WO2017094909A1

WO2017094909A1 - Heat ray shielding microparticle, heat ray shielding microparticle dispersion solution, heat ray shielding film, heat ray shielding glass, heat ray shielding dispersion body, and heat ray shielding laminated transparent base material

Info

Publication number: WO2017094909A1
Application number: PCT/JP2016/085973
Authority: WO
Inventors: 美香岡田; 足立　健治
Original assignee: 住友金属鉱山株式会社
Priority date: 2015-12-02
Filing date: 2016-12-02
Publication date: 2017-06-08
Also published as: MY191130A

Abstract

The objective of the invention is to provide a heat ray shielding microparticle, a heat ray shielding microparticle dispersion solution, a heat ray shielding film, a heat ray shielding glass, a heat ray shielding dispersion body, and a heat ray shielding laminated transparent base material such that when a structure body such as a window material is applied, heat ray shielding properties can be exhibited to suppress skin irritations while enabling the use of a communication apparatus, an imaging apparatus, sensors, and the like which use near-infrared light that has passed through the structure body, the heat ray shielding film, the heat ray shielding glass, the dispersion body, or the laminated transparent base material. Provided are the heat ray shielding microparticle, the heat ray shielding microparticle dispersion solution, the heat ray shielding film, the heat ray shielding glass, the heat ray shielding dispersion body, and the heat ray shielding laminated transparent base material, the heat ray shielding microparticle being a composite tungsten oxide microparticle having a heat ray shielding function. If the visible radiation transmittance is 85% when only the light absorption by the composite tungsten oxide microparticle is calculated, the mean value of transmittance in a wavelength range of 800 to 900 nm is between 30% and 60% inclusive, the mean value of the transmittance in a wavelength range of 1200 to 1500 nm is 20% or lower, and the transmittance at the wavelength of 2100 nm is 22% or lower.

Description

Heat ray shielding fine particles, heat ray shielding fine particle dispersion, heat ray shielding film, heat ray shielding glass, heat ray shielding dispersion, and heat ray shielding laminated transparent base material

The present invention relates to a heat ray shielding fine particle, a heat ray shielding fine particle dispersion, a heat ray shielding film, a heat ray, which have good visible light permeability and have an excellent heat ray shielding function, and which transmit near infrared light having a predetermined wavelength. The present invention relates to a shielding glass, a heat ray shielding dispersion, and a heat ray shielding laminated transparent base material.

Various technologies have been proposed so far as heat ray shielding techniques that have good visible light transmittance and reduce solar radiation transmittance while maintaining transparency. Among them, the heat ray shielding technology using conductive fine particles, a dispersion of conductive fine particles, and a laminated transparent base material has excellent heat ray shielding properties and low cost compared to other technologies, and has radio wave permeability. Further, there are advantages such as high weather resistance.

For example, Patent Document 1 discloses that a transparent resin containing tin oxide fine powder in a dispersed state or a transparent synthetic resin containing tin oxide fine powder contained in a dispersed state is formed into a sheet or film. An infrared-absorbing synthetic resin molded product laminated on a material has been proposed.

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

Further, the applicant discloses in Patent Document 3 a selective permeable membrane coating solution and a selectively permeable membrane in which at least one of titanium nitride fine particles and lanthanum boride fine particles is dispersed.

However, the heat ray shielding structures such as infrared-absorbing synthetic resin molded products disclosed in Patent Documents 1 to 3 are not sufficient in heat ray shielding performance when high visible light transmittance is required. There was a point. For example, as an example of specific numerical values of the heat ray shielding performance of the heat ray shielding structures disclosed in Patent Documents 1 to 3, the visible light transmittance calculated based on JIS R 3106 (in the present invention, simply “ When it is 70%, the solar transmittance calculated based on JIS R 3106 (in the present invention, it may be simply referred to as “sunlight transmittance”). ) Exceeded 50%.

Accordingly, the applicant has disclosed an infrared shielding material fine particle dispersion in which infrared shielding material fine particles are dispersed in a medium, and the infrared shielding material fine particles are represented by the general formula M _x W _y O _z (wherein element M is H , He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, One or more elements selected from 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 are hexagonal, Patent Document 4 discloses a heat ray shielding dispersion comprising at least one kind of fine particles having a tetragonal or cubic crystal structure, wherein the infrared shielding material fine particles have a particle diameter of 1 nm to 800 nm. As disclosed.

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

In addition, the applicant has a general formula M _a WO _c (where 0.001 ≦ a ≦ 1.0, 2.2 ≦ c ≦ 3.0, M elements are Cs, Rb, K, Tl, In, Ba, One or more elements selected from Li, Ca, Sr, Fe, and Sn), and containing composite tungsten oxide fine particles having a hexagonal crystal structure, and represented by the general formula M _a WO _c When the powder color of the composite tungsten oxide shown is evaluated in the L ^* a ^* b ^* color system, L ^* is 25 to 80, a ^* is −10 to 10, and b ^* is −15 to 15. An ultraviolet / near-infrared light shielding dispersion characterized by the above is disclosed as Reference 5.

In Patent Document 5, the composite tungsten oxide fine particles represented by the general formula M _a WO _c and the iron oxide fine particles are used together at a certain ratio, thereby having a predetermined visible light transmittance, and a near-infrared shielding property. At the same time, an ultraviolet / near-infrared light shielding dispersion and an ultraviolet / near-infrared light shielding body having an ultraviolet shielding property and having a bronze color tone with excellent design and low saturation were obtained.

JP-A-2-136230 JP-A-8-259279 Japanese Patent Laid-Open No. 11-181336 International Publication Number WO2005 / 037932 JP 2008-231164 A

However, the composite tungsten oxide fine particles represented by the general formula M _x W _y O _z , the heat ray shielding dispersion, the heat ray shielding film, the heat ray shielding glass, the heat ray shielding fine particle dispersion, and the laminated transparent base material using the same. As a result of expanding the range of use in the market, new challenges were discovered.
The problem is that the composite tungsten oxide fine particles described by the general formula M _x W _y O _z , the heat ray shielding film or heat ray shielding glass containing the composite tungsten oxide fine particles, and the dispersion containing the composite tungsten oxide fine particles When a body or a heat ray shielding laminated transparent base material 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 greatly reduced in light passing through the window material or the like. It is.
Near-infrared light in this wavelength region is almost invisible to the human eye, and can be oscillated by a light source such as an inexpensive near-infrared LED, so communication and imaging equipment using near-infrared light Widely used in sensors, etc. However, a structure such as a window material using a composite tungsten oxide fine particle represented by the general formula M _x W _y O _z , a structure such as a heat ray shielding body, a heat ray shielding base material, a dispersion, and a laminated transparent base material Absorbs near-infrared light in the wavelength region strongly with heat rays.
As a result, a structure such as a window material using the composite tungsten oxide fine particles represented by the general formula M _x W _y O _z , a heat ray shielding film, a heat ray shielding glass, a dispersion, and a laminated transparent substrate are used. In some cases, communication using near-infrared light, use of imaging devices, sensors, and the like are restricted.

For example, when the heat ray shielding film using the composite tungsten oxide fine particles described in Patent Document 4 is attached to a window of a general house, it is composed of an infrared oscillator placed indoors and an infrared receiver placed outdoors. The near-infrared light communication between the intrusion detection devices was interrupted, and the devices did not operate normally.

Despite the existence of the above problems, heat ray shielding films using composite tungsten oxide fine particles, structures such as window materials, dispersions and heat ray shielding laminated transparent base materials have a high ability to cut the heat rays greatly. Use has expanded in market areas where shielding is desired. However, when such a structure, such as a heat ray shielding film or window material, a dispersion or a heat ray shielding laminated transparent base material is used, wireless communication using near infrared light, imaging equipment, sensors, etc. can be used. It was not possible.

In addition, the general formula M _x W _y O or composite tungsten oxide fine particles expressed by _z, the heat ray shielding dispersion using the same heat ray shielding film, solar control glass, heat-ray shielding fine particle dispersion and the combined transparent substrate However, the heat ray with a wavelength of 2100 nm was not sufficiently shielded.

For example, when the heat ray shielding film using the composite tungsten oxide fine particles described in Patent Document 4 was attached to a window of a general house, the heat felt tingling on the skin indoors.

The present invention has been made under the above-mentioned circumstances. And when the problem which it is going to solve is applied to structures, such as a window material, while exhibiting a heat ray shielding characteristic and suppressing the irritating feeling to skin, the structure, the heat ray shielding film, or Heat ray shielding glass, heat ray shielding fine particles, heat ray shielding fine particle dispersion, heat ray shielding film, enabling use of communication equipment, imaging equipment, sensors, etc. using near-infrared light through the dispersion or laminated transparent substrate, It is to provide a heat ray shielding glass, a heat ray shielding dispersion, and a heat ray shielding laminated transparent base material.

The present inventors have made various studies in order to solve the above-described problems.
For example, even when a heat ray shielding film, heat ray shielding glass, a heat ray shielding dispersion, and a heat ray shielding laminated transparent base material are used, communication devices, imaging devices, sensors, etc. that use near infrared light can be used. Therefore, it was considered that the transmittance of near-infrared light in the wavelength region of 800 to 900 nm should be improved. If the transmittance of near-infrared light in the wavelength region is simply improved, the concentration of the composite tungsten oxide fine particles in the film, the concentration of the composite tungsten oxide fine particles in the heat ray shielding film or the heat ray shielding glass, the heat ray shielding It has also been considered that the concentration of the composite tungsten oxide fine particles in the dispersion or the heat ray shielding laminated transparent base material may be appropriately reduced.
However, when the concentration of the composite tungsten oxide fine particles and the concentration of the composite tungsten oxide fine particles in the heat ray shielding dispersion or the heat ray shielding laminated transparent base material are decreased, the heat ray absorption ability with the wavelength region of 1200 to 1800 nm as the bottom is reduced. At the same time, the heat ray shielding effect is lowered, and the skin feels irritated.

Here, it is considered that sunlight gives the skin a sense of irritability because of the large influence of heat rays with a wavelength of 1500-2100 nm (for example, Yoshikazu Ozeki et al. 33-99, 13 (1999), which indicates that the absorbance of human skin is small for near infrared light with a wavelength of 700-1200 nm, but large for heat rays with a wavelength of 1500-2100 nm. This is considered to be the reason.

Based on the above findings, the present inventors have conducted various studies, and as a result, in the heat treatment (firing) step for producing the composite tungsten oxide fine particles represented by the general formula M _x WO _y , the reduced state By controlling the absorption within the wavelength range of 2100 nm while controlling the absorption at the wavelength of 800-900 nm while maintaining the heat absorption capability with the bottom of the wavelength range of 1200-1800 nm. It has been found that tungsten oxide fine particles can be obtained.

However, composite tungsten oxide fine particles having improved near-infrared light transmittance in the wavelength region of 800 to 900 nm have been conventionally used as an evaluation standard for heat ray shielding performance in a dispersion of heat ray shielding fine particles (for example, When the solar radiation transmittance was evaluated with respect to the visible light transmittance evaluated according to JIS R 3106.), there was a concern that it might be inferior to the composite tungsten oxide according to the prior art.
In view of this, the composite tungsten oxide fine particles produced by controlling the reduction state during the heat treatment were further examined.

The composite tungsten oxide fine particles whose transmittance for near-infrared light having a wavelength of 800 to 900 nm is improved by controlling the reduction state during the heat treatment described above are the composite tungsten oxide fine particles according to the related art. In comparison, it was found that the performance as heat ray shielding fine particles is not inferior.
This is because, in the composite tungsten oxide fine particles having improved transmittance of near infrared light having a wavelength of 800 to 900 nm, the transmittance for visible light is also increased. Therefore, the concentration of the composite tungsten oxide fine particles per unit area can be set higher. This is because, as a result of this higher concentration setting, transmission of heat rays with a wavelength of 1500 to 2100 nm can be suppressed.

As a result of the above studies, the present inventors are composite tungsten oxide fine particles having a heat ray shielding function, and the visible light transmittance is 85% when only light absorption by the composite tungsten oxide fine particles is calculated. Sometimes, the average value of the transmittance in the wavelength range of 800 to 900 nm is 30% or more and 60% or less, the average value of the transmittance in the wavelength range of 1200 to 1500 nm is 20% or less, and the wavelength is 2100 nm. The present invention was completed by conceiving a heat ray shielding fine particle characterized by having a transmittance of 22% or less.

Furthermore, the present inventors also used a heat ray shielding material, a heat ray shielding film, a heat ray shielding glass, a heat ray shielding dispersion and a laminated transparent substrate using the composite tungsten oxide fine particles according to the present invention as a heat ray shielding material. It was also found that the performance is not inferior to the composite tungsten oxide fine particles according to the prior art from the viewpoint of suppressing the irritating feeling on the skin.

