Laminated structure for solar radiation shading

Abstract

To provide a laminated structure for cutting off sunlight which has near infrared absorption characteristics and visible light permeability, and is also excellent in weather resistance.SOLUTION: A laminated structure for cutting off sunlight has two laminated boards selected from plate glass and plate-shaped plastic, and an intermediate layer arranged between the two laminated boards, in which the one or more members selected from the laminated boards and the intermediate layer contain sunlight cutting off function material particles, and the sunlight cutting off function material particles contain particles of a composite tungsten oxide represented by general formula MxWyOz, in the general formula, an element M is one or more elements selected from H, He, an alkali metal, an alkali earth metal, a rare earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi and I, and 0.001≤x / y≤1 and 3.0<z / y).SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a laminated structure for solar shading. [Background technology]

[0002] Conventionally, a laminated structure for solar shading has been proposed as safety glass for use in automobiles, etc., in which a solar shading layer is sandwiched between two sheets of glass to form a laminated glass. Such a laminated structure for solar shading is intended to block incoming solar energy and reduce the cooling load and people's sense of heat.

[0003] For example, Patent Document 1 discloses laminated glass in which a soft resin layer containing a heat ray shielding metal oxide, either tin oxide or indium oxide, having a particle size of 0.1 μm or less, is interposed between a pair of glass plates.

[0004] Patent Document 2 discloses a laminated glass having an interlayer film between at least two transparent glass plates, characterized in that functional ultrafine particles having a particle size of 0.2 μm or less are dispersed in the interlayer film. Examples of the functional ultrafine particles include metals such as Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, and Mo, oxides, nitrides, and sulfides, or doped with Sb or F, or composites of at least two or more of these, or mixtures of the above-mentioned single substances or composites with organic resins or coatings of organic resins.

[0005] However, the conventional laminated glass disclosed in Patent Documents 1 and 2 both have the problem that they do not provide sufficient solar radiation shielding function when high visible light transmittance is required.

[0006] Therefore, the applicant of this patent has developed a compound having the general formula W y O z(However, W is tungsten, O is oxygen, and 2.0 < x / y < 3.0) fine particles of tungsten oxide and / or general formula M x W y O z (However, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.0 < z / y ≦ 3.0) An intermediate layer containing fine particles of composite tungsten oxide is provided between two sheets of laminated glass selected from plate glass, plastic, and plastic containing particles having a solar radiation shielding function. A solar radiation shielding laminated structure is proposed. As described in Patent Document 3, in the laminated glass for solar radiation shielding to which composite tungsten oxide particles are applied, the solar radiation transmittance at a visible light transmittance of 76.0% or less is improved to less than 50.0% in all cases.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0008] However, in recent years, performance such as weather resistance has also been required for solar radiation shielding laminated structures.

[0009] One aspect of the present invention aims to provide a solar radiation shielding laminated structure having near-infrared absorption characteristics, visible light transmittance, and excellent weather resistance.

Means for Solving the Problems

[0010] One aspect of the present invention includes two laminated plates selected from plate glass and plate-shaped plastic, an intermediate layer disposed between the two laminated plates, At least one member selected from the laminate and the intermediate layer contains solar radiation shielding functional material particles; The solar radiation shielding functional material particles are represented by the general formula M x W y O z (However, the M element is Cs, Li, Na, K, Rb, Cu, Ag, Ca, Sr, Ba, In, Tl , Sn, Yb, S i or One or more elements selected from the above, W is tungsten, O is oxygen, 0.001≦x / y≦1, 3.0 <z / y <3.4 ) containing composite tungsten oxide particles death, The particle diameter of the solar radiation shielding functional material particles is 10 nm or more and 100 nm or less. A laminated structure for solar shading is provided. Effect of the Invention

[0011] According to one aspect of the present invention, there is provided a laminated structure for solar radiation shading which has near-infrared absorbing properties, visible light transmittance, and excellent weather resistance. [Brief description of the drawings]

[0012] [Figure 1] FIG. 2 is an explanatory diagram of a hybrid plasma reactor used in Example 1. [Diagram 2] FIG. 1 is an explanatory diagram of a high-frequency plasma reaction apparatus used in Example 2. [Diagram 3] FIG. 2 is a cross-sectional view of an example of a solar radiation shading laminated structure. [Figure 4] FIG. 11 is a cross-sectional view of another example of the configuration of the solar radiation shading laminated structure. [Diagram 5] FIG. 11 is a cross-sectional view of another example of the configuration of the solar radiation shading laminated structure. [Figure 6] FIG. 11 is a cross-sectional view of another example of the configuration of the solar radiation shading laminated structure. [Figure 7] FIG. 11 is a cross-sectional view of another example of the configuration of the solar radiation shading laminated structure. [Figure 8] FIG. 11 is a cross-sectional view of another example of the configuration of the solar radiation shading laminated structure. [Figure 9] FIG. 11 is a cross-sectional view of another example of the configuration of the solar radiation shading laminated structure. [Figure 10] Cross-sectional view of another configuration example of the combined structure for solar radiation shielding.

Embodiments for Carrying Out the Invention

[0013] Hereinafter, the solar radiation shielding functional material particles that can be suitably used for the combined structure for solar radiation shielding according to the present embodiment, and the manufacturing method thereof will be first described in "1. Solar radiation shielding functional material particles" and "2. Manufacturing method of solar radiation shielding functional material particles". Thereafter, in "3. Combined structure for solar radiation shielding" and "4. Manufacturing method of dispersion liquid, additive liquid, and coating liquid of solar radiation shielding functional material particles", the combined structure for solar radiation shielding of the present embodiment, and the manufacturing method of dispersion liquid and the like that can be used when manufacturing the combined structure for solar radiation shielding will be described in detail. 1. Solar radiation shielding functional material particles The solar radiation shielding functional material particles according to the present embodiment can contain particles of a composite tungstate represented by the general formula M x W y O z Note that the M element in the above general formula is one or more elements selected from H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I. W is tungsten and O is oxygen. x, y, and z can satisfy 0.001 ≦ x / y ≦ 1 and 3.0 < z / y.

[0014]

[0015] In order to obtain a combined structure for solar radiation shielding with excellent weather resistance, it is conceivable that the solar radiation shielding functional material particles used are particles with excellent weather resistance. Therefore, in order to obtain solar radiation shielding functional material particles with excellent weather resistance, the inventors of the present invention have conducted intensive research. In this specification, excellent weather resistance means that the near-infrared absorption characteristics do not change significantly even when placed in a high-temperature environment.

[0016] ​ In general, it is known that materials containing free electrons show a reflection / absorption response due to plasma oscillation to electromagnetic waves with wavelengths of 200 nm to 2600 nm, which is the range around the solar radiation. It is also known that when the powder of the material containing free electrons is made into particles smaller than the wavelength of light, the geometric scattering in the visible light range (wavelengths of 380 nm to 780 nm) is reduced, and transparency in the visible light range is obtained. In this specification, the term "transparency" is used to mean low scattering and high transmittance for light in the visible light range.

[0017] General formula WO 3-a Tungsten oxide represented by the formula (1) and tungsten bronze, which is tungsten trioxide with an added electropositive element such as Na, are known to be conductive materials that contain free electrons. Analysis of single crystals of these materials suggests that the free electrons respond to light in the near-infrared region.

[0018] Generally, tungsten trioxide (WO 3 ) has no effective free electrons, so it has little absorption / reflection characteristics in the near-infrared region and is not effective as a near-infrared absorbing material. However, it is known that by reducing the ratio of oxygen to tungsten in tungsten trioxide to less than 3, free electrons are generated in the tungsten oxide.

[0019] Also, it has been conventional to add an element M to the tungsten oxide to form a composite tungsten oxide. This is because, with this composition, free electrons are generated in the composite tungsten oxide, and absorption characteristics derived from the free electrons appear in the near-infrared region, making it effective as a near-infrared absorbing material with a wavelength of around 1000 nm.

[0020] The inventors of the present invention have further studied tungsten oxide and composite tungsten oxide in order to obtain solar radiation shielding functional material particles with excellent weather resistance. As a result, they have found that the tungsten oxide represented by the general formula M x W y O zIn the solar radiation shielding functional material particles containing particles of a composite tungsten oxide represented by the following, it has been found that by setting 3.0 < z / y with respect to y and z in the above general formula, both near-infrared absorption characteristics and weather resistance can be achieved, and the present invention has been completed.

[0021] The solar radiation shielding functional material particles of the present embodiment are, as described above, of the general formula M x W y O z It can contain particles of a composite tungsten oxide represented by. The solar radiation shielding functional material particles of the present embodiment can also be composed of particles of a composite tungsten oxide represented by the above general formula. However, even in this case, it does not exclude containing inevitable components mixed in during the manufacturing process or the like.

[0022] Here, the M element in the above general formula is, from the viewpoint of enhancing stability, as described above, H, He, an alkali metal, an alkaline earth metal, a rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, and is preferably one or more elements selected from these. In particular, from the viewpoint of particularly improving the optical characteristics and weather resistance as a near-infrared absorbing material, the M element is more preferably one belonging to an alkali metal, an alkaline earth metal element, a transition metal element, a Group 4B element, or a Group 5B element.

[0023] When the particles of the composite tungsten oxide contain a crystal having a hexagonal crystal structure, the transmittance of the particles in the visible light region is particularly improved, and the absorption in the near-infrared region is particularly improved. The hexagonal crystal structure is formed by six octahedrons formed by WO 6 units gathering to form a hexagonal void (tunnel), with the M element arranged in the void to form one unit, and a large number of these units gathering to form the structure.

[0024] In addition, the composite tungsten oxide particles are not limited to those containing crystals having a hexagonal crystal structure, and may be, for example, the above unit structure, i.e., WO 6 If the structure has a structure in which six octahedrons formed as units are assembled to form hexagonal voids and the M element is arranged in the voids, the transmittance in the visible light region can be particularly improved and the absorption in the near infrared region can be particularly improved. Therefore, even if the composite tungsten oxide particles do not contain crystals having a hexagonal crystal structure and only have the above unit structure, a high effect can be obtained.

[0025] As described above, when the composite tungsten oxide particles contain a structure in which cations of M element are added to hexagonal voids, the absorption in the near infrared region is particularly improved. Here, generally, when an M element with a large ionic radius is added, a hexagonal crystal or the above structure is easily formed. Specifically, when the composite tungsten oxide contains one or more elements selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn as the M element, the hexagonal crystal or the above structure is easily formed. For this reason, the composite tungsten oxide particles preferably contain one or more elements selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn as the M element, and more preferably, the M element is one or more elements selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn.

[0026] Furthermore, in particles of a composite tungsten oxide containing one or more elements selected from Cs and Rb among these M elements having a large ionic radius, hexagonal crystals or the above-mentioned structure are easily formed, and the particles can achieve both absorption in the near-infrared region and transmission in the visible light region and exhibit particularly high performance.

[0027] When the particles of the composite tungsten oxide having a hexagonal crystal structure have a uniform crystal structure, x / y, which indicates the content ratio of the M element to 1 mole of tungsten, is preferably 0.2 or more and 0.5 or less, and more preferably 0.33. When the value of x / y is 0.33, it is considered that the element M is arranged in all of the hexagonal voids.

[0028] Composite tungsten oxide particles containing crystals other than the above-mentioned hexagonal crystals, such as tetragonal crystals or cubic crystals, are also effective as a near-infrared absorbing material.

[0029] The cubic and tetragonal composite tungsten oxides each have a suitable range and upper limit of the amount of element M added that are derived from the structure, and the upper limit of x / y, which is the content ratio of M element to 1 mole of tungsten, is 1 mole in the case of cubic crystals, and about 0.5 moles in the case of tetragonal crystals. Note that the upper limit of x / y, which is the content ratio of M element to 1 mole of tungsten, varies depending on the type of M element, etc., but in the case of tetragonal crystals, ... it is about 0.5 moles that is easy to industrially manufacture.

[0030] However, it is difficult to simply define these structures, and the above ranges are merely examples showing basic ranges, and the present invention is not limited to these.

[0031] The absorption position in the near-infrared region tends to change depending on the crystal structure contained in the composite tungsten oxide particles, and the absorption position in the near-infrared region tends to move to the longer wavelength side in tetragonal crystals than in cubic crystals, and furthermore, the hexagonal crystals tend to move to the longer wavelength side than in tetragonal crystals. In addition, accompanying the change in the absorption position, the absorption in the visible light region is the least in hexagonal crystals, followed by tetragonal crystals, and the cubic crystals are the most. Therefore, it is preferable to select the crystal system to be contained according to the required performance. For example, when used in an application that requires more transmission of light in the visible light region and more absorption of light in the near-infrared region, it is preferable that the composite tungsten oxide particles contain hexagonal crystals. However, the tendency of the optical characteristics described here is merely a rough tendency, and it also changes depending on the type of added element, the added amount, and the amount of oxygen, and the present invention is not limited thereto.

[0032] By using the above-described control of the oxygen amount and the addition of element M that generates free electrons in combination for the composite tungsten oxide, a more efficient near-infrared absorbing material with excellent weather resistance can be obtained. The general formula of the composite tungsten oxide, which is a near-infrared absorbing material obtained by combining the control of the oxygen amount and the addition of an element that generates free electrons, is M x W y O z When described as above, x and y can satisfy 0.001 ≦ x / y ≦ 1, and preferably satisfy 0.20 ≦ x / y ≦ 0.37.

[0033] Also, y and z in the above general formula satisfy the relationship of 3.0 < z / y, preferably satisfy 3.0 < z / y < 3.4, more preferably satisfy 3.0 < z / y < 3.3, and even more preferably satisfy 3.0 < z / y < 3.22.

