygen. And 0.001 ≦ a / b ≦ 0.1, 0.20 ≦ b / (a + c) ≦ 0.61, 2.2 ≦ d / (a + c) ≦ 3.0, and has a hexagonal crystal structure. The heat ray shielding fine particles according to claim 1, wherein the heat ray shielding fine particles have a particle diameter of 1 nm or more and 800 nm or less. A heat ray shielding fine particle dispersion liquid obtained by dispersing a heat ray shielding fine particle of claim 1 or 2 in a liquid medium selected from the group consisting of water, an organic solvent, a grease, and a liquid Resin, plasticizer for liquid plastic, or a mixture of these. The heat ray shielding fine particle dispersion liquid according to claim 3, wherein the content of the heat ray shielding fine particles contained in the liquid medium is 0.01% by mass or more and 50% by mass or less. The heat ray shielding microparticle dispersion according to claim 3 or 4, wherein the transmittance of light having a wavelength of 850 nm when the visible light transmittance is 85% in the case where only the light absorption by the heat ray shielding microparticles is calculated The minimum value of the transmittance of 23% or more and 45% or less and the wavelength of 1200 to 1800 nm is 15% or less. A heat ray shielding film or a heat ray shielding glass, characterized in that a coating layer is provided on at least one side of a transparent substrate selected from a transparent film substrate or a transparent glass substrate, and the coating layer is a bonding layer containing heat ray shielding particles. resins, the heat ray shielding fine lines in the formula _{A a} M _b W _c O _d of the composite tungsten oxide indicated, and A is selected from Mo, Ru, Cr, Ni, V, Co, Fe, Mn, Ti One or more elements of Ge, Sn, Ga, Pb, Bi, In, Sb, Pd, and Tl, and M is one or more elements selected from the group consisting of alkali metals and alkaline earth metals, W is tungsten, and O is oxygen. And 0.001 ≦ a / b ≦ 0.1, 0.20 ≦ b / (a + c) ≦ 0.61, 2.2 ≦ d / (a + c) ≦ 3.0, and the composite tungsten oxide fine particles have a hexagonal crystal structure. The heat ray shielding film or the heat ray shielding glass according to claim 6, wherein the composite tungsten oxide fine particles have a diameter of 1 nm or more and 800 nm or less. The heat ray shielding film or the heat ray shielding glass according to claim 6 or 7, wherein the binder resin is a UV curable resin binder. The heat ray shielding film or the heat ray shielding glass according to any one of claims 6 to 8, wherein the coating layer has a thickness of 10 μm or less. The heat ray shielding film according to any one of claims 6 to 9, wherein the transparent film substrate is a polyester film. The heat ray shielding film or the heat ray shielding glass according to any one of claims 6 to 10, wherein a content per unit projection area of the heat ray shielding fine particles contained in the coating layer is 0.1 g/m ² or more or more 5.0 g/m ² or less. The heat ray shielding film or the heat ray shielding glass according to any one of claims 6 to 11, wherein when the visible light transmittance of the transparent substrate is 70%, the transmittance at a wavelength of 850 nm is 23% or more and 45 Below %, and exists at a wavelength of 1200~1800 The minimum transmittance of the range of nm is 15% or less. A heat ray shielding fine particle dispersion, characterized by comprising at least a heat ray shielding fine particles and the thermoplastic resin, the heat ray shielding fine particles such as the following lines of the composite tungsten oxide microparticles: represented by the general formula _{A a} M _b W _c O _d A is one or more elements selected from the group consisting of Mo, Ru, Cr, Ni, V, Co, Fe, Mn, Ti, Ge, Sn, Ga, Pb, Bi, In, Sb, Pd, and Tl, M system One or more elements selected from the group consisting of alkali metals and alkaline earth metals, W is tungsten, O is oxygen, 0.001 ≦ a/b ≦ 0.1, 0.20 ≦ b / (a + c) ≦ 0.61, 2.2 ≦ d / (a + c) ≦ 3.0 and having a hexagonal crystal structure. The heat ray shielding fine particle dispersion according to claim 13, wherein the thermoplastic resin is any one of the following: selected from the group consisting of polyethylene terephthalate resin, polycarbonate resin, acrylic resin, and styrene resin. , polyamide resin, polyethylene resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluororesin, ethylene. a resin of a vinyl acetate copolymer, a resin group of polyvinyl acetal resin; or a mixture of two or more resins selected from the group of the above resins; or 2 selected from the group of resins described above A copolymer of the above resins. The heat ray shielding fine particle dispersion according to claim 13 or 14, wherein the composite tungsten oxide fine particles have a diameter of 1 nm or more and 800 nm or less. The heat ray shielding fine particle dispersion according to any one of claims 13 to 15, which comprises 0.5% by mass or more and 80.0% by mass or less of the above composite tungsten oxide fine particles. The heat ray shielding fine particle dispersion according to any one of claims 13 to 16, wherein the heat ray shielding fine particle dispersion is in a sheet shape, a plate shape or a film shape. The heat ray shielding fine particle dispersion according to any one of claims 13 to 17, wherein the content of the heat ray shielding fine particles per unit projection area included in the heat ray shielding fine particle dispersion is 0.1 g/m ² or more 5.0 g/m ² or less. The heat ray shielding fine particle dispersion according to any one of claims 13 to 18, wherein, when the visible light transmittance of the thermoplastic resin is 70%, the transmittance of near-infrared light having a wavelength of 850 nm is 23% or more and 45 Below %, the minimum of the transmittance of the heat ray having a wavelength of 1200 to 1800 nm is 15% or less. An interlayer transparent substrate for heat ray shielding, characterized in that the heat ray shielding fine particle dispersion of any one of claims 13 to 19 is present between a plurality of transparent substrates. The interlayer transparent substrate for heat ray shielding according to claim 20, wherein the transmittance of the near-infrared light having a wavelength of 850 nm is 23% or more and 45% or less, and the minimum transmittance of the heat ray having a wavelength of 1200 to 1800 nm is 15 %the following.