JP2017106007A - Heat ray shielding dispersion and heat ray shielding laminate transparent substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat ray shielding dispersion and a heat ray shielding laminate transparent substrate exhibiting heat ray shielding property and suppressing sizzling feeling to skin when applied to a structure such as a window material and capable of using the structure, the heat ray shielding film or a heat ray shielding glass, a communication device, an imaging device a sensor using near infrared light via the dispersion or a laminate transparent substrate or the like.SOLUTION: There is provided a heat ray shielding fine particle dispersion containing: a heat ray shielding fine particle which is a composite tungsten oxide fine particle having heat ray shielding functions and has a hexagonal system crystal structure, lattice constant of a c axis of 7.56Å to 8.82Å and average permeability with wavelength in a range of 800 to 900 nm of 30% to 50%, average permeability with wavelength in a range of 1200 to 1500 nm of 20% or less and permeability at wavelength of 2100 nm of 22% or less when visible light permeability of 85% when only light absorption by the composite tungsten oxide fine particle is calculated; and a thermoplastic resin.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a heat ray shielding dispersion that transmits near infrared light having a predetermined wavelength while having good visible light transmittance and an excellent heat ray shielding function, 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 have a problem that the heat ray shielding performance is not sufficient 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 the visible light transmittance is sometimes 70%, the solar radiation 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, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0) Composite tungsten oxide fine particles Patent application title: A heat-ray shielding dispersion comprising one or more kinds of fine particles having a crystal structure of tetragonal, tetragonal, or cubic crystals, wherein the infrared shielding material fine particles have a particle diameter of 1 nm to 800 nm. It was disclosed as Reference 4.

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%.

Further, the applicant has the general formula M _a WO _c (where 0.001 ≦ a ≦ 1.0, 2.2 ≦ c ≦ 3.0, and the M element is 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 JP-A-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 the body or 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 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 Provided heat ray shielding glass, heat ray shielding dispersion enabling use of near infrared light through the dispersion and laminated transparent substrate, imaging device, sensor, etc., and heat ray shielding laminated transparent substrate It is to be.

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, the concentration of the composite tungsten oxide fine particles in the heat ray shielding dispersion or the heat ray shielding laminated transparent base material in the film are decreased, the heat ray absorbing ability with the wavelength range of 1200 to 1800 nm as the bottom. At the same time, the heat ray shielding effect is lowered, and the skin feels irritated.

  Here, it is considered that the sunlight gives the skin a sensation due to the large influence of heat rays with a wavelength of 1500 to 2100 nm (for example, Yoshikazu Ozeki et al. 33-99, 13 (1999), which shows 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 Is controlled within a predetermined range, while maintaining the heat ray absorption capability with the wavelength range of 1200 to 1800 nm as the bottom, the absorption of the wavelength range of 800 to 900 nm is controlled, and the absorption capability in the wavelength range of 2100 nm is improved. It has been found that tungsten oxide fine particles can be obtained.

However, the composite tungsten oxide fine particles having improved near-infrared light transmittance in the wavelength region of 800 to 900 nm are 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.

And the composite tungsten oxide microparticles | fine-particles which improved the transmittance | permeability of near-infrared light with a wavelength of 800-900 nm by controlling the reduction | restoration state in the case of the heat processing mentioned above are the composite tungsten oxide microparticles | fine-particles which concern on the prior art. In comparison, it was found that the performance as heat ray shielding fine particles is not inferior.
This is because the composite tungsten oxide fine particles with improved transmittance of near-infrared light having a wavelength of 800 to 900 nm have high visible light transmittance. Therefore, the concentration of the composite tungsten oxide fine particles per unit area can be set higher. This is because, as a result of the higher concentration setting, it is possible to suppress the transmission of heat rays having a wavelength of 1500 to 2100 nm.

  As a result of the above studies, the present inventors have disclosed composite tungsten oxide fine particles having a heat ray shielding function, a hexagonal crystal structure, and a c-axis lattice constant of 7.56 to 8.82 cm. The present invention was completed by conceiving the heat ray shielding fine particles characterized by the above.