[0034] According to the study of the present applicant, for composite tungsten oxide particles having a hexagonal crystal structure, when z / y = 3, the value of x / y becomes 0.33, and it is considered that element M is arranged in all of the hexagonal voids.

[0035] It has been confirmed by chemical analysis that the composite tungsten oxide particles contained in the solar radiation shielding functional material particles according to the present embodiment have z / y exceeding 3. On the other hand, it has been confirmed by powder X-ray diffraction that the composite tungsten oxide particles contained in the solar radiation shielding functional material particles according to the present embodiment may take at least one of a tetragonal, cubic, and hexagonal tungsten bronze structure when z / y = 3. Therefore, the particles of the composite tungsten oxide contained in the solar radiation shielding functional material particles according to the present embodiment preferably contain crystals having one or more crystal structures selected from hexagonal, tetragonal, and cubic crystals. By containing crystals having the above crystal structures, particularly excellent near-infrared absorption characteristics and visible light transmittance characteristics can be exhibited.

[0036] Incidentally, it is believed that oxygen atoms penetrate into the crystals of composite tungsten oxide particles when the z / y value exceeds 3. As a result, it is believed that the penetration of oxygen atoms into the crystals prevents the crystals of the composite tungsten oxide particles from being altered even when exposed to heat or moisture, thereby realizing excellent weather resistance.

[0037] The crystal structure of the composite tungsten oxide particles contained in the solar radiation shielding material particles according to this embodiment can be confirmed from the X-ray diffraction pattern by powder X-ray diffraction method (θ-2θ method).

[0038] The solar radiation shielding functional material particles of this embodiment exhibit light transmission characteristics having a maximum value in the wavelength range of 350 nm to 600 nm and a minimum value in the wavelength range of 800 nm to 2100 nm, and can exhibit excellent near-infrared absorption effect and weather resistance. It is more preferable that the solar radiation shielding functional material particles of this embodiment have a maximum value in the wavelength range of 440 nm to 600 nm and a minimum value in the wavelength range of 1150 nm to 2100 nm.

[0039] In addition, the particle diameter of the solar radiation shielding functional material particles according to this embodiment is preferably 100 nm or less. From the viewpoint of exhibiting better near-infrared absorbing properties, the particle diameter is more preferably 10 nm or more and 100 nm or less, even more preferably 10 nm or more and 80 nm or less, particularly preferably 10 nm or more and 60 nm or less, and most preferably 10 nm or more and 40 nm or less. When the particle diameter of the solar radiation shielding functional material particles is in the range of 10 nm or more and 40 nm or less, the best near-infrared absorbing properties are exhibited.

[0040] Here, the particle size refers to the size of each individual particle of the solar radiation shielding material that is not aggregated, that is, the particle size of each individual particle.

[0041] The particle size here does not include the size of an aggregate of the solar radiation shielding material particles, and is different from the dispersed particle size.

[0042] The particle size here can be calculated by, for example, measuring the particle size of a plurality of particles using a transmission electron microscope (TEM) or the like while the solar radiation shielding functional material particles are dispersed. Since the solar radiation shielding functional material particles are usually irregular in shape, the diameter of the smallest circle circumscribing the particle can be taken as the particle size of the particle. For example, when the particle sizes of a plurality of particles are measured for each particle as described above using a transmission electron microscope, it is preferable that the particle sizes of all particles satisfy the above range. The number of particles to be measured is not particularly limited, but is preferably, for example, 10 to 50.

[0043] In addition, from the viewpoint of exhibiting excellent near-infrared absorbing properties, the crystallite diameter of the composite tungsten oxide particles is preferably 10 nm or more and 100 nm or less, more preferably 10 nm or more and 80 nm or less, even more preferably 10 nm or more and 60 nm or less, and particularly preferably 10 nm or more and 40 nm or less. If the crystallite diameter is in the range of 10 nm or more and 40 nm or less, particularly excellent near-infrared absorbing properties are exhibited. The crystallite diameter of the composite tungsten oxide particles contained in the solar radiation shielding functional material particles can be calculated by the Rietveld method from the X-ray diffraction pattern measured by the powder X-ray diffraction method (θ-2θ method).

[0044] The general formula of the composite tungsten oxide contained in the composite tungsten oxide particles is M x W y O z In the case where the M element contains one or more elements selected from Cs and Rb and the composite tungsten oxide has a hexagonal crystal structure, the lattice constant of the composite tungsten oxide is preferably 7.3850 Å or more and 7.4186 Å or less for the a-axis and 7.5600 Å or more and 7.6240 Å or less for the c-axis. By setting the above lattice constant for the composite tungsten oxide, particularly excellent properties can be realized in terms of near-infrared absorption characteristics and weather resistance. In the above case, it is more preferable that the M element is composed of one or more elements selected from Cs and Rb. The above lattice constant can be calculated using the Rietveld method.

[0045] In addition, since the solar radiation shielding functional material particle dispersion containing the composite tungsten oxide particles according to this embodiment largely absorbs light in the near infrared region, particularly light with a wavelength of about 1000 nm, the transmitted color tone is often blue to green.

[0046] The dispersion particle diameter of the solar radiation shielding functional material particles of this embodiment can be selected according to the purpose of use. First, when used in an application that requires transparency, it is preferable that the dispersion particle diameter is 800 nm or less. This is because particles with a dispersion particle diameter of 800 nm or less do not completely shield light by scattering, and can maintain visibility in the visible light range while efficiently maintaining transparency.

[0047] In particular, when transparency in the visible light region is important, it is preferable to further consider scattering by particles. Note that the dispersed particle size includes the size of an aggregate of the solar radiation shielding material particles, and is different from the particle size described above.

[0048] When the reduction of scattering by the above particles is important, the dispersion particle diameter of the solar radiation shielding functional material particles of this embodiment is preferably 200 nm or less, more preferably 10 nm or more to 200 nm or less, and even more preferably 10 nm or more to 100 nm or less. This is because if the dispersion particle diameter is small, the scattering of light in the visible light region of wavelengths 380 nm or more to 780 nm or less due to geometric scattering or Mie scattering is reduced, and it is possible to avoid the dispersion containing the solar radiation shielding functional material particles of this embodiment becoming like cloudy glass and not being able to obtain clear transparency. That is, when the dispersion particle diameter is 200 nm or less, the above geometric scattering or Mie scattering is reduced and the Rayleigh scattering region is reached. In the Rayleigh scattering region, the scattered light is proportional to the sixth power of the dispersed particle diameter, so that the scattering is reduced and the transparency is improved as the dispersed particle diameter decreases. Furthermore, when the dispersed particle diameter is 100 nm or less, the scattered light is very small, which is preferable. From the viewpoint of avoiding light scattering, it is preferable that the dispersed particle diameter is small, and if the dispersed particle diameter is 10 nm or more, industrial production is easy.

[0049] By setting the dispersed particle diameter to 800 nm or less, the haze (haze value) of the dispersion of the solar radiation shielding functional material particles in which the solar radiation shielding functional material particles are dispersed in a medium can be set to 10% or less at a visible light transmittance of 85% or less. In particular, by setting the dispersed particle diameter to 100 nm or less, the haze can be set to 1% or less.

[0050] Incidentally, the light scattering of the solar radiation shielding functional material particle dispersion must take into consideration the aggregation of the solar radiation shielding functional material particles, and must be examined in terms of the dispersed particle size. 2. Manufacturing method for solar radiation shielding functional material particles A configuration example of a method for producing solar radiation shielding functional material particles will be described. According to the method for producing solar radiation shielding functional material particles of this embodiment, the above-mentioned solar radiation shielding functional material particles can be produced. Therefore, some of the matters already described will not be described.

[0051] The solar radiation shielding functional material particles of this embodiment contain the above-mentioned general formula M x W y O z The composite tungsten oxide particles represented by the formula (I) can be produced by, for example, the following solid-phase reaction method or plasma method.

[0052] Each method will be explained below. (1) Solid-state reaction method When composite tungsten oxide particles are produced by a solid-state reaction method, the following steps can be included.

[0053] A tungsten compound and an M element compound are mixed to prepare a raw material mixture (mixing step). It is preferable to blend and mix the raw material mixture so that the substance amount ratio (molar ratio) of the M element to tungsten in the raw material mixture is the ratio of x to y in the above general formula of the target composite tungsten oxide particles.

[0054] The raw material mixture obtained in the mixing step is heat-treated in an atmosphere containing oxygen (first heat treatment step).

[0055] The heat-treated product obtained after the first heat treatment step is heat-treated in a reducing gas atmosphere, a mixed gas atmosphere of a reducing gas and an inert gas, or an inert gas atmosphere (second heat treatment step).

[0056] After the second heat treatment step, a crushing process or the like may be carried out as necessary so that the particles of the solar radiation shielding functional material have a desired particle size.

[0057] The solar radiation shielding functional material particles of the present embodiment, including the composite tungsten oxide particles obtained by the above steps, have sufficient near-infrared absorbing power and have properties preferable for solar radiation shielding functional material particles. In addition, the solar radiation shielding functional material particles can be excellent in weather resistance.

[0058] Each step will be described in detail below. (Mixing process) The tungsten compound to be subjected to the mixing step is, for example, tungstic acid (H 2 WO 4 ), ammonium tungstate, tungsten hexachloride, and a tungsten hydrate obtained by hydrolyzing tungsten hexachloride dissolved in alcohol by adding water and then evaporating the solvent.

[0059] The M element compound to be subjected to the mixing step may be, for example, one or more selected from the group consisting of oxides, hydroxides, nitrates, sulfates, chlorides, and carbonates of the M element.

[0060] In the mixing step, when the tungsten compound and the M element compound are mixed, the mass ratio (M:W) of the M element (M) to tungsten (W) in the resulting raw material mixture is adjusted to satisfy the desired general formula M x W y O z It is preferable to mix the raw materials so that x:y is equal to the above.

[0061] The mixing method is not particularly limited, and either wet mixing or dry mixing can be used. In the case of wet mixing, the mixed liquid obtained after wet mixing is dried to obtain a mixed powder of the M element compound and the tungsten compound. The drying temperature and time after wet mixing are not particularly limited.

[0062] The dry mixing may be carried out using a known mixing device such as a commercially available crusher, kneader, ball mill, sand mill, paint shaker, etc., and there are no particular limitations on the mixing conditions such as the mixing time and mixing speed. (First heat treatment process) The heat treatment temperature in the first heat treatment step is not particularly limited, but is preferably higher than the temperature at which the composite tungsten oxide particles crystallize, and more preferably from 500°C to 1000°C, more preferably from 500°C to 800°C. (Second heat treatment process) In the second heat treatment step, as described above, heat treatment can be performed in a reducing gas atmosphere, a mixed gas atmosphere of a reducing gas and an inert gas, or an inert gas atmosphere at a temperature of 500° C. or higher and 1200° C. or lower.

[0063] When a reducing gas is used in the second heat treatment step, the type of reducing gas is not particularly limited, but hydrogen (H 2 ) is preferable. When hydrogen is used as the reducing gas, its concentration may be appropriately selected depending on the firing temperature and the amount of the starting materials, and is not particularly limited. For example, it is 20 vol% or less, preferably 10 vol% or less, and more preferably 7 vol% or less. When the concentration of the reducing gas is 20 vol% or less, WO 2 which does not have a solar radiation shielding function due to rapid reduction can be obtained. 2 This is because the generation of (2) Plasma method The solar radiation shielding functional material particles of this embodiment contain the above-mentioned general formula M x W y O z The composite tungsten oxide particles represented by the formula (I) can also be produced by, for example, a plasma method. When producing solar radiation shielding functional material particles by a plasma method, the following steps can be included.

[0064] As a starting material, a raw material mixture of a tungsten compound and an M element compound, or a composite tungsten oxide precursor represented by the general formula M x W y O z´ is prepared (raw material preparation step).

[0065] The starting material prepared in the raw material preparation step is supplied into the plasma together with a carrier gas, and through an evaporation and condensation process, the target composite tungsten oxide particles are generated (reaction step). (Raw material preparation step) When preparing a raw material mixture of a tungsten compound and an M element compound as a starting material, it is preferable to blend and mix each raw material so that the molar ratio (M:W) of the M element (M) to tungsten (W) in the raw material mixture of the tungsten compound and the M element compound is equal to the ratio x:y of x to y in the above general formula of the target composite tungsten oxide.

[0066] As the tungsten compound and the M element compound, the same materials as those described in the solid-phase reaction method can be preferably used, and thus the description is omitted here.

[0067] Also, in the composite tungsten oxide precursor represented by the general formula M x W y O z´ M can be the above-described M element, W can be tungsten, and O can be oxygen, and it is preferable that x, y, and z´ satisfy 0.001 ≦ x / y ≦ 1 and 2.0 < z´ / y.

[0068] In the composite tungsten oxide precursor represented by the general formula M x W y O z´ for example, it can be synthesized by the above-described solid-phase reaction method. It is preferable that x / y in such a composite tungsten oxide precursor is a material that matches x / y in the particles of the composite tungsten oxide represented by the target general formula M x W y O z (Reaction step)​ As a carrier gas for transporting the starting materials in the reaction step, a mixed gas of an inert gas and oxygen gas can be used.

[0069] The plasma can be generated, for example, in an atmosphere of an inert gas alone or a mixed gas of an inert gas and hydrogen gas. The plasma is not particularly limited, but thermal plasma is preferable. The raw material supplied into the plasma is evaporated instantly, and the evaporated raw material is condensed on the way to the plasma tail flame, and is rapidly cooled and solidified outside the plasma flame to generate composite tungsten oxide particles. According to the plasma method, for example, composite tungsten oxide particles having a single crystal phase can be generated.