That is, the first invention for solving the above-described problem is
A composite tungsten oxide fine particle having a heat ray shielding function, and a transmittance in a wavelength range of 800 to 900 nm when the visible light transmittance is 85% when only light absorption by the composite tungsten oxide fine particle is calculated. The average value is 30% or more and 60% or less, the average value of transmittance in the wavelength range of 1200 to 1500 nm is 20% or less, and the transmittance at wavelength 2100 nm is 22% or less. These are heat ray shielding fine particles.
The second invention is
In the L ^* a ^* b ^* color system, the powder color of the composite tungsten oxide fine particles is L ^* of 30 to 55, a ^* of −6.0 to −0.5, and b ^* of −10. It is a heat ray shielding fine particle characterized by being 0 or more and 0 or less.
The third invention is
The composite tungsten oxide fine particles have the general formula M _x WO _y (where M is one or more elements selected from Cs, Rb, K, Tl and Ba, 0.1 ≦ x ≦ 0.5, 2. 2 ≦ y ≦ 3.0).
The fourth invention is:
The composite tungsten oxide fine particles are heat ray shielding fine particles having a hexagonal crystal structure and a c-axis lattice constant of 7.56 to 8.82.
The fifth invention is:
The heat ray shielding fine particles have a particle diameter of 1 nm or more and 800 nm or less.
The sixth invention is:
The heat ray shielding fine particles are dispersed in a liquid medium, and the liquid medium is selected from water, organic solvents, oils and fats, liquid resins, plasticizers for liquid plastics, or a mixture thereof. This is a heat ray shielding fine particle dispersion.
The seventh invention
It is a heat ray shielding fine particle dispersion in which the content of the heat ray shielding fine particles contained in the liquid medium is 0.01% by mass or more and 80% by mass or less.
The eighth invention
Tungstic acid and a hydroxide powder of one or more elements selected from Cs, Rb, K, Tl, and Ba are mixed at a predetermined ratio to obtain a mixed powder.
One or more elements selected from Cs, Rb, K, Tl, and Ba are reduced by heating the mixed powder under an H ₂ gas supply of 0.8% or less using an inert gas as a carrier. It is a manufacturing method of the heat ray shielding fine particles characterized by obtaining a composite tungsten oxide powder containing.
The ninth invention
A method for producing a heat ray shielding fine particle dispersion, comprising a dispersion step of dispersing the heat ray shielding fine particles obtained in the eighth invention in a liquid medium to obtain a heat ray shielding fine particle dispersion.
The tenth invention is
Furthermore, it is a heat ray shielding fine particle dispersion characterized by containing at least one selected from an ultraviolet absorber, HALS, and an antioxidant.
The eleventh invention is
A composite tungsten oxide fine particle having a heat ray shielding function, and a transmittance in a wavelength range of 800 to 900 nm when a visible light transmittance is 85% when only light absorption by the composite tungsten oxide fine particle is calculated. Heat ray shielding fine particles having an average value of 30% or more and 60% or less, an average value of transmittance in the wavelength range of 1200 to 1500 nm of 20% or less, and a transmittance of wavelength 2100 nm of 22% or less It is a heat ray shielding film or heat ray shielding glass characterized by including these.
The twelfth invention is
The composite tungsten oxide fine particles have a hexagonal crystal structure, and the c-axis lattice constant is 7.56 to 8.82, which is a heat ray shielding film or heat ray shielding glass.
The thirteenth invention is
A heat ray comprising a coating layer on at least one surface of a transparent substrate selected from a transparent film substrate and a transparent glass substrate, wherein the coating layer is a binder resin layer containing the heat ray shielding fine particles It is a shielding film or heat ray shielding glass.
The fourteenth invention is
The binder resin is a heat ray shielding film or a heat ray shielding glass, which is a UV curable resin binder.
The fifteenth invention
A heat ray shielding film or a heat ray shielding glass, wherein the coating layer has a thickness of 10 μm or less.
The sixteenth invention is
The transparent film base material is a polyester film, and is a heat ray shielding film.
The seventeenth invention
It is a heat ray shielding film or heat ray shielding glass whose content per unit projected area of the heat ray shielding fine particles contained in the coating layer is 0.1 g / m ² or more and 5.0 g / m ² or less.
The eighteenth invention
When the visible light transmittance is 70%, the average transmittance in the wavelength range of 800 to 900 nm is 13% to 40%, and the average transmittance in the wavelength range of 1200 to 1500 nm is 8%. The heat ray shielding film or the heat ray shielding glass is characterized in that the transmittance at a wavelength of 2100 nm is 9% or less.
The nineteenth invention
A mixing step in which tungstic acid and a hydroxide powder of one or more elements selected from Cs, Rb, K, Tl, and Ba are mixed at a predetermined ratio to obtain a mixed powder;
One or more elements selected from Cs, Rb, K, Tl, and Ba are reduced by heating the mixed powder under an H ₂ gas supply of 0.8% or less using an inert gas as a carrier. A firing step of obtaining a composite tungsten oxide powder comprising:
A step of uniformly mixing the composite tungsten oxide powder into a transparent resin to obtain a heat ray shielding fine particle dispersion;
And a step of coating the heat ray shielding fine particle dispersion on a transparent film substrate or a transparent glass substrate. A method for producing a heat ray shielding film or a heat ray shielding glass.
The twentieth invention is
Furthermore, it is a heat ray shielding glass or a heat ray shielding film characterized by containing at least one selected from an ultraviolet absorber, HALS, and an antioxidant.
The twenty-first invention
A composite tungsten oxide fine particle having a heat ray shielding function, and a transmittance in a wavelength range of 800 to 900 nm when a visible light transmittance is 85% when only light absorption by the composite tungsten oxide fine particle is calculated. Heat ray shielding fine particles having an average value of 30% or more and 60% or less, an average value of transmittance in the wavelength range of 1200 to 1500 nm of 20% or less, and a transmittance of wavelength 2100 nm of 22% or less It is a heat ray shielding fine particle dispersion characterized by including.
The twenty-second invention relates to
The composite tungsten oxide fine particles have a hexagonal crystal structure, and the c-axis lattice constant is 7.56 to 8.82 to provide a heat ray shielding fine particle dispersion.
The twenty-third invention
The thermoplastic resin is polyethylene terephthalate resin, polycarbonate resin, acrylic resin, styrene resin, polyamide resin, polyethylene resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluororesin, ethylene / vinyl acetate copolymer, polyvinyl One resin selected from the group of resins called acetal resins;
Or a mixture of two or more resins selected from the resin group,
Or it is any one of the copolymer of 2 or more types of resin selected from the said resin group, It is a heat ray shielding fine particle dispersion characterized by the above-mentioned.
The twenty-fourth invention is
A heat ray shielding fine particle dispersion comprising the composite tungsten oxide particles in an amount of 0.5% by mass or more and 80.0% by mass or less.
The twenty-fifth invention
The heat ray shielding fine particle dispersion is in the form of a sheet, a board, or a film.
The twenty-sixth invention
A heat ray shielding fine particle dispersion, wherein a content of the heat ray shielding fine particles per unit projected area contained in the heat ray shielding fine particle dispersion is from 0.1 g / m ^{2 to} 5.0 g / m ^2. is there.
The twenty-seventh invention
When the visible light transmittance is 70%, the average transmittance in the wavelength range of 800 to 900 nm is 13% to 40%, and the average transmittance in the wavelength range of 1200 to 1500 nm is 8%. The heat ray shielding fine particle dispersion is characterized in that the transmittance at a wavelength of 2100 nm is 5% or less.
The twenty-eighth invention is
A heat ray shielding laminated transparent substrate, wherein the heat ray shielding fine particle dispersion according to any one of the twenty-first to twenty-seventh aspects is present between a plurality of transparent substrates.
The twenty-ninth invention
When the visible light transmittance is 70%, the average transmittance at a wavelength of 800 to 900 nm is 12% to 40%, and the average transmittance at a wavelength of 1200 to 1500 nm is 8% or less. In addition, the heat ray shielding laminated transparent base material is characterized in that the transmittance at a wavelength of 2100 nm is 8.0% or less.
The thirtieth invention is
A mixing step in which tungstic acid and a hydroxide powder of one or more elements selected from Cs, Rb, K, Tl, and Ba are mixed at a predetermined ratio to obtain a mixed powder;
One or more elements selected from Cs, Rb, K, Tl, and Ba are reduced by heating the mixed powder under an H ₂ gas supply of 0.8% or less using an inert gas as a carrier. A firing step of obtaining a composite tungsten oxide powder comprising:
And a step of uniformly mixing the composite tungsten oxide powder into a transparent resin to obtain a heat ray shielding fine particle dispersion.
The thirty-first invention is
A heat ray shielding laminated transparent base material production method comprising a step of sandwiching the heat ray shielding fine particle dispersion according to the thirtieth invention between the transparent base materials.
The thirty-second invention
A method for producing a heat ray shielding laminated transparent base material, comprising the step of forming the heat ray shielding fine particle dispersion described in the thirtieth invention into a film shape or a board shape.
The thirty-third invention
Furthermore, it is a heat ray shielding fine particle dispersion or a heat ray shielding laminated transparent base material characterized by containing one or more selected from ultraviolet absorbers, HALS and antioxidants.

The heat ray shielding film, the heat ray shielding glass, the heat ray shielding dispersion, and the heat ray shielding laminated transparent base material produced using the heat ray shielding fine particles and the heat ray shielding fine particle dispersion according to the present invention exhibit the heat ray shielding properties, and to the skin. In addition to suppressing the jerky feeling, communication devices, imaging devices, sensors, and the like using near infrared light can be used even when these structures and the like are interposed.

It is the transmittance | permeability profile for every wavelength of the composite tungsten oxide fine particle dispersion liquid which concerns on this invention. It is the transmittance | permeability profile for every wavelength of the heat ray shielding film which concerns on this invention. It is the transmittance | permeability profile for every wavelength of the heat ray shielding matching transparent base material which concerns on this invention.

Hereinafter, for embodiments for carrying out the present invention, [a] heat ray shielding fine particles, [b] method of producing heat ray shielding fine particles, [c] heat ray shielding fine particle dispersion and production method thereof, [d] heat ray shielding film and heat ray The production method of the shielding glass, [e] the production method of the heat ray shielding fine particle dispersion, and [f] the production method of the heat ray shielding laminated transparent substrate will be described in this order.

[A] Heat ray shielding fine particles (composite tungsten oxide fine particles)
The heat ray shielding fine particles according to the present invention have an average transmittance of 30% to 60% at a wavelength of 800 to 900 nm when the visible light transmittance is 85% when only light absorption by the composite tungsten oxide fine particles is calculated. Composite tungsten oxide fine particles having an average transmittance of 20% or less in a wavelength range of 1200 to 1500 nm and a transmittance of 2100 nm or less at 22% or less.
When expressed by the general formula M _x WO _y , the element M is one or more elements selected from one or more elements selected from Cs, Rb, K, Tl, and Ba, and W is Tungsten and O is oxygen. The composite tungsten oxide fine particles satisfy 0.1 ≦ x ≦ 0.5 and 2.2 ≦ y ≦ 3.0.
Furthermore, it is a composite tungsten oxide fine particle having a hexagonal crystal structure, and a heat ray shielding fine particle having a c-axis lattice constant of 7.56 to 8.82.

As for the addition amount of the element M, the value of x is preferably 0.18 or more and 0.5 or less, more preferably 0.18 or more and 0.33 or less. This is because if the value of x is 0.18 or more and 0.33 or less, a hexagonal crystal single phase is easily obtained, and the heat ray absorption effect is sufficiently exhibited. In addition to hexagonal crystals, tetragonal crystals and orthorhombic crystals represented by M _0.36 WO _3.18 (Cs ₄ W ₁₁ O ₃₅ ) may precipitate, but these precipitates do not affect the heat ray absorption effect.

The value of y is preferably 2.2 ≦ y ≦ 3.0, more preferably 2.7 ≦ y ≦ 3.0.
In the composite tungsten oxide, part of oxygen may be substituted with another element. Examples of the other elements include nitrogen, sulfur, and halogen.

The particle diameter of the composite tungsten oxide fine particles according to the present invention can be appropriately selected according to the intended use of the composite tungsten oxide fine particles and the heat ray shielding film / heat ray shielding substrate produced using the dispersion liquid. It is preferably 1 nm or more and 800 nm. If the particle diameter is 800 nm or less, strong near infrared absorption by the composite tungsten oxide fine particles according to the present invention can be exhibited. If the particle diameter is 1 nm or more, industrial production is easy. It is.

When the heat ray shielding film is used for applications requiring transparency, the composite tungsten oxide fine particles preferably have a dispersed particle diameter of 40 nm or less. If the composite tungsten oxide fine particles have a dispersed particle diameter of less than 40 nm, light scattering due to Mie scattering and Rayleigh scattering of the fine particles is sufficiently suppressed, and visibility in the visible light wavelength region is maintained. This is because the transparency can be maintained efficiently. When used for applications such as windshields for automobiles where transparency is required, the dispersion particle diameter of the composite tungsten oxide fine particles should be 30 nm or less, preferably 25 nm or less in order to further suppress scattering.

The composite tungsten oxide fine particles according to the present invention have improved near-infrared light transmittance in the wavelength region of 800 to 900 nm while ensuring the heat absorption ability of the wavelength of 1200 to 1500 nm with the wavelength of 1200 to 1800 nm as the bottom. The reason why the heat ray absorption capability of 2100 nm is secured is considered to be due to the electronic structure of the composite tungsten oxide fine particles and the light absorption mechanism derived from the electronic structure.

In the composite tungsten oxide fine particles represented by the general formula M _x WO _{y according} to the present invention, the element M is one type selected from one or more types of elements selected from Cs, Rb, K, Tl, and Ba. Of these elements, W is tungsten and O is oxygen. The composite tungsten oxide fine particles have a hexagonal crystal structure that satisfies 0.1 ≦ x ≦ 0.5 and 2.2 ≦ y ≦ 3.0.

The value of x, which is the amount of element M added, is preferably 0.18 or more and 0.5 or less, and more preferably 0.18 or more and 0.33 or less. This is because if the value of x is 0.18 or more and 0.33 or less, a hexagonal crystal single phase is easily obtained, and the heat ray absorption effect is sufficiently exhibited. In addition to hexagonal crystals, tetragonal crystals and orthorhombic crystals represented by M _0.36 WO _3.18 (Cs ₄ W ₁₁ O ₃₅ ) may precipitate, but these precipitates do not affect the heat ray absorption effect.

(Heat treatment conditions in the production of composite tungsten oxide fine particles)
The present inventors produced composite tungsten oxide fine particles in the same manner as in Example 3 described later, except that four levels of heat treatment conditions of <heat treatment conditions 1 to 4> described below were used.

<Heat treatment condition 1>
After carrying out a heat reduction treatment at a temperature of 500 ° C. for 30 minutes under a 0.3% H ₂ gas supply using N ₂ gas as a carrier, firing was performed at a temperature of 800 ° C. for 1 hour in an N ₂ gas atmosphere. .

<Heat treatment condition 2>
This is the same as the heat treatment according to Example 1 described later.
After the N ₂ gas subjected to heat reduction treatment for 4 hours at a temperature of 500 ° C. under 0.3% H ₂ gas supply was a carrier, was subjected to 1 hour calcination at a temperature of 800 ° C. under N ₂ gas atmosphere .

<Heat treatment condition 3>
This is the same as the heat treatment according to Example 3 described later.
After the N ₂ gas subjected to heat reduction treatment for 6 hours at a temperature of 500 ° C. under 0.3% H ₂ gas supply was a carrier, was subjected to 1 hour calcination at a temperature of 800 ° C. under N ₂ gas atmosphere .

<Heat treatment condition 4>
This is the same as the heat treatment according to Comparative Example 1 described later.
A heat reduction treatment was performed at a temperature of 550 ° C. for 1 hour under a 5% H ₂ gas supply using N ₂ gas as a carrier, and then firing was performed at a temperature of 800 ° C. for 1 hour in an N ₂ gas atmosphere.

Except for using the cesium tungsten bronze produced under the four levels of the above-mentioned <heat treatment conditions 1 to 4>, the same operation as in Example 1 described later was performed to shield the heat rays according to samples 1 to 4 A fine particle dispersion was obtained.

The average dispersed particle size of the composite tungsten oxide fine particles (cesium tungsten bronze fine particles) according to the present invention in each heat ray shielding fine particle dispersion sample was measured and found to be in the range of 20 to 30 nm.

<Summary of heat treatment conditions 1 to 4>
The present inventors control the reduction treatment to a weaker side by controlling the temperature condition and the atmospheric condition in the heat treatment for producing the composite tungsten oxide fine particles, and only absorb light by the composite tungsten oxide particles. When the visible light transmittance when calculated is 85%, the average value of the transmittance at a wavelength of 800 to 900 nm is 30% or more and 60% or less, and the average value of the transmittance at a wavelength of 1200 to 1500 nm is Composite tungsten oxide particles having a transmittance of 20% or less and a transmittance at a wavelength of 2100 nm of 22% or less could be obtained.
The composite tungsten oxide fine particles had a hexagonal crystal structure and a c-axis lattice constant of 7.56 to 8.82.
Further, since the composite tungsten oxide fine particles have increased transmittance in the visible light region, the concentration of the composite tungsten oxide fine particles in the heat ray shielding film can be slightly increased.

