JP6413969B2 - Dispersion for forming solar shading body and solar shading body using the dispersion - Google Patents

Description

  The present invention is applied to window materials for vehicles, buildings, offices, general houses, etc., as well as single glass, laminated glass, plastics and fibers used for telephone boxes, show windows, lighting lamps, transparent cases, etc. The present invention relates to a dispersion for forming a solar shading body using solar shading particles that are transparent to light in the visible light region and absorb in light in the near infrared region, and a solar shading body using the dispersion.

As a method for removing and reducing heat components from an external light source such as sunlight or a light bulb, conventionally, for example, a film made of a material that reflects infrared rays is formed on the glass surface, and the glass is used as a heat ray reflective glass or the like. It was done. As the infrared reflecting material, metal oxides such as FeO _x , CoO _x , CrO _x , and TiO _x and metal materials such as Ag, Au, Cu, Ni, and Al have been selected and used.

However, these metal oxides and metal materials have the property of reflecting or absorbing visible light as well as infrared rays that greatly contribute to heat. For this reason, in the heat ray reflective glass etc. in which the film of these metal oxides or metal materials was formed, there existed a problem that visible light transmittance fell.
In particular, a heat ray shielding base material used for building materials, vehicles, telephone boxes and the like requires high transmittance in the visible light region. Therefore, in order to remove / reduce the heat component, when using the metal oxide or the infrared reflecting material of the metal material, the film thickness of the coating has to be very thin.

  In order to form a thin film of metal oxide or metal material, a thin film having a thickness of 10 nm is formed by using a physical film forming method such as a spray baking method, a CVD method, a sputtering method, or a vacuum evaporation method. A method of forming a film is employed. However, these film forming methods require a large-scale apparatus and vacuum equipment, and there are drawbacks in productivity and large area, and there is a drawback that the manufacturing cost of the film becomes high.

  Furthermore, with infrared reflective materials selected from metal oxides and metal materials, if the heat component is removed / reduced from an external light source such as sunlight to increase heat ray shielding characteristics, the reflectance in the visible light region also increases at the same time. There is a tendency to end up. For this reason, there also existed a fault which gave the heat-shielding base material the glossy appearance like a mirror and impaired the beauty | look.

On the other hand, a film formed using these materials has a relatively low electric resistance value. For this reason, the reflection of radio waves becomes high. For example, when used in building materials, vehicles, etc., radio waves from mobile phones, TVs, radios, etc. are reflected and cannot be received, or radio interference is caused in the surrounding area. There were also disadvantages. In order to improve the defect, the reflectance of light in the visible light region is low and the reflectance of light in the infrared region is high, and the surface resistance value is approximately 10 ⁶ Ω / □ (read as ohm-per-square) or more. There is a need for a solar radiation shield that can be controlled easily.

Here, antimony-containing tin oxide (sometimes referred to as “ATO” in the present invention) or indium-containing tin oxide (this material) is a material having high visible light transmittance and excellent solar radiation shielding function. In the invention, it may be described as “ITO”). These materials do not give a glaring appearance due to their relatively low visible light reflectivity.
However, since the plasma frequency of these materials is in the near infrared region, the reflection / absorption effect is not yet sufficient in the near infrared region close to visible light. Furthermore, since these materials have a low solar shielding power per unit mass, there is a problem that the amount of use is increased to obtain a high solar shielding function, and the cost is high.

  In addition, a transparent base material that has a simple and low cost solar shading function by applying a coating solution containing the solar shading material fine particles on an appropriate base material and forming a solar shading film on the base material. It has also been proposed to manufacture.

  For example, Patent Document 1 discloses that the hexaboride possesses a large amount of free electrons, and the hexaboride has a maximum transmittance in the visible light region by being finely dispersed into fine particles. It is disclosed that a strong plasma reflection occurs in the near-infrared region close to the light region and the transmittance becomes minimum.

  Patent Document 2 discloses a coating solution for forming a sunscreen film containing hexaboride fine particles as a sunscreen material in a binder.

  Patent Document 3 discloses that tungsten oxide fine particles and a solar radiation shielding material used for a solar radiation shielding material that can be applied to various existing base materials and can reduce infrared transmittance while keeping visible light transmittance high. A manufacturing method, a dispersion for forming a sunscreen using the tungsten oxide fine particles, and a sunscreen are disclosed.

  Patent Document 4 discloses that ATO fine particles and hexaboride fine particles are selected from various materials having a high visible light transmittance and an excellent heat ray shielding function, and these are used in combination. ing. Additive liquid for producing heat ray shielding resin sheet material in which fine particles of heat ray shielding component are dispersed, the solar radiation shielding characteristics are improved by using the combined use, and the amount of ATO used is reduced to reduce the material cost. It is disclosed that a heat ray shielding resin sheet material having a high light transmittance in the visible light region, a low reflectance, and a low light transmittance in the near infrared region can be obtained.

