JP2011063741A - Heat ray shielding resin sheet material, heat ray shielding resin sheet material laminate and building structure using these - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat ray shielding resin sheet material and a heat ray shielding resin sheet material laminate which are excellent not only in visible light transmission and heat ray shielding property but in heat resistance, and a building structure using these. <P>SOLUTION: The heat ray shielding resin sheet material contains fine particles having heat ray shielding function in a resin, wherein the fine particles comprise fine particles of a tungsten multiple oxide B having a hexagonal crystal structure in which lithium is contained as solid solution. The tungsten multiple oxide B is represented by general formula: LixMyWOz (wherein Li is lithium; M is one or more elements selected from Cs, Rb, K, Na, Ba, Ca, Sr and Mg; W is tungsten; O is oxygen; 0.0001≤x<0.1; 0.1≤y≤0.5; and 2.2≤z≤3.0), and has a larger lattice constant ratio c/a than a tungsten multiple oxide A represented by the general formula: MyWOz (wherein M, W and O are identical with the above M, W and O; 0.1≤y≤0.5; and 2.2≤z≤3.0), the lattice constant ratio c/a being 1.027300-1.029000. The fine particles have a dispersed particle size of 1-500 nm. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is used for openings such as roofs and walls of buildings, arcades, ceiling domes, and windows of vehicles, and is a heat ray shielding resin sheet material and heat ray shielding resin that have good visible light permeability and excellent heat ray shielding properties. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet material laminate and a building structure using the same, and in particular, a heat ray shielding resin sheet material and a heat ray shielding resin sheet material layer that are excellent in heat resistance and moisture heat resistance in addition to the visible light transmittance and heat ray shielding properties. The present invention relates to improvement of a body and a building structure using the same.

  Conventionally, so-called openings such as windows of various buildings and vehicles have been made of a transparent glass plate or resin plate for taking in sunlight. However, the sun rays include ultraviolet rays and infrared rays in addition to visible rays, and in particular, near infrared rays of 800 to 2500 nm out of infrared rays are called heat rays and cause the indoor temperature to rise by entering from the opening. .

  Therefore, in recent years, as a window material for various buildings and vehicles, etc., a heat ray shielding material that shields heat rays while sufficiently taking in visible light and maintains the brightness while simultaneously suppressing the temperature rise in the room has been studied. Various means for that purpose have been proposed.

  For example, Patent Document 1 proposes a heat ray shielding plate in which a heat ray reflective film obtained by depositing a metal on a transparent resin film is bonded to a transparent substrate such as a glass plate, an acrylic plate, or a polycarbonate plate. However, the heat reflecting film itself is not only very expensive, but also requires a complicated process such as an adhesion process, which causes a disadvantage of a very high cost. Moreover, since the adhesiveness of a transparent base material and a heat ray reflective film is not good, there existed a problem that a heat ray reflective film peeled with a time-dependent change.

  Many heat-ray shielding plates have been proposed in which a metal or metal oxide is directly vapor-deposited on the surface of a transparent substrate, and a heat-ray shielding film is applied, but a vapor deposition system that requires high vacuum and high-precision atmosphere control is used. Therefore, there is a problem in that mass productivity is poor, versatility is poor, and a heat ray shielding plate is very expensive.

  In addition to the method of applying a heat ray reflective film or a heat ray shielding film on the transparent substrate as a means for heat ray shielding, for example, Patent Literature 2 and Patent Literature 3 include a transparent resin such as an acrylic resin and a polycarbonate resin, A heat ray shielding plate formed by kneading mica coated with titanium oxide as heat ray reflecting particles has been proposed.

  In these heat ray shielding plates, it is necessary to add a large amount of heat ray reflective particles in order to improve the heat ray shielding performance. However, if the amount of addition of the heat ray reflective particles is increased, the visible light transmittance is lowered. there were. On the contrary, if the addition amount of the heat ray reflective particles is decreased, the visible light transmittance is increased, but the heat ray shielding property is lowered. Therefore, it is difficult to satisfy the heat ray shielding property and the visible light transmittance at the same time. Further, when a large amount of heat ray reflective particles are blended, there is also a drawback in strength that the physical properties, in particular, impact resistance and toughness of the transparent resin as the base material are lowered.

  On the other hand, the present applicant, in Patent Document 4, pays attention to the hexaboride fine particles having a large amount of free electrons as a component having a heat ray shielding effect, and the hexaboride fine particles are dispersed in the polycarbonate resin or the acrylic resin. Alternatively, a heat ray shielding resin sheet material in which hexaboride fine particles and ITO fine particles and / or ATO fine particles are dispersed has already been proposed.

  The optical properties of the heat-shielding resin sheet material to which hexaboride fine particles alone or hexaboride fine particles and ITO fine particles and / or ATO fine particles are applied have a maximum visible light transmittance in the visible light region and a near infrared region. Therefore, the visible light transmittance is 70% or more and the solar transmittance is improved to the 50% level.

  However, higher heat ray shielding properties are required, and there is still room for improvement in the heat ray shielding resin sheet material.

  Therefore, the applicant of the present invention disclosed in Patent Document 5 as tungsten fine particles represented by the general formula WOx (2.45 ≦ x ≦ 2.999) and / or the general formula MyWOz as fine particles having a heat ray shielding function. By applying composite tungsten oxide fine particles represented by (0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) and having a hexagonal crystal structure, the visible light transmittance is 70%. As described above, the heat ray shielding resin sheet material whose solar radiation transmittance is improved from the late 30% to the late 40% is proposed.

  However, the heat-ray shielding resin sheet material to which the tungsten oxide fine particles and / or the composite tungsten oxide fine particles having a hexagonal crystal structure are applied may not be sufficiently satisfied in some cases. There was room left.

JP-A 61-277437 JP-A-5-78544 JP-A-2-173060 JP 2003-327717 A Japanese Patent No. 4182357

  The present invention has been made paying attention to such problems, and the problem is that while maintaining excellent visible light transmittance, it can exhibit high heat ray shielding properties, and also has heat and moisture resistance. An object of the present invention is to provide an excellent heat ray shielding resin sheet material, a heat ray shielding resin sheet material laminate, and a building structure using these.

  Therefore, in order to solve the above-mentioned problems, the present inventors have conducted intensive research. As a result, the general formula MyWOz (where M is selected from Cs, Rb, K, Na, Ba, Ca, Sr, and Mg). One or more elements, W is tungsten, O is oxygen, composite tungsten oxide represented by 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) Produced by reacting a compound having a lithium element such as lithium carbonate with a compound of the general formula LixMyWOz (where Li is lithium, M is Cs, One or more elements selected from Rb, K, Na, Ba, Ca, Sr, and Mg, W is tungsten, O is oxygen, 0.0001 ≦ x <0.1, 0.1 ≦ y ≦ 0 .5, 2.2 ≦ z ≦ 3. ), A composite tungsten oxide having a hexagonal crystal structure in which lithium is solid-dissolved (referred to as composite tungsten oxide B to distinguish it from the composite tungsten oxide A before lithium is solid-solved), It has been discovered that it has excellent visible light transmittance and heat ray shielding properties, as well as excellent heat and moisture resistance, and the heat ray shielding resin sheet material to which this composite tungsten oxide B is applied also has excellent visible light transmittance. At the same time, it has been discovered that it exhibits high heat-ray shielding properties and is excellent in heat resistance and moist heat resistance. The present invention has been completed based on such technical findings.

That is, the invention according to claim 1
In a heat ray shielding resin sheet material containing fine particles having a heat ray shielding function in a resin base material that transmits visible light,
The fine particles having the heat ray shielding function are represented by the general formula LixMyWOz (where Li is lithium, M is one or more elements selected from Cs, Rb, K, Na, Ba, Ca, Sr, Mg, W is Tungsten, O is oxygen, 0.0001 ≦ x <0.1, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) The ratio of lattice constant c / a is selected from the general formula MyWOz (where M is selected from Cs, Rb, K, Na, Ba, Ca, Sr, Mg). 1 or more elements, W is tungsten, O is oxygen, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) Greater than / a, the numerical value is 1.027300 to 1.029000 There, and wherein the dispersed particle diameter of 1nm or more 500nm or less.

The invention according to claim 2
In the heat ray shielding resin sheet material according to the invention of claim 1,
General formula MyWOz (where M is one or more elements selected from Cs, Rb, K, Na, Ba, Ca, Sr, Mg, W is tungsten, O is oxygen, 0.1 ≦ y ≦ 0 .5, 2.2 ≦ z ≦ 3.0) and a mixture of a compound having a lithium element and a compound having a lithium element is calcined in the atmosphere or in an inert gas atmosphere, and then reduced gas. The fine particles of the composite tungsten oxide B according to claim 1 represented by the general formula LixMyWOz are obtained by heat treatment in an atmosphere or a mixed atmosphere of a reducing gas and an inert gas,
The invention according to claim 3
In the heat ray shielding resin sheet material according to the invention of claim 1 or 2,
The content of the fine particles having a heat ray shielding function is 0.05 g to 45 g per 1 m ^{2 of the} heat ray shielding resin sheet material,
The invention according to claim 4
In the heat ray shielding resin sheet material according to any one of claims 1 to 3,
The fine particles having a heat ray shielding function are
The fine particles of the composite tungsten oxide B according to claim 1 represented by the general formula LixMyWOz;
Sb, V, Nb, Ta, Zr, F, Zn, Al, Ti, Pb, Ga, Re, Ru, P, Ge, In, Sn, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Tb, Lu, Sr, at least one of oxide fine particles, composite oxide fine particles, and boride fine particles containing two or more elements selected from the group consisting of It is characterized by comprising fine particles.