When the shape of the transmittance profile of the composite tungsten oxide particles according to the present invention described above is compared with the transmission profile of the composite tungsten oxide particles according to the prior art, the following features (1) to (3) are obtained. I have it.
(1) In the composite tungsten oxide particles according to the present invention, the visible light transmission band region extends to a wavelength range of 800 to 900 nm, which is a near-infrared light region, and has a high transmittance even in the wavelength region. It is what you have.
(2) The composite tungsten oxide particles according to the present invention have a substantially constant transmittance value in the wavelength region of 1200 to 1500 nm.
(3) The composite tungsten oxide particles according to the present invention have heat ray shielding performance even at a wavelength of 2100 nm.

[B] Method for producing heat ray shielding fine particles The composite tungsten oxide fine particles according to the present invention can be obtained by heat-treating a tungsten compound starting material in a reducing gas atmosphere.

First, the tungsten compound starting material will be described.
The tungsten compound starting material according to the present invention is a mixture containing a single element or a compound of tungsten and element M. Tungsten acid powder, tungsten trioxide powder, tungsten dioxide powder, tungsten oxide hydrate powder, tungsten hexachloride powder, ammonium tungstate powder, or tungsten hexachloride powder is dissolved in alcohol and then dried. Or tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol and then adding water to precipitate and drying it. One or more selected from a tungsten compound powder obtained by drying an ammonium tungstate aqueous solution and a metal tungsten powder are preferable. Examples of the raw material of element M include element M alone, chloride salts, nitrates, sulfates, oxalates, oxides, carbonates, tungstates, hydroxides, etc. of element M, but are not limited thereto. Not.

The above-mentioned tungsten compound starting material is weighed, mixed and mixed in a predetermined amount satisfying 0.1 ≦ x ≦ 0.5. At this time, it is preferable that the respective materials related to tungsten and the element M are uniformly mixed as much as possible, preferably at the molecular level. Therefore, it is most preferable that the above-mentioned raw materials are mixed in the form of a solution, and it is preferable that each raw material is soluble in a solvent such as water or an organic solvent.
If each raw material is soluble in a solvent such as water or an organic solvent, the tungsten compound starting raw material according to the present invention can be produced by volatilizing the solvent after thoroughly mixing each raw material and the solvent. However, even if there is no soluble solvent in each raw material, the tungsten compound starting raw material according to the present invention can be produced by mixing each raw material sufficiently uniformly by a known means such as a ball mill.

Next, heat treatment in a reducing gas atmosphere will be described. The starting material is preferably heat-treated at a temperature of from 300 ° C. to 900 ° C., more preferably from 500 to 800 ° C., and even more preferably from 500 to 600 ° C. If it is 300 ° C. or higher, the formation reaction of the composite tungsten oxide having a hexagonal crystal structure according to the present invention proceeds, and if it is 900 ° C. or lower, the composite tungsten oxide fine particles having a structure other than the hexagonal crystal or metallic tungsten are not intended. It is preferable that a side reaction product is hardly generated.

The reducing gas at this time is not particularly limited, but H ₂ is preferable. Then, when H ₂ is used as the reducing gas, the composition of the reducing atmosphere, for example, Ar, is preferably mixed at a volume ratio of 2.0% of H ₂ in an inert gas such as N _2, more The mixture is preferably 0.1 to 0.8%, more preferably 0.1 to 0.5%. If H ₂ is 0.1% to 0.8% by volume, the reduction can proceed efficiently while controlling the reduction state to a condition suitable for the present invention. Conditions such as the reduction temperature and reduction time, and the type and concentration of the reducing gas can be appropriately selected according to the amount of the sample.
If necessary, after performing a reduction treatment in a reducing gas atmosphere, a heat treatment may be performed in an inert gas atmosphere. In this case, the heat treatment in an inert gas atmosphere is preferably performed at a temperature of 400 ° C. or higher and 1200 ° C. or lower.
As a result, composite tungsten oxide fine particles having a hexagonal crystal structure can be obtained. The c-axis lattice constant of the composite tungsten oxide fine particles is preferably 7.56 to 8.82 and more preferably 7.56 to 7.61. Further, the powder color of the composite tungsten oxide fine particles is such that L ^* is 30 to 55, a ^* is -6.0 to -0.5, and b ^* is -10 in the L ^* a ^* b ^* color system. ~ -0.

It is preferable from the viewpoint of improving the weather resistance that the heat ray shielding fine particles according to the present invention are surface-treated and coated with a compound containing at least one selected from Si, Ti, Zr, and Al, preferably an oxide. . In order to perform the surface treatment, a known surface treatment may be performed using an organic compound containing one or more selected from Si, Ti, Zr, and Al. For example, the heat ray shielding fine particles according to the present invention and an organosilicon compound may be mixed and subjected to a hydrolysis treatment.

[C] Heat ray shielding fine particle dispersion and production method thereof The heat ray shielding fine particle dispersion according to the present invention is obtained by dispersing heat ray shielding fine particles in a liquid medium.
The heat ray shielding fine particle dispersion according to the present invention is obtained by adding the composite tungsten oxide fine particles according to the present invention, an appropriate amount of a dispersant, a coupling agent, a surfactant and the like to a liquid medium, if desired. And the fine particles are dispersed in a liquid medium to obtain a dispersion.
The heat ray shielding fine particle dispersion is a dispersion of the conventional composite tungsten oxide fine particles in various fields where other conventional materials that strongly absorb near-infrared rays, such as the composite tungsten oxide disclosed in Patent Document 4, are used. It can be used in the same manner as the liquid.

Hereinafter, the heat ray shielding fine particle dispersion according to the present invention is [1] medium, [2] heat ray shielding fine particles, [3] dispersant, coupling agent, [4] ultraviolet absorber, [5] light stabilizer, [ 6) Antioxidant and [7] Dispersion treatment method will be described in this order. In the present invention, the heat ray shielding fine particle dispersion may be simply referred to as “dispersion”.

[1] Medium The medium of the heat ray shielding fine particle dispersion is required to have a function for maintaining the dispersibility of the heat ray shielding fine particles and a function for preventing the occurrence of coating defects when the heat ray shielding fine particle dispersion is applied. .
As the medium, water, an organic solvent, an oil or fat, a liquid resin, a liquid plasticizer for plastics, or a mixture thereof can be selected to produce a heat ray shielding dispersion.

As the organic solvent satisfying the above requirements, various solvents such as alcohols, ketones, hydrocarbons, glycols and waters can be selected. Specifically, alcohol solvents such as methanol, ethanol, 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol and diacetone alcohol; ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone Ester solvents such as 3-methyl-methoxy-propionate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene Glycol derivatives such as glycol ethyl ether acetate; Amides such as N-methylformamide, dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene Can be mentioned. Of these, organic solvents having low polarity are preferable, and isopropyl alcohol, ethanol, 1-methoxy-2-propanol, dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether acetate, n-butyl acetate and the like are more preferable. preferable. These solvents can be used alone or in combination of two or more.

As the liquid resin, methyl methacrylate or the like is preferable. Liquid plasticizers include plasticizers that are compounds of monohydric alcohols and organic acid esters, ester plasticizers such as polyhydric alcohol organic acid ester compounds, and phosphorus compounds such as organic phosphate plasticizers. A preferable example is an acid plasticizer. Of these, triethylene glycol di-2-ethyl hexaonate, triethylene glycol di-2-ethyl butyrate, and tetraethylene glycol di-2-ethyl hexaonate are more preferable because of their low hydrolyzability.

[2] Heat ray shielding fine particles The content of the heat ray shielding fine particles in the dispersion according to the present invention is preferably 0.01% by mass to 50% by mass. If the content of the heat ray shielding fine particles is 0.01% by mass or more, it is suitable for the production of a coating layer on a transparent substrate selected from a transparent film substrate or a transparent glass substrate described later, a plastic molded body, and the like. A heat ray shielding fine particle dispersion can be obtained. On the other hand, when 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. From this viewpoint, the content of the heat ray shielding fine particles in the more preferable organic solvent dispersion is 1% by mass or more and 35% by mass or less.

The heat ray shielding fine particles in the medium are preferably dispersed with an average dispersed particle size of 40 nm or less. If the average dispersed particle size of the heat ray shielding fine particles is 40 nm or less, the optical characteristics such as haze in the heat ray shielding film produced using the heat ray shielding fine particle dispersion according to the present invention are more preferably improved.

[3] Dispersant, coupling agent Dispersant, coupling agent, and surfactant can be selected according to the application, but have an amine-containing group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group. It is preferable. These functional groups are adsorbed on the surface of the composite tungsten oxide fine particles, prevent aggregation of the composite tungsten oxide fine particles, and have an effect of uniformly dispersing the heat ray shielding fine particles according to the present invention even in the heat ray shielding film.

Suitable dispersants include, but are not limited to, phosphate ester compounds, polymeric dispersants, silane coupling agents, titanate coupling agents, aluminum coupling agents, and the like. It is not a thing.

Specifically, the dispersant preferably has one or more types selected from an amine-containing group, a hydroxyl group, a carboxyl group, a sulfo group, a phosphoric acid group, or an epoxy group as a functional group. The dispersant having any of the functional groups described above is adsorbed on the surface of the composite tungsten oxide particles and / or tungsten oxide particles, and can more reliably prevent aggregation of the composite tungsten oxide particles and / or tungsten oxide particles. it can. For this reason, since composite tungsten oxide particles and / or tungsten oxide particles can be more uniformly dispersed in the pressure-sensitive adhesive layer, it can be suitably used.

The polymer dispersant may be any main chain selected from polyester, polyether, polyacryl, polyurethane, polyamine, polystyrene, and aliphatic, or polyester, polyether, poly It is preferable that the dispersant has a main chain in which two or more kinds of unit structures selected from acrylic, polyurethane, polyamine, polystyrene, and aliphatic are copolymerized.

Further, a metal coupling agent such as a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent can be added to the heat ray shielding fine particle dispersion to be used as a dispersing agent.

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

In addition to the dispersant, the coupling agent, and the surfactant, the heat ray shielding fine particle dispersion according to the present invention includes, as necessary, an ultraviolet absorber, an antioxidant, a light stabilizer, a tackifier, a colorant ( Pigments and dyes), additives such as antistatic agents, and the like may be included.

[4] Ultraviolet absorber When the heat ray shielding fine particle dispersion according to the present invention further contains an ultraviolet absorber, it is possible to further cut off light in the ultraviolet region, and to increase the effect of suppressing the temperature rise. . In addition, the heat ray shielding fine particle dispersion according to the present invention contains an ultraviolet absorber, so that the inside of a car or a building having a window to which a near infrared ray shielding film produced using the heat ray shielding fine particle dispersion is attached, It can suppress the deterioration of sunburn, furniture, and interior, which are the effects of ultraviolet rays on humans and interiors.

Also, the coating film containing the composite tungsten oxide particles and / or tungsten oxide particles, which are the heat ray shielding fine particles according to the present invention, may cause a photo-coloring phenomenon in which the transmittance decreases due to long-term exposure to strong ultraviolet rays. However, even when the heat ray shielding fine particle dispersion according to the present invention contains an ultraviolet absorber, the occurrence of the photo-coloring phenomenon can be suppressed.

The ultraviolet absorber is not particularly limited, and can be arbitrarily selected according to the influence on the visible light transmittance of the heat ray shielding fine particle dispersion, the ultraviolet absorbing ability, durability, and the like. Examples of ultraviolet absorbers include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, salicylic acid compounds, triazine compounds, benzotriazolyl compounds, and benzoyl compounds, and inorganic ultraviolet absorbers such as zinc oxide, titanium oxide, and cerium oxide. Etc. In particular, the ultraviolet absorber preferably contains one or more selected from benzotriazole compounds and benzophenone compounds. This is because the benzotriazole compound and the benzophenone compound can greatly increase the visible light transmittance of the heat ray shielding fine particle dispersion even when a concentration sufficient to absorb ultraviolet rays is added, and long-term strong ultraviolet rays can be obtained. This is because the durability against exposure is high.

Further, it is more preferable that the ultraviolet absorber contains a compound represented by the following chemical formula 1 and / or chemical formula 2, for example.

The content of the ultraviolet absorber in the heat ray shielding fine particle dispersion according to the present invention is not particularly limited, and can be arbitrarily selected according to required visible light transmittance, ultraviolet shielding ability, and the like. However, the content (content ratio) of the ultraviolet absorber in the heat ray shielding fine particle dispersion is preferably, for example, 0.02% by mass or more and 5.0% by mass or less. This is because, if the content of the ultraviolet absorber is 0.02% by mass or more, light in the ultraviolet region that cannot be absorbed by the composite tungsten oxide particles can be sufficiently absorbed. Further, if the content is 5.0% by mass or less, the UV absorber is more reliably prevented from precipitating in the heat ray shielding fine particle dispersion, and has a great influence on the transparency and design of the heat ray shielding fine particle dispersion. Is not given.

[5] Light Stabilizer The heat ray shielding fine particle dispersion according to the present invention may further contain a hindered amine light stabilizer (in the present invention, simply described as “HALS”). .
As described above, in the heat ray shielding fine particle dispersion and the near infrared shielding film according to the present invention, the ultraviolet absorbing ability can be enhanced by containing the ultraviolet absorber. However, depending on the environment in which the heat ray shielding fine particle dispersion or near-infrared shielding film according to the present invention is put into practical use and the type of the ultraviolet absorber, the ultraviolet absorber deteriorates with long-term use, and the ultraviolet absorbing ability decreases. May end up. On the other hand, the heat ray shielding fine particle dispersion according to the present invention contains HALS, thereby preventing the deterioration of the ultraviolet absorber, and the ultraviolet ray absorbing ability of the heat ray shielding fine particle dispersion and the near infrared shielding film according to the present invention. It can contribute to maintenance of.

As described above, the near-infrared shielding film according to the present invention may cause a photo-coloring phenomenon in which the transmittance decreases due to long-term exposure to strong ultraviolet rays. Therefore, by adding HALS to the heat ray shielding fine particle dispersion according to the present invention to produce a near-infrared shielding film, photo-coloring is performed in the same manner as when an ultraviolet absorber or a metal coupling agent having an amino group is added. Occurrence of the phenomenon can be suppressed.

In addition, the effect which suppresses the photo coloring phenomenon by containing HALS in the near-infrared shielding film which concerns on this invention is clearly the effect which suppresses the photo coloring phenomenon by addition of the metal coupling agent which has an amino group. Based on a different mechanism.
For this reason, the effect of suppressing the photo-coloring phenomenon due to the further addition of HALS and the effect of suppressing the photo-coloring phenomenon due to the addition of the metal coupling agent having an amino group are not contradictory, but rather synergistic. To work.
Further, in HALS, there are cases where the compound itself has a UV-absorbing ability. In this case, the addition of the compound can combine the above-described effects of adding the ultraviolet absorber and the effects of adding HALS.

However, the type of HALS to be added is not particularly limited, depending on the effect on the visible light transmittance of the heat ray shielding fine particle dispersion, compatibility with the ultraviolet absorber, durability against ultraviolet rays, and the like. Can be arbitrarily selected.