JP 2000-72484 A JP 2001-262061 A JP 2005-187323 A JP 2003-327717 A

  According to the study by the present inventors, a solar radiation shielding body obtained using a dispersion for forming a solar radiation shielding body using the ATO fine particles and the hexaboride fine particles has excellent solar radiation shielding properties. However, in the solar shield formed by kneading the solar shield-forming dispersion into the solar shield-forming base material and forming it into a plate shape, sheet shape, or film shape, weather resistance, particularly wet heat characteristics, that is, wet heat It was found that the hydrolysis resistance under the atmosphere is not satisfactory and has room for improvement.

  The present invention has been made under the above-described circumstances, and the problem to be solved is a solar radiation shielding body having excellent solar radiation shielding characteristics and weather resistance, particularly wet heat characteristics, and the solar radiation shielding body. It is providing the dispersion liquid for solar radiation shielding body formation for forming.

The present inventors have conducted intensive research to solve the above problems.
Specifically, in a dispersion for forming a solar shading material in which a solar shading fine particle and a dispersing agent in which ATO fine particles and hexaboride fine particles are combined are dispersed in a solvent, attention is paid to the effect of the dispersing agent. And examined. And when a solar radiation shielding body is formed using the dispersion liquid for solar radiation shielding body containing the dispersing agent which has an amine value and an acid value is 19 mgKOH / g or less, the heat-and-moisture resistance characteristic of the obtained solar radiation shielding body As a result, the present invention has been completed.

The first invention for solving the above-described problems is as follows.
A dispersion for forming a sunscreen, in which sunscreen particles and a dispersant are dispersed in a solvent,
The solar shading fine particles have the general formula XB ₆ (where X is La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr, Ca 1 or more selected from the group of the above) and antimony-containing tin oxide ( ATO ) fine particles, and the average primary particle size of the hexaboride fine particles and the ATO fine particles is It is 200 nm or less, the content of the hexaboride fine particles in the dispersion for forming the sunscreen is 0.01% by mass to 3.0% by mass, and the content of the ATO fine particles is 10.0% by mass. % To 30.0% by mass, and the hexaboride fine particles and the ATO fine particles are blended in a mass ratio of 0.1: 99.9 to 13.8: 86.2,
The dispersant is a dispersion for forming a solar radiation shielding body, wherein the amine value is 10 mgKOH / g or more and 29 mgKOH / g or less , and the acid value is 19 mgKOH / g or less.
The second invention is
The ATO fine particles have a tap density of 1.85 g / cm ³ or less, a specific surface area of 5 to 110 m ² / g, and a powder color L ^* of 40 to 65 according to the L ^* a ^* b ^* color system. Yes, a ^* is -5 to -1, b ^* is -11 to -1,
The hexaboride fine particles have a lattice constant of 0.4100 to 0.4160 nm, a powder color L ^* according to L ^* a ^* b ^* color system of 30 to 60, and a ^* of −5 to 10. And b ^* is -10 to 2, which is a dispersion for forming a solar shading body.
The third invention is
The dispersion for forming the sunscreen further comprises ZrO ₂ , TiO ₂ , Si ₃ N ₄ , SiC, SiO ₂ , Al ₂ O ₃ , Y ₂ O ₃ , ZnO, CeO ₂ , Fe (OH) ₃ , FeOOH. A dispersion for forming a sunscreen, comprising at least one compound selected from the group consisting of:
The fourth invention is:
The solar shading body is characterized in that a film including the solar shading body forming dispersion is formed on a substrate.
The fifth invention is:
The solar radiation shielding body is characterized in that the base material is a transparent base material.
The sixth invention is:
The said transparent base material is 1 type selected from glass, a resin film, and a resin board, It is a solar radiation shielding body characterized by the above-mentioned.
The seventh invention
The solar shading material, wherein the solar shading material forming base material into which the solar shading material forming dispersion is kneaded is formed into a shape selected from a plate shape, a sheet shape, and a film shape. Is the body.

  The solar shield obtained by forming a coating film on a substrate using the dispersion for forming a solar shield according to the present invention, and the dispersion for forming the solar shield are kneaded into the base material for forming the solar shield. The solar shield formed into any one of a plate shape, a sheet shape, and a film shape is an industrially useful solar shield that is excellent in weather resistance, particularly moisture and heat resistance.

Hereinafter, embodiments for carrying out the present invention will be described in detail.
The dispersion for forming solar radiation shielding material according to the present invention is a dispersion for forming solar radiation shielding material in which solar radiation shielding particles and a dispersing agent are dispersed in a solvent, and the solar radiation shielding fine particles have the general formula XB _6. (However, X is one or more selected from the group of La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr, Ca) The hexaboride fine particles and the ATO fine particles, wherein the hexaboride fine particles and the ATO fine particles have an average primary particle size of 200 nm or less, The content of the fluoride fine particles is 0.01% by mass or more and 3.0% by mass or less, the content of the ATO fine particles is 10.0% by mass or more and 30.0% by mass or less, the hexaboride fine particles and the above ATO fine particles are 0.1: 99.9 in mass ratio 13.8: formulated in a range of 86.2, the dispersant has an amine value and acid value is for forming a solar radiation-shielding body dispersions or less 19 mgKOH / g.

  The dispersion for solar radiation shielding body according to the present invention will be described in order of (1) solar radiation shielding fine particles, (2) dispersant, (3) solvent, (4) binder, (5) other additives, Further, (6) a dispersion for forming a solar shield and (7) a solar shield according to the present invention will be described.