Next, the invention according to claim 5 is:
In the heat ray shielding resin sheet material according to any one of claims 1 to 4,
The resin base material is composed of polycarbonate resin or acrylic resin,
The invention according to claim 6
The heat ray shielding resin sheet material according to any one of claims 1 to 5, a surface sheet layer constituting one surface of the sheet material, and a surface sheet layer constituting the other one surface of the sheet material, It is constituted in a hollow multilayer structure having an intermediate sheet layer formed between the two surface sheet layers, and a connection sheet layer connecting the sheet layers,
The invention according to claim 7 provides:
In the heat ray shielding resin sheet material according to the invention of claim 6,
All of the sheet layer contains fine particles having a heat ray shielding function according to any one of claims 1 to 4,
The invention according to claim 8 provides:
In the heat ray shielding resin sheet material according to the invention of claim 6,
Only one layer of the surface sheet layer constituting one surface of the sheet material contains fine particles having a heat ray shielding function according to any one of claims 1 to 4,
The invention according to claim 9 is:
In the heat ray shielding resin sheet material according to the invention of claim 6,
The fine particles having a heat ray shielding function according to any one of claims 1 to 4 are contained only in two layers of the surface sheet layer constituting the surface of the sheet material.

The invention according to claim 10 is
A resin film containing an ultraviolet absorber is formed on at least one sheet surface of the heat ray shielding resin sheet material according to any one of claims 1 to 9,
The invention according to claim 11 is:
An abrasion-resistant hard coat layer is formed on at least one sheet surface of the heat ray shielding resin sheet material according to any one of claims 1 to 9.

Next, the invention according to claim 12 is:
In the heat ray shielding resin sheet laminate,
It is obtained by laminating the heat ray shielding resin sheet material according to any one of claims 1 to 11 on another resin sheet material,
The invention according to claim 13 is:
In building structures,
The heat ray shielding resin sheet material according to any one of claims 1 to 11 and / or the heat ray shielding resin sheet material laminate according to claim 12 is used.

According to the heat ray shielding resin sheet material according to the present invention containing fine particles having a heat ray shielding function in a resin base material that transmits visible light,
The fine particles having a heat ray shielding function are represented by the general formula LixMyWOz (where Li is lithium, M is one or more elements selected from Cs, Rb, K, Na, Ba, Ca, Sr, Mg, W is Tungsten, O is oxygen, 0.0001 ≦ x <0.1, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) The ratio of lattice constant c / a is selected from the general formula MyWOz (where M is selected from Cs, Rb, K, Na, Ba, Ca, Sr, Mg). 1 or more elements, W is tungsten, O is oxygen, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) Greater than / a, the numerical value is 1.027300 to 1.029000 There, and is characterized in that the dispersion particle diameter of 1nm or more 500nm or less.

  The composite tungsten oxide B fine particles having a hexagonal crystal structure in which lithium represented by the general formula LixMyWOz has a solid solution has excellent visible light transmittance and heat ray shielding properties, and also has excellent heat and moisture resistance. Therefore, by applying the composite tungsten oxide B fine particles as the fine particles having a heat ray shielding function, the heat ray can maintain high visible light transmittance and at the same time exhibit high heat ray shielding properties and also has excellent heat and moisture resistance. It becomes possible to provide a shielding resin sheet material and a heat ray shielding resin sheet material laminate, and a building structure using these.

The schematic diagram of the crystal structure of the composite tungsten oxide which has a hexagonal crystal. The schematic diagram of the hexagonal close-packed lattice for demonstrating ratio c / a of a lattice constant. Sectional drawing which shows the heat ray shielding resin sheet material which has a hollow 3 layer structure. Sectional drawing which shows the heat ray shielding resin sheet material which has a hollow 7 layer structure.

  Hereinafter, embodiments of the present invention will be described in detail.

[A] Heat ray shielding resin sheet material The heat ray shielding resin sheet material according to the present invention containing fine particles having a heat ray shielding function in a resin base material that transmits visible light, the fine particles having a heat ray shielding function are represented by the general formula LixMyWOz ( However, Li is lithium, M is one or more elements selected from Cs, Rb, K, Na, Ba, Ca, Sr, and Mg, W is tungsten, O is oxygen, 0.0001 ≦ x <0 0.1, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0), which is composed of fine particles of composite tungsten oxide B having a hexagonal crystal structure in which lithium is dissolved. The ratio c / a of the lattice constant is the general formula MyWOz (where M is one or more elements selected from Cs, Rb, K, Na, Ba, Ca, Sr, Mg, W is tungsten, O is Oxygen, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) is larger than the lattice constant ratio c / a of the composite tungsten oxide A, the numerical value is 1.027300 to 1.029000, and the dispersed particle diameter is 1 nm or more and 500 nm or less. It is characterized by that.

(1) Fine particles having a heat ray shielding function The fine particles of the present invention having a heat ray shielding function are composed of fine particles of a composite tungsten oxide B having a hexagonal crystal structure in which lithium is represented by the general formula LixMyWOz. The lattice constant ratio c / a is larger than the lattice constant ratio c / a of the composite tungsten oxide A represented by the general formula MyWOz, and the numerical value thereof is 1.027300 to 1.029000, and The dispersed particle size is 1 nm or more and 500 nm or less.

  First, in the composite tungsten oxide represented by the general formula LixMyWOz and the general formula MyWOz, the composition ratio z of oxygen (O) when the composition of tungsten (W) is 1 is shown in parentheses of each general formula. It is 2.2 or more and 3.0 or less. When the composition ratio z is within this range, chemical stability as a material can be obtained, and therefore it can be applied as effective fine particles having a heat ray shielding function.

In addition, the composition ratio y of the element (M) when the composition of tungsten (W) is 1 is 0.1 or more and 0.5 from the viewpoint of optical characteristics as shown in parentheses of each general formula. The following is required. When the value of y is less than 0.1, the composite tungsten oxide represented by the general formula LixMyWOz and the general formula MyWOz becomes unstable as a compound, and foreign phases such as WO ₃ and WO ₂ are precipitated. In addition, the larger the value of y, the better the heat ray shielding function, but the maximum value at which the composite tungsten oxide stably exists as a compound is 0.5 or less, and preferably around 0.33.

Further, when the composite tungsten oxide fine particles represented by the general formula LixMyWOz and the general formula MyWOz have a hexagonal crystal structure, the transparency of the fine particles is improved in the visible light region and the absorption in the near infrared region ( That is, the heat ray shielding function is improved. This will be described with reference to FIG. 1, which is a schematic plan view of the hexagonal crystal structure. In FIG. 1, _six octahedrons formed by WO ₆ units indicated by reference numeral 1 are assembled to form a hexagonal void (tunnel), and the element (M) indicated by reference numeral 2 is arranged in the void. Thus, one unit is formed, and a large number of these one units are assembled to form a hexagonal crystal structure. When the cation of the element (M) is added to the hexagonal void, the absorption in the near infrared region is improved. Here, generally, when an element (M) having a large ionic radius is added, the hexagonal crystal is formed, which is preferable.

  When the composite tungsten oxide particles having a hexagonal crystal structure have a uniform crystal structure, the addition amount y of the element (M) is not less than 0.1 and not more than 0.5 as described above, and preferably 0.8. It is around 33. When the composition ratio z = 3 of oxygen (O), the value of y is 0.33, so that the element (M) is considered to be disposed in all hexagonal voids.

  Moreover, when the composite tungsten oxide B fine particles in which lithium represented by the general formula LixMyWOz is solid-dissolved have a tetragonal or cubic tungsten bronze structure in addition to the hexagonal crystal described above, the fine particles have a heat ray shielding function. It is valid. The absorption position in the near-infrared region tends to change depending on the crystal structure of the composite tungsten oxide B fine particles in which lithium is dissolved, and the absorption position in the near-infrared region is longer when it is a tetragonal crystal than a cubic crystal. It moves to the wavelength side, and when it is hexagonal, it tends to move to the longer wavelength side than when it is tetragonal. Further, accompanying the change in the absorption position, the absorption in the visible light region is the smallest in the hexagonal crystal, the next is the tetragonal crystal, and the cubic is the largest among them. Therefore, as described above, it is necessary to use hexagonal tungsten bronze for the purpose of transmitting light in the visible light region and shielding light in the near infrared region. However, the tendency of the optical characteristics described here is merely a rough tendency, and varies depending on the kind of additive element, the amount of addition, and the amount of oxygen, and is not limited to this. Accordingly, a composite tungsten oxide B produced by reacting a composite tungsten oxide A fine particle represented by the general formula MyWOz with a compound having a lithium element such as lithium carbonate and having a solid solution of lithium represented by the general formula LixMyWOz. Even if the fine particles contain some tetragonal or cubic tungsten bronze structures other than the hexagonal crystals described above, they can be used as the fine particles of the present invention having a heat ray shielding function.

Next, in the composite tungsten oxide B represented by the general formula LixMyWOz, the composition ratio x of lithium (Li) when the composition of tungsten (W) is 1 is shown in parentheses in the general formula. 0.0001 ≦ x <0.1. In the composite tungsten oxide having a hexagonal crystal structure, when the composition ratio of oxygen (O) is z = 3, other than hexagonal voids formed by assembling six octahedrons formed of the above WO ₆ units In addition, three octahedrons that are also formed in units of WO ₆ are assembled to form a triangular void (tunnel). That is, although there is a site different from the M element, it is considered that lithium is arranged in the triangular void.

  And the ratio c / a of the lattice constant in the composite tungsten oxide B represented by the general formula LixMyWOz (see the hexagonal close-packed lattice symbols a and c shown in the schematic diagram of FIG. 2) is a compound containing a lithium element. It is confirmed that the lattice constant ratio c / a of the composite tungsten oxide A represented by the general formula MyWOz before the reaction is larger than the lattice constant ratio c / a of the composite tungsten oxide B represented by LixMyWOz. Therefore, it is considered that lithium (Li) is in solid solution. More specifically, the ratio c / a of the lattice constant in the composite tungsten oxide B expressed by the general formula LixMyWOz is the ratio c of the lattice constant of the composite tungsten oxide A expressed by the general formula MyWOz as the starting material. More than 0.000050 compared to / a. On the other hand, the upper limit of the difference between the lattice constant ratio c / a of the composite tungsten oxide B and the lattice constant ratio c / a of the starting composite tungsten oxide A is 0.001700 or less. The reason why the upper limit is 0.001700 or less is that the lattice constant ratio c / a of the composite tungsten oxide B is larger than the lattice constant ratio c / a of the starting composite tungsten oxide A by more than 0.001700. This is because the lattice constant ratio c / a becomes excessive, the element (M), which will be described later, is easily desorbed, and the improvement effect on heat resistance and heat and moisture resistance decreases. And the ratio c / a of the lattice constant of the composite tungsten oxide B expressed by the general formula LixMyWOz needs to be 1.027300 to 1.029000.