Specific examples of HALS include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2 -[3- (3,5-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2 , 2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3 , 8-Triazaspiro [4,5] decane-2,4-dione, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl- 4-hydroxybenzyl -2-n-butyl malonate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6) -Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, (Mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4 -Butanetetracarboxylate, Mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ', β'-tetramethyl-3,9- [2,4,8,10- Tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, (Mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1 , 2,3,4-Butanetetracarboxylate, Mixed {2,2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [2,4 , 8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1,2 , 2,6,6-pentamethyl-4-piperidyl methacrylate, poly [(6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl)] [ (2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) iminol], dimethyl succinate and 4-hydroxy-2, 2,6 Polymer of 6-tetramethyl-1-piperidineethanol, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6, 6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-triazine-N, N′-bis ( Polycondensate of 2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethylpiperidyl) butylamine, bis (2) decanoic acid , 2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester and the like can be preferably used.

The HALS content in the heat ray shielding fine particle dispersion according to the present invention is not particularly limited, and may be arbitrarily selected according to the visible light transmittance, weather resistance, etc. required for the heat ray shielding fine particle dispersion. it can. The content (content ratio) of HALS in the heat ray shielding fine particle dispersion is preferably 0.05% by mass or more and 5.0% by mass or less, for example. This is because if the HALS content in the heat ray shielding fine particle dispersion is 0.05% by mass or more, the effect of the addition of HALS can be sufficiently exhibited in the heat ray shielding fine particle dispersion. Moreover, if the content is 5.0% by mass or less, it is possible to more reliably prevent HALS from precipitating in the heat ray shielding fine particle dispersion, which greatly affects the transparency and design of the heat ray shielding fine particle dispersion. It is because it does not give.

[6] Antioxidant The heat ray shielding fine particle dispersion according to the present invention may further contain an antioxidant (antioxidant).
When the heat ray shielding fine particle dispersion according to the present invention contains an antioxidant, other additives contained in the heat ray shielding fine particle dispersion, for example, composite tungsten oxide, tungsten oxide, dispersant, coupling agent, interface Oxidative deterioration of the activator, ultraviolet absorber, HALS and the like is suppressed, and the weather resistance of the near-infrared shielding film according to the present invention can be further improved.

Here, the antioxidant is not particularly limited, and can be arbitrarily selected depending on the influence on the visible light transmittance of the heat ray shielding fine particle dispersion and the desired weather resistance.
For example, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, and the like can be suitably used.

Specific examples of the antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis- (4-methyl-6-butylphenol), 2,2'-methylenebis- (4-ethyl-6-t-butylphenol) 4,4′-butylidene-bis- (3-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-hydroxy-5-tert-butylphenyl) butane, tetrakis [methylene- 3- (3 ′, 5′-butyl-4-hydroxyphenyl) propionate] methane, 1,3,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) Nor) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and bis (3,3′-tert-butylphenol) buty Rick acid glycol ester, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and the like can be preferably used.

The content of the antioxidant in the heat ray shielding fine particle dispersion according to the present invention is not particularly limited, and may be arbitrarily selected according to the visible light transmittance, weather resistance, etc. required for the heat ray shielding fine particle dispersion. Can do. However, the content (content ratio) of the antioxidant in the heat ray shielding fine particle dispersion according to the present invention is preferably 0.05% by mass or more and 5.0% by mass or less, for example. This is because if the content of the antioxidant is 0.05% by mass or more, the effect of the addition of the antioxidant can be sufficiently exhibited in the heat ray shielding fine particle dispersion. Moreover, if content is 5.0 mass% or less, it can prevent more reliably that antioxidant precipitates in a heat ray shielding fine particle dispersion liquid, and is large in the transparency and design of a heat ray shielding fine particle dispersion liquid. This is because it has no effect.

[7] Dispersion Treatment Method In the heat ray shielding fine particle dispersion according to the present invention, the heat ray shielding fine particle dispersion treatment method is arbitrarily selected from known methods as long as the heat ray shielding fine particles are uniformly dispersed in the liquid medium. For example, a method such as a bead mill, a ball mill, a sand mill, or ultrasonic dispersion can be used.
In order to obtain a uniform heat ray shielding fine particle dispersion, various additives and dispersants may be added, or the pH may be adjusted.

The heat ray shielding fine particle dispersion according to the present invention in which such heat ray shielding fine particles are dispersed in a liquid medium is placed in a suitable transparent container, and the light transmittance is measured as a function of wavelength using a spectrophotometer. be able to. The heat ray shielding fine particle dispersion according to the present invention has a visible light transmittance of 85% when only light absorption by the heat ray shielding fine particles is calculated (in the examples according to the present invention, simply “visible light transmittance is 85%”). The transmittance of near-infrared light at a wavelength of 800 to 900 nm is 30% or more and 60% or less, and the average value of the transmittance at a wavelength of 1200 to 1500 nm is 20%. The transmittance at a wavelength of 2100 nm is 22% or less.
In this measurement, adjusting the visible light transmittance to 85% when calculating only the light absorption by the heat ray shielding fine particles contained in the heat ray shielding fine particle dispersion has compatibility with the dispersion solvent or the dispersion solvent. This can be done easily by diluting with an appropriate solvent.

As described above, the heat ray shielding fine particle dispersion according to the present invention preferably has high transparency and near infrared shielding ability. The transparency of the heat ray shielding fine particle dispersion and the near-infrared shielding ability, that is, the heat shielding characteristics, respectively, are visible light transmittance, average value of transmittance in the wavelength range of 1200 to 1500 nm, and transmittance of wavelength 2100 nm. Evaluation can be performed by

The light transmittance profile of the heat ray shielding fine particle dispersion according to the present invention described above has a wavelength of 1200 compared to the light transmission profile when the composite tungsten oxide fine particles shown in Patent Document 4 and Patent Document 5 are used. The transmittance of near infrared light in the wavelength range of 800 to 900 nm is increased without greatly increasing the transmittance in the range of ˜1500 nm, and the heat ray absorption ability at the wavelength of 2100 nm is improved.

[D] Manufacturing method of heat ray shielding film and heat ray shielding glass Using the above-described heat ray shielding fine particle dispersion, a coating layer containing heat ray shielding fine particles is formed on a substrate film or a transparent substrate selected from substrate glass. Thus, a heat ray shielding film or a heat ray shielding glass can be produced.

A heat ray shielding film or a heat ray shielding glass is produced by mixing the above-mentioned heat ray shielding fine particle dispersion with a plastic or a monomer to produce a coating solution, and forming a coating film on a transparent substrate by a known method. Can do.
For example, a heat ray shielding film can be produced as follows.
A medium resin is added to the heat ray shielding fine particle dispersion described above to obtain a coating solution. After coating the coating liquid on the surface of the film substrate, if the solvent is evaporated and the resin is cured by a predetermined method, a coating film in which the heat ray shielding fine particles are dispersed in the medium can be formed.

As the medium resin for the coating film, for example, a UV curable resin, a thermosetting resin, an electron beam curable resin, a room temperature curable resin, a thermoplastic resin, or the like can be selected according to the purpose. Specifically, polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, ethylene vinyl acetate copolymer, polyester resin, polyethylene terephthalate resin, fluorine resin, polycarbonate resin, acrylic resin And polyvinyl butyral resin.
These resins may be used alone or in combination. However, among the media for the coating layer, it is particularly preferable to use a UV curable resin binder from the viewpoint of productivity, apparatus cost, and the like.

Also, a binder using a metal alkoxide can be used. Typical examples of the metal alkoxide include alkoxides such as Si, Ti, Al, and Zr. Binders using these metal alkoxides can be subjected to hydrolysis and polycondensation by heating or the like to form a coating layer made of an oxide film.

In addition, the film base material mentioned above is not limited to a film shape, For example, a board form or a sheet form may be sufficient. As the film base material, PET, acrylic, urethane, polycarbonate, polyethylene, ethylene vinyl acetate copolymer, vinyl chloride, fluorine resin, and the like can be used according to various purposes. However, the heat ray shielding film is preferably a polyester film, and more preferably a PET film.
Further, the surface of the film substrate is preferably subjected to a surface treatment in order to realize easy adhesion of the coating layer. In order to improve the adhesion between the glass substrate or the film substrate and the coating layer, it is also preferable to form an intermediate layer on the glass substrate or the film substrate and form the coating layer on the intermediate layer. The configuration of the intermediate layer is not particularly limited, and may be composed of, for example, a polymer film, a metal layer, an inorganic layer (for example, an inorganic oxide layer such as silica, titania, zirconia), an organic / inorganic composite layer, or the like. .

The method for providing the coating layer on the substrate film or the substrate glass is not particularly limited as long as it is a method capable of uniformly applying the heat ray shielding fine particle-containing dispersion 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 given.
For example, according to the bar coating method using a UV curable resin, a coating liquid in which the liquid concentration and additives are appropriately adjusted so as to have an appropriate leveling property, the thickness of the coating film and the content of the heat ray shielding fine particles are appropriately set. A coating film can be formed on a substrate film or substrate glass using a wire bar having a bar number that can satisfy the following conditions. And after removing the organic solvent contained in a coating liquid by drying, an ultraviolet-ray is irradiated and it hardens | cures, and a coating layer can be formed on a board | substrate film or board | substrate glass. At this time, the drying condition of the coating film varies depending on each component, the type of solvent and the use ratio, but is usually about 60 seconds to 140 ° C. for about 20 seconds to 10 minutes. There is no restriction | limiting in particular in ultraviolet irradiation, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, can be used suitably.
In addition, the adhesion between the substrate and the coating layer, the smoothness of the coating film at the time of coating, the drying property of the organic solvent, and the like can be controlled by the pre- and post-processes of forming the coating layer. Examples of the pre- and post-processes include a substrate surface treatment process, a pre-bake (substrate pre-heating) process, a post-bake (substrate post-heating) process, and the like, and can be appropriately selected. The heating temperature in the pre-bake process and / or the post-bake process is preferably 80 ° C. to 200 ° C., and the heating time is preferably 30 seconds to 240 seconds.

The thickness of the coating layer on the substrate film or the substrate glass is not particularly limited, but is practically preferably 10 μm or less, and more preferably 6 μm or less. If the thickness of the coating layer is 10 μm or less, in addition to exhibiting sufficient pencil hardness and scratch resistance, warping of the substrate film occurs when the coating layer is stripped of the solvent and the binder is cured. This is because the occurrence of process abnormalities such as these can be avoided.

The content of the heat ray shielding fine particles contained in the coating layer is not particularly limited, but the content per projected area of the film / glass / coating layer is 0.1 g / m ² or more and 5.0 g / m ² or less. Is preferred. If the content is 0.1 g / m ² or more, the heat ray shielding characteristics can be exhibited significantly 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, This is because the shielding film / glass / coating layer sufficiently maintains the visible light transmittance.

The optical characteristics of the manufactured heat ray shielding film and heat ray shielding glass are such that when the visible light transmittance is 70%, the transmittance at a wavelength of 850 nm is not less than 23% and not more than 45%, and exists in the wavelength range of 1200 to 1500 nm. The average transmittance is 20% or less. The visible light transmittance can be easily adjusted to 70% by adjusting the concentration of heat ray shielding fine particles in the coating liquid or adjusting the film thickness of the coating layer.

The limit value of the above transmittance profile is generally in the range of 1200 to 1500 nm compared to the transmission profile when using the composite tungsten oxide fine particles according to the prior art having an equivalent composition except for the element A. Without greatly increasing the average transmittance, the width of the visible light transmission band extends to the long wavelength side, and has a higher transmittance in the range of 800 to 900 nm. The limiting value of the above transmittance profile has a certain width even when composite tungsten oxide fine particles having the same composition and concentration are used, and it determines the size and shape of the fine particles, the aggregation state, and the dispersant. It should be noted that it may change depending on the refractive index of the dispersion solvent contained.

Further, in order to further impart an ultraviolet shielding function to the heat ray shielding film or the heat ray shielding glass according to the present invention, at least one kind of particles such as inorganic titanium oxide, zinc oxide, cerium oxide, organic benzophenone, benzotriazole, etc. The above may be added.

In addition, in order to improve the visible light transmittance of the heat ray shielding film or heat ray shielding glass according to the present invention, particles such as ATO, ITO, aluminum-added zinc oxide, indium tin composite oxide are further mixed in the coating layer. Also good. By adding these transparent particles to the coating layer, the transmittance near a wavelength of 750 nm is increased, while infrared light having a wavelength longer than 1200 nm is shielded, so that the transmittance of near infrared light is high, and heat rays A heat ray shield with high shielding properties can be obtained.

As for the optical characteristics of the heat ray shielding film or the heat ray shielding glass according to the present invention, when the visible light transmittance is 70%, the average value of the transmittance at a wavelength of 800 to 900 nm is 13% or more and 40% or less. The average transmittance in the range of 1200 to 1500 nm is 8% or less, and the transmittance at a wavelength of 2100 nm is 5% or less.

Here, adjusting the visible light transmittance to 70% means that when preparing the resin composition, the concentration of the heat-shielding fine particles contained in the organic solvent dispersion liquid, dispersion powder, plasticizer dispersion liquid or master batch described above. It is easy to adjust the amount of heat ray shielding fine particles, dispersed powder, plasticizer dispersion or masterbatch added, and the film thickness of the film.

It has been found that the shape of the transmittance profile of the heat ray shielding fine particles according to the present invention described above has the following features as compared with the transmission profile in the case of using the composite tungsten oxide fine particles according to the prior art. .
1) The heat ray shielding fine particles according to the present invention have a visible light transmission band region extending in a near infrared light region having a wavelength of 800 to 900 nm, and has a high transmittance in the region.
2) The heat ray shielding fine particles according to the present invention hardly change the average value of the transmittance existing in the wavelength range of 1200 to 1500 nm.
3) The heat ray shielding fine particles according to the present invention have a heat ray shielding performance with a wavelength of 2100 nm.

[E] Method for Producing Heat Ray Shielding Fine Particle Dispersion Regarding Method for Producing Heat Ray Shielding Fine Particle Dispersion [1] Powdery Heat Ray Shielding Fine Particle Dispersion, [2] Heat Ray Shielding Fine Particle Dispersion (heat ray (Shielding film, heat ray shielding sheet) will be described in this order.

[1] Powder-like heat ray shielding fine particle dispersion According to the present invention, heat ray shielding fine particles are dispersed in a dispersant by removing the organic solvent from the above-mentioned heat ray shielding fine particle dispersion using an organic solvent as a medium. Dispersed powder and plasticizer dispersion can be obtained. Moreover, according to the characteristic calculated | required by dispersion powder or a plasticizer dispersion liquid, a dispersing agent etc. can also be added to the above-mentioned heat ray shielding fine particle dispersion liquid.

As a method for removing the organic solvent from the heat ray shielding fine particle dispersion described above, the heat ray shielding fine particle dispersion is preferably dried under reduced pressure. Specifically, the heat ray shielding fine particle dispersion is dried under reduced pressure while stirring to separate the heat ray shielding fine particle-containing composition and the organic solvent component. Examples of the apparatus used for the reduced-pressure drying include a vacuum agitation type dryer, but any apparatus having the above functions may be used, and the apparatus is not particularly limited. Moreover, the pressure value at the time of pressure reduction in the drying step is appropriately selected.