  Furthermore, the present inventors are not inferior in performance as a heat ray shielding body even in a heat ray shielding dispersion or a laminated transparent substrate using the composite tungsten oxide fine particles according to the present invention described above. Also from the viewpoint of suppressing the feeling, it was also found that it is equivalent to the composite tungsten oxide fine particles according to the prior art.

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 when the visible light transmittance is 85% when only light absorption by the composite tungsten oxide fine particle is calculated, the transmittance in a wavelength range of 800 to 900 nm 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 second 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 to provide a heat ray shielding fine particle dispersion.
The third invention is
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 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 fifth invention is:
The heat ray shielding fine particle dispersion is in the form of a sheet, a board, or a film.
The sixth invention is:
The 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 0.1 g / m 2 or more and 5.0 g / m 2 or less.
The seventh invention
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 It is a heat ray shielding fine particle dispersion characterized by having a transmittance of 8% or less and a transmittance of 2100 nm at a wavelength of 5% or less.
The eighth invention
A heat ray shielding laminated transparent substrate, wherein the heat ray shielding fine particle dispersion according to any one of the first to seventh inventions is present between a plurality of transparent substrates.
The ninth invention
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 It is a heat ray shielding laminated transparent base material characterized by being 8% or less and having a transmittance of 2100 nm at a wavelength of 8.0% or less.
The tenth 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 eleventh invention is
A method for producing a heat-shielding laminated transparent base material, comprising a step of sandwiching the heat-ray shielding fine particle dispersion according to the tenth invention between the transparent base materials.
The twelfth 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 according to the tenth invention into a film shape or a board shape.
The thirteenth 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 laminated transparent base material according to the present invention exhibits a heat ray shielding characteristic and suppresses a sensation of feeling on the skin, and even when these structures are interposed, a communication device using near infrared light It is possible to use an imaging device, a sensor, or the like.

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] a method of producing heat ray shielding fine particles, [c] a method of producing a heat ray shielding fine particle dispersion, and [d] heat ray shielding combined transparent It demonstrates in order of the manufacturing method of a base material.

[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. The composite tungsten oxide fine particles have 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 a wavelength of 2100 nm.
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, it is preferable that the composite tungsten oxide fine particles 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 transmittance of near-infrared light in the wavelength region of 800 to 900 nm while ensuring the heat absorption capacity of 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 the 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 above-mentioned four levels of <heat treatment conditions 1 to 4>, heat ray shielding according to samples 1 to 4 is performed. A fine particle dispersion was obtained.

  When the average dispersed particle size of the composite tungsten oxide fine particles (cesium tungsten bronze fine particles) in each heat ray shielding fine particle dispersion sample according to the present invention was measured, it was 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.

  Based on the knowledge of the present inventors as described above, in the heat treatment for producing the composite tungsten oxide fine particles, the temperature condition and the atmospheric condition are controlled, thereby having a hexagonal crystal structure and a c-axis lattice constant. When the visible light transmittance is 85% when only the light absorption by the composite tungsten oxide particles is calculated, it is possible to obtain heat ray shielding fine particles characterized in that is 7.56 mm or more and 8.82 mm or less, The average value of the transmittance at a wavelength of 800 to 900 nm is 30% or more and 60% or less, the average value of the transmittance at a wavelength of 1200 to 1500 nm is 20% or less, and the transmittance at a wavelength of 2100 nm is 22 It was possible to obtain composite tungsten oxide particles having a ratio of not more than%.