  Further, the c-axis of the lattice constant in the composite tungsten oxide B represented by the general formula LixMyWOz is also the c-axis of the lattice constant of the composite tungsten oxide A represented by the general formula MyWOz before reacting with the compound having a lithium element. It is considered that lithium (Li) is in a solid solution also from the fact that it has been confirmed that it is more elongated. Here, the lithium (Li) is in solid solution means a state in which part or all of the added lithium supplied from the compound having a lithium element is in solid solution.

By the way, regarding the composite tungsten oxide B in which lithium represented by the general formula LixMyWOz is solid-solved, the reason why the heat resistance / moisture heat resistance is improved as compared with the composite tungsten oxide A represented by the general formula MyWOz at present. Although it is unknown, the present inventors infer as follows. First, it is the present inventor that the deterioration phenomenon of the heat ray shielding function under the wet heat condition of the composite tungsten oxide A represented by the general formula MyWOz is deeply related to the presence of moisture in the atmosphere of the composite tungsten oxide A. Etc. have been confirmed. The composite tungsten oxide A represented by the general formula MyWOz is an acidic oxide like WO ₃ and is unstable in moisture. When WO ₃ is immersed in water, the W component is eluted and the pH is lowered. When the composite tungsten oxide A represented by the general formula MyWOz is immersed in water, the W component is similarly eluted and the pH is lowered. At this time, when the element (M) is a basic element such as Cs, Rb, K, Na, Ba, Ca, Sr, etc., elution of the element (M) is promoted in the form of neutralizing the acidic aqueous solution. It is considered that the heat ray shielding function is lowered. In addition, even when no moisture is involved, the elemental (M) desorption occurs in the composite tungsten oxide A represented by the general formula MyWOz exposed at high temperatures. The composite tungsten represented by the general formula MyWOz This is confirmed by the change in the ratio c / a of the lattice constants before and after the oxide A was exposed to a high-temperature dry air atmosphere. On the other hand, the composite tungsten oxide B represented by the general formula LixMyWOz is considered to suppress elution and desorption of the element (M) because lithium (Li) is in solid solution. From such an idea, if the lithium (Li) composition ratio x of the composite tungsten oxide B represented by the general formula LixMyWOz is less than 0.0001, the amount of Li that suppresses elution and desorption of the element (M) Is insufficient, and a sufficient effect of the composite tungsten oxide B regarding heat resistance cannot be obtained. On the other hand, when the lithium (Li) composition ratio x is 0.1 or more, the heat resistance of the composite tungsten oxide B is deteriorated. Although the details of this reason are not clear, it is presumed that the element (M) is easily desorbed when the ratio c / a of the lattice constants becomes excessive as Li increases.

  By the way, the fine particles of the present invention having a heat ray shielding function composed of the composite tungsten oxide B in which lithium is solid-solved represented by the general formula LixMyWOz particularly absorbs light having a wavelength of around 1000 nm, so that its transmission color tone is blue. There are many things that become the system. Further, the dispersed particle size of the fine particles according to the present invention can be appropriately selected depending on the purpose of use. First, when used for the purpose of maintaining transparency, it is preferable to have a dispersed particle size of 500 nm or less. This is because a dispersed particle size smaller than 500 nm does not completely block light due to scattering, can maintain visibility in the visible light region, and can efficiently maintain transparency at the same time. In particular, when importance is attached to transparency in the visible light region, it is preferable to further consider scattering by particles.

  When importance is attached to the reduction of scattering by the particles, the dispersed particle diameter is 200 nm or less, preferably 100 nm or less. The reason for this is that if the dispersed particle diameter of the particles is small, the scattering of light in the visible light region of 400 nm to 780 nm due to geometrical scattering or Mie scattering is reduced, and as a result, the heat ray shielding resin sheet material becomes like frosted glass. This is because it is possible to avoid the adverse effect that clear transparency cannot be obtained. That is, when the dispersed particle diameter is 200 nm or less, the geometric scattering or Mie scattering is reduced and a Rayleigh scattering region is obtained. This is because in the Rayleigh scattering region, the scattered light decreases in inverse proportion to the sixth power of the particle diameter, so that scattering is reduced and transparency is improved as the dispersed particle diameter decreases. Furthermore, when the dispersed particle size is 100 nm or less, the scattered light is preferably extremely small. From the viewpoint of avoiding light scattering, it is preferable that the dispersed particle size is small. If the particle size is 1 nm or more, industrial production is possible.

By the way, the heat ray shielding performance of the heat ray shielding resin sheet material is determined by the content per sheet unit area of the fine particles (heat ray shielding component) having the heat ray shielding function composed of the composite tungsten oxide B. If a predetermined amount of the heat ray shielding component is dispersed per area, the desired heat ray shielding performance corresponding to the content of the heat ray shielding component is exhibited regardless of the thickness of the sheet. Therefore, the content of the heat ray shielding component with respect to the resin base material is preferably determined according to required optical properties, mechanical properties of the heat ray shielding resin sheet material, and the like. Even if the heat ray shielding component content per unit area that satisfies the heat ray shielding characteristics, the content per unit volume increases as the resin sheet material becomes thinner, and the wear strength and impact resistance of the resin sheet increase. descend. Further, the heat ray shielding component may be raised on the surface of the heat ray shielding resin sheet material, which may impair the appearance. Therefore, when the heat ray shielding resin sheet material is thin, specifically, fine particles having a heat ray shielding function composed of the composite tungsten oxide B so that the above-described disadvantage does not occur even when the thickness is about 20 to 30 μm. The content of (heat ray shielding component) is preferably 45 g or less per 1 m ² of the heat ray shielding resin sheet material. On the other hand, when the content per 1 m ^{2 of the} heat ray shielding component is reduced, the heat ray shielding characteristics are lowered. Therefore, the content that exerts the practical heat ray shielding characteristics is about 0.1 per 1 m ² of the heat ray shielding resin sheet material. It is preferable that it is 05 g or more.

  The surface of the fine particles of the present invention having a heat ray shielding function composed of the composite tungsten oxide B is coated with an oxide containing one or more elements of Si, Ti, Zr, and Al. It is preferable from the viewpoint of improving the weather resistance of the fine particles.

  In addition to the fine particles of the composite tungsten oxide B represented by the general formula LixMyWOz, the fine particles of the present invention having a heat ray shielding function are further added to Sb, V, Nb, Ta, Zr, F, Zn, Al Ti, Pb, Ga, Re, Ru, P, Ge, In, Sn, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Tb, Lu, Sr And oxide fine particles containing two or more elements selected from the group consisting of Ca, composite oxide fine particles, and boride fine particles.

(2) Production of fine particles having a heat ray shielding function composed of composite tungsten oxide B (2-1) General formula LixMyWOz (where Li is lithium, M is Cs, Rb, K, Na, Ba, Ca, Sr) One or more elements selected from Mg, W is tungsten, O is oxygen, 0.0001 ≦ x <0.1, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3. In order to produce a composite tungsten oxide B fine particle having a hexagonal crystal structure in which lithium represented by 0 is dissolved, first, a general formula MyWOz (where M is Cs, Rb, K, Na, Ba, One or more elements selected from Ca, Sr, and Mg, W is tungsten, O is oxygen, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) Composite tungsten oxide A obtained by synthesizing tungsten oxide A A compound containing lithium element is added to the element, and the mixture is fired in the atmosphere or in an inert gas atmosphere, and then fired in a reducing gas atmosphere or a mixed atmosphere of a reducing gas and an inert gas (heat treatment). Can be manufactured.

  When the mixture of the composite tungsten oxide A fine particles and the compound containing lithium element is baked in the atmosphere or an inert gas atmosphere and then baked (heat treatment) in a mixed atmosphere of a reducing gas and an inert gas, Although it will not specifically limit if the density | concentration of the reducing gas in active gas is suitably selected according to baking (heat processing) temperature, Preferably it is 20 vol% or less, More preferably, it is 10 vol% or less, More preferably, it is 7-0.01 vol. %. This is because when the concentration of the reducing gas in the inert gas is 20 vol% or less, rapid reduction of the composite tungsten oxide A fine particles can be avoided.

  The firing temperature may be appropriately selected according to the atmosphere, but when firing a mixture of the composite tungsten oxide A fine particles and the compound containing lithium element in the air, the temperature is higher than 650 ° C. and 1000 ° C. or lower. The firing (heat treatment) temperature in the reducing gas atmosphere or in the mixed atmosphere of reducing gas and inert gas is 400 ° C. or higher and 1000 ° C. or lower, preferably 500 ° C. or higher and 900 ° C. or lower. The firing (heat treatment) time may be appropriately selected according to the amount of treatment, but 5 minutes or more and 10 hours or less is sufficient. In addition, lithium carbonate is desirable for the compound having a lithium element.

  Further, when a mixture of the composite tungsten oxide A fine particles and the compound containing lithium element is baked in an atmosphere of an inert gas alone, it is more than 200 ° C. and less than 600 ° C. from the viewpoint of shortening the manufacturing time and single phase. The temperature is preferably more than 300 ° C. and less than 500 ° C., more preferably more than 350 ° C. and less than 450 ° C.

If the calcination (heat treatment) temperature is too low, it takes time to diffuse lithium atoms, which is not productive. Conversely, if the firing (heat treatment) temperature is too high, a heterogeneous phase is generated. On the other hand, when the mixture of the composite tungsten oxide A fine particles and the compound containing lithium element is fired in the air or in an inert gas atmosphere, and then fired (heat treatment) in a mixed atmosphere of a reducing gas and an inert gas. The temperature at which WO ₂ is not generated may be appropriately selected according to the reducing gas concentration. The firing (heat treatment) time at this time may be appropriately selected according to the selected temperature.