By using the reduced-pressure drying method, the removal efficiency of the organic solvent from the heat ray shielding fine particle dispersion is improved, and the dispersion powder and the plasticizer dispersion according to the present invention are not exposed to a high temperature for a long time. It is preferable that the heat ray shielding fine particles dispersed in the dispersion powder or the plasticizer dispersion liquid do not aggregate. Furthermore, the productivity of the dispersion powder and the plasticizer dispersion is increased, and it is easy to collect the evaporated organic solvent, which is preferable from the viewpoint of environmental considerations.

In the dispersion powder or plasticizer dispersion according to the present invention obtained after the drying step, the remaining organic solvent is preferably 5% by mass or less. If the remaining organic solvent is 5% by mass or less, no bubbles are generated when the dispersion powder or plasticizer dispersion is processed into a heat ray-shielded transparent base material, and the appearance and optical properties are kept good. Because.
Moreover, the masterbatch which concerns on this invention can be obtained by disperse | distributing a heat ray shielding fine particle, dispersion | distribution powder, and a plasticizer dispersion liquid in resin, and pelletizing the said resin.

In addition, after uniformly mixing the heat ray shielding fine particles, dispersed powder, plasticizer dispersion, thermoplastic resin granules or pellets, and other additives as necessary, vent type uniaxial or biaxial A master batch can also be obtained by kneading with an extruder and processing into a pellet by a general method of cutting a melt-extruded strand. In this case, examples of the shape include a columnar shape and a prismatic shape. It is also possible to adopt a so-called hot cut method in which the molten extrudate is directly cut. In this case, it is common to take a shape close to a sphere.

In addition to the dispersing agent, coupling agent, and surfactant, if necessary, an ultraviolet absorber, an antioxidant, a light stabilizer, and a tackifier are added to the granular heat ray shielding fine particle dispersion according to the present invention. Additives such as colorants, colorants (pigments, dyes, etc.) and antistatic agents can also be added.

When the heat ray shielding fine particle dispersion according to the present invention further contains an ultraviolet absorber, it is possible to further cut off the light in the ultraviolet region, thereby enhancing the effect of suppressing the temperature rise. Further, the heat ray shielding fine particle dispersion according to the present invention contains an ultraviolet absorber, so that the interior of the automobile having a heat ray shielding film or a window to which the heat ray shielding sheet is prepared using the heat ray shielding fine particle dispersion according to the present invention. UV effects on people and interiors of buildings, sunburn, furniture, and interior deterioration can be suppressed.

In addition, the line shielding film or the heat ray shielding sheet containing the composite tungsten oxide particles and / or tungsten oxide particles, which are the heat ray shielding fine particles according to the present invention, is a photo-coloring phenomenon in which the transmittance is reduced by long-term exposure to strong ultraviolet rays. May occur. However, even when the heat ray shielding fine particle dispersion according to the present invention contains an ultraviolet absorber, the occurrence of the photo-coloring phenomenon can be suppressed.

The ultraviolet absorber is not particularly limited, and has an influence on the visible light transmittance of the heat ray shielding film or the heat ray shielding sheet produced using the heat ray shielding fine particle dispersion according to the present invention, the ultraviolet ray absorbing ability, and the durability. It can be arbitrarily selected according to the sex and the like.
As the ultraviolet absorber, those described in [c] Heat ray shielding fine particle dispersion and production method thereof [4] Ultraviolet absorber column can be used.

The content of the ultraviolet absorber in the heat ray shielding fine particle dispersion according to the present invention is not particularly limited, and can be arbitrarily selected according to required visible light transmittance, ultraviolet shielding ability, and the like. However, the content (content ratio) of the ultraviolet absorber in the heat ray shielding fine particle dispersion is preferably, for example, 0.02% by mass or more and 5.0% by mass or less. This is because, if the content of the ultraviolet absorber is 0.02% by mass or more, light in the ultraviolet region that cannot be absorbed by the composite tungsten oxide particles can be sufficiently absorbed. Moreover, if content is 5.0 mass% or less, it will prevent more reliably that a ultraviolet absorber will precipitate in a heat ray shielding fine particle dispersion, and the heat ray shielding film and heat ray which were produced using the heat ray shielding fine particle dispersion will be used. This is because the transparency and design properties of the shielding sheet are not greatly affected.

In addition, the heat ray shielding fine particle dispersion according to the present invention may further contain a hindered amine light stabilizer (may be described as “HALS” in the present invention).
As described above, in the near-infrared shielding film produced using the heat ray shielding fine particle dispersion according to the present invention, the ultraviolet absorbing ability can be enhanced by containing an ultraviolet absorber.
However, depending on the environment in which the near-infrared shielding film produced using the heat ray shielding fine particle dispersion according to the present invention is put into practical use and the type of the ultraviolet absorber, the ultraviolet absorber deteriorates with long-term use, Absorption capacity may decrease. On the other hand, since the heat ray shielding fine particle dispersion according to the present invention contains HALS, the ultraviolet absorber is prevented from being deteriorated, and the ultraviolet ray absorption of the line shielding fine particle dispersion according to the present invention, the near infrared shielding film, or the like is prevented. It can contribute to maintenance of ability.

As described above, the near-infrared shielding film according to the present invention may cause a photo-coloring phenomenon in which the transmittance decreases due to long-term exposure to strong ultraviolet rays. Therefore, even when HALS is contained in the heat ray shielding fine particle dispersion according to the present invention to produce a near-infrared shielding film or the like, as in the case of adding an ultraviolet absorber or a metal coupling agent having an amino group, Occurrence of a coloring phenomenon can be suppressed.

In addition, in the heat ray shielding fine particle dispersion according to the present invention, the effect of suppressing the photo-coloring phenomenon by containing HALS is the effect of suppressing the photo-coloring phenomenon due to the addition of the metal coupling agent having an amino group. It is based on a distinctly different mechanism.

For this reason, the effect of suppressing the photo-coloring phenomenon due to the further addition of HALS and the effect of suppressing the photo-coloring phenomenon due to the addition of the metal coupling agent having an amino group are not contradictory, but rather synergistic. To work.
Further, in HALS, there are cases where the compound itself has a UV-absorbing ability. In this case, the addition of the compound can combine the above-described effect of adding the ultraviolet absorber and the effect of adding HALS.

However, the type of HALS to be added is not particularly limited, and has an effect on the visible light transmittance of a near-infrared shielding film using a heat ray shielding fine particle dispersion, compatibility with an ultraviolet absorber, ultraviolet rays, etc. Can be arbitrarily selected according to the durability of the material.

As HALS, those described in [c] Heat ray shielding fine particle dispersion and its production method [5] Light stabilizer column can be used.

In the heat ray shielding fine particle dispersion according to the present invention, the content of HALS is not particularly limited, and the visible light transmittance, weather resistance, etc. required for a near infrared ray shielding film using the heat ray shielding fine particle dispersion, etc. It can be arbitrarily selected depending on the case. The HALS content (content ratio) of the heat ray shielding fine particle dispersion liquid is preferably 0.05% by mass or more and 5.0% by mass or less, for example. If the content of HALS in the heat ray shielding fine particle dispersion liquid is 0.05% by mass or more, the effect of adding HALS can be sufficiently exerted by a near infrared ray shielding film produced using the heat ray shielding fine particle dispersion. It is because it can do. Moreover, if content is 5.0 mass% or less, it can prevent more reliably that HALS precipitates in a heat ray shielding fine particle dispersion liquid, the near-infrared shielding film produced using the heat ray shielding fine particle dispersion, etc. This is because it does not significantly affect the transparency and design of the film.

Moreover, the heat ray shielding fine particle dispersion of this embodiment can further contain an antioxidant (antioxidant).
When the heat ray shielding fine particle dispersion according to the present invention contains an antioxidant, other additives contained in the heat ray shielding fine particle dispersion, such as composite tungsten oxide, tungsten oxide, dispersant, coupling agent, interface, are included. Oxidative deterioration of the activator, ultraviolet absorber, HALS and the like is suppressed, and the weather resistance of the near-infrared shielding film according to the present invention can be further improved.

Here, the antioxidant is not particularly limited, and may be arbitrarily selected according to the influence on visible light transmittance and the like of a near-infrared shielding film using the heat ray shielding fine particle dispersion, a desired weather resistance, and the like. You can choose.
For example, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, and the like can be suitably used.

As the antioxidant, those described in [c] Heat ray shielding fine particle dispersion and its production method [6] Antioxidant column can be used.

The content of the antioxidant in the heat ray shielding fine particle dispersion according to the present invention is not particularly limited, and visible light transmittance, weather resistance, etc. required for a near infrared ray shielding film using the heat ray shielding fine particle dispersion, etc. It can be arbitrarily selected according to. However, the content (content ratio) of the antioxidant in the heat ray shielding fine particle dispersion according to the present invention is preferably 0.05% by mass or more and 5.0% by mass or less, for example. This is because if the content of the antioxidant is 0.05% by mass or more, the effect of the addition of the antioxidant can be sufficiently exerted by a near infrared shielding film using a heat ray shielding fine particle dispersion. It is. Moreover, if content is 5.0 mass% or less, it can prevent more reliably that antioxidant will precipitate in a heat ray shielding fine particle dispersion, the near-infrared shielding film using a heat ray shielding fine particle dispersion, etc. This is because it does not significantly affect the transparency and design of the film.

As described above, the near-infrared shielding film using the heat ray shielding fine particle dispersion according to the present invention preferably has high transparency and near-infrared shielding ability. The transparency of the near-infrared shielding film and the like, and the near-infrared shielding ability, that is, the heat shielding property, are respectively the visible light transmittance, the average value of the transmittance in the wavelength range of 1200 to 1500 nm, and the transmittance of the wavelength 2100 nm. Evaluation can be performed by

[2] Sheet- or film-form heat ray shielding fine particle dispersion The sheet-form or film-form according to the present invention is obtained by uniformly mixing the dispersion powder, plasticizer dispersion, or masterbatch according to the present invention into a transparent resin. The heat ray shielding fine particle dispersion can be produced. From the sheet-like or film-like heat ray shielding fine particle dispersion, the heat ray shielding property of the composite tungsten oxide fine particles according to the prior art is ensured, and the transmittance of near-infrared light having a wavelength of 800 to 900 nm is improved. A heat ray shielding sheet or a heat ray shielding film can be produced.

When manufacturing the heat ray shielding sheet | seat and heat ray shielding film which concern on this invention, various thermoplastic resins can be used for resin which comprises the said sheet | seat and film. And if it considers that the heat ray shielding sheet and heat ray shielding film which concern on this invention are applied to various window materials, it is preferable that it is a thermoplastic resin with sufficient transparency.
Specifically, resin groups such as polyethylene terephthalate resin, polycarbonate resin, acrylic resin, styrene resin, polyamide resin, polyethylene resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluorine resin, ethylene / vinyl acetate copolymer A preferred resin can be selected from a resin selected from the group consisting of two or more resins selected from the resin group, or a copolymer of two or more resins selected from the resin group. .

Furthermore, when the heat ray shielding sheet according to the present invention is used as it is as a board-like window material, it is highly transparent and has general characteristics required as a window material, that is, rigidity, light weight, long-term durability, cost. In view of the above, polyethylene terephthalate resin, polycarbonate resin, and acrylic resin are preferable, and polycarbonate resin is more preferable.
On the other hand, when the heat ray shielding sheet or the heat ray shielding film according to the present invention is used as an intermediate layer of a heat ray shielding laminated glass described later, from the viewpoint of adhesion to a transparent substrate, weather resistance, penetration resistance, etc., a polyvinyl acetal resin And ethylene / vinyl acetate copolymer are preferable, and polyvinyl butyral resin is more preferable.

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 have sufficient flexibility and adhesion to a transparent substrate, for example, When the thermoplastic resin is a polyvinyl acetal resin, it is preferable to further add a plasticizer.
As a plasticizer, the substance used as a plasticizer with respect to the thermoplastic resin which concerns on this invention can be used. For example, as a plasticizer used for a heat ray shielding film composed of a polyvinyl acetal resin, a plasticizer that is a compound of a monohydric alcohol and an organic acid ester, a plasticizer that is an ester system such as a polyhydric alcohol organic acid ester compound, Examples include phosphoric acid plasticizers such as organic phosphoric acid plasticizers. Any plasticizer is preferably liquid at room temperature. Among these, a plasticizer that is an ester compound synthesized from a polyhydric alcohol and a fatty acid is preferable.

After kneading the dispersion powder or plasticizer dispersion or masterbatch, the thermoplastic resin, and plasticizer and other additives as desired, the kneaded product is obtained by a known method such as an extrusion molding method or an injection molding method. For example, a heat ray shielding sheet can be produced by forming a flat or curved sheet material.
A well-known method can be used for the formation method of a heat ray shielding sheet or a heat ray shielding film. For example, a calendar roll method, an extrusion method, a casting method, an inflation method, or the like can be used.

[F] Method for producing heat-shielding laminated transparent base material Heat-shielding comprising the heat-ray shielding sheet or the heat-ray shielding film according to the present invention as an intermediate layer between a plurality of transparent substrates made of a sheet glass or plastic material. The laminated transparent substrate will be described.
The heat ray shielding laminated transparent base material according to the present invention is obtained by sandwiching an intermediate layer from both sides using a transparent base material. As the transparent substrate, plate glass transparent in the visible light region, plate-like plastic, or film-like plastic is used. The material of the plastic is not particularly limited and can be selected according to the application. For example, when used for a transportation device such as an automobile, the viewpoint of ensuring the transparency of the driver or passenger of the transportation device. In addition, transparent resins such as polycarbonate resin, acrylic resin, and polyethylene terephthalate resin are preferred. In addition, PET resin, polyamide resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluorine resin, etc. can be used. is there.

The heat-shielding laminated transparent base material according to the present invention can also be obtained by laminating and integrating a plurality of opposing inorganic glasses that are sandwiched between the heat-ray shielding sheet and the heat-ray shielding film according to the present invention by a known method. It is done. The obtained heat-shielding laminated inorganic glass can be used mainly as an inorganic glass for the front of an automobile or a window of a building.

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 laminated transparent base material according to the present invention is not particularly limited, but the content per projected area of the sheet / film is 0.1 g / m. It is preferable that it is ² or more and 5.0 g / m < ² > or less. If it is 0.1 g / m ² or more, the heat ray shielding property can be exhibited significantly as compared with the case where no heat ray shielding fine particles are contained, and if it is 5.0 g / m ² or less, the heat ray shielding sheet / film is visible light. This is because the transparency of the film is not completely lost.

The optical properties of the heat ray shielding film or the heat ray shielding glass according to the present invention are such that when the visible light transmittance is 70%, the average value of the transmittance at a wavelength of 800 to 900 nm is 12% or more and 40% or less. The average transmittance in the range of 1200 to 1500 nm is 8% or less, and the transmittance at a wavelength of 2100 nm is 8.0% or less.