(1) Fine particles for solar shading The fine particles for solar shading used in the dispersion for forming a solar shield according to the present invention are a combination of hexaboride fine particles and ATO fine particles.
The solar shielding fine particles will be described below in the order of a) hexaboride fine particles, b) ATO fine particles, and c) solar shielding fine particles.

a) Hexaboride fine particles The hexaboride fine particles according to the present invention have an average primary particle size of 200 nm or less, a crystal structure of a simple cubic lattice, a lattice constant of 0.4100 to 0.4160 nm, and L The powder color in the ^* a ^* b ^* color system is preferably such that L ^* is 30 to 60, a ^* is -5 to 10, and b ^* is -10 to 2.

Here, the average primary particle diameter is a value calculated as follows.
That is, hexaboride fine particles, a dispersing agent, beads, and the like are placed in a solvent and loaded into, for example, a paint shaker, and the hexaboride particles are pulverized and dispersed. It is a value calculated by TEM-EDS analysis of the obtained hexaboride fine particles after removing the solvent by evaporating and removing the dispersant by thermal decomposition after the treatment.

The boride fine particles are represented by the general formula XB _m (where X is La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr, Ca). Borides represented by XB _4, XB _6, XB _{12, and the} like. However, when it is used as a material for solar radiation shielding, it is preferable that 4 ≦ m <6.3. That is, the hexaboride fine particles according to the present invention are preferably mainly composed of XB ₄ and XB ₆ among the borides described above, and may further partially include XB ₁₂ .

Here, m is a chemical analysis of the obtained powder containing boride fine particles, and indicates the atomic ratio of B to one atom of the X element. The produced powder containing boride fine particles is actually a mixture of XB _4, XB _6, XB _{12, and the} like. For example, even in the case of hexaboride which is a typical boride fine particle, even if it is a single phase in X-ray diffraction measurement, 5.8 <m <6.2 is actually obtained, and a small amount of other phases are included. It is thought that there is.
Here, when m> 4, the generation of XB, XB _{2 and the} like is suppressed, and the reason is unknown, but the solar radiation shielding characteristics are improved.
On the other hand, when m ≦ 6.3, the generation of boron oxide particles, which are boron compounds other than boride fine particles, is suppressed. Since the boron oxide particles are hygroscopic, if the formation of boron oxide particles in the boride fine particle powder is suppressed, the moisture resistance of the boride fine particle powder is ensured, and the solar radiation shielding characteristics are maintained over time. Deterioration is suppressed, which is preferable. Therefore, it is preferable to suppress the formation of boron oxide particles by setting m ≦ 6.3.

The hexaboride fine particles according to the present invention can be produced by, for example, a solid phase reaction method, an evaporation quenching method, or a gas phase method such as a plasma CVD method.
As a method for producing hexaboride fine particles according to the present invention, a method for producing LaB ₆ (lanthanum hexaboride) by a solid-phase reaction method will be described as an example, and the above-described powder characteristics are provided. If so, the manufacturing method is not limited.

In the solid phase reaction method, a reducing agent is added to a boron compound and a lanthanum compound, and these are reacted at a high temperature to produce lanthanum hexaboride. However, under normal reaction conditions for producing lanthanum hexaboride, the average primary particle diameter becomes coarse powder exceeding 400 nm, and desired optical characteristics cannot be obtained.
Therefore, for example, by pulverizing lanthanum hexaboride particles by a mechanical method such as a jet mill or a bead mill in the subsequent step, or by adding a grain growth inhibitor during the solid phase reaction between the boron compound and the lanthanum compound, Prepare by controlling the particle size distribution. As a result, lanthanum hexaboride fine particles having an average primary particle diameter of 200 nm or less can be obtained.

  In order to use the obtained lanthanum hexaboride fine particles in the dispersion for forming a solar shield according to the present invention, it is necessary that light scattering by the particles is small and the transparency is excellent. For this reason, the average primary particle diameter of the lanthanum hexaboride fine particles is preferably 200 nm or less, and more preferably 100 nm or less.

  It is preferable that the average primary particle diameter of the lanthanum hexaboride fine particles is 200 nm or less. If the average primary particle diameter of the fine particles is 200 nm or less, the wavelength is 380 to 780 nm due to geometric scattering or Mie scattering. This is because it is possible to avoid a phenomenon in which the light in the visible light region is scattered to become frosted glass, and clear transparency cannot be obtained.

Furthermore, when the average primary particle diameter of the lanthanum hexaboride fine particles is 200 nm or less, the geometric scattering and Mie scattering are reduced, and a Rayleigh scattering region is obtained. In the Rayleigh scattering region, the scattered light decreases in inverse proportion to the sixth power of the particle diameter, so that the scattering is reduced and the transparency is improved as the average primary particle diameter decreases. Therefore, when the average primary particle diameter is 100 nm or less, the scattered light becomes very small and the transmittance is further improved.
However, since transparency may not be required depending on the application, the average primary particle diameter of the lanthanum hexaboride fine particles may be appropriately set within a range of 2 nm to 10 μm.