(2-2) Next, the above general formula LixMyWOz (where Li is lithium, M is one or more elements selected from Cs, Rb, K, Na, Ba, Ca, Sr, Mg, W is Tungsten, O is oxygen, 0.0001 ≦ x <0.1, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) A raw material for obtaining a composite tungsten oxide B having a general formula MyWOz (where M is one or more elements selected from Cs, Rb, K, Na, Ba, Ca, Sr, Mg, A method for producing a composite tungsten oxide A represented by W is tungsten, O is oxygen, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) will be described.

Tungsten acid (H ₂ WO ₄ ), ammonium tungstate, tungsten hexachloride, tungsten hydrate obtained by adding water to tungsten hexachloride dissolved in alcohol and hydrolyzing it, and then evaporating the solvent. As a compound having at least one selected tungsten compound and M element (Cs, Rb, K, Na, Ba, Ca, Sr, Mg), tungstate, chloride, nitrate, sulfate, oxalate , Oxides, carbonates, hydroxides, and other compounds having M element are dry-mixed, and the resulting mixed powder is mixed with an inert gas alone or in a mixed gas atmosphere of an inert gas and a reducing gas. It can be manufactured by one-step firing in steps, or the mixed powder can be fired in a mixed gas atmosphere of inert gas and reducing gas in the first step. An example is a method of producing by two-stage firing in an inert gas atmosphere in the second step. Note that tungsten oxide fine particles may be used instead of the tungsten compound.

  Moreover, the following method is illustrated as a manufacturing method different from the said method.

That is, as a tungsten compound, hydration of tungsten obtained by adding water to tungstic acid (H ₂ WO ₄ ), ammonium tungstate, tungsten hexachloride, tungsten hexachloride dissolved in alcohol, hydrolyzing it, and then evaporating the solvent. The mixture prepared by wet-mixing one or more tungsten compounds selected from the above and an aqueous solution containing the M element salt is dried to obtain a dried powder, and the resulting dried powder is converted into an inert gas. It is manufactured by firing in one step in a single step or in a mixed gas atmosphere of an inert gas and a reducing gas, or the dried powder is mixed in an inert gas and reducing gas atmosphere in the first step. And a method of producing by performing two-stage firing in which the second step is performed in an inert gas atmosphere. Note that tungsten oxide fine particles may be used instead of the tungsten compound. The salt of the M element is not particularly limited, and examples thereof include nitrates, sulfates, chlorides and carbonates. Moreover, the drying temperature and time at the time of drying the said liquid mixture prepared by wet mixing are not specifically limited.

  When the mixed powder or dry powder is fired in a mixed gas atmosphere of an inert gas and a reducing gas, the concentration of the reducing gas in the inert gas can be selected as appropriate depending on the firing temperature. Although not limited, Preferably it is 20 vol% or less, More preferably, it is 10 vol% or less, More preferably, it is 7-0.01 vol%. This is because when the concentration of the reducing gas in the inert gas is 20 vol% or less, rapid reduction of the mixed powder or dry powder can be avoided.

The firing temperature may be appropriately selected depending on the atmosphere, but when the mixed powder or dry powder is fired in an atmosphere of an inert gas alone, the composite tungsten oxide A fine particles represented by the general formula MyWOz are used. From the viewpoint of the crystallinity and coloring power, it exceeds 500 ° C. and is 1200 ° C. or less, preferably 1100 ° C. or less, more preferably 1000 ° C. or less. On the other hand, when the mixed powder or the dried powder is fired in a mixed gas atmosphere of an inert gas and a reducing gas, a temperature at which WO ₂ is not generated may be appropriately selected according to the reducing gas concentration. Furthermore, when producing composite tungsten oxide A fine particles by two-stage firing, firing is performed at 100 ° C. or more and 650 ° C. or less in a mixed gas atmosphere of an inert gas and a reducing gas at the first step. The conditions for firing at over 500 ° C. and below 1200 ° C. in an inert gas atmosphere are exemplified as preferred conditions from the viewpoint of near-infrared shielding properties. The firing treatment time at this time may be appropriately selected according to the firing temperature, but 5 minutes or more and 10 hours or less is sufficient.

Here, tungstic acid (H ₂ WO ₄ ), ammonium tungstate, tungsten hexachloride, tungsten hydrate obtained by adding water to tungsten hexachloride dissolved in alcohol and hydrolyzing it, and then evaporating the solvent, and A compound having M element such as tungstate, chloride, nitrate, sulfate, oxalate, oxide, carbonate, hydroxide, etc., for one or more tungsten compounds selected from tungsten oxide fine particles Is added using the dry mixing method described above, the compound having the element M is preferably an oxide or hydroxide.

  The dry mixing may be performed with a commercially available grinder, kneader, ball mill, sand mill, paint shaker, or the like.

[B] Production of heat ray shielding resin sheet material The method for producing the heat ray shielding resin sheet material according to the present invention, which includes fine particles having a heat ray shielding function in a resin base material that transmits visible light, includes fine particles having a heat ray shielding function (heat rays Any method that can uniformly disperse the shielding component in the resin substrate can be selected. For example, it is possible to use a method in which the fine particles are directly added to the resin and uniformly melt-mixed. In particular, a method of preparing an additive solution in which the fine particles are dispersed in a solvent and molding a resin sheet using a molding composition obtained by mixing the additive solution with a resin or a resin raw material is simple and preferable.

  The method for dispersing the heat ray shielding component (fine particles having a heat ray shielding function) in the resin is not particularly limited as long as the fine particles can be uniformly dispersed in the resin. However, as described above, an additive solution in which the fine particles are dispersed in an arbitrary solvent is used. The method used is preferred. For example, by using a method such as bead mill, ball mill, sand mill, ultrasonic dispersion or the like, the fine particles are dispersed in an arbitrary solvent to obtain an additive liquid for producing a heat ray shielding resin sheet material.

  The dispersion solvent used in the additive solution for producing the heat ray shielding resin sheet material is not particularly limited, and can be selected according to the conditions for forming the resin to be blended and the resin sheet material, and is a general organic solvent. Can be used. Moreover, you may adjust pH by adding an acid and an alkali as needed. Furthermore, in order to further improve the dispersion stability of the fine particles in the resin, various surfactants, coupling agents and the like can be added as a dispersant.

  In order to produce a heat ray shielding resin sheet material using the above additive solution, generally, the additive solution is added to the base resin, mixed with a ribbon blender, tumbler, Nauter mixer, Henschel mixer, super Fine particles were uniformly dispersed in the resin using a method of uniformly melting and mixing with a mixer such as a mixer or planetary mixer, and a kneader such as a Banbury mixer, kneader, roll, single screw extruder or twin screw extruder. Prepare the mixture.

  Various types of transparent resins can be used as the base resin, but polycarbonate resins and acrylic resins can be preferably used from the viewpoint of optical characteristics, mechanical characteristics, raw material costs, and the like. And when the resin used as the base material is a polycarbonate resin, the above additive solution is added to the dihydric phenols used as the raw material of the resin, mixed uniformly by a known method, and a carbonate precursor exemplified by phosgene By reacting, a mixture in which fine particles (heat ray shielding component) are uniformly dispersed in the resin can be prepared. In the case of an acrylic resin, an additive solution is added to methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc., which are the raw materials for the acrylic resin, and mixed uniformly by a known method, and suspension polymerization or bulk polymerization is performed. A mixture in which fine particles (heat ray shielding component) are uniformly dispersed in an acrylic resin can be prepared by polymerizing by a known method. Moreover, in the resin used as a base material, an organic ultraviolet absorber and other coloring pigments may be contained as necessary.

  Further, the solvent of the additive solution is removed by a known method, and the resulting powder is added to the resin to prepare a mixture in which fine particles (heat ray shielding component) are uniformly dispersed in the resin. can do.

  Then, the heat ray shielding resin sheet material according to the present invention is obtained by subjecting a mixture in which the above-mentioned fine particles (heat ray shielding component) are uniformly dispersed in a resin to a planar shape by a known molding method such as injection molding, extrusion molding, compression molding or the like. Or can be produced by molding into a curved surface. Furthermore, after heat-shielding resin sheet material can also be produced by the same method after once pelletizing the mixture in which fine particles are uniformly dispersed in the resin by a granulator.

  In addition, the thickness of the heat ray shielding resin sheet material can be adjusted to an arbitrary thickness as necessary from a thick plate shape to a thin film shape.

  Moreover, you may form the resin film containing an ultraviolet absorber in the surface of at least 1 sheet | seat of the said heat ray shielding resin sheet material. For example, a coating film is formed by applying a coating solution prepared by dissolving a UV absorber such as benzotriazole or benzophenone in various binders on the heat ray shielding resin sheet material, and curing the coating film to absorb UV rays. A film can be formed. By forming the ultraviolet ray absorbing film, the weather resistance of the heat ray shielding resin sheet material can be improved, and the heat ray shielding resin sheet material can also have an ultraviolet ray shielding effect.

  Further, an abrasion-resistant hard coat layer may be formed on at least one sheet surface of the heat ray shielding resin sheet material. For example, a silicate-based or acrylic-based scratch-resistant hard coat layer can be formed on the heat ray shielding resin sheet material. By forming the hard coat layer, it becomes possible to improve the scratch resistance of the heat ray shielding resin sheet material, and the heat ray shielding resin sheet material can be used for a window of a vehicle or an automobile.

  In addition, the polycarbonate resin used as the resin base material of the said heat ray shielding resin sheet material is obtained by making bivalent phenols and a carbonate type precursor react with a solution method or a fusion method. Examples of the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, , 2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-methyl) Representative examples include phenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, and the like. Further, a preferred dihydric phenol is a bis (4-hydroxyphenyl) alkane series, and those having bisphenol A as a main component are particularly preferred.