The optical characteristics of the heat ray shielding sheet according to the present invention are such that when the visible light transmittance is 70%, the average value of the transmittance at a wavelength of 800 to 900 nm is 12% to 40%, and the wavelength is 1200 to The average value of transmittance in the 1500 nm range is 8% or less, and the transmittance at a wavelength of 2100 nm is 8.0% or less.

The optical characteristics of the heat-shielding laminated structure according to the present invention are such that when the visible light transmittance is 70%, the average value of the transmittance at a wavelength of 800 to 900 nm is 12% or more and 40% or less, and the wavelength The average transmittance in the range of 1200 to 1500 nm is 8% or less, and the transmittance at a wavelength of 2100 nm is 8.0% or less.

Here, adjusting the visible light transmittance to 70% is to prepare the resin composition, the concentration of the heat ray shielding fine particles contained in the heat ray shielding fine particle dispersion, the dispersion powder, the plasticizer dispersion or the master batch described above. It is easy to adjust the amount of heat ray shielding fine particles, dispersed powder, plasticizer dispersion or masterbatch added, and the film thickness of the film or sheet.

It has been found that the shape of the transmittance profile of the heat ray shielding fine particles according to the present invention described above has the following features as compared with the transmission profile in the case of using the composite tungsten oxide fine particles according to the prior art. .
1. In the heat ray shielding fine particles according to the present invention, the region of the visible light transmission band extends to the region of wavelength 800 to 900 nm, which is the region of near infrared light, and has high transmittance in the region.
2. The heat ray shielding fine particles according to the present invention hardly change the average value of transmittance existing in the wavelength range of 1200 to 1500 nm.
3. The heat ray shielding fine particles according to the present invention have a heat ray shielding performance with a wavelength of 2100 nm.

Hereinafter, the present invention will be described more specifically with reference to examples.
However, the present invention is not limited to the following examples.

In Examples 1 to 3 and Comparative Example 1, the powder color of the heat ray shielding fine particles was measured using a spectrophotometer U-4100 manufactured by Hitachi, Ltd., and evaluated by the L ^* a ^* b ^* color system. .
Further, in Examples 1 to 3 and Comparative Example 1, the transmittance of the heat ray shielding fine particle dispersion with respect to light having a wavelength of 300 to 2100 nm was measured by a spectrophotometer cell (manufactured by GL Sciences Inc., model number: S10-SQ-1, The dispersion was held in (material: synthetic quartz, optical path length: 1 mm), and measurement was performed using a spectrophotometer U-4100 manufactured by Hitachi, Ltd.
At the time of the measurement, the transmittance was measured in a state where the solvent of the dispersion (methyl isobutyl ketone) was filled in the above-described cell, and a baseline for transmittance measurement was obtained. As a result, the spectral transmittance and visible light transmittance described below are calculated only for light absorption by the heat ray shielding fine particles, excluding contributions from light reflection on the cell surface for spectrophotometers and light absorption of the solvent. It will be.

Specifically, the transmittance when the visible light transmittance is 85% can be obtained by the following procedure.
First, the transmittance T1 (λ) of the spectrophotometer cell filled with methyl isobutyl ketone is measured. Next, the transmittance T2 (λ) of the spectrophotometer cell filled with the dispersion containing the heat ray absorbing fine particles is measured. Then, T2 (λ) is divided by T1 (λ) as shown in Equation 2.

T3 (λ) = 100 × T2 (λ) / T1 (λ)... Equation 2

Here, T3 (λ) is a transmittance curve as heat ray absorbing fine particles excluding the influence of absorption and reflection of the substrate. Note that λ means wavelength.

Therefore, the transmittance curve T4 (λ) when the visible light transmittance is 85% can be calculated by Equation 3 using the Lambert Beer equation.

T4 (λ) = 100 × (T3 (λ) / 100) ^ a (Equation 3)

Note that “^” is a mathematical symbol that means a power, and A ^ B means “A to the power of B”. “A” is a variable that takes a real value. A specific value of a is determined so that the visible light transmittance calculated by JIS R 3106 is 85% based on T4 (λ).

The average dispersed particle size of the heat ray shielding fine particles was measured using a Microtrac particle size distribution meter manufactured by Nikkiso Co., Ltd.
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.

In Examples 4 to 16 and Comparative Examples 4 to 6, the transmittance of the heat ray shielding film, the heat ray shielding glass, the heat ray shielding sheet, and the laminated transparent base material in each example is the spectrophotometer manufactured by Hitachi, Ltd. Measured with a total of U-4100, the visible light transmittance was calculated based on JIS R 3106: 1998, based on the measured light transmittance in the wavelength region of 300-2100 nm.

In Examples 1 to 8 and Comparative Examples 1 to 3, the transmittances of the heat ray shielding heat ray shielding sheet, the heat ray shielding film, the heat ray shielding laminated glass sheet, and the laminated transparent base material in each example were manufactured by Hitachi, Ltd. The visible light transmittance was calculated based on JIS R 3106: 1998 based on the measured light transmittance in the wavelength region of 300 to 2100 nm.

[Example 1] (MIBK dispersion of Cs _0.30 WO ₃ )
Each powder of tungstic acid (H ₂ WO ₄ ) and cesium hydroxide (CsOH) was weighed at a ratio corresponding to Cs / W (molar ratio) = 0.30 / 1.00, and then thoroughly mixed in an agate mortar. A mixed powder was obtained. The powder mixture, after the _{N 2} gas was reduced for 4 hours at a temperature of the heated 500 ° C. under 0.3% _{H 2} gas supply was a carrier, 800 ° C. under _{N 2} gas atmosphere, for 1 hour After firing, it has hexagonal crystal, the a-axis lattice constant is 7.4131ｃ, the c-axis lattice constant is 7.5885 色, the powder color is L ^* a ^* b ^* color system, L ^* is A cesium tungsten bronze powder (hereinafter referred to as “powder A”) having 41.86, a ^* of −2.90, and b ^* of −6.76 was obtained. The measurement results are shown in Table 1.
Acrylic polymer dispersant having 20% by mass of powder A and a group containing an amine as a functional group (an acrylic dispersant having an amine value of 48 mgKOH / g and a decomposition temperature of 250 ° C.) (hereinafter abbreviated as “dispersant a”). ) 10% by mass and 70% by mass of methyl isobutyl ketone were weighed. These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads and pulverized and dispersed for 10 hours to obtain a heat ray shielding fine particle dispersion (hereinafter referred to as “dispersion A”). Here, when the average dispersed particle diameter of the heat ray shielding fine particles in the dispersion A was measured, it was 25 nm.

Dispersion A was appropriately diluted with MIBK and placed in a 10 mm thick rectangular container, and the spectral transmittance was measured. From the transmittance profile obtained by adjusting the dilution rate so that the visible light transmittance is 85%, the average value of the transmittance at a wavelength of 800 to 900 nm is 45.5%, and the transmittance at a wavelength of 1200 to 1500 nm. The average value was 12.8%, and the transmittance at a wavelength of 2100 nm was 15.5. Compared with the cesium tungsten bronze produced by the conventional method shown in Comparative Example 1 below, it was confirmed that the visible light transmission band was clearly broadened and the heat ray shielding performance at a wavelength of 2100 nm was improved. The powder color measurement results of Powder A are shown in Table 1, and the transmittance measurement results are shown in Table 2 and FIG.

To 100 parts by weight of dispersion A, 50 parts by weight of Aronix UV-3701 manufactured by Toa Gosei Co., Ltd., which is an ultraviolet curable resin for hard coat (hereinafter referred to as UV-3701), was mixed to form a heat ray shielding fine particle coating liquid (hereinafter referred to as coating). Liquid A) and this coating liquid was applied onto a PET film (Teijin HPE-50) using a bar coater to form a coating film. The same PET film was used in 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 with a high-pressure mercury lamp to produce a heat ray shielding film provided with a coating film containing heat ray shielding fine particles. .

In the above-mentioned heat ray shielding film production, the visible light transmittance was set to 70% by adjusting the heat ray shielding fine particle concentration of the coating solution and the film thickness of the coating film.
When the optical properties of this heat ray shielding film were measured, the transmittance profile showed an average transmittance of 27.9% at a wavelength of 800 to 900 nm, an average transmittance of 4.2% at a wavelength of 1200 to 1500 nm, and a wavelength. The transmittance at 2100 nm was measured to be 5.4%, and the haze was measured to be 0.9%. The results are shown in Table 3, and the transmittance profile for each wavelength is shown in FIG.

Dispersant a was further added to Dispersion A so that the mass ratio of Dispersant a and composite tungsten oxide fine particles was [Dispersant a / Compound tungsten oxide fine particles] = 3. Next, methyl isobutyl ketone was removed from this composite tungsten oxide fine particle dispersion A using a spray dryer to obtain composite tungsten oxide fine particle dispersion powder (hereinafter referred to as dispersion powder A).

A predetermined amount of dispersed powder A is added to the polycarbonate resin, which is a thermoplastic resin, so that the heat ray shielding sheet (2.0 mm thickness) produced is 70%, and the composition for producing the heat ray shielding sheet is obtained. Was prepared.

This composition for producing a heat ray shielding sheet was kneaded at 280 ° C. using a twin-screw extruder, extruded from a T-die to obtain a sheet material having a thickness of 2.0 mm by a calendar roll method, and the heat ray shielding according to Example 1 A sheet was obtained.
When the optical properties of the heat ray shielding sheet according to Example 1 obtained were measured, the visible light transmittance was 70%, the average value of transmittance at a wavelength of 800 to 900 nm was 26.8%, and the wavelength at 1200 to 1500 nm. The average transmittance was 3.7%, the transmittance at a wavelength of 2100 nm was 2.6%, and the haze was 0.5%. The results are listed in Table 5.

[Example 2] (MIB dispersion of Cs _0.20 WO ₃ )
Each powder of tungstic acid (H ₂ WO ₄ ) and cesium hydroxide (CsOH) was weighed at a ratio corresponding to Cs / W (molar ratio) = 0.20 / 1.00, and then thoroughly mixed in an agate mortar. A mixed powder was obtained. The mixed powder was heated under 0.8% H ₂ gas supply using N ₂ gas as a carrier and subjected to a reduction treatment at a temperature of 550 ° C. for 20 minutes, and then at 800 ° C. for 1 hour in an N ₂ gas atmosphere. After firing, it has hexagonal crystal, the a-axis lattice constant is 7.4143ｃ, the c-axis lattice constant is 7.5766Å, the powder color is L ^* a ^* b ^* color system, L ^* is A cesium tungsten bronze powder (hereinafter abbreviated as “powder B”) having 47.55, a ^* of −5.17, and b ^* of −6.07 was obtained. The measurement results are shown in Table 1.
Acrylic polymer dispersant having 20% by mass of powder B and an amine-containing group as a functional group (an acrylic dispersant having an amine value of 48 mg KOH / g and a decomposition temperature of 250 ° C.) (hereinafter referred to as dispersant b) 10 Mass% and methyl isobutyl ketone 70 mass% were weighed. These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads and pulverized and dispersed for 10 hours to obtain a heat ray shielding fine particle dispersion (hereinafter abbreviated as “dispersion B”). Here, when the average dispersed particle diameter of the heat ray shielding fine particles in the dispersion B was measured, it was 23 nm.

The spectral transmittance was measured in the same manner as in Example 1 except that the dispersion B was used. From the transmittance profile obtained by adjusting the dilution rate so that the visible light transmittance is 85%, the average value of the transmittance at a wavelength of 800 to 900 nm is 55.7%, and the transmittance at a wavelength of 1200 to 1500 nm. The average value was 18.3%, and the transmittance at a wavelength of 2100 nm was 18.5. Compared with the cesium tungsten bronze produced by the conventional method shown in Comparative Example 1 below, it was confirmed that the visible light transmission band was clearly broadened and the heat ray shielding performance at a wavelength of 2100 nm was improved. The measurement result of the powder color of the powder B is shown in Table 1, and the measurement result of the transmittance is shown in Table 2 and FIG.

A heat ray shielding film provided with a coating film containing heat ray shielding fine particles was produced in the same manner as in Example 1 except that the dispersion solution B was used as a heat ray shielding coating solution (hereinafter, coating solution B).

In the above-mentioned heat ray shielding film production, the visible light transmittance was set to 70% by adjusting the heat ray shielding fine particle concentration of the coating solution and the film thickness of the coating film.
When the optical properties of the heat ray shielding film were measured, the transmittance profile showed an average transmittance of 37.7% at a wavelength of 800 to 900 nm, an average transmittance of 7.2% at a wavelength of 1200 to 1500 nm, and a wavelength. The transmittance at 2100 nm was measured to be 7.0%, and the haze was measured to be 1.0%. The results are shown in Table 3, and the transmittance profile for each wavelength is shown in FIG.

Example except that the dispersant b was further added to the dispersion B, and the mass ratio of the dispersant b and the composite tungsten oxide fine particles was adjusted to be [dispersant b / composite tungsten oxide fine particles] = 3. In the same manner as in No. 1, composite tungsten oxide fine particle dispersion powder (hereinafter referred to as dispersion powder B) was obtained.

A heat ray shielding sheet according to Example 2 was obtained in the same manner as Example 1 except that the dispersed powder B was used.
When the optical characteristics of the heat ray shielding sheet according to Example 2 obtained were measured, the visible light transmittance was 70%, the average value of transmittance at a wavelength of 800 to 900 nm was 36.6%, and the wavelength at 1200 to 1500 nm. The average transmittance was measured to be 6.4%, the transmittance at a wavelength of 2100 nm was 3.4%, and the haze was 0.6%. The results are listed in Table 5.

[Example 3] (MIBK dispersion of Cs _0.33 WO ₃ )
Each powder of tungstic acid (H ₂ WO ₄ ) and cesium hydroxide (CsOH) was weighed at a ratio corresponding to Cs / W (molar ratio) = 0.33 / 1.00, and then thoroughly mixed in an agate mortar. A mixed powder was obtained. The mixed powder was heated under a 0.3% H ₂ gas supply using N ₂ gas as a carrier and subjected to reduction treatment at a temperature of 500 ° C. for 6 hours, and then at 800 ° C. for 1 hour in an N ₂ gas atmosphere. calcined to have a hexagonal, 7.4097A lattice constant of a-axis, is at 7.6033Å lattice constant of c-axis, the powder ^color, the L ^* a * ^{b *} color system, ^{L *} is A cesium tungsten bronze powder (hereinafter abbreviated as “powder C”) having 39.58, a ^* of −1.63, and b ^* of −7.33 was obtained. The measurement results are shown in Table 1.
Acrylic polymer dispersant having 20% by mass of powder C and a group containing amine as a functional group (an acrylic dispersant having an amine value of 48 mg KOH / g and a decomposition temperature of 250 ° C.) (hereinafter referred to as dispersant c) 10 Mass% and methyl isobutyl ketone 70 mass% were weighed. These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads and pulverized and dispersed for 10 hours to obtain a heat ray shielding fine particle dispersion (hereinafter abbreviated as “dispersion C”). Here, when the average dispersed particle diameter of the heat ray shielding fine particles in the dispersion C was measured, it was 25 nm.