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 conventional technique, the following features (1) to (3) are obtained. It is what you have.
(1) In the composite tungsten oxide particles according to the present invention, the visible light transmission band region extends to a wavelength region 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 a wavelength range 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 can be dissolved 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 300 ° C. or more and 900 ° C. or less, more preferably 500 to 800 ° C. or less, and further preferably 500 to 600 ° C. or less. 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 Preferably 0.1 to 0.8% mixed, more preferably 0.1 to 0.5% mixed. If 0.1% ~0.8% H ₂ by volume ratio, while controlling the conditions suitable reducing state in the present invention, efficiently reducing can proceed. 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, 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. 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] Method for producing heat ray shielding fine particle dispersion About method for producing heat ray shielding fine particle dispersion [1] Method for producing granular heat ray shielding fine particle dispersion, [2] Heat ray shielding fine particle dispersion in sheet shape or film shape It demonstrates in order of the manufacturing method of a body (a heat ray shielding film, a heat ray shielding sheet).

[1] Method for producing granular heat ray shielding fine particle dispersion Heat ray shielding fine particles are dispersed in an organic solvent together with a dispersant, a coupling agent and / or a surfactant to obtain an organic solvent dispersion. obtain. After that, by removing the organic solvent from the organic solvent dispersion, the dispersion powder in which the heat ray shielding fine particles are dispersed in the dispersant, the plasticizer dispersion dispersed in the plasticizer, the master batch dispersed in the resin, etc. The heat ray shielding fine particle dispersion according to the invention can be obtained.

Moreover, in addition to a dispersing agent, a coupling agent, and a surfactant, an ultraviolet absorber, an antioxidant, a light stabilizer, a tackifier, a colorant (if necessary) are added to the heat ray shielding fine particle dispersion according to the present invention. Pigments and dyes), additives such as antistatic agents, and the like can also be added.
Hereinafter, (1) solvent, (2) dispersant, coupling agent, (3) ultraviolet absorber, (4) light stabilizer, (5) antioxidant, (6) dispersed powder, plasticizer dispersion, The production method of the master batch and (7) the characteristics of the heat ray shielding fine particle dispersion will be described in this order.

(1) Solvent As the organic solvent, various solvents such as alcohol, ketone, hydrocarbon, glycol, and water 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 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.
However, among these, organic solvents with low polarity are preferable, and in particular, 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. Is more preferable. These solvents can be used alone or in combination of two or more.

(2) Dispersant, coupling agent Dispersant, coupling agent, and surfactant can be selected according to the application, but have an amine-containing group, hydroxyl group, carboxyl group, or 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 phosphate 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.

  Furthermore, 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 added amount of the dispersant is desirably in the range of 10 parts by weight to 1000 parts by weight, 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 and the coupling agent, the heat ray shielding fine particle dispersion according to the present invention includes, as necessary, a light stabilizer, an ultraviolet absorber, an antioxidant, a tackifier, a colorant (a pigment or a dye). Etc.) and additives such as antistatic agents may be contained.

(3) 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 light in the ultraviolet region, and to enhance 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. 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 increase the visible light transmittance of the heat ray shielding film and the heat ray shielding sheet liquid even when a concentration sufficient to absorb ultraviolet rays is added, and is powerful. This is because the durability against long-term exposure to ultraviolet rays is high.

  Moreover, 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. 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.

(4) Light Stabilizer The heat ray shielding fine particle dispersion according to the present invention may further contain a hindered amine light stabilizer (sometimes referred to 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.

  In addition, 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.

  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-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-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-tetra Oxaspiro (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 ( 2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethylpiperidyl) butylamine polycondensate, decanedioic acid bis (2 , 2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester and the like can be suitably 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. As long as the HALS content in the heat ray shielding fine particle dispersion liquid is 0.05% by mass or more, the effect of adding HALS is sufficiently exhibited by a near-infrared shielding film or the like produced using the heat ray shielding fine particle dispersion. It is because it can. 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.

(5) Antioxidant 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.

  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-butylphenol) ) Butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and bis (3,3'-tert-butylphenol) Butyric acid glycol ester, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and the like can be suitably 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.

(6) Manufacturing method of heat ray shielding fine particle dispersion The method of dispersing the heat ray shielding fine particles in the organic solvent can be arbitrarily selected as long as the fine particles are uniformly dispersed in the organic solvent. For example, methods such as a bead mill, a ball mill, a sand mill, and ultrasonic dispersion can be used.