  As acrylic resins, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate are used as main raw materials, and acrylic acid esters having 1 to 8 carbon atoms, vinyl acetate, styrene, acrylonitrile, methacryloyl as necessary. A polymer or copolymer using nitrile or the like as a copolymerization component is used. Further, an acrylic resin polymerized in multiple stages can also be used.

  As described above, fine particles composed of the composite tungsten oxide B having a hexagonal crystal structure in which lithium represented by the general formula LixMyWOz is dissolved are uniformly dispersed in the resin material to form a sheet. Therefore, without using a high-cost physical film-forming method or a complicated bonding process, the heat ray shielding resin sheet can maintain excellent visible light transmittance and at the same time exhibits high heat ray shielding properties and is excellent in heat resistance and moisture heat resistance. It becomes possible to provide the material.

[C] Heat ray shielding resin sheet material configured in a hollow multilayer structure Next, as a preferable form of the heat ray shielding resin sheet material, a surface sheet layer constituting one surface of the sheet material, and other sheet material A surface sheet layer constituting one surface of the sheet, an intermediate sheet layer formed between the two surface sheet layers, and a connection sheet layer connecting the sheet layers. A heat ray shielding resin sheet material is preferred.

  As such a heat ray shielding resin sheet material, the heat ray shielding resin sheet material 10 having a hollow three-layer structure shown in FIG. 3 and the heat ray shielding resin sheet material 20 having a hollow seven layer structure shown in FIG. 4 will be described as examples. In the heat ray shielding resin sheet material 10 (FIG. 3), an intermediate sheet layer 13 is provided between the facing surface sheet layer 11 and the surface sheet layer 12 so as to be substantially parallel to the surface sheet layers 11 and 12. A connection sheet layer 14 that is substantially orthogonal to the surface sheet layers 11 and 12 and the intermediate sheet layer 13 is formed by connecting and integrating the surface sheet layers 11 and 12 and the intermediate sheet layer 13. The surface sheet layers 11 and 12 and the intermediate sheet layer 13 form a three-layer structure, and a hollow portion 15 is formed surrounded by the surface sheet layers 11 and 12, the intermediate sheet layer 13, and the connection sheet layer 14.

  Further, the heat ray shielding resin sheet material 20 (FIG. 4) has four intermediate sheet layers 23, 24, 25, and 26 substantially parallel and substantially between the facing surface sheet layer 21 and the surface sheet layer 22. Connecting sheet layers 27 provided at equal pitches and orthogonal to these surface sheet layers 21, 22 and intermediate sheet layers 23, 24, 25, and 26 are provided with these surface sheet layers 21, 22, intermediate sheet layer 23, 24, 25 and 26 are connected and integrated, and a substantially sinusoidal connection sheet layer 28 meandering at the arrangement pitch of the connection sheet layers 27 is in contact with the top sheet layers 21 and 22, and the intermediate sheet layers 23, 24 are connected. , 25 and 26, and these face sheet layers 21, 22, 23, 24, 25 and 26 are connected and integrated. The surface sheet layers 21 and 22, the intermediate sheet layers 23, 24, 25, and 26 and the connection sheet layer 28 constitute a seven-layer structure, and the surface sheet layers 21 and 22, the intermediate sheet layers 23, 24, 25, 26, A hollow portion 29 is formed surrounded by the connection sheet layers 27 and 28.

  In the heat ray shielding resin sheet material having a hollow multi-layer structure as described above, fine particles having a heat ray shielding function in all of the sheet layers (that is, a composite having a hexagonal crystal structure in which lithium represented by the general formula LixMyWOz is dissolved) Fine particles of tungsten oxide B, or Sb, V, Nb, Ta, Zr, F, Zn, Al, Ti, Pb, Ga, Re, Ru, P, Ge added to the composite tungsten oxide B fine particles Two or more elements selected from the group consisting of In, Sn, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Tb, Lu, Sr, and Ca Of the surface sheet layer constituting one surface of the sheet material may be included. May be contained fine particles having the heat ray shielding function only in the layer may contain fine particles having the heat ray shielding function only two layers of the topsheet layer constituting the surface of the sheet material.

  For example, in the heat ray shielding resin sheet material 10 shown in FIG. 3, all the sheets of the surface sheet layers 11, 12, the intermediate sheet layer 13, and the connection sheet layer 14 are prepared using an existing multilayer hollow sheet manufacturing apparatus or the like. The layer may contain fine particles having the heat ray shielding function, or only the surface sheet layer 11 or only the surface sheet layers 11 and 12 may contain fine particle oxide fine particles having the heat ray shielding function. Moreover, in the heat ray shielding resin sheet material 20 shown in FIG. 4, similarly, the surface sheet layers 21 and 22 and the intermediate sheet layers 23, 24, 25, and 26 are used using an existing multilayer hollow sheet manufacturing apparatus or the like. In addition, the fine particles having the heat ray shielding function may be included in all the sheet layers of the connection sheet layers 27 and 28, or only the surface sheet layer 21 or 22 or only the surface sheet layers 21 and 22 described above. Fine particles having a function may be contained.

  By making the heat ray shielding resin sheet material into a hollow multilayer structure as described above, an air layer having a heat insulating effect can be provided between the top sheet and the intermediate sheet, for example, the sun absorbed by the top surface sheet on the outdoor side Since the release of energy to the indoor side is suppressed and the solar energy is efficiently released to the outdoor side, the heat ray shielding effect is improved.

  Further, by including the above-mentioned fine particles having the heat ray shielding function in only one or two layers of the surface sheet layer of the hollow multilayer structure, for example, fine particles having a larger heat ray shielding function in the outdoor surface sheet. It becomes possible to make the composition contain. And by adopting the configuration, for example, it is possible to further improve the above-described suppression of solar energy to the indoor side while keeping the fine particles per unit area of the heat ray shielding resin sheet material constant.

[D] Heat ray shielding resin sheet material laminate and building structure Any one of the heat ray shielding resin sheet materials described above is laminated on another resin sheet material in accordance with the application to obtain a heat ray shielding resin sheet material laminate. This is also a preferable configuration. By using a heat ray shielding resin sheet material as a heat ray shielding resin sheet material laminate, it is possible to obtain a laminate exhibiting various mechanical properties, and use the heat ray shielding resin sheet material for all or part of the laminate. Thereby, the laminated body which has a desired optical characteristic can be obtained.

  And it is also preferable to comprise a building structure using the said heat ray shielding resin sheet material and a heat ray shielding resin sheet material laminated body individually or in mixture of both, respectively. For example, a heat ray shielding resin sheet material can be fixed to an aluminum skeleton with bolts to efficiently shield a wider range of solar energy. Moreover, the temperature rise in a vehicle can be efficiently suppressed by processing a heat ray shielding resin sheet material into an arbitrary shape and using it as a rear window or sunroof for automobiles. Furthermore, a heat ray shielding resin sheet material laminated body obtained by laminating a heat ray shielding resin sheet material and glass is produced, and the sun ray which is incident by being directly fitted to the window frame of the vehicle with the heat ray shielding resin sheet material facing the outside. It is possible to provide functions such as shielding the energy to reduce the load on the air conditioner and at the same time preventing the scattering of glass due to stepping stones.

  Thus, the building structure in which the above-mentioned heat ray shielding resin sheet material and / or heat ray shielding resin sheet material laminate is used is the roof of a building, dome, skylight, arcade, carport, green house, building It can be widely used for windows, building walls, vehicle windows, automobile windows, and the like.

  Hereinafter, examples of the present invention will be specifically described with reference to comparative examples, but the present invention is not limited to the following examples.

  Here, the visible light (wavelength range: 380 nm to 780 nm) transmittance and solar radiation (wavelength range: 200 nm to 2600 nm) transmittance of the heat ray shielding resin sheet materials according to the respective examples and comparative examples were measured by “Spectrum” manufactured by Hitachi, Ltd. It measured using "photometer U-4000". The solar radiation transmittance is an index indicating the heat ray shielding performance.

  The haze value was measured based on JIS K 7105 using “HR-200” manufactured by Murakami Color Research Laboratory Co., Ltd. Furthermore, the average dispersed particle diameter was an average value measured by a measuring apparatus using a dynamic light scattering method [ELS-800 manufactured by Otsuka Electronics Co., Ltd.].

[Example 1]
An aqueous solution in which 7.43 kg of cesium carbonate was dissolved in 6.70 kg of water was added to 34.57 kg of tungstic acid (H ₂ WO ₄ ). After mixing, water was removed while stirring at 100 ° C. to dry powder. Got.

Next, while supplying 5% H ₂ gas with N ₂ gas as a carrier (that is, in a mixed gas atmosphere of an inert gas and a reducing gas), the dry powder is heated and heated at a temperature of 800 ° C. After baking for 5.5 hours, Cs _0.33 WO ₃ fine particles (that is, composite tungsten oxide A fine particles) were obtained. As a result of identifying the crystal phase of the calcined powder obtained by the calcining treatment by X-ray diffraction, it was Cs _0.33 WO ₃ single phase, and the lattice constant ratio c / a was 1.027547.

Next, 10 g of the above-mentioned Cs _0.33 WO ₃ fine particles and 2.68 × 10 ⁻³ g of lithium carbonate were sufficiently mixed in a crusher and baked in the atmosphere at 800 ° C. for 6 hours, and then N ₂ Li _0.002 Cs _0.33 WO ₃ fine particles (that is, composite tungsten oxide B fine particles) by heat-treating at 800 ° C. for 20 minutes while supplying 1.6% H ₂ gas using a gas as a carrier. Manufactured. As a result of identifying the crystal phase of the calcined powder by X-ray diffraction, only the peak attributed to Cs _0.33 WO ₃ was observed. The ratio c / a of the lattice constant is 1.027630, which is larger than the ratio c / a of the lattice constant of the Cs _0.33 WO ₃ fine particles not containing lithium, and lithium is dissolved. It was confirmed that

Next, 8% by weight of the above Li _0.002 Cs _0.33 WO ₃ fine particles (8% by weight in terms of Cs _0.33 WO ₃ ), 8% by weight of a polymeric dispersant (solid content 40%), toluene 84 A heat ray in which Li _0.002 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) were dispersed by weighing and weighting in a paint shaker containing 0.3 mmφZrO ₂ beads for 8 hours. A dispersion (A liquid) for producing a shielding resin sheet material was obtained.