In general, hexaboride fine particles are powders colored in gray black, brown black, green black, etc. depending on the production conditions, but the particle diameter of the powder is sufficiently small compared to the visible light wavelength, and is shielded from sunlight. When uniformly dispersed in the body, visible light permeability can be ensured while sufficiently maintaining the infrared light shielding ability.
The reason for this is not known in detail, but these hexaboride particles have a large amount of free electrons in the particles, and the absorption energy of indirect transition between bands due to free electrons inside and on the surface of the particles is just visible. ~ Because it is near the near infrared region, it is considered that heat rays in this wavelength region are selectively reflected and absorbed.

According to the study by the present inventors, a specific surface area of hexaboride fine particles is set to 10 m ² / g or more, and a dispersion for forming a solar shading film in which the hexaboride fine particles are uniformly dispersed in a solvent is used. The formed solar radiation shielding film had a maximum value of transmittance between wavelengths of 400 nm and 700 nm, and had a minimum value of transmittance between wavelengths of 700 nm and 1800 nm. Furthermore, it was found that the difference between the maximum value and the minimum value of the transmittance was 15 points or more.
On the other hand, in view of human vision, the wavelength range of visible light wavelength is 380 nm to 780 nm, and considering that the visibility is a bell-shaped peak with a wavelength near 550 nm, visible light is transmitted through the solar radiation shielding film. It can be understood that other heat rays are effectively reflected or absorbed.

Furthermore, the solar radiation shielding ability per unit mass of the hexaboride fine particles according to the present invention is very high. For example, the effect can be obtained when the amount used is 1/10 or less (mass ratio) compared to ITO fine particles and ATO fine particles. Demonstrate.
In addition, the present inventors can further improve only the solar radiation shielding property while maintaining a certain visible light transmittance by using the hexaboride fine particles in combination with the ITO fine particles and / or the ATO fine particles. I found out. As a result, it was also found that the total amount of solar shielding particles used can be reduced and the production cost can be reduced.

  In addition, the hexaboride microparticles according to the present invention are also absorbent in the visible light region. For this reason, the absorption in the visible light region of the solar shading film can be controlled by controlling the amount of hexaboride fine particles added to the solar shading body. As a result, the solar radiation shielding film according to the present invention can have additional functions such as brightness adjustment and privacy protection.

The hexaboride fine particles according to the present invention have a powder color L ^* of 30 to 60 in the L ^* a ^* b ^* color system (JIS Z8729) recommended by the International Commission on Illumination (CIE). It is preferable to use those in the range where a ^* is −5 to 10 and b ^* is −10 to 2. This is because, when the powder color is in the above-described range, absorption derived from localized surface plasmon resonance due to free electrons of hexaboride fine particles is exhibited, and the solar radiation shielding effect is ensured.

  It is preferable that the boride fine particles applied to the solar shield are not oxidized on the surface, but usually the boride fine particles obtained are often slightly oxidized, and the surface is oxidized during the fine particle dispersion process. Something is unavoidable. However, if it is slightly oxidized, there is no change in the effectiveness of expressing the solar radiation shielding effect. The above-described characteristic range of the powder color is considered to be related to the degree of particle surface oxidation at which the boride fine particles can secure the solar shading effect.

In the hexaboride fine particles (XB ₆ ), the higher the completeness as a crystal, the greater the solar radiation shielding effect. However, even if the crystallinity is low and an extremely broad diffraction peak is generated by X-ray diffraction, the basic bonds inside the fine particles are composed of X element and B bonds, and the average primary particle diameter is 200 nm. In the following, the crystal structure is a simple cubic lattice, the lattice constant is 0.4100 to 0.4160 nm, the powder color according to the L ^* a ^* b ^* color system is L ^* is 30 to 60, and a ^* is If it is -5-10 and b ^* is in the range which is -10-2, it is possible to express a desired solar shading effect.

b) ATO fine particles The ATO fine particles according to the present invention preferably have an average primary particle diameter of 200 nm or less. And it is preferable that a tap density is 1.85 g / cm < ³ > or less. When the ATO fine particles have the above-mentioned fine particle properties, pulverization and dispersion with a medium stirring mill or the like proceed smoothly in the mixing step when producing the dispersion for forming a sunscreen according to the present invention.

The ATO fine particles according to the present invention preferably have a specific surface area of 5 to 110 m ² / g. When the specific surface area of the ATO fine particles is within the range, the solar shading effect is secured in the solar shading body forming dispersion according to the present invention.

  If the ATO fine particles having the above average primary particle diameter, tap density and specific surface area are dispersed in a solvent to produce the dispersion for forming the solar shielding body, the dispersion of the ATO fine particles becomes stable, and the dispersion at that time The particle diameter can be 200 nm or less.

The powder color of the ATO fine particles according to the present invention is such that L ^* is 40 to 65 in the powder color evaluated by the L ^* a ^* b ^* color system recommended by the International Commission on Illumination (CIE). , A ^* is preferably -5 to -1, and b ^* is preferably -11 to -1. This is because if the powder color is within the above-described range, a desired solar radiation shielding effect can be obtained.