  The concentration of the heat ray shielding fine particles with respect to the organic solvent in the organic solvent dispersion is preferably 1% by mass or more and 50% by mass or less. When the concentration of the heat ray shielding fine particles with respect to the organic solvent is 1% by mass or more, it is possible to avoid a situation in which the amount of the organic solvent to be removed is excessive and the manufacturing cost is increased. On the other hand, if the concentration of the heat ray shielding fine particles with respect to the organic solvent is 50% by mass or less, the fine particles are likely to aggregate and the dispersion of the fine particles becomes difficult, or the viscosity of the liquid is remarkably increased and the handling becomes difficult. This is because it can be avoided.

  The heat ray shielding fine particles in the organic solvent dispersion 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.

  By removing the organic solvent from the organic solvent dispersion, the dispersion powder and the plasticizer dispersion according to the present invention can be obtained. As a method for removing the organic solvent from the organic solvent dispersion, the organic solvent dispersion is preferably dried under reduced pressure. Specifically, the organic solvent 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 organic solvent dispersion is improved, and the dispersion powder and 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 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 and dispersed powder in resin, and pelletizing the said resin.

  In addition, after uniformly mixing the heat ray shielding fine particles and the dispersion powder, thermoplastic resin granules or pellets, and other additives as necessary, kneaded in a vent type uniaxial or biaxial extruder, A master batch can also be obtained by 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.

(7) Characteristics of heat ray shielding fine particle dispersion 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. And transparency, such as a near-infrared shielding film, and near-infrared shielding ability, ie, a heat-shielding characteristic, respectively, are visible light transmittance, the average value of the transmittance | permeability in the range of wavelength 1200-1500nm, and the transmittance | permeability of wavelength 2100nm. Evaluation can be performed by

[2] Method for producing sheet- or film-shaped heat ray shielding fine particle dispersion The dispersion powder, plasticizer dispersion, or masterbatch according to the present invention is uniformly mixed into a transparent resin, whereby the sheet-form according to the present invention is obtained. Alternatively, a film-like 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 with 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.

[D] 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 base materials made of plate glass or plastic. 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.

  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 12% or more and 40% or less, and the wavelength The average value of the 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.

  Further, the optical properties 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% or more and 40% or less, and the wavelength is 1200 to 1200. 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.

  Further, the optical characteristics of the heat ray 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 value of the 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% 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 by adjusting the amount of heat ray shielding fine particles, dispersed powder, plasticizer dispersion or master batch, 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. 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.

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 4 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 with 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 is measured by a spectrophotometer cell (manufactured by GL Sciences Inc., model number: S10-SQ-1, The dispersion was held in a 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 1 to 8 and Comparative Examples 1 to 3, the transmittance of the 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 is the spectrum manufactured by Hitachi, Ltd. described above. Measured with a photometer 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.

[Example 1] (heat ray shielding sheet using 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 7.4131Å, the c-axis lattice constant is 7.5885Å, the powder color is L ^* a ^* b ^* color system, L ^* is A cesium tungsten bronze powder (hereinafter abbreviated 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 when the dilution rate is adjusted and measured 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 measurement results of the powder color of the powder A are shown in Table 1, and the measurement results of the transmittance are shown in Table 2.
Dispersant a was further added to Dispersion A and prepared such that the mass ratio of Dispersant a and composite tungsten oxide fine particles was [Dispersant a / composite 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 obtained heat ray shielding sheet according to Example 1 were measured, the visible light transmittance was 70%, the average value of the 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 3.

[Example 2] (heat ray shielding sheet using 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. Baked, has hexagonal crystal, a-axis lattice constant of 7.4143Å, c-axis lattice constant of 7.5766Å, 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 −5.16, 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 referred to 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 becomes 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 results of the powder color of the powder B are shown in Table 1, and the measurement results of the transmittance are shown in Table 2.
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 properties of the obtained heat ray shielding sheet according to Example 2 were measured, the visible light transmittance was 70%, the average value of the 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 3.