Next, the concentration of Li _0.002 Cs _0.33 WO ₃ fine particles (that is, composite tungsten oxide B fine particles) in the obtained dispersion for heat ray shielding resin sheet material (liquid A) in the polycarbonate resin is _0.00 . Add to 05 wt%, mix with a blender, melt and knead uniformly with a twin screw extruder, extrude to a thickness of 2 mm using a T-die, and fine particles with a heat ray shielding function (composite tungsten oxide) A heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) in which the product B fine particles) were uniformly dispersed throughout was produced.

The content of Li _0.002 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) per 1 m ^{2 of the} obtained heat ray shielding resin sheet material was 1.2 g. However, the specific gravity of the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) was calculated as 1.2 g / cm ³ (hereinafter the same). Further, the dispersed particle diameter of the composite tungsten oxide B fine particles in the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) was 67 nm.

  And when the optical characteristic of the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) which concerns on Example 1 was measured, as shown in Table 1, the solar radiation transmittance | permeability in case of visible light transmittance | permeability 70.7% is 34. The haze value was 1.2% at 0.5%.

  Next, in order to investigate the heat resistance and heat-and-moisture resistance of the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) according to Example 1, an accelerated deterioration test was performed.

  That is, the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) according to Example 1 was exposed to an air atmosphere at 120 ° C., and the rate of change in visible light transmittance after 72 hours (hereinafter referred to as ΔVLT) and The rate of change in solar radiation transmittance (hereinafter referred to as ΔST) was examined. Hereinafter, the accelerated deterioration test exposed to an air atmosphere at 120 ° C. is abbreviated as a heat resistance test and is expressed as “heat resistance” in Table 1.

  As a result, ΔVLT after 72 hours in the heat resistance test was 0.61% and ΔST after 72 hours was 0.12%, confirming the improvement in heat resistance as compared with Comparative Example 1 described below.

  Further, the polycarbonate sheet material produced in the same manner as in the heat resistance test described above was exposed to an atmosphere of 80 ° C. and 95% HR, and ΔVTL and ΔST after 72 hours were measured. Hereinafter, the accelerated deterioration test exposed to an 80 ° C. and 95% HR atmosphere is abbreviated as a wet heat resistance test, and is indicated as “moisture heat resistance” in Table 1.

  As a result, ΔVLT after 72 hours in the heat and humidity resistance test was 1.21%, and ΔST after 72 hours was 0.52%, confirming an improvement in moisture and heat resistance compared to Comparative Example 1 described below. .

[Example 2]
In place of the condition of Example 1 in which 2.68 × 10 ⁻³ g of lithium carbonate was added to 10 g of Cs _0.33 WO ₃ fine particles, except that 6.71 × 10 ⁻³ g of lithium carbonate was added. In the same manner as in Example 1, Li _0.005 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) according to Example 2 were produced.

In addition, as a result of identification of the crystal phase by X-ray diffraction of the baked powder according to Example 2, only a peak attributed to Cs _0.33 WO ₃ was observed. The ratio c / a of the lattice constant is 1.027659, which is larger than the ratio c / a of the lattice constant of the Cs _0.33 WO ₃ fine particles not containing lithium, and the lithium is dissolved. It was confirmed that

Next, production of a heat ray shielding resin sheet material was carried out in the same manner as in Example 1 so that Li _0.005 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) would be 8 wt% in terms of Cs _0.33 WO _3. Dispersion liquid (A liquid) was prepared, and this heat ray shielding resin sheet material dispersion liquid (A liquid) was added to polycarbonate resin with Li _0.005 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B). Example in which fine particles having a heat ray shielding function (composite tungsten oxide B fine particles) are uniformly dispersed in the same manner as in Example 1 except that the concentration of fine particles is 0.05% by weight. The heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) which concerns on 2 was produced.

The content of Li _0.005 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) per 1 m ^{2 of the} obtained heat ray shielding resin sheet material was 1.2 g. Further, the dispersed particle diameter of the composite tungsten oxide B fine particles in the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) was 63 nm.

  And like Example 1, when the optical characteristic of the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) which concerns on Example 2 was measured, as shown in Table 1, when visible light transmittance | permeability is 69.0% The solar transmittance was 32.07%, and the haze value was 1.1%.

  In addition, ΔVLT after 72 hours in the heat resistance test was 0.57% and ΔST after 72 hours was 0.08%, confirming improvement in heat resistance as compared with Comparative Example 1 described below. Note that the wet heat resistance test was not performed in Example 2.

[Example 3]
In place of the condition of Example 1 in which 2.68 × 10 ⁻³ g of lithium carbonate was added to 10 g of Cs _0.33 WO ₃ fine particles, except that 1.34 × 10 ⁻² g of lithium carbonate was added. In the same manner as in Example 1, Li _0.010 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) according to Example 3 were produced.

In addition, as a result of identification of the crystal phase by X-ray diffraction of the baked powder according to Example 3, only a peak attributed to Cs _0.33 WO ₃ was observed. Further, the ratio c / a of the lattice constant is 1.027798, which is larger than the ratio c / a of the lattice constant of the Cs _0.33 WO ₃ fine particles not containing lithium, and the lithium is dissolved. It was confirmed that

Next, production of a heat ray shielding resin sheet material was carried out in the same manner as in Example 1 so that Li _0.010 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) would be 8 wt% in terms of Cs _0.33 WO _3. A dispersion liquid (A liquid) was prepared, and this heat ray shielding resin sheet material dispersion liquid (A liquid) was added to a polycarbonate resin with Li _0.010 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B). Example in which fine particles having a heat ray shielding function (composite tungsten oxide B fine particles) are uniformly dispersed in the same manner as in Example 1 except that the concentration of fine particles is 0.05% by weight. A heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) according to 3 was produced.

The content of Li _0.010 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) per 1 m ^{2 of the} obtained heat ray shielding resin sheet material was 1.2 g. Further, the dispersed particle diameter of the composite tungsten oxide B fine particles in the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) was 63 nm.

  And like Example 1, when the optical characteristic of the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) which concerns on Example 3 was measured, as shown in Table 1, when the visible light transmittance | permeability is 70.7% The solar transmittance was 34.2% and the haze value was 1.1%.

  In addition, the ΔVLT after 72 hours in the heat resistance test was 0.53%, and the ΔST after 72 hours was 0.05%, confirming improvement in heat resistance as compared with Comparative Example 1 described below. In Example 3, the wet heat resistance test was not performed.

[Example 4]
Dispersion liquid for manufacturing a heat ray-shielding resin sheet material (Liquid A) in which Li _0.002 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) prepared in Example 1 were dispersed using a vacuum dryer ) Was removed from the organic solvent (toluene) to produce a heat ray shielding resin sheet material powder (A powder).

Next, the concentration of Li _0.002 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) in the obtained heat ray shielding resin sheet material production powder (A powder) with respect to the polycarbonate resin is 0.00. Fine particles having a heat ray shielding function (added to a weight of 05%, mixed with a blender, uniformly melt-kneaded with a twin screw extruder, extruded to a thickness of 2 mm using a T-die ( A heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) according to Example 4 in which the composite tungsten oxide B fine particles) were uniformly dispersed throughout was produced.

By the way, the Li _0.002 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) according to Example 1 dispersed in the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) according to Example 4 are: As described in Example 1, only the peak attributed to Cs _0.33 WO ₃ is observed, and the lattice constant ratio c / a is 1.027630.

The content of Li _0.002 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) per 1 m ^{2 of the} obtained heat ray shielding resin sheet material was 1.2 g. Further, the dispersed particle diameter of the composite tungsten oxide B fine particles in the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) was 47 nm.

  And like Example 1, when the optical characteristic of the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) according to Example 4 was measured, as shown in Table 1, when the visible light transmittance was 70.9% The solar transmittance was 34.6%, and the haze value was 1.2%.

  In addition, ΔVLT after 72 hours in the heat resistance test was 0.62%, and ΔST after 72 hours was 0.12%, confirming improvement in heat resistance as compared with Comparative Example 1 described below. In Example 4, the wet heat resistance test was not performed.

[Comparative Example 1]
Example in which Cs _0.33 WO ₃ fine particles (composite tungsten oxide A fine particles) produced in Example 1 are applied as fine particles having a heat ray shielding function, and Cs _0.33 WO ₃ fine particles are 8% by weight. A heat ray shielding resin sheet material dispersion (A liquid) was prepared in the same manner as in Example 1, and a heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) according to Comparative Example 1 was produced in the same manner as in Example 1. did.

The Cs _0.33 WO ₃ fine particles according to Comparative Example 1 were Cs _0.33 WO ₃ single phase as in Example 1, and the lattice constant ratio c / a was 1.027547.

The content of Cs _0.33 WO ₃ fine particles (composite tungsten oxide A fine particles) per 1 m ^{2 of} the obtained heat ray shielding resin sheet material was 1.2 g. Further, the dispersed particle diameter of the composite tungsten oxide A fine particles in the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) was 70 nm.

  And like Example 1, when the optical characteristic of the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) which concerns on the comparative example 1 was measured, as shown in Table 1, when the visible light transmittance | permeability is 70.0% The solar transmittance was 35.3% and the haze value was 1.1%.

  In addition, ΔVLT after 72 hours in the heat resistance test is 1.30%, ΔST after 72 hours is 0.86%, and ΔVLT after 72 hours in the heat and humidity resistance test is 1.99%, The ΔST after 72 hours was 1.15%, which was confirmed to be inferior in heat resistance as compared with Examples 1 to 4 and also inferior in moist heat resistance as compared with Example 1.