[0070] The plasma used in the method for producing solar radiation shielding functional material particles of this embodiment is preferably, for example, any one of DC arc plasma, high frequency plasma, microwave plasma, low frequency AC plasma, or a combination of these, or one obtained by an electrical method in which a magnetic field is applied to DC plasma, by a high output laser, or by a high output electron beam or ion beam. In any case where a thermal plasma is used, it is preferably a thermal plasma having a high temperature part of 10000K or more, more preferably 10000K or more and 25000K or less, and in particular, it is preferably a plasma in which the particle generation time can be controlled.

[0071] A specific example of the configuration of the reaction step in the method for producing solar radiation shielding material particles of this embodiment by the plasma method will be described with reference to FIG.

[0072] The apparatus shown in FIG. 1 is a hybrid plasma reactor 10 that combines a DC plasma device with a radio frequency plasma device.

[0073] The hybrid plasma reactor 10 has a water-cooled quartz double tube 11 and a reaction vessel 12 connected to the water-cooled quartz double tube 11. In addition, a vacuum exhaust device 13 is connected to the reaction vessel 12.

[0074] A DC plasma torch 14 is provided above the water-cooled quartz double tube 11, and the DC plasma torch 14 is provided with a plasma generation gas supply port 15.

[0075] It is configured so that sheath gas for generating high-frequency plasma and for protecting the quartz tube can be supplied along the inner wall of the water-cooled quartz double tube 11 outside the plasma region, and a sheath gas inlet 16 is provided on the upper flange of the water-cooled quartz double tube 11.

[0076] A water-cooled copper coil 17 for generating high-frequency plasma is disposed around the water-cooled quartz double tube 11 .

[0077] A raw material powder carrier gas supply port 18 is provided near the DC plasma torch 14 and is connected by piping to a raw material powder supply device 19 that supplies raw material powder.

[0078] A gas supply device 20 can be connected to the plasma generation gas supply port 15, the sheath gas inlet 16, and the raw material powder supply device 19 by piping, so that a predetermined gas can be supplied to each member from the gas supply device 20. If necessary, supply ports can be provided in addition to the above-mentioned members so as to cool the members in the apparatus or create a predetermined atmosphere, and these can be connected to the gas supply device 20.

[0079] An example of the configuration of a method for producing composite tungsten oxide particles using the above-mentioned hybrid plasma reactor 10 will be described.

[0080] First, the reaction system consisting of the water-cooled quartz double tube 11 and the reaction vessel 12 is evacuated by the vacuum exhaust device 13. The degree of vacuum at this time is not particularly limited, but for example, it can be evacuated to about 0.1 Pa (about 0.001 Torr). After the reaction system is evacuated, argon gas is supplied from the gas supply device 20, and the reaction system can be filled with argon gas. For example, it is preferable that the reaction system be an argon gas flow system at 1 atmosphere.

[0081] Thereafter, a plasma gas can be supplied into the reaction vessel 12. The plasma gas is not particularly limited, but may be, for example, argon gas, a mixed gas of argon and helium (Ar-He mixed gas), a mixed gas of argon and nitrogen (Ar-N 2 Any gas selected from the group consisting of a mixture of gases, neon, helium, and xenon can be used.

[0082] The flow rate of the plasma gas to be supplied is not particularly limited, but it can be introduced from the plasma generating gas supply port 15 at a flow rate of preferably 3 L / min to 30 L / min, more preferably 3 L / min to 15 L / min. Then, DC plasma can be generated.

[0083] On the other hand, outside the plasma region, along the inner wall of the water-cooled quartz double tube 11, a sheath gas for generating high-frequency plasma and protecting the quartz tube can be supplied in a swirling manner from a sheath gas inlet 16. There are no particular limitations on the type and supply rate of the sheath gas, but for example, argon gas is supplied at 20 L / min to 50 L / min and hydrogen gas is supplied at 1 L / min to 5 L / min to generate high-frequency plasma.

[0084] A high-frequency power supply can then be applied to the water-cooled copper coil 17 for generating high-frequency plasma. The conditions of the high-frequency power supply are not particularly limited, but for example, a high-frequency power supply with a frequency of about 4 MHz and an output of 15 kW to 50 kW can be applied.

[0085] After such hybrid plasma is generated, the raw material can be introduced from a raw material powder carrier gas supply port 18 by a raw material powder supply device 19 using a carrier gas. There is no particular limitation on the carrier gas, and for example, a mixed gas consisting of argon gas at 1 L / min to 8 L / min and oxygen gas at 0.001 L / min to 0.8 L / min can be used.

[0086] The starting material mixture or composite tungsten oxide precursor is introduced into the plasma to carry out the reaction. The supply rate of the starting material from the raw material powder carrier gas supply port 18 is not particularly limited, but is preferably 1 g / min to 50 g / min, more preferably 1 g / min to 20 g / min.

[0087] By setting the supply rate of the starting material to 50 g / min or less, the ratio of the starting material passing through the center of the plasma flame can be sufficiently increased, the ratio of unreacted materials and intermediate products can be suppressed, and the production ratio of the desired composite tungsten oxide particles can be increased. Also, by setting the supply rate of the starting material to 1 g / min or more, the productivity can be increased.

[0088] The starting material supplied to the plasma instantly evaporates in the plasma and undergoes a condensation process to generate composite tungsten oxide particles with an average primary particle size of 100 nm or less.

[0089] The particle size of the composite tungsten oxide particles obtained by the manufacturing method of this embodiment can be easily controlled by the plasma output, plasma flow rate, the amount of raw material powder supplied, and the like.

[0090] After the reaction, the composite tungsten oxide particles produced are deposited in the reaction vessel 12 and can be recovered.

[0091] The method for producing the solar radiation shielding functional material particles of this embodiment has been described above. The solar radiation shielding functional material particles obtained by this production method can be evaluated and confirmed, for example, by the following method.

[0092] For example, the constituent elements of the solar radiation shielding functional material particles obtained by the above-mentioned method for producing solar radiation shielding functional material particles can be quantitatively analyzed by chemical analysis. The analytical method is not particularly limited, but for example, the M element and tungsten can be analyzed by plasma emission spectrometry, and oxygen can be analyzed by inert gas impulse heating fusion infrared absorption spectrometry.

[0093] The crystal structure of the composite tungsten oxide particles contained in the solar radiation shielding material particles can be confirmed by powder X-ray diffraction.

[0094] The particle size of the solar radiation shading functional material particles can be confirmed by particle size measurement based on TEM observation or dynamic light scattering method. 3. Solar radiation shielding laminated structure Next, the solar radiation-shielding laminated structure of this embodiment will be described.

[0095] The solar-shading laminated structure of this embodiment (hereinafter also referred to as "laminated structure") has two laminated plates selected from glass sheets and plastic sheets, and an intermediate layer disposed between the two laminated plates. That is, the solar-shading laminated structure of this embodiment has a structure in which an intermediate layer is interposed between the two laminated plates. In addition, in the solar-shading laminated structure of this embodiment, one or more members selected from the laminated plates and the intermediate layer can contain solar-shading functional material particles. Specifically, either one or both of the laminated plates and the intermediate layer can contain solar-shading functional material particles. In addition, when the laminated plate contains solar-shading functional material particles, for example, either one of the two laminated plates, or both of the two laminated plates can contain solar-shading functional material particles.

[0096] As the solar radiation shielding functional particles, the above-mentioned solar radiation shielding functional particles can be used, and therefore the description thereof will be omitted here.

[0097] The members of the laminated structure of this embodiment will be described below. (1) Laminated board In the laminated structure of this embodiment, the laminated plates are plates that sandwich the intermediate layer from both sides, and can be made of plate glass or plate-shaped plastic that is transparent in the visible light range. The plate-shaped plastic can also contain the above-mentioned solar radiation shielding functional material particles, so it can also be a plate-shaped plastic containing solar radiation shielding functional material particles.

[0098] More specifically, the laminate may be made of, for example, a glass plate or a plastic plate having optical properties that allow light to pass through in the visible light range.

[0099] The two laminated plates selected from the above-mentioned plate glass and plate-shaped plastic include the cases of plate glass and plate glass, plate glass and plate-shaped plastic, and plate-shaped plastic and plate-shaped plastic. As described above, the plate-shaped plastic may contain solar radiation shielding functional material particles. For example, when the two laminated plates are composed of two plate-shaped plastic, one of the plate-shaped plastic or both of the plate-shaped plastic may contain solar radiation shielding functional material particles.

[0100] When a plate-shaped plastic is used for the laminated plate of the solar shading laminated structure, the material of the plastic is appropriately selected according to the application of the solar shading laminated structure, and is not particularly limited. For example, when the solar shading laminated structure is used for a transport device such as an automobile, transparent resins such as polycarbonate resin, acrylic resin, and polyethylene terephthalate resin are preferable from the viewpoint of ensuring the see-through of the driver and passengers of the transport device. That is, the plate-shaped plastic preferably contains one or more resins selected from polycarbonate resin, acrylic resin, and polyethylene terephthalate resin. The see-through can be improved by the plate-shaped plastic containing one or more resins selected from the above resin group such as polycarbonate resin.

[0101] However, the material of the plastic used for the plate-shaped plastic is not limited to the above resin. Any other resin such as PET (polyethylene terephthalate) resin, polyamide resin, polyvinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluororesin, etc. can be used as the plastic.

[0102] Examples of the configuration of the cladding plate used in the laminated structure of this embodiment include the following configuration A and configuration B.

[0103] As an example of form A, a form in which a glass plate or the above-mentioned plate-shaped plastic is used as it is as the laminating plate can be mentioned.

[0104] As an example of form B, solar radiation shielding functional material particles are incorporated into a plastic plate, and the plastic plate is used as a plastic plate containing solar radiation shielding functional material particles.

[0105] Next, in embodiment B, a method for incorporating solar radiation shielding functional material particles into plastic will be described. (Method of manufacturing plate-shaped plastic containing solar radiation shielding material particles) When the solar radiation shielding functional material particles are kneaded into plastic (resin), the plastic is heated to a temperature near the melting point of the plastic (for example, about 200 to 300°C), and the solar radiation shielding functional material particles are mixed with the plastic. Then, the mixture of the plastic and the solar radiation shielding functional material particles is pelletized, and the pellets can be molded into a desired shape such as a film or sheet by a desired method. The method for molding the pellets is not particularly limited, and examples thereof include extrusion molding, inflation molding, solution casting, and casting. The thickness of the plate-shaped plastic having a film shape, sheet shape, board shape, etc. at this time may be appropriately selected depending on the purpose of use of the laminated structure. The amount of the solar radiation shielding functional material particles added to the plastic can be arbitrarily selected depending on the thickness of the plate-shaped plastic, the required optical properties, mechanical properties, etc. The amount of the solar radiation shielding functional material particles added to the plastic is generally preferably 50% by weight or less relative to the plastic. (2) Middle Class Next, the intermediate layer of the laminated structure of this embodiment will be described.

[0106] The intermediate layer may have, for example, an intermediate film. The intermediate film is preferably a film that has optical properties of transmitting light in the visible light region and mechanical properties of having penetration resistance. The intermediate film may contain a resin material, and the resin material may preferably be a synthetic resin.

[0107] The intermediate layer may also contain particles of a solar radiation shielding material as described above.

[0108] The following seven forms are examples of intermediate layers:

[0109] In the first embodiment, the intermediate layer is formed of an intermediate film containing particles of a solar radiation shielding material.

[0110] In embodiment 2, the intermediate layer is made of two or more interlayer films, and at least one of the two or more interlayer films contains particles of a solar radiation shielding material.

[0111] In a third embodiment, the intermediate layer has a solar radiation shielding layer containing solar radiation shielding functional material particles arranged on the inner surface of at least one of the laminated boards, and an interlayer film laminated on the solar radiation shielding layer.

[0112] As form 4, any of the following forms can be mentioned: (a) A form in which the intermediate layer has a laminate of two or more interlayer films including a ductile resin film substrate and a solar radiation shielding layer containing solar radiation shielding functional material particles arranged on one side of the ductile resin film substrate; (b) A form in which the intermediate layer has a laminate of two or more interlayer films including a ductile resin film substrate, and the ductile resin film substrate is a solar radiation shielding layer containing solar radiation shielding functional material particles therein.

[0113] In a fifth embodiment, the intermediate layer has an interlayer film and a solar radiation shielding layer that is disposed on one surface of the interlayer film and contains solar radiation shielding functional material particles.

[0114] As an example of embodiment 6, the intermediate layer may be a laminate having an adhesive layer, a solar radiation shielding layer containing solar radiation shielding functional material particles, and a peeling layer, and further having one or more interlayer layers on the peeling layer side of the laminate. In this embodiment, the intermediate layer is bonded to the inner surface of one of the laminates by the adhesive layer.

[0115] In the seventh embodiment, the intermediate layer does not contain particles of a solar radiation shielding material.

[0116] The intermediate layer of the above forms 1 to 6 includes at least one interlayer film containing a synthetic resin, and the intermediate layer can be said to have at least one layer of a solar-shading interlayer film containing a synthetic resin and solar-shading functional material particles disposed in the synthetic resin as the interlayer film.

[0117] Among them, the intermediate layer of form 4(a) and form 5 has at least one intermediate film containing a synthetic resin, and the intermediate layer has, as the intermediate film, a support intermediate film containing a synthetic resin, and a solar radiation-shielding intermediate film formed on at least one surface of the support intermediate film, the support intermediate film containing a synthetic resin and solar radiation-shielding functional material particles disposed in the synthetic resin. Particularly in the case of form 4(a), the support intermediate film is a resin film having ductility.