  The crystallite diameter of the ATO fine particles according to the present invention is preferably 4 to 125 nm. More preferably, it is 5-80 nm, More preferably, it is 6-60 nm. If the crystallite diameter is 4 nm or more and 125 nm or less, the desired solar radiation shielding effect is obtained in the solar radiation shielding body-forming dispersion according to the present invention.

  In the ATO fine particles according to the present invention, regarding the influence of the crystallite diameter on the solar radiation shielding function, the larger the specific surface area, the smaller the crystallite diameter. It can be seen that there is a negative correlation. Here, although details are unknown, it is presumed that the crystallite diameter has an influence on the solar radiation shielding function similarly to the specific surface area, and there is an optimum range of the crystallite diameter with respect to the solar radiation shielding function.

And the solar shielding body which adjusted the dispersion state so that the dispersion particle diameter when dispersing the ATO microparticles | fine-particles which concern on this invention in a solvent, and setting it as the dispersion liquid for solar radiation shielding formation concerning this invention will be 200 nm or less. It is desirable to form a solar shield using a forming dispersion. If the dispersed particle diameter is 200 nm or less, the haze value can be suppressed, and a desired solar radiation shielding effect can be obtained.
Here, the dispersed particle diameter means the aggregate particle diameter of the ATO fine particles dispersed in the solvent, and can be measured by various commercially available particle size distribution meters. For example, sampling can be performed from a dispersion in which ATO fine particles are dispersed in a solvent, and measurement can be performed using ESL-800 manufactured by Otsuka Electronics Co., Ltd. based on the principle of dynamic light scattering.

An example of the method for producing ATO fine particles according to the present invention will be described below.
First, an alcohol solution in which an antimony compound is dissolved and an alkali solution are dropped in parallel to a tin compound solution having a liquid temperature of 50 ° C. or lower, or an alcohol in which a tin compound solution and an antimony compound are dissolved in an alkali solution at 50 ° C. or lower. The solution is dropped in parallel to form and precipitate a hydroxide, which is a fine particle precursor containing tin and antimony. Note that HCl may be added to the tin compound solution in advance. If the solution temperature is 50 ° C. or lower, the concentration of tin compound and antimony compound in the system will not change due to evaporation of water as a solvent, etc. Easy to obtain. Furthermore, if the solution temperature is 50 ° C. or lower, the growth of the fine particle precursor is suppressed, and desired optical characteristics can be obtained in the ATO fine particles. On the other hand, the lower limit of the solution temperature is not particularly limited, but for example, a cooling device or the like is newly required to lower the temperature below room temperature, and device costs and production costs are generated. It is preferable to do.

  The amount of antimony compound added to the above-described tin compound solution is preferably 1 to 20% by mass, more preferably 3 to 15% by mass in terms of element with respect to tin oxide, from the viewpoint of desired optical properties. is there. In addition, the tin compound and antimony compound to be used are not particularly limited, and examples thereof include tin chloride, tin nitrate, tin sulfide, antimony chloride, and antimony bromide. Examples of the alkaline solution used as the precipitating agent include aqueous solutions of ammonium hydrogen carbonate, ammonia water, sodium hydroxide, potassium hydroxide, and the like, and ammonium hydrogen carbonate and ammonia water are particularly preferable. And the alkali concentration of the said alkali solution should just be more than the chemical equivalent required for a tin compound and an antimony compound to become a hydroxide, More preferably, it is good to set it as 3 times the equivalent-equivalent. The parallel dropping time of the alcohol solution and the alkali solution or the alcohol solution and the tin compound solution is 0.5 minutes or more from the viewpoint of the particle size and productivity of the precipitated hydroxide, and is 60 minutes. In the following, it is desirable to set it for 30 minutes or less. In order to make the system uniform after completion of the dropping, the aqueous solution is continuously stirred, and the temperature of the aqueous solution at that time should be the same as the temperature at the time of the parallel dropping, and should be 50 ° C. or less. preferable. The duration of stirring is not particularly limited, but it is 0.5 minutes or more from the viewpoint of productivity, and 30 minutes or less, preferably 15 minutes or less.

  Next, decantation is repeatedly performed on the precipitate, and the precipitate is sufficiently washed until the electrical conductivity of the supernatant of the washing solution in the decantation is 1 mS / cm or less, and filtered. When impurities such as chloride ions and sulfate ions remaining in the precipitate exceed 1.5% by mass, the solid solution of antimony with respect to tin oxide is inhibited in the firing step, and the desired optical characteristics are not exhibited. It is preferable to sufficiently wash and filter until the conductivity of the supernatant of the cleaning liquid in decantation is 1 mS / cm or less. If the electrical conductivity of the supernatant is 1 mS / cm or less, the amount of impurities remaining in the precipitate can be 1.5% by mass or less.

The washed precipitate is wet-treated with an alcohol solution to obtain a wet-treated product, and then calcined, if necessary, one or more elements selected from Si, Al, Zr, and Ti are converted into oxides. You may dry, after immersing in the alcohol solution made to contain less than 15 mass%. By performing the treatment, one or more elements selected from Si, Al, Zr, and Ti exist independently in the vicinity of the ATO fine particles, and the grain growth is suppressed during the firing of the ATO fine particles. On the other hand, if the content of these elements in terms of oxides is less than 15% by mass, the solar shielding properties of the ATO fine particles are ensured, which is preferable.
When the above-described wet treatment is performed, the concentration of the alcohol solution is preferably 50% or more. This is because if the concentration of the alcohol solution is 50% or more, the ATO fine particles can be prevented from becoming a massive strong aggregate. Here, the alcohol used in the alcohol solution is not particularly limited, but is preferably an alcohol having excellent solubility in water and having a boiling point of 100 ° C. or lower. Examples include methanol, ethanol, propanol, and tert-butyl alcohol.