[Comparative Example 2]
As in Example 1, except that 0.266 g of lithium carbonate was added instead of the condition of Example 1 in which 2.68 × 10 ⁻³ g of lithium carbonate was added to 10 g of Cs _0.33 WO ₃ fine particles. Thus, Li _0.20 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) according to Comparative Example 2 were produced.

As a result of identifying the crystal phase of the fired powder according to Comparative Example 2 by X-ray diffraction, only the peak attributed to Cs _0.33 WO ₃ was observed. Further, the ratio c / a of the lattice constant is 1.029114, which is larger than the ratio c / a of the lattice constant of the Cs _0.33 WO ₃ fine particles not containing lithium, and lithium is dissolved. It was confirmed that

Next, production of a heat ray shielding resin sheet material was carried out in the same manner as in Example 1 so that Li _0.20 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) would be 8 wt% in terms of Cs _0.33 WO _3. Dispersion liquid (Liquid A) was prepared, and a heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) according to Comparative Example 2 was produced in the same manner as in Example 1.

The content of Li _0.20 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) per 1 m ^{2 of the} obtained heat ray shielding resin sheet material was 1.2 g. Further, the dispersed particle diameter of the composite tungsten oxide B fine particles in the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) was 64 nm.

  And like Example 1, when the optical characteristic of the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) which concerns on the comparative example 2 was measured, as shown in Table 1, when visible light transmittance | permeability is 70.0% The solar transmittance was 35.5% and the haze value was 1.1%.

  In addition, ΔVLT after 72 hours in the heat resistance test was 1.90%, and ΔST after 72 hours was 1.61%, which was confirmed to be inferior in heat resistance as compared with Examples 1 to 4 described above. It was done. In Comparative Example 2, the wet heat resistance test was not performed.

[Example 5]
A dispersion (Liquid A) for producing a heat ray shielding resin sheet material in which Li _0.002 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) prepared in Example 1 are dispersed is used with respect to a polycarbonate resin. , Li _0.002 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) were added so that the concentration was 0.05% by weight, mixed with a blender, and uniformly melt-kneaded with a twin-screw extruder. Thereafter, it was coextruded on a 2 mm thick polycarbonate sheet to a thickness of 50 μm, and the 2 mm thick polycarbonate sheet and fine particles (composite tungsten oxide B having a heat ray shielding function) laminated on the sheet. A heat ray shielding polycarbonate laminate (heat) according to Example 5 composed of a heat ray shielding resin sheet material having a thickness of 50 μm in which fine particles are uniformly dispersed throughout. To prepare a shielding resin sheet material laminate).

Content of Li _0.002 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) per 1 m ^{2 of the} heat ray shielding resin sheet material in the obtained heat ray shielding polycarbonate laminate (heat ray shielding resin sheet laminate). Was 1.2 g. Moreover, the dispersed particle diameter of the composite tungsten oxide B fine particles in the heat ray shielding resin sheet material was 52 nm.

  And like Example 1, when the optical characteristic of the heat ray shielding polycarbonate laminated body (heat ray shielding resin sheet material laminated body) which concerns on Example 5 was measured, as shown in Table 1, visible light transmittance | permeability 70.2% The solar transmittance at that time was 34.6%, and the haze value was 1.1%.

  In addition, ΔVLT after 72 hours in the heat resistance test was 0.62%, and ΔST after 72 hours was 0.12%, confirming an improvement in heat resistance as compared with Comparative Example 1. In Example 5, the wet heat resistance test was not performed.

[Example 6]
After mixing 30% by weight of antimony-doped tin oxide (ATO) fine particles with a specific surface area of 43.7 m ² / g, 65% by weight of methyl isobutyl ketone, and 5% of a dispersant, the mixture was filled into a container with 0.15 mmφ glass beads. A dispersion of ATO fine particles (liquid B) was prepared by performing a bead mill dispersion treatment for 5 hours.

Next, a dispersion for producing a heat ray shielding resin sheet material (Liquid A) in which Li _0.002 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) prepared in Example 1 are dispersed, and the ATO fine particles described above. (Liquid B) was added to the polycarbonate resin so that the concentration of Li _0.002 Cs _0.33 WO ₃ fine particles was 0.024 wt% and the concentration of the ATO fine particles was 0.015 wt%. , Mixed with a blender, uniformly melt-kneaded with a twin screw extruder, extruded to a thickness of 2 mm using a T-die, and fine particles having a heat ray shielding function (Li _0.002 Cs _0.33 WO ₃ fine particles and A heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) according to Example 6 in which ATO fine particles) were uniformly dispersed throughout was produced.

The content of the fine particles (Li _0.002 Cs _0.33 WO ₃ fine particles and ATO fine particles) per 1 m ^{2 of the} obtained heat ray shielding resin sheet material was 0.58 g. Further, the dispersed particle size of the fine particles (Li _0.002 Cs _0.33 WO ₃ fine particles) in the heat ray-shielding polycarbonate sheet material (heat ray-shielding resin sheet material) was 56 nm.

  And like Example 1, when the optical characteristic of the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) based on Example 6 was measured, as shown in Table 1, when the visible light transmittance was 71.0% The solar transmittance was 34.7%, and the haze value was 1.1%.

  In addition, ΔVLT after 72 hours in the heat resistance test was 0.62%, and ΔST after 72 hours was 0.12%, confirming an improvement in heat resistance as compared with Comparative Example 1. In Example 6, the above heat and humidity resistance test was not performed.

[Example 7]
20% by weight of lanthanum hexaboride (LaB ₆ ) particles having an average particle diameter of about 1 μm, 5% by weight of a polymeric dispersant, and 75% by weight of toluene are dispersed for 24 hours in a paint shaker containing 0.3 mmφZrO ₂ beads. Thus, a dispersion (liquid C) of LaB ₆ particles having an average dispersed particle diameter of 86 nm was prepared.

Next, a dispersion for manufacturing a heat ray shielding resin sheet (Liquid A) in which Li _0.002 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) prepared in Example 1 are dispersed, and LaB ₆ described above. The particle dispersion (liquid C) is mixed with polycarbonate resin so that the concentration of Li _0.002 Cs _0.33 WO ₃ fine particles is 0.022 wt% and the concentration of the LaB ₆ particles is 0.001 wt%. Add, mix with a blender, melt and knead uniformly with a twin screw extruder, extrude to a thickness of 2 mm using a T-die, and fine particles having a heat ray shielding function (Li _0.002 Cs _0.33 WO ₃ A heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) according to Example 7 in which fine particles and LaB ₆ particles) were uniformly dispersed throughout was produced.

The content of the fine particles (Li _0.002 Cs _0.33 WO ₃ fine particles and LaB ₆ particles) per 1 m ^{2 of the} obtained heat ray shielding resin sheet material was 0.53 g. Further, the dispersed particle diameter of the fine particles (Li _0.002 Cs _0.33 WO ₃ fine particles) in the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) was 62 nm.

  And like Example 1, when the optical characteristic of the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) which concerns on Example 7 was measured, as shown in Table 1, when visible light transmittance | permeability is 70.3%. The solar transmittance was 34.3%, and the haze value was 1.3%.

  In addition, ΔVLT after 72 hours in the above heat test was 0.67%, and ΔST after 72 hours was 0.15%, confirming the improvement in heat resistance as compared with Comparative Example 1 above. In Example 7, the wet heat resistance test was not performed.

[Example 8]
Li _0.002 Cs _0.33 WO ₃ fine particles 9.4 wt% (Cs _0.33 WO ₃ equivalent 8 wt%), polymeric dispersant (solid content 40%) 8 wt%, toluene 82.6 The weight% was weighed and replaced with the paint shaker for 8 hours using a paint shaker containing 0.3 mmφZrO ₂ beads. A heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) was produced in the same manner as in Example 1.

The content of Li _0.002 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) per 1 m ^{2 of the} obtained heat ray shielding resin sheet material was 1.2 g. Moreover, the dispersed particle diameter of the composite tungsten oxide B fine particles in the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) was 100 nm.

  And like Example 1, when the optical characteristic of the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) which concerns on Example 8 was measured, as shown in Table 1, when visible light transmittance | permeability is 70.0% The solar transmittance was 34.4% and the haze value was 1.3%.

  In the heat resistance test, ΔVLT after 72 hours was 0.58%, and ΔST after 72 hours was 0.07%, confirming the improvement in heat resistance as compared with Comparative Example 1. In Example 8, the wet heat resistance test was not performed.

[Example 9]
Li _0.002 Cs _0.33 WO ₃ fine particles 9.4 wt% (Cs _0.33 WO ₃ equivalent 8 wt%), polymeric dispersant (solid content 40%) 8 wt%, toluene 82.6 The weight% was weighed, and the pulverization / dispersion treatment time in the paint shaker was changed to 4 hours in place of the conditions of Example 1 in which the pulverization / dispersion treatment was performed for 8 hours in the paint shaker containing 0.3 mmφZrO ₂ beads. A heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) was produced in the same manner as in Example 1.

The content of Li _0.002 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) per 1 m ^{2 of the} obtained heat ray shielding resin sheet material was 1.1 g. Further, the dispersed particle diameter of the composite tungsten oxide B fine particles in the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) was 180 nm.

  And like Example 1, when the optical characteristic of the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) which concerns on Example 9 was measured, as shown in Table 1, when the visible light transmittance | permeability is 70.0% The solar transmittance was 36.4% and the haze value was 1.8%.

  In addition, ΔVLT after 72 hours in the heat resistance test was 0.47%, and ΔST after 72 hours was 0.02%, confirming an improvement in heat resistance as compared with Comparative Example 1 above. In Example 9, the wet heat resistance test was not performed.

[Comparative Example 3]
As in Example 1, except that 0.133 g of lithium carbonate was added instead of the condition of Example 1 in which 2.68 × 10 ⁻³ g of lithium carbonate was added to 10 g of Cs _0.33 WO ₃ fine particles. Thus, Li _0.10 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) according to Comparative Example 3 were produced.