The spectral transmittance was measured in the same manner as in Example 1 except that Dispersion C was used. From the transmittance profile obtained by adjusting the dilution rate so that the visible light transmittance is 85%, the average value of the transmittance at a wavelength of 800 to 900 nm is 33.4%, and the transmittance at a wavelength of 1200 to 1500 nm. The average value was 11.6%, and the transmittance at a wavelength of 2100 nm was 21.4%. Compared with the cesium tungsten bronze produced by the conventional method shown in Comparative Example 1 below, it was confirmed that the visible light transmission band was clearly broadened and the heat ray shielding performance at a wavelength of 2100 nm was improved. The powder color measurement results of powder C are shown in Table 1, and the transmittance measurement results are shown in Table 2 and FIG.

A heat ray shielding film provided with a coating film containing heat ray shielding fine particles was prepared in the same manner as in Example 1 except that the dispersion liquid C was used as a heat ray shielding coating solution (hereinafter, coating solution C).

In the above-mentioned heat ray shielding film production, the visible light transmittance was set to 70% by adjusting the heat ray shielding fine particle concentration of the coating solution and the film thickness of the coating film.
When the optical properties of this heat ray shielding film were measured, the transmittance profile showed an average transmittance of 17.6% at a wavelength of 800 to 900 nm, an average transmittance of 3.6% at a wavelength of 1200 to 1500 nm, and a wavelength. The transmittance at 2100 nm was measured as 8.7%, and the haze was measured as 1.0%. The results are shown in Table 3, and the transmittance profile for each wavelength is shown in FIG.

Example except that the dispersant c was further added to the dispersion C and the mass ratio of the dispersant c and the composite tungsten oxide fine particles was adjusted to be [dispersant c / composite tungsten oxide fine particles] = 3. In the same manner as in No. 1, composite tungsten oxide fine particle dispersion powder (hereinafter referred to as dispersion powder C) was obtained.

A heat ray shielding sheet according to Example 3 was obtained in the same manner as Example 1 except that the dispersed powder C was used.
When the optical characteristics of the heat ray shielding sheet according to Example 3 obtained were measured, the visible light transmittance was 70%, the average value of transmittance at a wavelength of 800 to 900 nm was 16.7%, and the wavelength at 1200 to 1500 nm. The average transmittance was 3.1%, the transmittance at a wavelength of 2100 nm was 4.2%, and the haze was 0.6%. The results are listed in Table 5.

[Example 4] (MIBK dispersion of Cs _0.33 WO ₃ )
100 parts by weight of powder C, 1 part by weight of a benzotriazole-based ultraviolet absorber (manufactured by BASF, TINUVIN 384-2) containing benzotriazole compound, bis (2,2,6,6-tetramethyl-1- (octyl) decanedioate Oxy) -4-piperidinyl) ester, 1 part by weight of an amino ether HALS (manufactured by BASF, TINUVIN 123) containing a reaction product of 1,1-dimethylethyl hydroperoxide and octane, and as an antioxidant, isooctyl-3- ( A hindered phenolic antioxidant (trade name: IRGANOX1135, manufactured by BASF) containing 3,5-di-t-butyl-4-hydroxyphenyl) propionate was weighed to 1 part by mass. These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads, and pulverized and dispersed for 10 hours to obtain a heat ray shielding fine particle dispersion (hereinafter abbreviated as “dispersion D”). Here, when the average dispersed particle diameter of the heat ray shielding fine particles in the dispersion D was measured, it was 25 nm.

The spectral transmittance was measured in the same manner as in Example 1 except that the dispersion D was used. From the transmittance profile obtained by adjusting the dilution rate so that the visible light transmittance is 85%, the average value of the transmittance at a wavelength of 800 to 900 nm is 34.2%, and the transmittance at a wavelength of 1200 to 1500 nm. The average value was 10.4%, and the transmittance at a wavelength of 2100 nm was 21.2%. Compared with the cesium tungsten bronze produced by the conventional method shown in Comparative Example 1 below, it was confirmed that the visible light transmission band was clearly broadened and the heat ray shielding performance at a wavelength of 2100 nm was improved. The measurement results of the transmittance are shown in Table 2 and FIG.

A heat ray shielding film provided with a coating film containing heat ray shielding fine particles was produced in the same manner as in Example 1 except that the dispersion solution D was used as a heat ray shielding coating solution (hereinafter, coating solution D).

Example except that the dispersant c was further added to the dispersion D and the mass ratio of the dispersant c and the composite tungsten oxide fine particles was adjusted to be [dispersant c / composite tungsten oxide fine particles] = 3. In the same manner as in No. 1, composite tungsten oxide fine particle dispersion powder (hereinafter referred to as dispersion powder D) was obtained.

A heat ray shielding sheet according to Example 4 was obtained in the same manner as Example 1 except that the dispersed powder D was used.
When the optical properties of the heat ray shielding sheet according to Example 4 obtained were measured, the visible light transmittance was 70%, the average value of the transmittance at wavelengths of 800 to 900 nm was 17.3%, and the wavelengths at 1200 to 1500 nm. The average transmittance was 3.1%, the transmittance at a wavelength of 2100 nm was 4.2%, and the haze was 0.6%. The results are listed in Table 5.

[Comparative Example 1] (MIBK dispersion of Cs _0.33 WO ₃ )
Example 3 except that heating was performed with 5% H ₂ gas supplied using N ₂ gas as a carrier, reduction treatment was performed at a temperature of 550 ° C. for 1 hour, and then baking was performed at 800 ° C. for 1 hour in an N ₂ gas atmosphere. In the same manner as above, it has hexagonal crystal, the a-axis lattice constant is 7.4080４０, the c-axis lattice constant is 7.6111Å, and the powder color is L ^* a ^* b ^* color system in the L ^* Was obtained, and a cesium tungsten bronze powder according to Comparative Example 1 (hereinafter abbreviated as “powder E”) having an a ^{* of} 36.11, a ^* of 0.52, and b ^* of −5.54 was obtained. The measurement results are shown in Table 1.
When a dispersion was prepared using this powder together with a dispersant and a solvent using a paint shaker, the average dispersed particle size was 23 nm.
Then, when the spectral transmittance was measured by adjusting the dilution rate so that the visible light transmittance was 85%, from the transmittance profile, the average value of the transmittance at a wavelength of 800 to 900 nm was 26.0. %, The average transmittance at a wavelength of 1200 to 1500 nm was 13.3%, and the transmittance at a wavelength of 2100 nm was 24.4%.
From the above, it was confirmed that the average value of the transmittance at a wavelength of 800 to 900 nm was lower than that of Examples 1 to 3, and the transmittance of the transmittance at a wavelength of 2100 nm was high. The measurement result of the powder color of the powder E is shown in Table 1, and the measurement result of the transmittance is shown in Table 2 and FIG.

A heat ray shielding film provided with a coating film containing heat ray shielding fine particles was produced in the same manner as in Example 1 except that the dispersion E was used as a heat ray shielding coating solution (hereinafter, coating solution E).

In the above-mentioned heat ray shielding film production, the visible light transmittance was set to 70% by adjusting the heat ray shielding fine particle concentration of the coating solution and the film thickness of the coating film.
The optical properties of this heat ray shielding film were measured. From the transmittance profile, the average value of the transmittance at a wavelength of 800 to 900 nm was 12.1%, the average value of the transmittance at a wavelength of 1200 to 1500 nm was 4.5%, and the wavelength The transmittance at 2100 nm was measured as 10.6% and the haze as 0.9%. The results are shown in Table 3, and the transmittance profile for each wavelength is shown in FIG.

Example except that the dispersant c was further added to the dispersion E, and the mass ratio of the dispersant c and the composite tungsten oxide fine particles was adjusted to be [dispersant c / composite tungsten oxide fine particles] = 3. In the same manner as in No. 1, composite tungsten oxide fine particle dispersion powder (hereinafter referred to as dispersion powder E) was obtained.

A heat ray shielding sheet according to Comparative Example 1 was obtained in the same manner as Example 1 except that Dispersed Powder E was used.
When the optical properties of the heat ray shielding sheet according to Comparative Example 1 obtained were measured, the visible light transmittance was 70%, the average value of the transmittance at a wavelength of 800 to 900 nm was 11.3%, and the wavelength at 1200 to 1500 nm. The average transmittance was measured to be 3.9%, the transmittance at a wavelength of 2100 nm was 5.1%, and the haze was 0.6%. The results are listed in Table 5.

[Example 5] (heat ray shielding glass using Cs _0.30 WO ₃ )
The coating liquid A was coated on a 10 cm × 10 cm × 2 mm inorganic clear glass with 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 with a high-pressure mercury lamp, thereby preparing a heat ray shielding glass on which a coating film containing heat ray shielding fine particles was formed.

In the above-described heat ray shielding glass production, the visible light transmittance was set to 70% by adjusting the heat ray shielding fine particle concentration of the coating solution or the film thickness of the coating film.
When the optical properties of this heat ray shielding glass were measured, it was found from the transmittance profile that the average value of transmittance at a wavelength of 800 to 900 nm was 24.3%, the average value of transmittance at a wavelength of 1200 to 1500 nm was 3.2%, and the wavelength The transmittance at 2100 nm was measured to be 4.5%, and the haze was measured to be 0.5%. The results are listed in Table 4.

[Example 6] (heat ray shielding glass using Cs _0.20 WO ₃ )
A heat ray shielding glass was produced in the same manner as in Example 5 except that the coating liquid B was used.

In the above-described heat ray shielding glass production, the visible light transmittance was set to 70% by adjusting the heat ray shielding fine particle concentration of the coating solution or the film thickness of the coating film.
The optical properties of this heat ray shielding glass were measured. From the transmittance profile, the average value of transmittance at a wavelength of 800 to 900 nm was 33.4%, the average value of transmittance at a wavelength of 1200 to 1500 nm was 5.7%, and the wavelength The transmittance at 2100 nm was measured to be 6.0%, and the haze was measured to be 0.4%. The results are listed in Table 4.

[Example 7] (Heat-shielding glass using Cs _0.33 WO ₃ )
A heat ray shielding glass was produced in the same manner as in Example 5 except that the coating liquid C was used.

In the above-described heat ray shielding glass production, the visible light transmittance was set to 70% by adjusting the heat ray shielding fine particle concentration of the coating solution or the film thickness of the coating film.
When the optical properties of this heat ray shielding glass were measured, it was found from the transmittance profile that the average value of transmittance at a wavelength of 800 to 900 nm was 14.9%, the average value of transmittance at a wavelength of 1200 to 1500 nm was 2.7%, and the wavelength The transmittance at 2100 nm was measured to be 7.5%, and the haze was measured to be 0.5%. The results are listed in Table 4.

[Example 8] (Heat shielding glass using Cs _0.33 WO ₃ )
A heat ray shielding glass was produced in the same manner as in Example 5 except that the coating liquid D was used.

[Comparative Example 2] (heat ray shielding glass using Cs _0.33 WO ₃ )
A heat ray shielding glass was produced in the same manner as in Example 5 except that the coating liquid E was used.

In the above-described heat ray shielding glass production, the visible light transmittance was set to 70% by adjusting the heat ray shielding fine particle concentration of the coating solution or the film thickness of the coating film.
When the optical properties of this heat ray shielding glass were measured, it was found from the transmittance profile that the average value of transmittance at wavelengths of 800 to 900 nm was 10.0%, the average value of transmittance at wavelengths of 1200 to 1500 nm was 3.4%, and the wavelength The transmittance at 2100 nm was measured as 9.2%, and the haze as 0.5%. The results are listed in Table 4.

[Example 9] (Heat ray shielding masterbatch using Cs _0.33 WO ₃ )
The dispersion powder C produced in Example 3 and the polycarbonate resin pellets were mixed so that the concentration of the composite tungsten oxide fine particles was 2.0% by mass and uniformly mixed using a blender to obtain a mixture. The mixture was melt kneaded at 290 ° C. using a twin screw extruder, the extruded strand was cut into pellets, and the master batch according to Example 9 for a heat ray shielding transparent resin molded product (hereinafter referred to as master batch C) was used. Was obtained.).
A predetermined amount of a master batch C was added to the polycarbonate resin pellets to prepare a composition for manufacturing a heat ray shielding sheet according to Example 9. In addition, the said predetermined quantity is an quantity from which the visible light transmittance | permeability of the heat ray shielding sheet | seat (1.0-mm thickness) manufactured becomes 70%.

The composition for producing a heat ray shielding sheet according to Example 9 was kneaded at 280 ° C. using a twin-screw extruder, extruded from a T die, and used as a sheet material having a thickness of 1.0 mm by a calendar roll method. The heat ray shielding sheet which concerns on was obtained.
When the optical characteristics of the heat ray shielding sheet according to Example 9 obtained were measured, the visible light transmittance was 70%, the average value of transmittance at a wavelength of 800 to 900 nm was 27.0%, and the wavelength at 1200 to 1500 nm. The average value of the transmittance was 4.3%, the transmittance at a wavelength of 2100 nm was 3.6%, and the haze was 0.6%. The results are listed in Table 5.
From the above results, it was confirmed that a masterbatch, which is a heat ray shielding fine particle dispersion that can be suitably used for producing a heat ray shielding sheet, can be produced in the same manner as the dispersion powder of Example 3.

[Comparative Example 3] (heat ray shielding masterbatch using Cs _0.33 WO ₃ )
A masterbatch (hereinafter referred to as masterbatch E) according to Comparative Example 3 for a heat ray shielding transparent resin molded article was obtained in the same manner as Example 5 except that the dispersion powder E produced in Comparative Example 1 was used. It was.
A heat ray shielding sheet according to Comparative Example 3 was obtained in the same manner as in Example 5 except that a predetermined amount of a master batch E was added to the polycarbonate resin pellets.
When the optical properties of the heat ray shielding sheet according to Comparative Example 3 obtained were measured, the visible light transmittance was 70%, the average value of the transmittance at a wavelength of 800 to 900 nm was 11.7%, and the wavelength at 1200 to 1500 nm. The average value of the transmittance was measured to be 3.9%, the transmittance at a wavelength of 2100 nm was 5.3%, and the haze was 0.5%. The results are listed in Table 5.

[Example 10] (Heat ray shielding film and heat ray shielding laminated transparent base material using Cs _0.30 WO ₃ )
A plasticizer triethylene glycol-di-2-ethylbutyrate is added to a polyvinyl butyral resin, and the weight ratio of the polyvinyl butyral resin to the plasticizer is [polyvinyl butyral resin / plasticizer] = 100/40. The resulting mixture was made. A predetermined amount of the dispersion powder A prepared in Example 1 was added to this mixture to prepare a composition for manufacturing a heat ray shielding film. In addition, the said predetermined amount is an amount with which the visible light transmittance of the manufactured heat ray shielding laminated transparent base material is 70%.