  In the above-described wet treatment, the filtered and washed precipitate may be put into an alcohol solution and stirred, and the time and stirring speed at this time may be appropriately selected according to the amount of treatment. The amount of the alcohol solution at the time when the precipitate is put into the alcohol solution may be a liquid amount that can ensure fluidity that can easily stir the precipitate. The stirring time and the stirring speed are appropriately selected on the condition that a precipitate containing a part that has been partially aggregated during filtration and washing is uniformly mixed in the alcohol solution until there is no aggregated part. In addition, the temperature of the wet treatment may be usually performed at room temperature, but it is of course possible to carry out the heating while heating to the extent that the alcohol is not lost by evaporation. Preferably, the heating is performed at a temperature below the boiling point of the alcohol. When heated at a temperature below the boiling point of the alcohol, the situation where the alcohol is evaporated and lost during the wet process is avoided, and the effect of the wet process is ensured, thereby avoiding the situation where the wet processed product becomes a strong aggregate. Because you can.

  After the above-described wet treatment, the wet-treated product is heat-dried while being wet with alcohol. The drying temperature and drying time of the wet processed product are not particularly limited. After the wet treatment, even if the wet processed product is dried, it does not become a strong agglomerate. Therefore, the drying temperature and the drying time are appropriately set according to the processing amount of the wet processed product and the conditions of the processing apparatus. You can choose. By the drying treatment, the ATO fine particle precursor subjected to the wet treatment can be obtained.

  The ATO fine particles precursor subjected to the wet treatment can be heated to 500 ° C. or higher and lower than 1100 ° C. in an air atmosphere and baked for 30 minutes to 5 hours to produce the ATO fine particles according to the present invention. By heating to 500 ° C. or higher, antimony can be sufficiently dissolved in tin oxide. On the other hand, by heating without exceeding 1100 ° C., coarsening of the particle diameter of the ATO fine particles can be avoided, and a solar radiation shielding body having high transparency to visible light can be obtained as described later.

  The manufactured ATO fine particles have almost no light absorption in the visible light region, and the absorption derived from plasmon resonance is large in the wavelength region of 1000 nm or more, and the transmittance decreases from the near infrared region toward the longer wavelength side. To go.

  As a result, by using the hexaboride fine particles and ATO fine particles according to the present invention in combination, it is possible to efficiently shield sunlight in the near infrared region while maintaining high visible light transmittance. The solar shading characteristics are improved as compared with the case where hexaboride fine particles and ATO fine particles are used alone.

  As described above, the average primary particle diameter of the ATO fine particles used in the present invention is preferably 200 nm or less, more preferably 100 nm or less. Fine particles having an average primary particle size smaller than 200 nm, or aggregated and not coarse particles, and if the dispersed particle size is 200 nm or less, it does not become a light scattering source, does not generate haze, and has a visible light transmittance. Can be secured.

c) Solar shading fine particles The dispersion for forming a solar shading body according to the present invention is obtained by dispersing solar shading fine particles and a dispersant in a solvent. The content of the hexaboride fine particles in the dispersion is 0.01% by mass to 3.0% by mass, and the content of the ATO fine particles is 10.0% by mass to 30.0% by mass. It is what. When the content of each fine particle is within the above range, a sufficient solar radiation shielding effect can be obtained, the viscosity of the dispersion liquid is maintained, and the pot life of the dispersion liquid is ensured.
Further, the mixing of the hexaboride fine particles and the ATO fine particles is preferably in the range of 0.1: 99.9 to 13.8: 86.2 in terms of mass ratio from the viewpoint of optical characteristics and cost reduction.

  As described above, by using the hexaboride fine particles and ATO fine particles described above to produce the solar shield-forming dispersion according to the present invention, the solar shield-forming dispersion has excellent dispersibility and low haze. It will be a thing. By using the dispersion for forming a sunscreen, it is possible to obtain a sunscreen that has excellent shielding performance in the infrared region and near-infrared region and has high light transmittance in the visible light region.

(2) Dispersant The dispersion for forming a sunscreen according to the present invention is a dispersion of the ATO fine particles, hexaboride fine particles, and a dispersant, which are sunscreen fine particles, in a solvent.
The dispersant needs to contain a dispersant having an amine value and an acid value of 19 mgKOH / g or less. The dispersant having the amine value and an acid value of 19 mgKOH / g or less is composed of an ATO fine particle having a particle size obtained by the above-described solid-phase reaction method or the like in the range of about 0.1 μm to 30 μm. The boride particles are added to pulverize and disperse the particles so as to be refined to a particle diameter of 200 nm or less suitable for use as a solar shading material and to suppress reaggregation.