In addition, as a result of the identification of the crystal phase by X-ray diffraction of the fired powder according to Comparative Example 3, only the peak attributed to Cs _0.33 WO ₃ was observed. Further, the lattice constant ratio c / a is 1.029107, which is larger than the lattice constant ratio c / a of the Cs _0.33 WO ₃ fine particles not containing lithium, and lithium is dissolved. It was confirmed that

Next, production of a heat ray shielding resin sheet material was carried out in the same manner as in Example 1 so that Li _0.10 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) would be 8 wt% in terms of Cs _0.33 WO _3. Dispersion liquid (Liquid A) was prepared, and a heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) according to Comparative Example 3 was produced in the same manner as in Example 1.

The content of Li _0.10 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) per 1 m ^{2 of the} obtained heat ray shielding resin sheet material was 1.2 g. Further, the dispersed particle diameter of the composite tungsten oxide B fine particles in the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) was 64 nm.

  And like Example 1, when the optical characteristic of the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) which concerns on the comparative example 3 was measured, as shown in Table 1, when the visible light transmittance | permeability is 70.0% The solar transmittance was 35.3% and the haze value was 1.1%.

  In addition, ΔVLT after 72 hours in the heat resistance test was 1.84%, and ΔST after 72 hours was 1.57%, which was confirmed to be inferior in heat resistance as compared with Examples 1 to 9 described above. It was done. In Comparative Example 3, the wet heat resistance test was not performed.

［評 価］
（１）Ｃｓ_０．３３ＷＯ_３微粒子（複合タングステン酸化物Ａ微粒子）の格子定数の比ｃ／ａよりも大きく、その数値が１．０２９０００以下であるリチウムが固溶した「複合タングステン酸化物Ｂ微粒子」を、熱線遮蔽機能を有する微粒子として適用した実施例１〜９に係る熱線遮蔽ポリカーボネートシート材（熱線遮蔽樹脂シート材）と熱線遮蔽ポリカーボネート積層体（熱線遮蔽樹脂シート材積層体）は、可視光透過率６９．０〜７１．０％のときの日射透過率が全て３７％未満であり、上記耐熱試験における７２時間後のΔＶＬＴが全て１．０％未満、７２時間後のΔＳＴも全て０．５％未満であり、しかも、実施例１の上記耐湿熱試験における７２時間後のΔＶＬＴは１．２１％で、７２時間後のΔＳＴは０．５２％である。

[Evaluation]
(1) “Compound Tungsten Oxide B” in which lithium having a value larger than the lattice constant ratio c / a of Cs _0.33 WO ₃ fine particles (composite tungsten oxide A fine particles) and having a numerical value of 1.029000 or less The heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) and the heat ray shielding polycarbonate laminate (heat ray shielding resin sheet material laminate) according to Examples 1 to 9 in which “fine particles” are applied as fine particles having a heat ray shielding function are visible. The solar transmittances when the light transmittance is 69.0 to 71.0% are all less than 37%, ΔVLT after 72 hours in the heat test is less than 1.0%, and ΔST after 72 hours is all 0 In addition, the ΔVLT after 72 hours in the above-described wet heat resistance test of Example 1 is 1.21%, and the ΔST after 72 hours is 0.52%.

  Therefore, the heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) and the heat ray shielding polycarbonate laminate (heat ray shielding resin sheet material laminate) according to Examples 1 to 9 have excellent visible light transmittance and good heat ray shielding properties. It is confirmed that it can be widely used for building roofs, domes, skylights, arcades, carports, green houses, building windows, building walls, vehicle windows, automotive windows, etc. And it is confirmed that it is excellent in heat resistance and heat-and-moisture resistance of visible light transmittance and heat ray shielding performance.

(2) On the other hand, a heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) according to Comparative Example 1 in which Cs _0.33 WO ₃ fine particles (composite tungsten oxide A fine particles) are applied as fine particles having a heat ray shielding function, Although the solar radiation transmittance when the visible light transmittance is 70.0% is less than 36%, ΔVLT after 72 hours in the heat resistance test exceeds 1.30% and 1.0%, and after 72 hours. ΔST is also inferior to each example because it exceeds 0.86% and 0.5%. In addition, ΔVLT after 72 hours in the heat and humidity resistance test is 1.99%, and ΔST after 72 hours is 1.15. It is confirmed that there is a problem in heat resistance / humidity heat resistance of visible light transmittance and heat ray shielding performance.

(3) The composition ratio x of Li element is 0.20 and 0.10, which is outside the above-mentioned “0.0001 ≦ x <0.1” range, and Cs _0.33 WO ₃ fine particles ( Li _0.20 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) and Li which are larger than the lattice constant ratio c / a of the composite tungsten oxide A fine particles) and whose numerical value exceeds 1.029000 Heat ray shielding polycarbonate sheet material (heat ray shielding resin sheet material) according to Comparative Example 2 and Comparative Example 3 in which _0.10 Cs _0.33 WO ₃ fine particles (composite tungsten oxide B fine particles) are applied as fine particles having a heat ray shielding function The solar radiation transmittance when the visible light transmittance is 70.0% is less than 36%, but the ΔVLT after 72 hours in the heat resistance test is 1.90% and 1.84%, respectively. In addition, ΔST after 72 hours was 1.61% and 1.57%, respectively, exceeding 0.5%, which is inferior to each example. Similar to Comparative Example 1, visible light transmittance and heat ray shielding It is confirmed that there is a problem with the heat and moisture resistance of the performance.

  Since the heat ray shielding resin sheet material and the heat ray shielding resin sheet material laminate according to the present invention are excellent in heat resistance in addition to visible light permeability and heat ray shielding properties, the roof, dome, skylight, arcade of buildings It has industrial applicability widely used for carports, green houses, building windows, building walls, vehicle windows, automobile windows and the like.

1 WO ₆ units 2 Element (M)
DESCRIPTION OF SYMBOLS 10 Heat ray shielding resin sheet material 11 Surface sheet layer 12 Surface sheet layer 13 Intermediate sheet layer 14 Connection sheet layer 20 Heat ray shielding resin sheet material 21 Surface sheet layer 22 Surface sheet layer 23 Intermediate sheet layer 24 Intermediate sheet layer 25 Intermediate sheet layer 26 Intermediate Sheet layer 27 Connection sheet layer 28 Connection sheet layer

Claims (13)

In a heat ray shielding resin sheet material containing fine particles having a heat ray shielding function in a resin base material that transmits visible light,
The fine particles having the heat ray shielding function are represented by the general formula LixMyWOz (where Li is lithium, M is one or more elements selected from Cs, Rb, K, Na, Ba, Ca, Sr, Mg, W is Tungsten, O is oxygen, 0.0001 ≦ x <0.1, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) The ratio of lattice constant c / a is selected from the general formula MyWOz (where M is selected from Cs, Rb, K, Na, Ba, Ca, Sr, Mg). 1 or more elements, W is tungsten, O is oxygen, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) Greater than / a, the numerical value is 1.027300 to 1.029000 There, and the heat ray shielding resin sheet material, characterized in that the dispersion particle diameter of 1nm or more 500nm or less.   General formula MyWOz (where M is one or more elements selected from Cs, Rb, K, Na, Ba, Ca, Sr, Mg, W is tungsten, O is oxygen, 0.1 ≦ y ≦ 0 .5, 2.2 ≦ z ≦ 3.0) and a mixture of a compound having a lithium element and a compound having a lithium element is calcined in the atmosphere or in an inert gas atmosphere, and then reduced gas. The fine particles of the composite tungsten oxide B according to claim 1 expressed by the general formula LixMyWOz are obtained by heat treatment in an atmosphere or a mixed atmosphere of a reducing gas and an inert gas. Item 2. The heat ray shielding resin sheet material according to Item 1. 3. The heat ray shielding resin sheet material according to claim 1, wherein the content of the fine particles having a heat ray shielding function is 0.05 g to 45 g per 1 m ² of the heat ray shielding resin sheet material. The fine particles having a heat ray shielding function are
The fine particles of the composite tungsten oxide B according to claim 1 represented by the general formula LixMyWOz;
Sb, V, Nb, Ta, Zr, F, Zn, Al, Ti, Pb, Ga, Re, Ru, P, Ge, In, Sn, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Tb, Lu, Sr, at least one of oxide fine particles, composite oxide fine particles, and boride fine particles containing two or more elements selected from the group consisting of The heat ray shielding resin sheet material according to any one of claims 1 to 3, comprising fine particles.   The heat ray shielding resin sheet material according to any one of claims 1 to 4, wherein the resin base material is composed of a polycarbonate resin or an acrylic resin.   The heat ray shielding resin sheet material according to any one of claims 1 to 5, a surface sheet layer constituting one surface of the sheet material, and a surface sheet layer constituting the other one surface of the sheet material, A heat ray shielding resin sheet material comprising a hollow multilayer structure having an intermediate sheet layer formed between the two surface sheet layers and a connection sheet layer connecting the sheet layers.   The heat ray shielding resin sheet material according to claim 6, wherein all of the sheet layer contains fine particles having a heat ray shielding function according to claim 1.   The fine particles having a heat ray shielding function according to any one of claims 1 to 4 are contained in only one layer of the surface sheet layer constituting one surface of the sheet material. Heat ray shielding resin sheet material.   The heat ray according to claim 6, wherein the fine particles having the heat ray shielding function according to any one of claims 1 to 4 are contained only in two layers of the surface sheet layer constituting the surface of the sheet material. Shielding resin sheet material.   A heat ray shielding resin sheet material, wherein a resin film containing an ultraviolet absorber is formed on at least one sheet surface of the heat ray shielding resin sheet material according to claim 1.   A heat-ray shielding resin sheet material, wherein an abrasion-resistant hard coat layer is formed on at least one sheet surface of the heat-ray shielding resin sheet material according to claim 1.   A heat ray shielding resin sheet material laminate obtained by laminating the heat ray shielding resin sheet material according to any one of claims 1 to 11 on another resin sheet material.   The heat ray shielding resin sheet material in any one of Claims 1-11, and / or the heat ray shielding resin sheet material laminated body of Claim 12 are used, The building structure characterized by the above-mentioned.

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