[Example 3] (heat ray shielding sheet using 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 referred to 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 the dispersion C was used. From the transmittance profile obtained by adjusting the dilution rate so that the visible light transmittance becomes 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 measurement results of powder color of powder C are shown in Table 1, and the measurement results of transmittance are shown in Table 2.
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 properties of the obtained heat ray shielding sheet according to Example 3 were measured, the visible light transmittance was 70%, the average value of the 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 3.

[Example 4] (heat ray shielding sheet using Cs _0.33 WO ₃ )
1 part by mass of benzotriazole-based UV absorber (manufactured by BASF, TINUVIN384-2) containing benzotriazole compound and 100 parts by mass of powder C, bis (2,2,6,6-tetramethyl-1- (octyl) decanedioate Oxy) -4-piperidinyl) ester, 1 part by mass of an amino ether HALS (manufactured by BASF, TINUVIN123) containing a reaction product of 1,1-dimethylethyl hydroperoxide and octane, as an antioxidant, isooctyl-3- ( A hindered phenol-based antioxidant (manufactured by BASF, trade name: IRGANOX 1135) containing 3,5-di-t-butyl-4-hydroxyphenyl) propionate was weighed so as to be 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 liquid 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.
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 at wavelengths of 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 3.

[Comparative Example 1] (heat ray shielding sheet using 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 a hexagonal crystal, the a-axis lattice constant is 7.4080Å, the c-axis lattice constant is 7.6111Å, and the powder color is L ^* a ^* b ^{* in the} color system ^. Was 36.11, a ^* was 0.52, and b ^* was −5.54. Thus, a cesium tungsten bronze powder according to Comparative Example 1 (hereinafter abbreviated as “powder E”) was obtained. The measurement results are shown in Table 1.

When a dispersion (hereinafter abbreviated as “dispersion E”) of this powder was prepared using a paint shaker together with a dispersant and a solvent, the average dispersed particle size was 23 nm.
And when the spectral transmittance when measuring by adjusting a dilution rate so that visible light transmittance might be 85% was measured, the average value of the transmittance in wavelength 800-900 nm was 26.0 from the transmittance profile. %, 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.

  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 obtained heat ray shielding sheet according to Comparative Example 1 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 3.

[Example 5] (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 5 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 5. 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 5 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 properties of the obtained heat ray shielding sheet according to Example 5 were measured, the visible light transmittance was 70%, the average value of the 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 3.
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 2] (heat ray shielding masterbatch using Cs _0.33 WO ₃ )
A masterbatch (hereinafter referred to as masterbatch E) according to Comparative Example 2 for 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. Obtained.
A heat ray shielding sheet according to Comparative Example 2 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 pellet.
When the optical characteristics of the heat ray shielding sheet according to Comparative Example 2 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 3.

[Evaluation of Examples 1 to 5 and Comparative Examples 1 and 2]
In the heat ray shielding fine particles according to Examples 1 to 5, 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 having a wavelength of 800 to 900 nm while ensuring high heat-shielding characteristics exhibited by the composite tungsten oxide fine particles, and the irritability to the skin was reduced. .

  The heat ray shielding sheets according to Examples 1 to 5 have a wavelength of 800 to when the visible light transmittance is 85% as compared with the heat ray shielding sheets using the conventional composite tungsten oxide fine particles according to Comparative Examples 1 and 2. The average transmittance of near-infrared light at 900 nm is high, and the transmittance at wavelengths of 1200 to 1500 nm and 2100 nm is low. From this result, it was found that high transmittance was obtained with near-infrared light having a wavelength of 800 to 900 nm while ensuring high heat-shielding characteristics exhibited by the composite tungsten oxide fine particles, and the irritability to the skin was reduced. .