[0118] The intermediate layer of form 4(ii) has at least one intermediate film containing a synthetic resin, and the intermediate layer is a ductile resin film as the intermediate film, and the intermediate layer can be said to be a form having a solar-shielding intermediate film containing solar-shielding functional material particles within the resin film. (Interlayer) The configuration of the intermediate film that the intermediate layer may have will be described.

[0119] From the viewpoints of optical properties of transmitting visible light, mechanical properties of having penetration resistance, and material costs, the interlayer film preferably contains a synthetic resin, and the synthetic resin is more preferably a vinyl resin or an ionomer resin. When the intermediate layer has a plurality of interlayer films, the synthetic resin contained in each interlayer film may be the same or different.

[0120] The vinyl resin is not particularly limited, and examples thereof include polyvinyl acetal represented by polyvinyl butyral, polyvinyl chloride, vinyl chloride-ethylene copolymer, vinyl chloride-ethylene-glycidyl methacrylate copolymer, vinyl chloride-ethylene-glycidyl acrylate copolymer, vinyl chloride-glycidyl methacrylate copolymer, vinyl chloride-glycidyl acrylate copolymer, polyvinylidene chloride, vinylidene chloride-acrylonitrile copolymer, polyvinyl acetate ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, polyvinyl acetal-polyvinyl butyral mixture, etc. However, from the viewpoint of adhesion to glass or plastic used in the laminate, transparency, etc., when the interlayer contains a vinyl resin as a synthetic resin, the synthetic resin is particularly preferably polyvinyl acetal represented by polyvinyl butyral or ethylene-vinyl acetate copolymer.

[0121] The ionomer resin is not particularly limited, and various known ionomer resins can be used, and the resin can be selected as desired depending on the intended use of the laminated structure. For example, ethylene-based ionomers, styrene-based ionomers, ionomer elastomers, perfluorocarbon ionomers, urethane ionomers, etc. are known as ionomer resins, and as described above, any ionomer resin can be selected and used depending on the intended use, required performance, etc. In addition, only one type of ionomer resin can be used for the interlayer film of the laminated structure, but two or more types of ionomer resins can be used in combination.

[0122] The laminated structure of the present embodiment can be suitably used, for example, as a window material for automobiles or buildings, a film for vinyl greenhouses, etc. For this reason, it is preferable that the ionomer resin contained in the interlayer film of the laminated structure has excellent transparency, high visible light transmittance, a low haze value, and excellent penetration resistance and weather resistance. In addition, when the interlayer film is directly disposed on a laminated plate, it is preferable that the interlayer film also has excellent adhesion to the laminated plate.

[0123] From the above viewpoints, it is more preferable that the ionomer resin contains an ethylene-based ionomer, and in particular, it is even more preferable that the ionomer resin is an ethylene-based ionomer.

[0124] The metal ions contained in the ionomer resin are not particularly limited, and for example, an ionomer resin containing one or more metal ions selected from zinc, magnesium, lithium, potassium, and sodium can be used. In particular, an ionomer resin containing zinc ions can be preferably used.

[0125] Specific examples of the ionomer resin include metal element ionomers of ethylene-acrylic acid-acrylic acid ester copolymers, metal element ionomers of ethylene-acrylic acid-methacrylic acid ester copolymers, metal element ionomers of ethylene-methacrylic acid-acrylic acid ester copolymers, metal element ionomers of ethylene-methacrylic acid-methacrylic acid ester copolymers, etc. Note that the metal ions contained in any of the ionomer resins are not particularly limited, and may contain ions of one or more metals selected from, for example, zinc, magnesium, lithium, potassium, and sodium.

[0126] More specifically, examples of ionomer resins that can be preferably used include the Surlyn (registered trademark) series from DuPont, the Hi-Milan (registered trademark) series from Mitsui-DuPont Polychemicals, and the IOTEK (registered trademark) series from Exxon Mobil Chemical.

[0127] The interlayer can be formed by a known method, such as a calendar roll method, an extrusion method, a casting method, or an inflation method.

[0128] When the interlayer film contains solar radiation shielding functional material particles and a vinyl resin, the interlayer film can be produced, for example, by the following procedure. For example, an additive liquid in which solar radiation shielding functional material particles are dispersed in a plasticizer is added to a vinyl resin, and the resulting mixture is kneaded to prepare a vinyl resin composition in which the particles are uniformly dispersed. The prepared vinyl resin composition is then formed into a sheet to produce the interlayer film. When forming the vinyl resin composition into a sheet, a heat stabilizer, an antioxidant, an ultraviolet shielding material, etc. may be blended as necessary, and an adhesion regulator such as a metal salt may also be blended to control the penetration of the sheet.

[0129] The configuration of the laminated structure will be described below with reference to Fig. 3 to Fig. 10 for examples of combinations of the above-mentioned laminated boards of Form A and Form B and intermediate layers of Forms 1 to 7, using a vinyl resin as an intermediate film as an example. Fig. 3 to Fig. 10 are schematic cross-sectional views of the solar radiation-shading laminated structure.

[0130] In the following description, when a description is made such as "Mode A-1," it means that the configuration is a combination of Mode A and Mode 1. (Form A-1) Fig. 3 shows a cross-sectional view of an example of a solar radiation-shading laminated structure of Form A-1. As shown in Fig. 3, a solar radiation-shading laminated structure 501 of Form A-1 has an intermediate layer 521 sandwiched between two laminated plates 51. The intermediate layer 521 is composed of an intermediate film 621 containing solar radiation-shading functional material particles 611 and a synthetic resin 612, i.e., a solar radiation-shading intermediate film. The solar radiation-shading functional material particles 611 are preferably dispersed and contained in the synthetic resin 612.

[0131] As shown in FIG. 3, a laminated structure for solar shading is manufactured, for example, as follows, using plate glass or plate-shaped plastic that does not contain solar shading functional material particles as the laminated plate and intermediate layer 521 composed of an intermediate film that contains synthetic resin and solar shading functional material particles.

[0132] A liquid containing particles of a solar radiation shielding material dispersed in a plasticizer is added to a vinyl resin to prepare a vinyl resin composition, which is then molded into a sheet to obtain a sheet of a solar radiation shielding interlayer film. The sheet of the solar radiation shielding interlayer film is then sandwiched between two laminates selected from glass sheets and plastic sheets and laminated together to form a solar radiation shielding laminated structure.

[0133] In the above description, the additive liquid is a plasticizer dispersion liquid in which solar radiation shielding functional material particles are dispersed in a plasticizer, but the present invention is not limited to such a form. For example, the vinyl resin composition may be prepared by adding a dispersion liquid in which solar radiation shielding functional material particles are dispersed in a dispersion medium other than a plasticizer to a vinyl resin, and adding the plasticizer separately.

[0134] By the above procedure, a laminated structure for shading solar radiation can be manufactured that has excellent visible light transmittance, high solar radiation shielding properties, i.e., high near-infrared absorbing properties, and a small haze value. Furthermore, according to the manufacturing method described here, the laminated structure for shading solar radiation can be manufactured easily and at low production costs. In addition, since the above-mentioned solar radiation shielding functional material particles are used, the laminated structure for shading solar radiation can have excellent weather resistance. (Form B-1) Next, a laminated structure in which Mode B and Mode 1 are combined will be described.

[0135] The laminated structure of form B-1 uses a plate-shaped plastic containing solar radiation shielding material particles as at least one of the laminated plates, and the intermediate layer is composed of an intermediate film containing solar radiation shielding material particles and a synthetic resin. The solar radiation shielding material particles are preferably dispersed and contained in the synthetic resin.

[0136] Therefore, except that at least one of the two glass plates and the plastic plate that do not contain solar radiation shielding functional material particles is replaced with a plastic plate that contains solar radiation shielding functional material particles, it has the same configuration as the laminated structure of form A-1 and can be manufactured in the same manner.

[0137] Like the laminated structure of Form A-1, the laminated structure of Form B-1 can be a laminated structure for shading sunlight that has excellent visible light transmittance, high solar radiation shielding properties, i.e., high near-infrared absorbing properties, and a small haze value. Furthermore, according to the manufacturing method described here, the laminated structure for shading sunlight is easy to manufacture, and a laminated structure for shading sunlight can be manufactured at low production costs. In addition, since the above-mentioned solar radiation shielding functional material particles are used, a laminated structure for shading sunlight that has excellent weather resistance can be obtained. (Form A-2) Next, a laminated structure of Form A-2 in which Form A and Form 2 are combined will be described.

[0138] Fig. 4 shows a cross-sectional view of an example of a solar radiation shading laminated structure 502 of form A-2. As shown in Fig. 4, the solar radiation shading laminated structure 502 has an intermediate layer 522 sandwiched between two laminated plates 51. The intermediate layer 522 has an intermediate film 621 (first intermediate film) containing solar radiation shading functional material particles 611 and a synthetic resin 612, and an intermediate film 622 (second intermediate film) not containing the solar radiation shading functional material particles 611. The intermediate film 621 contains solar radiation shading functional material particles and serves as a solar radiation shading intermediate film.

[0139] In the intermediate layer 522 , the intermediate film 621 is sandwiched between the intermediate films 622 .

[0140] 4, a laminated structure 502 uses a glass plate or a plastic plate not containing solar radiation shielding material particles as the laminated plate 51. The intermediate layer 522 has two or more interlayer films, at least one of which is composed of an interlayer film 621 containing solar radiation shielding material particles.

[0141] The laminated structure 502 shown in FIG. 4 is manufactured, for example, as follows. The additive liquid in which the solar radiation shielding functional material particles are dispersed in a plasticizer, as described in the form A-1, is added to a vinyl resin to prepare a vinyl resin composition. The vinyl resin composition is then formed into a sheet to obtain a sheet of a solar radiation shielding interlayer film to be the interlayer film 621. Next, the solar radiation shielding interlayer film sheet is laminated with another sheet of an interlayer film that does not contain solar radiation shielding functional material particles, or is interposed between two interlayer film sheets that do not contain solar radiation shielding functional material particles to form a laminate to be the intermediate layer 522. Next, the laminate to be the intermediate layer 522 can be sandwiched between two laminated plates selected from sheet glass and sheet-shaped plastic and bonded together to form a solar radiation shielding laminated structure.

[0142] As in the case of Form A-1, when producing the interlayer film 621, a vinyl resin composition may be prepared by adding a dispersion in which solar radiation shading functional material particles are dispersed in a dispersion medium other than a plasticizer to a vinyl resin, and then adding a plasticizer separately. This makes it possible to produce a solar radiation shading laminated structure that has excellent visible light transmittance while also having high solar radiation shading properties, i.e., high near-infrared absorption properties, and a small haze value, at low production costs. In addition, since the above-mentioned solar radiation shading functional material particles are used, a solar radiation shading laminated structure with excellent weather resistance can be obtained.

[0143] According to the laminated structure of form A-2, the adhesion between the interlayer sheet not containing solar radiation shading functional material particles and two laminated plates selected from glass plates and plastic plates can be increased, so that the strength of the solar radiation shading laminated structure is appropriately increased, which is preferable.

[0144] The laminated structure of form A-2 is not limited to the above configuration. For example, a PET (polyethylene terephthalate) film having an Al film, Ag film, or the like formed on at least one side by a sputtering method or the like can be prepared, and the PET film can be interposed between the interlayer films to form an intermediate layer. Also, an appropriate additive can be added to the sheet of the interlayer film 622 that does not contain solar radiation shielding functional material particles. By interposing the film or adding an additive to the interlayer film, functions such as UV protection and color adjustment can be added. (Form B-2) Next, a laminated structure of Form B-2, which is a combination of Form B and Form 2, will be described.

[0145] The laminated structure of form B-2 uses a plate-shaped plastic containing solar radiation shielding material particles as at least one of the laminated plates, and the intermediate layer has two or more interlayer films, at least one of which can be composed of an interlayer film containing solar radiation shielding material particles.

[0146] The solar-shading laminated structure of Form B-2 can be manufactured in the same manner as Form A-2, except that at least one of the two glass plates and the plastic plate that do not contain solar-shading functional material particles is replaced with a plastic plate that contains solar-shading functional material particles.

[0147] This makes it possible to manufacture a laminated structure for shading with excellent visible light transmittance and high solar radiation shielding properties, i.e., high near-infrared absorbing properties, and a small haze value, at low production costs. In addition, since the above-mentioned solar radiation shielding functional material particles are used, the laminated structure for shading with excellent weather resistance can be obtained.

[0148] The laminated structure of Form B-2, like Form A-2, can also enhance the adhesion between the interlayer sheet not containing solar radiation shading functional material particles and two laminated plates selected from glass plates and plastic plates. This is preferable because it moderately enhances the strength of the solar radiation shading laminated structure. (Form A-3) Next, a laminated structure of Form A-3, which is a combination of Form A and Form 3, will be described.

[0149] A cross-sectional view of an example of a solar-shading laminated structure according to Form A-3 is shown in Fig. 5. As shown in Fig. 5, a solar-shading laminated structure 503 has a structure in which an intermediate layer 523 is sandwiched between two laminated plates 51. The intermediate layer 523 has an intermediate film 622 that does not contain solar-shading functional material particles, and a solar-shading layer 63 that contains solar-shading functional material particles 611 and a synthetic resin 631 arranged on the intermediate film 622.

[0150] The laminated structure 503 shown in Fig. 5 uses a glass plate or a plastic plate not containing solar radiation shielding material particles as the laminated plate 51. The intermediate layer 523 has a solar radiation shielding layer 63 containing a synthetic resin 631 and solar radiation shielding material particles 611, which are arranged on the inner surface 51A of at least one of the glass plates or plastic plates, and an intermediate film 622 superimposed on the solar radiation shielding layer 63. The solar radiation shielding layer 63 is also an intermediate film and corresponds to a solar radiation shielding intermediate film. However, as described later, the solar radiation shielding layer 63 is formed using one of the laminated plates 51 as a support, and can be an intermediate film having a thinner thickness than those in the cases of the first and second embodiments.