The composition for production was kneaded and mixed at 70 ° C. for 30 minutes using a three-roll mixer to obtain a mixture. The mixture was heated to 180 ° C. with a mold extruder to form a film having a thickness of about 1 mm and wound on a roll to prepare a heat ray shielding film according to Example 10.
The heat ray shielding film according to Example 10 was cut into 10 cm × 10 cm, and sandwiched between two inorganic clear glass plates having the same dimensions and having a thickness of 3 mm to obtain a laminate. Next, this laminate was put into a rubber vacuum bag, the inside of the bag was evacuated and kept at 90 ° C. for 30 minutes, and then returned to room temperature and taken out from the bag. And the said laminated body was put into the autoclave apparatus, the pressure 12kg / cm < ² >, and the pressure heating were carried out for 20 minutes at the temperature of 140 degreeC, and the heat ray shielding laminated glass sheet concerning Example 10 was produced.

When the optical characteristics of the heat-shielding transparent substrate according to Example 10 were measured, when the visible light transmittance was 70%, the average value of the transmittance at a wavelength of 800 to 900 nm was 23.4%, and the wavelength was 1200 to 1500 nm. The average value of the transmittance was 3.6%, the transmittance at a wavelength of 2100 nm was 4.3%, and the haze was 0.8%. The results are shown in Table 6, and the transmittance profile for each wavelength is shown in FIG.

[Example 11] (Heat ray shielding film and heat ray shielding laminated transparent substrate using Cs _0.20 WO ₃ )
A heat ray shielding film according to Example 11 was produced in the same manner as in Example 10 except that a predetermined amount of the dispersion powder B produced in Example 2 was added to a mixture of the polyvinyl butyral resin and the plasticizer.
A heat ray shielding laminated glass sheet according to Example 11 was produced in the same manner as in Example 10 except that the heat ray shielding film according to Example 11 was used.

When the optical properties of the heat-shielding transparent substrate according to Example 11 were measured, when the visible light transmittance was 70%, the average value of the transmittance at a wavelength of 800 to 900 nm was 32.0%, and the wavelength was 1200 to 1500 nm. The average value of the transmittance was 6.1%, the transmittance at a wavelength of 2100 nm was 5.6%, and the haze was 0.6%. The results are shown in Table 6, and the transmittance profile for each wavelength is shown in FIG.

[Example 12] (Heat ray shielding film and heat ray shielding laminated transparent base material using Cs _0.33 WO ₃ )
A heat ray shielding film according to Example 12 was produced in the same manner as in Example 10 except that a predetermined amount of the dispersion powder C produced in Example 3 was added to a mixture of the polyvinyl butyral resin and the plasticizer.
A heat ray shielding laminated glass sheet according to Example 12 was produced in the same manner as in Example 10 except that the heat ray shielding film according to Example 12 was used.

When the optical properties of the heat-shielding transparent substrate according to Example 12 were measured, when the visible light transmittance was 70%, the average value of the transmittance at a wavelength of 800 to 900 nm was 15.3%, and the wavelength was 1200 to 1500 nm. The average value of the transmittance was 3.1%, the transmittance at a wavelength of 2100 nm was 6.9%, and the haze was 1.0%. The results are shown in Table 6, and the transmittance profile for each wavelength is shown in FIG.

[Comparative Example 4] (Heat ray shielding film and heat ray shielding laminated transparent substrate using Cs _0.33 WO ₃ )
A heat ray shielding film according to Comparative Example 4 was produced in the same manner as in Example 10 except that a predetermined amount of the dispersion powder D produced in Comparative Example 1 was added to a mixture of the polyvinyl butyral resin and the plasticizer.
A heat ray shielding laminated glass sheet according to Comparative Example 4 was produced in the same manner as Example 10 except that the heat ray shielding film according to Comparative Example 4 was used.

When the optical characteristics of the heat-shielding transparent substrate according to Comparative Example 4 were measured, when the visible light transmittance was 70%, the average value of the transmittance at a wavelength of 800 to 900 nm was 10.6%, and the wavelength was 1200 to 1500 nm. The average transmittance was measured as 3.8%, the transmittance at a wavelength of 2100 nm was 8.3%, and the haze was 0.8%. The results are shown in Table 6, and the transmittance profile for each wavelength is shown in FIG.

[Evaluation of Examples 1 to 12 and Comparative Examples 1 to 4]
In the heat ray shielding fine particles according to Examples 1 to 4, near infrared light having a wavelength of 800 to 900 nm when the visible light transmittance is 85% as compared with Comparative Example 1 which is a conventional composite tungsten oxide fine particle. The average value of the transmittance is high, and the transmittance at a wavelength of 1200 to 1500 nm and a wavelength of 2100 nm is low. From this result, it was found that high transmittance was obtained with near-infrared light with a wavelength of 800 to 900 nm while ensuring the high heat-shielding characteristics exhibited by the composite tungsten oxide fine particles, and the irritating feeling on the skin was reduced. .

From the above results, the heat ray shielding film and the heat ray shielding sheet according to Examples 1 to 4, the heat ray shielding glass according to Examples 5 to 8, the heat ray shielding sheet according to Example 9, and the heat ray shielding combination according to Examples 10 to 12. In any of the glass sheets, the heat ray shielding film and the heat ray shielding sheet using the conventional composite tungsten oxide fine particles according to Comparative Example 1, the heat ray shielding glass using the conventional composite tungsten oxide fine particles according to Comparative Example 2, and the comparison Compared with the heat ray shielding sheet using the conventional composite tungsten oxide fine particles according to Example 3 and the heat ray shielding laminated glass sheet using the conventional composite tungsten oxide fine particles according to Comparative Example 4, the visible light transmittance is 85%. When the average value of the transmittance of near infrared light with a wavelength of 800 to 900 nm is high, the wavelength of 1200 to 1800 nm and the wavelength of 2100 nm Over-rate is low. From this result, it was found that high transmittance was obtained with near-infrared light with a wavelength of 800 to 900 nm while ensuring the high heat-shielding characteristics exhibited by the composite tungsten oxide fine particles, and the irritating feeling on the skin was reduced. .

Claims

A composite tungsten oxide fine particle having a heat ray shielding function, and a transmittance in a wavelength range of 800 to 900 nm when the visible light transmittance is 85% when only light absorption by the composite tungsten oxide fine particle is calculated. The average value is 30% or more and 60% or less, the average value of transmittance in the wavelength range of 1200 to 1500 nm is 20% or less, and the transmittance at wavelength 2100 nm is 22% or less. Heat ray shielding fine particles.
In the L * a * b * color system, the powder color of the composite tungsten oxide fine particles is L * of 30 to 55, a * of −6.0 to −0.5, and b * of −10. The heat ray shielding fine particles according to claim 1, wherein the heat ray shielding fine particles are 0 or more and 0 or less.
The composite tungsten oxide fine particles have the general formula M x WO y (where M is one or more elements selected from Cs, Rb, K, Tl and Ba, 0.1 ≦ x ≦ 0.5, 2. The heat ray shielding fine particles according to claim 1, wherein 2 ≦ y ≦ 3.0).
4. The heat ray according to claim 1, wherein the composite tungsten oxide fine particles have a hexagonal crystal structure, and a c-axis lattice constant is 7.56 to 8.82 μm. Shielding fine particles.
The heat ray shielding fine particles according to any one of claims 1 to 4, wherein the heat ray shielding fine particles have a particle diameter of 1 nm or more and 800 nm or less.
6. A dispersion liquid in which the heat ray shielding fine particles according to claim 1 are dispersed and contained in a liquid medium, wherein the liquid medium is used for water, organic solvents, oils and fats, liquid resins, and liquid plastics. A heat ray shielding fine particle dispersion selected from a plasticizer or a mixture thereof.
The heat ray shielding fine particle dispersion according to claim 6, wherein the content of the heat ray shielding fine particles contained in the liquid medium is 0.01% by mass or more and 80% by mass or less.
Tungstic acid and a hydroxide powder of one or more elements selected from Cs, Rb, K, Tl, and Ba are mixed at a predetermined ratio to obtain a mixed powder.
One or more elements selected from Cs, Rb, K, Tl, and Ba are reduced by heating the mixed powder under an H 2 gas supply of 0.8% or less using an inert gas as a carrier. A method for producing heat-ray shielding fine particles, comprising obtaining a composite tungsten oxide powder containing
A method for producing a heat ray shielding fine particle dispersion, comprising a dispersion step of dispersing the heat ray shielding fine particles obtained in claim 8 in a liquid medium to obtain a heat ray shielding fine particle dispersion.
The heat ray shielding fine particle dispersion according to claim 6 or 7, further comprising at least one selected from ultraviolet absorbers, HALS, and antioxidants.
A composite tungsten oxide fine particle having a heat ray shielding function, and a transmittance in a wavelength range of 800 to 900 nm when a visible light transmittance is 85% when only light absorption by the composite tungsten oxide fine particle is calculated. Heat ray shielding fine particles having an average value of 30% or more and 60% or less, an average value of transmittance in the wavelength range of 1200 to 1500 nm of 20% or less, and a transmittance of wavelength 2100 nm of 22% or less A heat ray shielding film or a heat ray shielding glass, comprising:
12. The heat ray shielding film or the heat ray shielding according to claim 11, wherein the composite tungsten oxide fine particles have a hexagonal crystal structure, and a c-axis lattice constant is 7.56 to 8.82. Glass.
It has a coating layer on at least one surface of a transparent substrate selected from a transparent film substrate or a transparent glass substrate, and the coating layer is a binder resin layer containing the heat ray shielding fine particles. Item 13. A heat ray shielding film or heat ray shielding glass according to Item 11 or 12.
The heat ray shielding film or the heat ray shielding glass according to claim 13, wherein the binder resin is a UV curable resin binder.
The heat ray shielding film or the heat ray shielding glass according to claim 13 or 14, wherein the coating layer has a thickness of 10 µm or less.
The heat ray shielding film according to any one of claims 13 to 15, wherein the transparent film substrate is a polyester film.
Heat ray shielding film according to the content per unit projected area of the heat ray shielding fine particles contained in the coating layer, any of 0.1 g / m 2 or more 5.0 g / m 2 or less is 13. 16 Or heat ray shielding glass.
When the visible light transmittance is 70%, the average value of the transmittance in the wavelength range of 800 to 900 nm is 13% or more and 40% or less, and the average value of the transmittance existing in the wavelength range of 1200 to 1500 nm is The heat ray shielding film or the heat ray shielding glass according to any one of claims 11 to 17, wherein the heat ray shielding film or the heat ray shielding glass has a transmittance of 8% or less and a transmittance of 2100 nm at a wavelength of 9% or less.
A mixing step in which tungstic acid and a hydroxide powder of one or more elements selected from Cs, Rb, K, Tl, and Ba are mixed at a predetermined ratio to obtain a mixed powder;
One or more elements selected from Cs, Rb, K, Tl, and Ba are reduced by heating the mixed powder under an H 2 gas supply of 0.8% or less using an inert gas as a carrier. A firing step of obtaining a composite tungsten oxide powder comprising:
A step of uniformly mixing the composite tungsten oxide powder into a transparent resin to obtain a heat ray shielding fine particle dispersion;
Coating the heat ray shielding fine particle dispersion on a transparent film substrate or a transparent glass substrate, and a method for producing a heat ray shielding film or a heat ray shielding glass.
The heat ray shielding glass or heat ray shielding film according to any one of claims 11 to 18, further comprising at least one selected from an ultraviolet absorber, HALS, and an antioxidant.
A composite tungsten oxide fine particle having a heat ray shielding function, and a transmittance in a wavelength range of 800 to 900 nm when a visible light transmittance is 85% when only light absorption by the composite tungsten oxide fine particle is calculated. Heat ray shielding fine particles having an average value of 30% or more and 60% or less, an average value of transmittance in the wavelength range of 1200 to 1500 nm of 20% or less, and a transmittance of wavelength 2100 nm of 22% or less A heat ray shielding fine particle dispersion comprising:
The heat ray shielding fine particle dispersion according to claim 21, wherein the composite tungsten oxide fine particles have a hexagonal crystal structure, and the c-axis lattice constant is 7.56 to 8.82.
The thermoplastic resin is polyethylene terephthalate resin, polycarbonate resin, acrylic resin, styrene resin, polyamide resin, polyethylene resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluororesin, ethylene / vinyl acetate copolymer, polyvinyl One resin selected from the group of resins called acetal resins;
Or a mixture of two or more resins selected from the resin group,
23. The heat ray shielding fine particle dispersion according to claim 21, wherein the heat ray shielding fine particle dispersion is any one of a copolymer of two or more resins selected from the resin group.
The heat ray shielding fine particle dispersion according to any one of claims 21 to 23, wherein the composite tungsten oxide particles are contained in an amount of 0.5 mass% to 80.0 mass%.
The heat ray shielding fine particle dispersion according to any one of claims 21 to 24, wherein the heat ray shielding fine particle dispersion has a sheet shape, a board shape, or a film shape.
26. The content of the heat ray shielding fine particles per unit projected area contained in the heat ray shielding fine particle dispersion is 0.1 g / m 2 or more and 5.0 g / m 2 or less. The heat ray shielding fine particle dispersion according to any one of the above.
When the visible light transmittance is 70%, the average value of the transmittance in the wavelength range of 800 to 900 nm is 13% or more and 40% or less, and the average value of the transmittance existing in the wavelength range of 1200 to 1500 nm is 27. The heat ray shielding fine particle dispersion according to any one of claims 21 to 26, which has a transmittance of 8% or less and a transmittance of 2100 nm at a wavelength of 5% or less.
A heat ray shielding laminated transparent base material, wherein the heat ray shielding fine particle dispersion according to any one of claims 21 to 27 is present between a plurality of transparent base materials.
When the visible light transmittance is 70%, the average value of the transmittance in the wavelength range of 800 to 900 nm is 12% or more and 40% or less, and the average value of the transmittance existing in the wavelength range of 1200 to 1500 nm is 29. The heat ray-shielding laminated transparent substrate according to claim 28, having a transmittance of 8% or less and a transmittance of 2100 nm at a wavelength of 8.0% or less.
A mixing step in which tungstic acid and a hydroxide powder of one or more elements selected from Cs, Rb, K, Tl, and Ba are mixed at a predetermined ratio to obtain a mixed powder;
The mixed powder is heated under an H 2 gas supply of 0.8% or less using an inert gas as a carrier for reduction treatment, and one or more kinds selected from Cs, Rb, K, Tl, and Ba are selected. A firing step for obtaining a composite tungsten oxide powder containing the element;
And a step of uniformly mixing the composite tungsten oxide powder into a transparent resin to obtain a heat ray shielding fine particle dispersion.
A method for producing a heat ray shielding laminated transparent base material, comprising a step of sandwiching the heat ray shielding fine particle dispersion according to claim 30 between the transparent base materials.
A process for producing a heat-ray shielding laminated transparent base material, comprising a step of forming the heat-ray shielding fine particle dispersion according to claim 30 into a film shape or a board shape.
The heat ray shielding fine particle dispersion or the heat ray shielding laminated transparent base material according to any one of claims 21 to 29, further comprising at least one selected from an ultraviolet absorber, HALS, and an antioxidant.