[Example 6] (Heat ray shielding film and heat ray shielding laminated transparent base material using Cs _0.30 WO ₃ )
The plasticizer triethylene glycol di-2-ethyl butyrate is added to the polyvinyl butyral resin so that the weight ratio of the polyvinyl butyral resin to the plasticizer is [polyvinyl butyral resin / plasticizer] = 100/40. A mixture prepared as described above was prepared. 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 6.
The heat ray shielding film according to Example 6 was cut to 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 6 was produced.

  When the optical properties of the heat ray shielding laminated transparent base material according to Example 6 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 4, and the transmittance profile for each wavelength is shown in FIG.

[Example 7] (heat ray shielding film and heat ray shielding laminated transparent base material using Cs _0.20 WO ₃ )
A heat ray shielding film according to Example 7 was produced in the same manner as in Example 6 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 7 was produced in the same manner as in Example 6 except that the heat ray shielding film according to Example 7 was used.

  When the optical properties of the heat-shielding transparent substrate according to Example 7 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 4, and the transmittance profile for each wavelength is shown in FIG.

[Example 8] (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 8 was produced in the same manner as in Example 6 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 8 was produced in the same manner as in Example 6 except that the heat ray shielding film according to Example 8 was used.

  When the optical characteristics of the heat ray shielding laminated transparent base material according to Example 8 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 4, and the transmittance profile for each wavelength is shown in FIG.

[Comparative Example 3] (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 Comparative Example 3 was produced in the same manner as in Example 6 except that a predetermined amount of the dispersion powder E 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 3 was produced in the same manner as in Example 6 except that the heat ray shielding film according to Comparative Example 3 was used.

  When the optical properties of the heat ray shielding laminated transparent base material according to Comparative Example 3 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 4, and the transmittance profile for each wavelength is shown in FIG.

[Evaluation of Examples 6 to 8 and Comparative Example 3]
The heat ray shielding laminated glass sheets according to Examples 6 to 8 have a wavelength when the visible light transmittance is 85% as compared with the heat ray shielding laminated glass sheet using the conventional composite tungsten oxide fine particles according to Comparative Example 3. The average transmittance of near-infrared light of 800 to 900 nm is high, and the transmittance of wavelengths 1200 to 1500 nm and wavelength 2100 nm is low. From this result, it was found that high transmittance was obtained with near-infrared light having a wavelength of 800 to 900 nm while ensuring high heat-shielding characteristics exhibited by the composite tungsten oxide fine particles, and the irritability to the skin was reduced. .

Claims (13)

  A composite tungsten oxide fine particle having a heat ray shielding function, and when the visible light transmittance is 85% when only light absorption by the composite tungsten oxide fine particle is calculated, the transmittance in a wavelength range of 800 to 900 nm 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:   2. The heat ray shielding fine particle dispersion 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. 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,
Alternatively, the heat ray shielding fine particle dispersion according to claim 1, wherein the heat ray shielding fine particle dispersion is a copolymer of two or more kinds of resins selected from the resin group.   The heat ray shielding fine particle dispersion according to any one of claims 1 to 3, wherein the composite tungsten oxide particles are contained in an amount of 0.5 mass% or more and 80.0 mass% or less.   The heat ray shielding fine particle dispersion according to any one of claims 1 to 4, wherein the heat ray shielding fine particle dispersion has a sheet shape, a board shape, or a film shape. 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 The heat ray shielding fine particle dispersion according to any one of claims 1 to 6, wherein the heat ray shielding fine particle dispersion 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 1 to 7 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 The heat ray shielding laminated transparent base material according to claim 8, wherein the transmittance is 2% or less and the transmittance at a wavelength of 2100 nm is 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;
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.   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 10 between transparent base materials.   The manufacturing method of the heat ray shielding laminated transparent base material which has the process of shape | molding the heat ray shielding fine particle dispersion of Claim 10 in a film form or board shape.   The heat ray shielding fine particle dispersion or the heat ray shielding laminated transparent base material according to any one of claims 1 to 9, further comprising at least one selected from an ultraviolet absorber, HALS, and an antioxidant.

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