[0151] The solar radiation shielding laminated structure 503 shown in FIG. 5 is manufactured, for example, as follows. An appropriate binder component is mixed with an additive liquid in which solar radiation shielding functional material particles are dispersed in a plasticizer or a dispersion medium to prepare a coating liquid. Examples of the binder component include inorganic binders such as silicate, and organic binders such as acrylic, vinyl, and urethane. A solar radiation shielding layer is formed on the surface 51A located on the inside of at least one of the laminated boards 51 using the prepared coating liquid. Next, a resin composition that does not contain solar radiation shielding functional material particles is formed into a sheet to obtain an intermediate film sheet. Then, the obtained intermediate film sheet is sandwiched and bonded between the surface 51A side located on the inside of at least one of the laminated boards 51 on which the solar radiation shielding layer is formed and the other laminated board 51 on which the solar radiation shielding layer is not formed. A method of forming a solar radiation shielding laminated structure by the above operations can be mentioned.

[0152] According to this method, the thickness of the solar radiation-shielding layer in the solar radiation-shielding laminated structure can be set to be thin. By setting the thickness to be thin, the solar radiation-shielding layer exhibits a reflecting effect in addition to an infrared ray absorbing effect, so that the solar radiation-shielding laminated structure can have improved solar radiation-shielding properties. This makes it possible to manufacture a solar radiation-shielding laminated structure having excellent visible light transmittance while also having high solar radiation-shielding properties, i.e., high near-infrared absorbing properties, and a small haze value, at low production costs. In addition, since the above-mentioned solar radiation-shielding functional material particles are used, a solar radiation-shielding laminated structure having excellent weather resistance can be obtained.

[0153] Furthermore, by adding appropriate additives to an interlayer sheet that does not contain solar radiation shielding functional material particles, it is possible to add functions such as UV protection and color adjustment. (Form B-3) Next, a laminated structure of Form B-3, which is a combination of Form B and Form 3, will be described.

[0154] The laminated structure of form B-3 uses a plate-shaped plastic containing solar radiation shielding material particles as at least one of the laminated plates, and the intermediate layer has a solar radiation shielding layer containing solar radiation shielding material particles formed on the inner surface of at least one of the laminated plates, and an intermediate film superimposed on the solar radiation shielding layer.

[0155] The solar-shading laminated structure of Form B-3 can be manufactured in the same manner as Form A-3, except that at least one of the two glass plates and the plastic plate that do not contain solar-shading functional material particles is replaced with a plastic plate that contains solar-shading functional material particles.

[0156] This method also allows the thickness of the solar radiation-shielding layer in the solar radiation-shielding laminated structure to be set thin, as in form A-3. By setting the thickness thin, the solar radiation-shielding layer exhibits a reflection effect in addition to an infrared ray absorption effect, so that the solar radiation-shielding laminated structure can have improved solar radiation-shielding properties. This allows a solar radiation-shielding laminated structure having excellent visible light transmittance while also having high solar radiation-shielding properties, i.e., high near-infrared absorbing properties, and a small haze value to be manufactured at low production costs. In addition, since the above-mentioned solar radiation-shielding functional material particles are used, a solar radiation-shielding laminated structure having excellent weather resistance can be obtained. Furthermore, by adding suitable additives to an interlayer sheet that does not contain solar radiation shielding functional material particles, it is possible to add functions such as UV protection and color adjustment. (Form A-4) Next, a laminated structure of Form A-4, which is a combination of Form A and Form 4, will be described. (A) Fig. 6 shows a cross-sectional view of an example of a solar radiation shading laminated structure 504 according to (A) of form A-4. That is, the intermediate layer has a laminate of two or more intermediate layers including a ductile resin film substrate and a solar radiation shading layer containing solar radiation shading functional material particles arranged on one side of the ductile resin film substrate.

[0157] As shown in FIG. 6, the solar radiation shielding laminated structure 504 has an intermediate layer 524 sandwiched between two laminated plates 51. In the intermediate layer 524, a solar radiation shielding layer 63 containing solar radiation shielding functional material particles 611 and a synthetic resin 631 is formed on a ductile resin film 64. The intermediate layer 524 is formed by sandwiching a laminate (sun radiation shielding film) of the resin film 64 and the solar radiation shielding layer 63 between intermediate films 622 that do not contain solar radiation shielding functional material particles. The ductile resin film 64 and the solar radiation shielding layer 63 are also intermediate films, and correspond to a supporting intermediate film and a solar radiation shielding intermediate film, respectively. However, as described later, the solar radiation shielding layer 63 is formed using a ductile resin film 64 as a support, and can be an intermediate film having a thinner film thickness than those in the first and second embodiments.

[0158] Furthermore, the degree of ductility of the ductile resin and ductile resin film is not particularly limited, and can be selected depending on the configuration of the laminated structure, the degree of ductility required for the laminated structure, and the like.

[0159] As shown in FIG. 6, a laminated structure for solar shading includes a laminate of two or more interlayer films including a ductile resin film substrate and a solar shading layer containing solar shading functional material particles arranged on one side of the ductile resin film substrate, and the laminated structure for solar shading includes a laminate of two or more interlayer films including a ductile resin film substrate and a solar shading layer containing solar shading functional material particles ... the solar shading layer is manufactured, for example, as follows.

[0160] For example, a solar radiation shielding layer is formed on one side of a ductile resin film using a dispersion liquid in which solar radiation shielding functional material particles are dispersed in a plasticizer or a dispersion medium, or a coating liquid prepared by mixing a binder component appropriately with an additive liquid. Examples of the binder component include inorganic binders such as silicate, and organic binders such as acrylic, vinyl, and urethane binders.

[0161] When forming a solar radiation shielding layer on one side of the ductile resin film substrate, the surface of the resin film may be previously subjected to a surface treatment such as corona treatment, plasma treatment, flame treatment, or primer layer coating treatment in order to improve adhesion to the resin binder.

[0162] Furthermore, a vinyl resin composition not containing solar radiation shielding functional material particles can be formed into a sheet to obtain an interlayer film sheet. The ductile resin film substrate having a solar radiation shielding layer formed on one side thereof is preferably disposed between the sheets of the interlayer film not containing solar radiation shielding functional material particles to form an intermediate layer. By adopting this configuration, the adhesion between the ductile resin film substrate having a solar radiation shielding layer formed on one side thereof and the laminated plate can be easily adjusted. Here, one layer of the two or more laminated interlayer films may of course contain solar radiation shielding functional material particles or appropriate additives having effects such as UV protection and color adjustment.

[0163] The obtained intermediate layer 524 is sandwiched between two laminated plates 51 selected from sheet glass or sheet-like plastic, and then bonded together to form a laminated structure 504 for blocking solar radiation. (b) An embodiment will be described in which the intermediate layer has a laminate of two or more intermediate layers including a ductile resin film substrate, and the ductile resin film substrate is a solar radiation shielding layer containing solar radiation shielding functional material particles therein.

[0164] 7 shows a cross-sectional view of an example of a solar radiation-shading laminated structure 505 according to (ii) of the embodiment A-4. That is, the intermediate layer has a laminate of two or more intermediate films including a ductile resin film substrate, and the ductile resin film substrate is a solar radiation-shading layer containing solar radiation-shading functional material particles therein.

[0165] As shown in FIG. 7, the solar radiation shading laminated structure 505 has an intermediate layer 525 sandwiched between two laminated plates 51.

[0166] The intermediate layer 525 has a ductile resin film 65 (sun radiation shielding film) containing solar radiation shielding functional material particles 611 and a ductile resin 651. In Fig. 7, the ductile resin film 65 is sandwiched between intermediate films 622 that do not contain solar radiation shielding functional material particles. The ductile resin film 65 is also an intermediate film and corresponds to a solar radiation shielding intermediate film.

[0167] The ductile resin film 65 can be manufactured, for example, as follows. The ductile resin 651 is heated to a temperature near its melting point (approximately 200°C to 300°C) and mixed with solar radiation shielding material particles to prepare a mixture. The mixture of the ductile resin and the solar radiation shielding material particles is pelletized and formed into a film, board, or the like by a predetermined method. For example, it can be formed by extrusion molding, inflation molding, solution casting, casting, or the like. The thickness of the film, board, or the like at this time may be appropriately selected depending on the purpose of use. The amount of the solar radiation shielding material particles 611 added to the ductile resin 651 can be varied depending on the thickness of the substrate and the required optical and mechanical properties, but is generally preferably 50% by weight or less of the resin.

[0168] Furthermore, a vinyl resin composition that does not contain solar radiation shielding functional material particles can be formed into a sheet to obtain a sheet of the intermediate film 622. A ductile resin film 65 containing solar radiation shielding functional material particles therein can be disposed between two sheets of the intermediate film 622 to form the intermediate layer 525.

[0169] The obtained intermediate layer 525 is sandwiched between two laminated plates 51 selected from sheet glass or sheet-like plastic, and then bonded together to form a laminated structure 505 for blocking solar radiation.

[0170] Here, it is of course possible to incorporate solar radiation shielding material particles in at least one layer of the two or more laminated interlayers 622. Furthermore, if desired, appropriate additives having effects such as UV protection and color adjustment can be freely and easily added to the interlayer 622 that does not contain solar radiation shielding material particles, thereby making it possible to obtain a solar radiation shielding laminated structure having multiple functions.

[0171] The manufacturing methods described in (a) and (b) above also enable the film thickness of the solar radiation-shielding layer in the solar radiation-shielding laminated structure to be set thin. By setting the film thickness thin, the solar radiation-shielding layer exerts a reflecting effect in addition to an infrared ray absorbing effect, and therefore the solar radiation-shielding properties can be improved. This allows a solar radiation-shielding laminated structure having excellent visible light transmittance while also having high solar radiation-shielding properties, i.e., high near-infrared absorbing properties, and a small haze value to be manufactured at low production costs. In addition, since the above-mentioned solar radiation-shielding functional material particles are used, a solar radiation-shielding laminated structure having excellent weather resistance can be obtained.

[0172] Furthermore, by adding suitable additives to an interlayer sheet that does not contain solar radiation shielding material particles, it is possible to add functions such as UV protection and color adjustment. (Form B-4) Next, a laminated structure of Form B-4, which is a combination of Form B and Form 4, will be described.

[0173] In the laminated structure of form B-4, at least one of the laminated plates can be made of a plastic plate containing solar radiation shielding material particles.

[0174] The intermediate layer may have any of the following configurations: The intermediate layer has a solar radiation shielding layer containing solar radiation shielding material particles formed on one side of a ductile resin film substrate, and an intermediate film having two or more laminated layers; or the intermediate layer has a solar radiation shielding layer containing solar radiation shielding material particles inside a ductile film substrate, and an intermediate film having two or more laminated layers.

[0175] The solar-shading laminated structure of Form B-4 can be manufactured in the same manner as Form A-4, except that at least one of the two glass plates and the plastic plate that do not contain solar-shading functional material particles is replaced with a plastic plate that contains solar-shading functional material particles.

[0176] This method also allows the thickness of the solar radiation-shielding layer in the solar radiation-shielding laminated structure to be set thin, as in the case of form A-4. By setting the thickness thin, the solar radiation-shielding layer exhibits a reflection effect in addition to an infrared ray absorption effect, so that the solar radiation-shielding properties can be improved. This allows a solar radiation-shielding laminated structure having excellent visible light transmittance, high solar radiation-shielding properties, i.e., high near-infrared absorbing properties, and a small haze value to be manufactured at low production costs. In addition, since the above-mentioned solar radiation-shielding functional material particles are used, a solar radiation-shielding laminated structure having excellent weather resistance can be obtained. Furthermore, by adding an appropriate additive to the sheet of the interlayer film that does not contain the solar radiation-shielding functional material particles, functions such as UV protection and color adjustment can be added. (Form A-5) Next, a laminated structure of Form A-5, which is a combination of Form A and Form 5, will be described.

[0177] Fig. 8 shows a cross-sectional view of an example of a solar-shading laminated structure according to Form A-5. As shown in Fig. 8, the solar-shading laminated structure 506 of Form A-5 has an intermediate layer 526 sandwiched between two laminated plates 51. The intermediate layer 526 has an intermediate film 621 (first intermediate film) containing solar-shading functional material particles 611 and a synthetic resin 612, and an intermediate film 622 (second intermediate film) not containing solar-shading functional material particles. The intermediate film 621 contains solar-shading functional material particles and serves as a solar-shading intermediate film.

[0178] The solar-shading laminated structure shown in FIG. 8, in which a glass plate or a plastic plate not containing solar-shading functional material particles is used as the laminated plate and the intermediate layer is a solar-shading interlayer film containing solar-shading functional material particles formed on one side of the interlayer film, is manufactured, for example, as follows.

[0179] First, a coating liquid is prepared by mixing a binder component with an additive liquid or a dispersion liquid in which solar radiation shielding material particles are dispersed in a plasticizer or a dispersion medium. As the binder component, for example, an inorganic binder such as silicate or an organic binder such as an acrylic, vinyl, or urethane binder can be used.

[0180] Next, the above coating liquid is applied to one side of an interlayer film sheet obtained by molding a resin composition not containing solar radiation shielding functional material particles into a sheet shape to form a solar radiation shielding interlayer film (sun radiation shielding layer) to obtain an interlayer film with a solar radiation shielding layer.

[0181] The interlayer film with the solar radiation shielding layer can be sandwiched between and bonded to two laminated sheets selected from glass sheets and plastic sheets to form a solar radiation shielding laminated structure.