  This is because, when pulverizing hexaboride particles with a medium stirring mill, for example, toluene, which is a nonpolar solvent, is used, and even if an average primary particle diameter of hexaboride particles is made to be fine particles having a diameter of 70 nm or less, This is because the inventors of the present invention have found that the slurry fine particles are re-agglomerated to gel the slurry and the hexaboride particles cannot be pulverized.

In order to avoid reaggregation of the hexaboride fine particles and gelation of the slurry, the present inventors conducted research. Then, hexaboride particles and an alcohol having a boiling point in the range of 60 ° C. or higher and 140 ° C. or lower are mixed to form a slurry, and the slurry has an amine value and an acid value of 19 mgKOH / g or less. After adding the dispersant, the pulverization treatment of the hexaboride particles is performed so that the pulverization and dispersion of the ATO fine particles and the hexaboride fine particles by a medium stirring mill or the like proceeds efficiently, and the obtained dispersion is It is because it discovered that it became the dispersion liquid for solar radiation shielding body which has a suitable liquid state.
As described above, a solar shading body is formed by using a solar shading fine particle in which the ATO fine particles and hexaboride fine particles according to the present invention described above are combined, and the dispersion for dispersing the sunscreen in the solvent. When formed, the heat-and-moisture resistance characteristics of the solar radiation shield obtained can be improved.

The above-described dispersant according to the present invention will be further described.
As described above, the dispersant according to the present invention needs to contain a dispersant having an amine value and an acid value of 19 mgKOH / g or less. Here, the amine value is not particularly limited as long as it has an amine value, but is preferably 5 to 100 mgKOH / g, and more preferably 5 to 30 mgKOH / g.
On the other hand, the acid value is required to be 19 mgKOH / g or less. Although the details are unknown because the acid value is 19 mgKOH / g or less, it has been found that the heat-and-moisture resistance characteristics of the solar radiation shield obtained are improved.

  If a commercially available product is used as a dispersant having an amine value and an acid value of 19 mgKOH / g or less that can be applied to the present invention, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK. -170, DISPERBYK-182, DISPERBYK-184, DISPERBYK-2155 (manufactured by Big Chemie Japan Co., Ltd.) An amino group such as a dispersant having an amino group such as Alusper PB821, Azisper PB822, Azisper PB824 (Ajinomoto Fine Techno Co., Ltd.) The dispersing agent, and the like are preferable.

(3) Solvent The solvent used in the dispersion for forming a sunscreen according to the present invention is not particularly limited, but according to coating conditions, coating environment, and whether or not an inorganic binder or resin binder is added. What is necessary is just to select suitably.
For example, water, ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol, diacetone alcohol and other alcohols, ethers such as methyl ether, ethyl ether, propyl ether, esters, acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, isobutyl Various organic solvents such as ketones such as ketones can be used. Moreover, you may adjust pH by adding an acid and an alkali as needed.

(4) Binder As the inorganic binder, a metal alkoxide of silicon, zirconium, titanium, or aluminum and a hydrolysis polymer thereof can be used. Moreover, as a resin binder, it is possible to use what contains resins, such as thermoplastic resins, such as an acrylic resin, thermosetting resins, such as an epoxy resin, ultraviolet curable resin, and electron beam curable resin.

(5) Other Additives In addition to the solar shielding fine particles, the dispersant and the solvent, the dispersion for forming the solar shielding body according to the present invention further includes ZrO ₂ , TiO ₂ , Si ₃ N ₄ , SiC, SiO _2. It is also preferable to add fine particles of at least one compound selected from Al ₂ O ₃ , Y ₂ O ₃ , ZnO, CeO ₂ , Fe (OH) ₃ , and FeOOH.

(6) Dispersion for forming solar shielding body The above-described hexaboride microparticles, ATO microparticles, and a dispersing agent are mixed with a predetermined solvent and uniformly dispersed in the solvent, so that the solar shielding body according to the present invention is used. A forming dispersion is obtained.
The dispersion method is not particularly limited as long as the hexaboride fine particles, the ATO fine particles, and the dispersant are uniformly dispersed in the dispersion. For example, a bead mill, a ball mill, a sand mill, a paint shaker, an ultrasonic homogenizer, and the like. And distributed processing using. Depending on the dispersion treatment conditions using these dispersion treatment equipment, the fine particles are also dispersed by the collision of the particles at the same time as the dispersion of the fine particles in the solvent (that is, pulverized / dispersed), and the finer particles are dispersed. Can do.

If the fine particles of the binder described in (4) and the other additives described in (5) are added, the solar shielding fine particles, the dispersant and the solvent are mixed to form a slurry, and the amine value is added to the slurry. And a dispersant having an acid value of 19 mgKOH / g or less is preferably added.
By adding the fine particles of the above-mentioned other additives to the dispersion for forming a solar shield according to the present invention, the film strength of the solar shield to be formed can be increased. In addition, as the addition amount of the fine particles of the compound described above, the value of [mass of fine particles of other additives described above / mass of fine particles for solar shading according to the present invention] × 100 is in the range of 0.1 to 250%. It is preferably set. If the addition amount is 0.1% or more, the effect of addition of the above-mentioned other additives is recognized. If the addition amount is 250% or less, the ratio of the solar shielding fine particles is reduced and the solar shielding function is lowered. This is because it can be avoided.