[0182] According to the above method, since a film containing solar radiation shading functional material particles is formed on the surface of the interlayer sheet, additives such as fillers can be further added to the solar radiation shading functional material particles as desired, thereby improving the solar radiation shading properties. This makes it possible to manufacture a solar radiation shading laminated structure having excellent visible light transmittance while also having high solar radiation shading properties, i.e., high near-infrared absorption properties, and a small haze value, at low production costs. In addition, since the above-mentioned solar radiation shading functional material particles are used, a solar radiation shading laminated structure with excellent weather resistance can be obtained. (Form B-5) Next, a laminated structure of Form B-5, which is a combination of Form B and Form 5, will be described.

[0183] The solar radiation shading laminated structure of form B-5 can use a plate-shaped plastic containing solar radiation shading material particles as at least one of the laminated plates, and can use an intermediate layer having a solar radiation shading layer containing solar radiation shading material particles formed on one surface of the intermediate film as the intermediate layer.

[0184] The solar-shading laminated structure of Form B-5 can be manufactured in the same manner as Form A-5, except that at least one of the two glass plates and plastic that do not contain solar-shading functional material particles is replaced with a plastic that contains solar-shading functional material particles.

[0185] This method also forms a film containing solar radiation shading functional material particles on the surface of the interlayer sheet, so that additives such as fillers can be added to the solar radiation shading functional material particles as desired, thereby improving the solar radiation shading properties. This makes it possible to manufacture a solar radiation shading laminated structure that has excellent visible light transmittance while also having high solar radiation shading properties, i.e., high near-infrared absorption properties, and a small haze value, at low production costs. In addition, because the above-mentioned solar radiation shading functional material particles are used, a solar radiation shading laminated structure with excellent weather resistance can be obtained. (Form A-6) Next, a laminated structure of Form A-6, which is a combination of Form A and Form 6, will be described.

[0186] The laminate is made of glass or a plastic plate that does not contain particles of a solar radiation shielding material. An adhesive layer of a laminate, which constitutes a part of an intermediate layer and is made of an adhesive layer, a solar radiation shielding layer containing particles of a solar radiation shielding material, and a peelable layer, laminated in this order, is adhered to the inner surface of one of the two laminates. The intermediate layer further has an intermediate film or an intermediate film of two or more layers that overlaps with the laminate on the peelable layer side of the laminate.

[0187] That is, the laminated structure of Form A-6 has a structure in which the layers are laminated in the order of one laminate / adhesive layer / sun-shielding layer containing solar-shielding functional material particles / peeling layer / interlayer film or two or more laminated interlayer films / other laminate. Note that the adhesive layer, the solar-shielding layer, and the peeling layer are also interlayer films.

[0188] The laminated structure of Form A-6 can be manufactured, for example, as follows. The manufacturing process will be described with reference to Fig. 9(A) to Fig. 9(C). Fig. 9(A) to Fig. 9(C) show cross-sectional views of an example of the laminated structure of Form A-6 in the manufacturing process.

[0189] 9(A), a release layer 66 is formed on one surface of a film sheet 67, and a solar radiation shielding layer 63 containing solar radiation shielding functional material particles 611 and a synthetic resin 631 is formed on the release layer 66. An adhesive layer 68 is formed on the solar radiation shielding layer 63 to form a laminate, thereby obtaining a transfer film 69.

[0190] Examples of the film sheet 67 include synthetic resin films such as polyester, polypropylene, polyethylene, polyethylene terephthalate, polycarbonate, polyimide, and fluorine, paper, and cellophane.

[0191] Examples of materials for the release layer 66 include wax, acrylic resin, and polyvinyl acetal such as polyvinyl butyral.

[0192] Examples of materials for the adhesive layer 68 include polyvinyl acetal such as polyvinyl butyral, polyvinyl chloride, vinyl chloride-ethylene copolymer, vinyl chloride-ethylene-glycidyl methacrylate copolymer, vinyl chloride-ethylene-glycidyl acrylate copolymer, polyvinylidene chloride, vinylidene chloride-acrylonitrile copolymer, polyamide, polymethacrylic acid ester, and acrylic acid ester copolymer.

[0193] Then, the adhesive layer 68 of the transfer film 69 is adhered under pressure to the inner surface of one of the laminating plates 51, and then the film sheet 67 is peeled off from the transfer film 69. Then, only the film sheet 67 is peeled off from the transfer film 69 due to the effect of the peeling layer 66.

[0194] The state where the film sheet 67 has been peeled off is the solar radiation shading film, as shown in Fig. 9(B). After peeling off this film sheet 67, it is bonded under pressure to the inner surface of the other glass plate or plastic laminate 51 via the above-mentioned interlayer 622 or a laminated interlayer of two or more layers. This makes it possible to obtain the solar radiation shading laminated structure 507 shown in Fig. 9(C).

[0195] 9(C), an example of the obtained solar radiation shading laminated structure 507 according to Form A-6 has an intermediate layer 527 sandwiched between the two laminated plates 51. The intermediate layer 527 is composed of an intermediate film 622 not containing solar radiation shading functional particles, a release layer 66, a solar radiation shading layer 63 containing solar radiation shading functional material particles 611, and an adhesive layer 68.

[0196] The above method can produce a laminated structure for shading sunlight that has excellent visible light transmittance, high sunlight shielding properties, i.e., high near-infrared absorbing properties, and a small haze value. Furthermore, the above method can produce a laminated structure for shading sunlight that is easy to produce and has low production costs. In addition, since the above-mentioned sunlight shielding functional material particles are used, the laminated structure for shading sunlight can have excellent weather resistance. In addition, the method can easily produce a sunlight shielding layer with a thin thickness, and further, by adding appropriate additives to the intermediate film, peeling layer, and adhesive layer, functions such as UV protection and color adjustment can be added. (Form B-6) Next, a laminated structure of Form B-6, which is a combination of Form B and Form 6, will be described.

[0197] In the solar radiation shading laminated structure of Form B-6, a plastic plate containing solar radiation shading functional material particles can be used as at least one of the laminated plates.

[0198] An adhesive layer of a laminate, which constitutes a part of the intermediate layer and is made up of an adhesive layer, a solar radiation shielding layer containing solar radiation shielding material particles, and a peelable layer laminated in this order, is adhered to the inner surface of one of the two laminated boards. The intermediate layer further has an intermediate film or two or more laminated intermediate films overlapping the laminate on the peelable layer side of the laminate.

[0199] In other words, the laminated structure of form B-6 has a structure in which the following layers are stacked in the order: one laminated board / adhesive layer / sun-shielding layer containing sun-shielding functional material particles / peeling layer / interlayer film or two or more laminated interlayer films / other laminated board.

[0200] The solar-shading laminated structure of Form B-6 can be manufactured in the same manner as Form A-6, except that at least one of the two glass plates and plastic that do not contain solar-shading functional material particles is replaced with a plastic that contains solar-shading functional material particles.

[0201] The above method can produce a laminated structure for shading sunlight that has excellent visible light transmittance, high sunlight shielding properties, i.e., high near-infrared absorbing properties, and a small haze value. Furthermore, the above method can produce a laminated structure for shading sunlight that is easy to produce and has low production costs. In addition, since the above-mentioned sunlight shielding functional material particles are used, the laminated structure for shading sunlight can have excellent weather resistance. In addition, the above method can also easily produce a sunlight shielding layer with a thin thickness, and further, by adding appropriate additives to the peeling layer and adhesive layer, functions such as UV protection and color adjustment can be added. (Form B-7) Next, a laminated structure of Form B-7, which is a combination of Form B and Form 7, will be described.

[0202] Fig. 10 shows a cross-sectional view of an example of a solar radiation-shading laminated structure according to Form B-7. As shown in Fig. 10, a solar radiation-shading laminated structure 508 of Form B-7 has an intermediate layer 528 sandwiched between a laminated plate 70 containing solar radiation-shading functional material particles 611 and a laminated plate 51 not containing the particles. The intermediate layer 528 is formed of an intermediate film 622 not containing solar radiation-shading functional material particles.

[0203] A laminated structure for shading sunlight, in which a plate-shaped plastic containing sunlight-shading functional material particles is used as at least one of the laminated plates and the intermediate layer is composed of an intermediate film that does not contain sunlight-shading functional material particles, for example, contains a vinyl-based resin, is manufactured, for example, as follows.

[0204] A plasticizer is added to a vinyl resin to prepare a vinyl resin composition, and the vinyl resin composition is formed into a sheet to obtain an interlayer sheet. At least one of the laminating plates sandwiching the interlayer sheet is a plate-like plastic containing solar radiation shielding material particles, and the other laminating plate is a glass plate or a plate-like plastic.

[0205] The above method can produce a laminated structure for shading sunlight that has excellent visible light transmittance, high sunlight shielding properties, i.e., high near-infrared absorbing properties, and a small haze value. Furthermore, the above method can produce a laminated structure for shading sunlight that is easy to manufacture and has low production costs. In addition, since the above-mentioned sunlight shielding functional material particles are used, the laminated structure for shading sunlight can have excellent weather resistance. Furthermore, by adding an appropriate additive to one or more members selected from the interlayer and the other laminate, functions such as UV protection and color adjustment can be added. 4. Manufacturing methods for dispersion liquid, additive liquid, and coating liquid of solar radiation shielding functional material particles The methods for producing the dispersion liquid, additive liquid, and coating liquid of the solar radiation shielding material particles that can be used when forming the above-mentioned interlayer film and the like will be described.

[0206] The method for producing the dispersion liquid and additive liquid of the solar radiation shielding functional material particles is not particularly limited, and any method can be used as long as the solar radiation shielding functional material particles can be uniformly dispersed in the plasticizer or dispersion medium. For example, a grinding and dispersion treatment method using a bead mill, a ball mill, a sand mill, a paint shaker, an ultrasonic homogenizer, etc. can be mentioned, and the dispersion liquid and additive liquid applicable to the production of the solar radiation shielding laminated structure of this embodiment can be prepared by dispersing the solar radiation shielding functional material particles in the plasticizer or dispersion medium.

[0207] The dispersion medium for dispersing the solar radiation shielding functional material particles is not particularly limited, and can be appropriately selected according to the conditions for forming the solar radiation shielding layer, etc., and the resins to be mixed when preparing the vinyl resin composition or the ionomer resin composition. As the dispersion medium, for example, one or more organic solvents selected from water, ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol, diacetone alcohol, and other alcohols, methyl ether, ethyl ether, propyl ether, dipropylene glycol monomethyl ether, and other ethers, esters, acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, isobutyl ketone, and other ketones, and glycol compounds such as dipropylene glycol monomethyl ether, can be used. In addition, an acid or an alkali may be added to adjust the pH as necessary. Furthermore, in order to further improve the dispersion stability of the particles in the coating liquid, various surfactants, coupling agents, and the like may of course be added.

[0208] Using the above-mentioned dispersion medium, a dispersion liquid of solar radiation shielding material particles or the like can be prepared.

[0209] The additive liquid is a liquid in which solar radiation shielding functional material particles are dispersed in a plasticizer instead of the above-mentioned dispersion medium. The plasticizer for adjusting the plasticity of the vinyl resin is not particularly limited, and for example, one or more selected from dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate, di-2-ethylhexyl adipate, diisodecyl adipate, epoxy fatty acid monoester, triethylene glycol-di-2-ethylbutyrate, triethylene glycol-di-2-ethylhexoate, dibutyl sebacate, dibutyl sebacate, etc. can be used.

[0210] In addition, when a plasticizer is used as a dispersion medium, the plasticizer has a high viscosity and may hinder the dispersion of the solar radiation shielding functional material particles. In such a case, the dispersion medium of the dispersion liquid can be replaced with a plasticizer to produce an additive liquid using the plasticizer as the dispersion medium.

[0211] The coating liquid is prepared by mixing the above-mentioned dispersion liquid or additive liquid with a suitable binder component. The dispersion medium of the coating liquid can be selected according to the binder component.

[0212] As the binder component, for example, an inorganic binder or an organic binder can be used and can be selected arbitrarily.

[0213] When an inorganic binder is used as the binder component, examples of the inorganic binder include metal alkoxides of silicon, zirconium, titanium, or aluminum, partial hydrolysis and condensation polymers thereof, and organosilazanes.

[0214] In addition, when an organic binder is used as the binder component, styrene-based, acrylic-based, UV-curable resin, vinyl-based, urethane-based, and epoxy-based resins can be used as the organic binder. These resins may be blended as monomers or oligomers, or these resins may be dissolved in the solvent of the coating liquid. When a monomer or oligomer is added to the coating liquid as an organic binder, a curing agent or other agent required for curing the monomer may be added or contained in the coating liquid when it is applied.

[0215] When metal alkoxides of silicon, zirconium, titanium, or aluminum, and their hydrolysis polymers are used as inorganic binders, it is preferable to set the substrate heating temperature after coating of the coating liquid to, for example, 100° C. or higher. By setting the substrate heating temperature to 100° C. or higher, the polymerization reaction of the alkoxide or its hydrolysis polymer contained in the coating film can be almost completed. By almost completing the polymerization reaction, it is possible to suppress water or organic solvents from remaining in the film, and to increase the visible light transmittance of the film after heating. For this reason, the heating temperature is preferably 100° C. or higher, and more preferably is higher than the boiling point of the dispersion medium, plasticizer, etc. in the coating liquid.

[0216] The dispersed particle size is an index for evaluating the dispersion state of the solar radiation shielding functional material particles in the dispersion liquid, the additive liquid, and the coating liquid. The dispersed particle size means the size of the aggregated particles formed by the aggregation of the solar radiation shielding functional material particles dispersed in the solvent, and can be measured by various commercially available particle size distribution meters. For example, it can be obtained by measuring with ELS-8000 manufactured by Otsuka Electronics Co., Ltd., which is based on the principle of dynamic light scattering method.

[0217] When the above-mentioned dispersion liquid, additive liquid, or coating liquid is applied to a suitable transparent substrate to form a coating film, the coating method is not particularly limited. The coating method may be any method that can apply the dispersion liquid or coating liquid evenly, thinly, and uniformly, such as spin coating, bar coating, spray coating, dip coating, screen printing, roll coating, or flow coating.

[0218] The dispersion state of the solar radiation shielding functional material particles of this embodiment in the dispersion liquid, additive liquid, and coating liquid can be confirmed by measuring the dispersion state of the solar radiation shielding functional material particles when the solar radiation shielding functional material particles are dispersed in a dispersion medium. For example, it can be confirmed by sampling a sample from a liquid in which the solar radiation shielding functional material particles of this embodiment exist as particles or particle aggregates in a dispersion medium, and measuring it with various commercially available particle size distribution meters. As the particle size distribution meter, for example, a known measuring device such as ELS-8000 manufactured by Otsuka Electronics Co., Ltd. based on the principle of dynamic light scattering method can be used.

[0219] From the viewpoint of optical properties, the dispersed particle size of the solar radiation shielding functional material particles is preferably 800 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less.

[0220] The lower limit of the dispersed particle size of the solar radiation shielding material is not particularly limited, but it is preferably, for example, 10 nm or more.

[0221] The particles of the solar radiation shielding functional material are preferably uniformly dispersed in the dispersion medium, plasticizer, etc.

[0222] By setting the dispersed particle diameter of the solar radiation shielding functional material particles to 800 nm or less, it is possible to prevent, for example, a near-infrared absorbing film (near-infrared shielding film) or a molded body (plate, sheet, etc.) manufactured using the solar radiation shielding functional material particle dispersion from becoming grayish in color with a monotonically decreasing transmittance.

[0223] The dispersed particle size refers to the particle size of a single particle of the solar radiation shielding material dispersed in the solar radiation shielding material particle dispersion liquid, or the particle size of an aggregate of the solar radiation shielding material particles. EXAMPLES

[0224] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. [Example 1] 36g of water to Cs 2 CO 3 Dissolve 23.5g of this in H 2 WO 4 The mixture was added to 109 g of the raw material and thoroughly stirred, and then dried to obtain a raw material mixture according to Example 1 (raw material preparation step).

[0225] Next, the reaction step was carried out using the raw material mixture prepared in the raw material preparation step, and using the hybrid plasma reactor 10 shown in FIG. 1 in which DC plasma and high frequency plasma are superimposed.

[0226] First, the reaction system was evacuated to about 0.1 Pa (about 0.001 torr) using the vacuum exhaust device 13, and then completely replaced with argon gas to create an argon flow system at 1 atmosphere.

[0227] DC plasma was generated by flowing argon gas at 8 L / min through the plasma generation gas supply port 15. The DC power input at this time was 6 kW.

[0228] Furthermore, argon gas at 40 L / min and hydrogen gas at 3 L / min were spirally flowed from the sheath gas inlet 16 along the inner wall of the water-cooled quartz double tube 11 as gases for generating high-frequency plasma and protecting the quartz tube, generating high-frequency plasma.

[0229] The high frequency power input at this time was set to 45 kW. After generating such a hybrid plasma, the raw material mixture according to Example 1 was supplied into the plasma from the raw material powder supplying device 19 at a supply rate of 2 g / min using a mixed gas of argon gas at 3 L / min and oxygen gas at 0.01 L / min as a carrier gas.

[0230] As a result, the raw material was instantly evaporated and condensed in the plasma tail flame to become fine particles. Particles (cesium tungsten oxide particles a), which are particles of the solar radiation shielding material, were collected at the bottom of the reaction vessel 12.

[0231] The particle size of the collected cesium tungsten oxide particles a was determined by TEM observation, and it was confirmed that the particle size of the 30 particles evaluated was 10 nm or more and 50 nm or less. The particle size was calculated by taking the diameter of the smallest circle circumscribing the particle to be evaluated as the particle size of the particle.

[0232] The quantitative analysis of Cs, W, and O of the collected cesium tungsten oxide particles a revealed that they were 14.7 wt%, 65.5 wt%, and 18.3 wt%, respectively. The chemical formula calculated from the quantitative analysis was Cs 0.31 WO 3.21 The composition column in Table 1 shows the analysis results.

[0233] The M element, i.e., Cs, was evaluated using a flame atomic absorption spectrometer (VARIAN, model: SpectrAA 220FS). W was evaluated using an ICP optical emission spectrometer (Shimadzu, model: ICPE9000). O was evaluated using an oxygen and nitrogen simultaneous analyzer (LECO, model: ON836). The same applies to the other examples and comparative examples.

[0234] The X-ray diffraction pattern of the cesium tungsten oxide particles a was measured by powder X-ray diffraction (θ-2θ method) using a powder X-ray diffractometer (X'Pert-PRO / MPD manufactured by PANalytical, Spectris Co., Ltd.). The crystal structure of the compound contained in the cesium tungsten oxide particles a was identified from the obtained X-ray diffraction pattern, and it was found to be hexagonal Cs 0.3 WO 3 The same peak was confirmed. As described above, the crystal structure of the obtained composite tungsten oxide can be identified by the X-ray diffraction pattern. In the case of this embodiment, as described above, the crystal structure of the compound contained in the particles of the composite tungsten oxide coincides with the peak of the similar hexagonal composite tungsten oxide. Therefore, it can be confirmed that the crystal structure of the composite tungsten oxide obtained in this embodiment, that is, cesium tungsten oxide, is hexagonal.

[0235] 5% by weight of cesium tungsten oxide particles a, 5% by weight of polymer dispersant, and 90% by weight of dipropylene glycol monomethyl ether were weighed out, and a 0.3 mm diameter ZrO 2 The particles were crushed for 1 hour using a paint shaker containing beads. This resulted in the preparation of a dispersion of solar radiation shading material particles. The crystallite size after removing the solvent from the dispersion of solar radiation shading functional material particles was 25 nm. The lattice constants were 7.4099 Å for the a-axis and 7.6090 Å for the c-axis. The crystallite size and lattice constants were calculated using the Rietveld method. The evaluation results are shown in Table 2.

[0236] Next, the obtained dispersion liquid (liquid A) was added to polyvinyl butyral, and triethylene glycol-di-2-ethyl butyrate was added thereto as a plasticizer, to prepare an interlayer film composition such that the concentration of cesium tungsten oxide particles a was 0.036 mass% and the concentration of polyvinyl butyral was 71.1 mass%. The prepared composition was kneaded with a roll and formed into a sheet of 0.76 mm thickness to prepare an interlayer film. The prepared interlayer film was sandwiched between two green glass substrates of 100 mm x 100 mm x approximately 2 mm thickness, heated to 80°C for temporary adhesion, and then heated at 140°C and 14 kg / cm 2The final bonding was carried out using an autoclave, and a laminated structure A was produced.

[0237] The solar radiation-shading laminated structure A according to Example 1 was evaluated by the following evaluation method. <Heat resistance evaluation> The obtained laminated structure A was subjected to a heat resistance test in which it was held in the atmosphere at 120° C. for 125 hours, and the visible light transmittance and the Δ value of the solar transmittance of the solar radiation shading structure were evaluated.

[0238] The visible light transmittance and solar radiation transmittance were measured using a spectrophotometer U-4000 manufactured by Hitachi, Ltd., and calculated according to JIS R 3106 (2019). The solar radiation transmittance is an index showing the heat ray shielding performance.

[0239] The visible light transmittance and the solar radiation transmittance were evaluated before and after the heat resistance test, and the Δ value of the visible light transmittance was calculated by (visible light transmittance after the heat resistance test) - (visible light transmittance before the heat resistance test). In Table 1, the Δ value is shown as the Δ visible light transmittance. The Δ value of the solar radiation transmittance was calculated by (solar radiation transmittance after the heat resistance test) - (solar radiation transmittance before the heat resistance test). In Table 1, the Δ value is shown as the Δ solar radiation transmittance.

[0240] If each Δ value is 1.0% or less, it means that the heat resistance is excellent. If the Δ value is greater than 1.0%, it means that the heat resistance is poor. The evaluation results are shown in Table 1.

[0241] The visible light transmittance and solar radiation transmittance shown in Table 1 are the evaluation results before the heat resistance test.

[0242] [Table 1]

[0243] [Table 2] [Example 2] Particles of a solar radiation shielding material were prepared using a high frequency plasma reactor 30 shown in FIG.

[0244] The high frequency plasma reaction device 30 has a water-cooled quartz double tube 31 and a reaction vessel 32 connected to the water-cooled quartz double tube 31. In addition, a vacuum exhaust device 33 is connected to the reaction vessel 32.

[0245] Above the water-cooled quartz double tube 31, a plasma generating gas supply port 34 is provided.

[0246] The water-cooled quartz double tube 31 is configured so that a sheath gas for generating high-frequency plasma and for protecting the quartz tube can be supplied along the inner wall thereof, and a sheath gas inlet 36 is provided on the upper flange of the water-cooled quartz double tube 31.

[0247] A water-cooled copper coil 37 for generating high-frequency plasma is disposed around the water-cooled quartz double tube 31 .

[0248] A raw material powder carrier gas supply port 38 is provided near the plasma generation gas supply port 34 and is connected by piping to a raw material powder supply device 39 that supplies raw material powder.

[0249] The plasma generating gas supply port 34, the sheath gas inlet 36, and the raw material powder supply device 39 can be connected to a gas supply device 40 by piping, so that a predetermined gas can be supplied to each member from the gas supply device 40. If necessary, supply ports can be provided other than the above-mentioned members to cool the members in the apparatus or to create a predetermined atmosphere, and these can be connected to the gas supply device 40.

[0250] In this embodiment, argon gas was first supplied at 30 L / min from the plasma generating gas supply port 34, and a mixture of argon gas and hydrogen gas at a flow rate of 40 L / min and 3 L / min was supplied in a spiral shape from the sheath gas inlet 36. The input of the high frequency power source at this time was 45 kW.

[0251] Next, the raw material mixture prepared in Example 1 was supplied into the plasma at a rate of 2 g / min from raw material powder supply device 39 using a mixed gas of 3 L / min argon gas and 0.01 L / min oxygen gas as a carrier gas.

[0252] As a result, the particle diameter of the solar radiation shielding functional material particles recovered at the bottom of the reaction vessel 32 was found to be 10 nm or more and 50 nm or less by TEM observation.

[0253] The X-ray diffraction pattern of the obtained solar radiation shielding functional material particles according to Example 2 was measured by powder X-ray diffraction method (θ-2θ method). The crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern, and it was found to be hexagonal Cs 0.3 WO 3 The same peak was observed.

[0254] A dispersion liquid and a laminated structure were prepared and evaluated in the same manner as in Example 1, except that the solar radiation shielding functional material particles according to Example 2 were used.

[0255] The results are shown in Tables 1 and 2. [Example 3] Solar radiation shielding functional material particles according to Example 3 were produced in the same manner as in Example 2, except that a mixed gas of 5 L / min argon gas and 0.01 L / min oxygen gas was used as the carrier gas in Example 2. Then, a dispersion liquid and a laminated structure were produced and evaluated in the same manner as in Example 1, except that the solar radiation shielding functional material particles according to Example 3 were used.

[0256] The results are shown in Tables 1 and 2. [Example 4] Except for using a mixed gas of 4 L / min argon gas and 0.01 L / min oxygen gas as the carrier gas, the solar radiation shielding functional material particles of Example 4 were produced in the same manner as Example 2. Then, except for using the solar radiation shielding functional material particles of Example 4, a dispersion liquid and a laminated structure were produced and evaluated in the same manner as Example 1.

[0257] The results are shown in Tables 1 and 2. [Example 5] Except for using a mixed gas of argon gas at 5 L / min and oxygen gas at 0.02 L / min as the carrier gas, the solar radiation shielding functional material particles according to Example 5 were produced in the same manner as in Example 2. Then, except for using the solar radiation shielding functional material particles according to Example 5, a dispersion liquid and a laminated structure were produced and evaluated in the same manner as in Example 1.

[0258] The results are shown in Tables 1 and 2. [Example 6] Particles of the solar radiation shielding functional material according to Example 6 were produced in the same manner as in Example 2, except that a mixed gas of 4.5 L / min argon gas and 0.02 L / min oxygen gas was used as the carrier gas, and the raw material mixture prepared in Example 1 was supplied into the plasma at a rate of 2.5 g / min. Then, a dispersion liquid and a laminated structure according to Example 6 were produced and evaluated in the same manner as in Example 1, except that the particles of the solar radiation shielding functional material according to Example 6 were used.

[0259] The results are shown in Tables 1 and 2. [Example 7] Li in 50g water 2 CO 3 Dissolve 6.65g of H 2 WO 4 The mixture was added to 150 g of the raw material and thoroughly stirred, and then dried to obtain a raw material mixture according to Example 7.

[0260] Particles of the solar radiation shielding functional material according to Example 7 were produced in the same manner as in Example 2, except that the raw material mixture according to Example 7 was supplied into the plasma in the same manner as in Example 2. Then, a dispersion liquid and a laminated structure according to Example 7 were produced and evaluated in the same manner as in Example 1, except that the particles of the solar radiation shielding functional material according to Example 7 were used.

[0261] The results are shown in Table 1. [Example 8] 43g of water with sodium 2 CO 3 Dissolve 2.74g of H 2 WO 4 The mixture was added to 130 g of the raw material and thoroughly stirred, and then dried to obtain a raw material mixture according to Example 8.

[0262] Particles of the solar radiation shielding functional material according to Example 8 were produced in the same manner as in Example 2, except that the raw material mixture according to Example 8 was supplied into the plasma in the same manner as in Example 2. Then, a dispersion liquid and a laminated structure according to Example 8 were produced and evaluated in the same manner as in Example 1, except that the particles of the solar radiation shielding functional material according to Example 8 were used.

[0263] The results are shown in Table 1. [Example 9] K in 59g of water 2 CO 3 Dissolve 13.43g of H 2 WO 4 The mixture was added to 180 g of the raw material and thoroughly stirred, and then dried to obtain a raw material mixture according to Example 9.

[0264] Particles of the solar radiation shielding functional material according to Example 9 were produced in the same manner as in Example 2, except that the raw material mixture according to Example 9 was supplied into the plasma in the same manner as in Example 2. Then, a dispersion liquid and a laminated structure according to Example 9 were produced and evaluated in the same manner as in Example 1, except that the particles of the solar radiation shielding functional material according to Example 9 were used.

[0265] The results are shown in Table 1. [Example 10] Rb in 50g water 2 CO 3 Dissolve 22.17g of H 2 WO 4 The mixture was added to 150 g of the raw material and thoroughly stirred, and then dried to obtain a raw material mixture according to Example 10.

[0266] Particles of the solar radiation shielding functional material according to Example 10 were produced in the same manner as in Example 2, except that the raw material mixture according to Example 10 was supplied into the plasma in the same manner as in Example 2. Then, a dispersion liquid and a laminated structure according to Example 10 were produced and evaluated in the same manner as in Example 1, except that the particles of the solar radiation shielding functional material according to Example 10 were used.

[0267] The results are shown in Table 1. [Example 11] Cu(NO 3 )23H 2Dissolve 30.16 g of O in H 2 WO 4 The mixture was added to 120 g of the raw material and thoroughly stirred, and then dried to obtain a raw material mixture according to Example 11.

[0268] Particles of the solar radiation shielding functional material according to Example 11 were produced in the same manner as in Example 2, except that the raw material mixture according to Example 11 was supplied into the plasma in the same manner as in Example 2. Then, a dispersion liquid and a laminated structure according to Example 11 were produced and evaluated in the same manner as in Example 1, except that the particles of the solar radiation shielding functional material according to Example 11 were used.

[0269] The results are shown in Table 1. [Example 12] Ag in 40g water 2 CO 3 Dissolve 0.66g of this in H 2 WO 4 The mixture was added to 120 g of the raw material and thoroughly stirred, and then dried to obtain a raw material mixture according to Example 12.

[0270] Particles of the solar radiation shielding functional material according to Example 12 were produced in the same manner as in Example 2, except that the raw material mixture according to Example 12 was supplied into the plasma in the same manner as in Example 2. Then, a dispersion liquid and a laminated structure according to Example 12 were produced and evaluated in the same manner as in Example 1, except that the particles of the solar radiation shielding functional material according to Example 12 were used.

[0271] The results are shown in Table 1. [Example 13] 53g of water with CaCO 3 Dissolve 6.42g of H 2 WO 4 The mixture was added to 160 g of the raw material and thoroughly stirred, and then dried to obtain a raw material mixture according to Example 13.

[0272] Particles of the solar radiation shielding functional material according to Example 13 were produced in the same manner as in Example 2, except that the raw material mixture according to Example 13 was supplied into the plasma in the same manner as in Example 2. Then, a dispersion liquid and a laminated structure according to Example 1 were produced and evaluated in the same manner as in Example 1, except that the particles of the solar radiation shielding functional material according to Example 13 were used.

[0273] The results are shown in Table 1. [Example 14] SrCO in 59 g water 3 Dissolve 8.50g of this in H 2 WO 4 The mixture was added to 180 g of the raw material and thoroughly stirred, and then dried to obtain a raw material mixture according to Example 14.

[0274] Particles of the solar radiation shielding functional material according to Example 14 were produced in the same manner as in Example 2, except that the raw material mixture according to Example 14 was supplied into the plasma in the same manner as in Example 2. Then, a dispersion liquid and a laminated structure were produced and evaluated in the same manner as in Example 1, except that the particles of the solar radiation shielding functional material according to Example 14 were used.

[0275] The results are shown in Table 1. [Example 15] 40g of water + BaCO 3 Dissolve 13.26g of H 2 WO 4 The mixture was added to 120 g of the raw material and thoroughly stirred, and then dried to obtain a raw material mixture according to Example 15.

[0276] Particles of the solar radiation shielding functional material according to Example 15 were produced in the same manner as in Example 2, except that the raw material mixture according to Example 15 was supplied into the plasma in the same manner as in Example 2. Then, a dispersion liquid and a laminated structure were produced and evaluated in the same manner as in Example 1, except that the particles of the solar radiation shielding functional material according to Example 15 were used.

[0277] The results are shown in Table 1. [Example 16] In 2 O 3 1.67g and H 2 WO 4 150 g of the mixture was thoroughly mixed in a grinder to obtain a raw material mixture according to Example 16.

[0278] Particles of the solar radiation shielding functional material according to Example 16 were produced in the same manner as in Example 2, except that the raw material mixture according to Example 16 was supplied into the plasma in the same manner as in Example 2. Then, a dispersion liquid and a laminated structure according to Example 1 were produced and evaluated in the same manner as in Example 1, except that the particles of the solar radiation shielding functional material according to Example 16 were used.

[0279] The results are shown in Table 1. [Example 17] 180g of water with TlNO 3 Dissolve 12.15g of H 2 WO 4 The mixture was added to 60 g of the raw material and thoroughly stirred, and then dried to obtain a raw material mixture according to Example 17.

[0280] The solar radiation shielding functional material particles of Example 17 were produced in the same manner as in Example 2, except that the raw material mixture of Example 17 was supplied into the plasma in the same manner as in Example 2. Then, a dispersion liquid and a laminated structure were produced and evaluated in the same manner as in Example 1, except that the solar radiation shielding functional material particles of Example 17 were used.

[0281] The results are shown in Table 1. [Example 18] SnO 2 17.18g and H 2 WO 4 150 g of the mixture was thoroughly mixed in a grinder to obtain a raw material mixture according to Example 18.

[0282] Particles of the solar radiation shielding functional material according to Example 18 were produced in the same manner as in Example 2, except that the raw material mixture according to Example 18 was supplied into the plasma in the same manner as in Example 2. Then, a dispersion liquid and a laminated structure were produced and evaluated in the same manner as in Example 1, except that the particles of the solar radiation shielding functional material according to Example 18 were used.

[0283] The results are shown in Table 1. [Example 19] Yb 2 O 3 17.98g and H 2 WO 4120 g of the mixture was thoroughly mixed in a grinder to obtain a raw material mixture according to Example 19.

[0284] Particles of the solar radiation shielding functional material according to Example 19 were produced in the same manner as in Example 2, except that the raw material mixture according to Example 19 was supplied into the plasma in the same manner as in Example 2. Then, a dispersion liquid and a laminated structure were produced and evaluated in the same manner as in Example 1, except that the particles of the solar radiation shielding functional material according to Example 19 were used.

[0285] The results are shown in Table 1. [Example 20] 17.25g of Nissan Chemical's Snowtex S and H 2 WO 4 The mixture was thoroughly mixed with 150 g of maltose in a grinder and then dried to obtain a raw material mixture according to Example 20.

[0286] Particles of the solar radiation shielding functional material according to Example 20 were produced in the same manner as in Example 2, except that the raw material mixture according to Example 20 was supplied into the plasma in the same manner as in Example 2. Then, a dispersion liquid and a laminated structure according to Example 20 were produced and evaluated in the same manner as in Example 1, except that the particles of the solar radiation shielding functional material according to Example 20 were used.

[0287] The results are shown in Table 1. [Comparative Example 1] Add 50g of water to cesium carbonate (Cs 2 CO 3 55.45 g of tungstic acid (H 2 WO 4 The mixture was added to 286 g of tungsten and cesium, thoroughly mixed, and then dried with stirring. The molar ratio of W to Cs in the dried product was W:Cs=1:0.33.

[0288] The dried product is 2 5% H with gas as carrier gas 2 The mixture was sintered at 800°C for 5.5 hours in a N2 gas atmosphere. 2 The gas was switched to only the gas, and the temperature was lowered to room temperature, to obtain cesium tungsten oxide particles, which are the solar radiation shielding functional material particles according to Comparative Example 1.

[0289] The X-ray diffraction pattern of the solar radiation shielding functional material particles according to Comparative Example 1 obtained was measured by the powder X-ray diffraction method (θ-2θ method). When the crystal structure contained in the particles was specified from the obtained X-ray diffraction pattern, hexagonal Cs 0.3 WO 3 The same peaks as those of were confirmed. The solar radiation shielding functional material particles according to Comparative Example 1 were coarser particles than the particles a obtained in Example 1.

[0290] 5% by weight of the solar radiation shielding functional material particles according to Comparative Example 1, 5% by weight of a polymer dispersant, and 90% by weight of dipropylene glycol monomethyl ether were weighed and placed in a paint shaker (manufactured by Asada Iron Works Co., Ltd.) containing 0.3 mmφ ZrO 2 beads, and a dispersion of the solar radiation shielding functional material particles according to Comparative Example 1 was prepared by pulverizing and dispersing for 20 hours. A combined structure was produced and evaluated in the same manner as in Example 1 except that the dispersion of the solar radiation shielding functional material particles according to Comparative Example 1 was used. The evaluation results are shown in Table 1.

[0291] In addition, for the composite tungstate oxide particles, which are the solar radiation shielding functional material particles obtained after removing the solvent from the dispersion of the solar radiation shielding functional material particles according to Comparative Example 1, the crystallite size and lattice constant were determined. The crystallite size was 9 nm.

[0292] The evaluation results are shown in Tables 1 and 2. (Summary) As is clear from Table 1, the solar radiation shielding functional material particles according to Examples 1 to 20 satisfied the relationship of 3.0 < z / y for z and y in the general formula M x W y O z of the contained composite tungstate oxide. It was also confirmed that the combined structures according to Examples 1 to 20 had a Δ value of 1.0% or less with respect to both the visible light transmittance and the solar radiation transmittance and were excellent in weather resistance.

[0293] In addition, as shown in Table 1, it was confirmed that the laminated structures of Examples 1 to 20 had solar transmittance of about 50% or less when the visible light transmittance was about 70%. In other words, it was confirmed that they had sufficient near-infrared absorption properties and visible light transmittance. [Explanation of symbols]

[0294] 501~508 Solar shading laminated structure 51, 70 Laminated board 521~528 Middle class 611 Solar radiation shielding functional material particles 612, 631 Synthetic resin 622 Interlayer

Claims

1. Two laminated sheets selected from sheet glass and sheet plastic; and an intermediate layer disposed between the two laminated plates, At least one member selected from the laminate and the intermediate layer contains solar radiation shielding functional material particles, The solar radiation shielding functional material particles are represented by the general formula M ｘ W ｙ O ｚ (wherein M element is one or more elements selected from Cs, Li, Na, K, Rb, Cu, Ag, Ca, Sr, Ba, In, Tl, Sn, Yb, and Si, W is tungsten, O is oxygen, and 0.001≦x / y≦1, 3.0<z / y<3.4) is contained, The solar radiation shielding laminated structure, wherein the particle diameter of the solar radiation shielding functional material particles is 10 nm or more and 100 nm or less.

2. 2. The solar radiation-shielding laminated structure according to claim 1, wherein the M element contains one or more elements selected from the group consisting of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, and Sn.

3. 3. The solar radiation-shading laminated structure according to claim 1, wherein the composite tungsten oxide particles contain crystals having one or more crystal structures selected from hexagonal, tetragonal, and cubic crystals.

4. The M element contains one or more elements selected from Cs and Rb, The composite tungsten oxide has a hexagonal crystal structure, The solar radiation shading laminated structure according to any one of claims 1 to 3, wherein the composite tungsten oxide has a lattice constant of an a-axis of 7.3850 Å or more and 7.4186 Å or less and a c-axis of 7.5600 Å or more and 7.6240 Å or less.

5. the intermediate layer includes at least one intermediate film containing a synthetic resin, The solar radiation shading laminated structure according to any one of claims 1 to 4, wherein the intermediate layer has at least one layer of a solar radiation shading intermediate film containing the synthetic resin and the solar radiation shading functional material particles disposed in the synthetic resin as the intermediate film.

6. the intermediate layer has at least one intermediate film containing a synthetic resin, The intermediate layer is an intermediate film, A supporting intermediate film containing the synthetic resin; 5. The solar radiation shading laminated structure according to claim 1, further comprising a solar radiation shading intermediate film formed on at least one surface of the support intermediate film, the solar radiation shading intermediate film containing the synthetic resin and the solar radiation shading functional material particles disposed in the synthetic resin.

7. 7. The solar radiation shading laminated structure according to claim 6, wherein the supporting intermediate film is a ductile resin film.

8. the intermediate layer has at least one intermediate film containing a synthetic resin, The solar-shading laminated structure according to any one of claims 1 to 4, wherein the intermediate layer is a ductile resin film as the intermediate film, and the resin film contains solar-shading functional material particles.

9. 9. The solar radiation-shielding laminated structure according to claim 5, wherein the synthetic resin is a vinyl resin or an ionomer resin.

10. The solar radiation-shading laminated structure according to any one of claims 1 to 9, wherein the plate-like plastic contains one or more types of resin selected from the group consisting of polycarbonate resin, acrylic resin, and polyethylene terephthalate resin.

Images