Further, from the viewpoint of imparting an ultraviolet shielding function to the solar radiation shielding body according to the present invention, fine particles such as TiO ₂ , ZnO, CeO ₂ , and / or benzophenone that is an organic ultraviolet absorber, You may add 1 type, or 2 or more types, such as benzotriazole.

(7) Solar shield The solar shield according to the present invention is formed by applying the above-described dispersion for forming a solar shield on an appropriate base material, or by applying the above-described dispersion for forming a solar shield to solar radiation shielding. It is obtained by kneading into a body-forming base material and molding it into any shape such as a plate, sheet, or film.
As the appropriate base material, a transparent base material is mainly used. The transparent substrate is not particularly limited as long as it is transparent, and either an organic substrate or an inorganic substrate can be used.
Examples thereof include organic base materials such as polycarbonate resin, acrylic resin, polyethylene resin, polyester resin, polypropylene resin, polystyrene resin, and polyvinyl chloride resin, and inorganic base materials such as glass. Moreover, the shape and manufacturing method of the said transparent base material may be whatever, and there is no limitation in particular. In addition, the transparent base material said by this invention is the concept containing not only a colorless and transparent base material but a colored transparent base material and a semi-transparent base material.

  Hereinafter, with respect to the method for producing a solar shading body according to the present invention, (a) a method of applying and forming a solar shading body-forming dispersion liquid on an appropriate substrate, and (b) a solar shading body forming dispersion liquid. The method of kneading into the forming base material and forming it into a predetermined shape will be described in this order, and (c) the weather resistance of the solar shading body according to the present invention will be described.

(A) Method of applying and forming a dispersion for forming a sunscreen on an appropriate substrate When forming a film by applying a dispersion for forming a sunscreen according to the present invention on a substrate, the coating method is particularly It is not limited. For example, any method may be used as long as the dispersion can be applied flatly and thinly and uniformly, such as spin coating, bar coating, spray coating, dip coating, screen printing, roll coating, and flow coating.

  When the visible light permeability is required for the solar radiation shielding body according to the present invention, a transparent substrate is used as the substrate. Specifically, a desired material can be selected from transparent substrates such as glass, resin film, and resin board.

As described above, it is also a preferable configuration that an inorganic binder or a resin binder is included in the dispersion for forming a solar shading body according to the present invention.
However, when the above-described dispersion for forming a sunscreen containing an inorganic binder is applied, the substrate heating temperature after application is set to 100 ° C. or higher, more preferably the boiling point of the solvent in the dispersion, or higher in the coating film. It is preferable to complete the polymerization reaction of the alkoxide contained or its hydrolysis polymer. In addition, the substrate heating temperature after coating is set to 100 ° C. or higher, more preferably the boiling point of the solvent in the dispersion liquid, thereby removing water and organic solvent in the coating film from the film, and visible light transmission through the coating film. The cause of the rate reduction can be removed, which is preferable.

  Moreover, what is necessary is just to harden | cure according to the hardening method suitable for the resin binder contained, when the dispersion liquid for solar radiation shielding body containing a resin binder is apply | coated. For example, if it is an ultraviolet curable resin, it may be irradiated with ultraviolet rays as appropriate, and if it is a room temperature curable resin, it may be left as it is after application. In this case, application to an existing window glass or the like is possible on site.

Furthermore, the solar radiation shielding body according to the present invention composed of the base material and the solar radiation shielding film formed thereon is composed of hexaboride fine particles and ATO fine particles, which are solar radiation shielding fine particles, in the coating film. Are preferably dispersed.
For this reason, the solar radiation shielding body according to the present invention is a solar radiation shielding body having an oxide thin film according to the prior art having a mirror-like surface because crystals are densely embedded in the film obtained by a physical film formation method. In comparison, the reflection in the visible light region is less, and it can be avoided that it has a glaring appearance. In addition, since the solar radiation shielding body according to the present invention has a plasma frequency from the visible light region to the near infrared light region, the plasma reflection resulting from this increases in the near infrared light region, and is excellent in the heat shielding effect.
In addition to the above characteristics, when it is desired to further suppress the reflection in the visible light region, the coating film of the solar radiation shielding material in which the solar radiation shielding fine particles of the present invention are dispersed is further reduced to a low level such as SiO ₂ or MgF _2. By forming a film having a refractive index, a multilayer film having a luminous reflectance of 1% or less can be easily obtained.

(B) A method for kneading a dispersion for forming a solar shading body into a base material for forming a solar shading body and forming it into a predetermined shape In order to manufacture the solar shading body according to the present invention, a base material for forming the solar shading body When kneading the above-described dispersion for forming a sunscreen into the resin, any known method can be used as long as the hexaboride fine particles and ATO fine particles are uniformly dispersed in the matrix resin. Just choose.

Further, after kneading as described above, the mixture is melt-mixed at a temperature near the melting point of the base resin, and further pelletized to form a known resin molding method, specifically, an injection molding method, a compression molding method, an extrusion molding method. , Etc., it can be formed into various shapes such as a plate shape, a sheet shape, or a film shape. By the said shaping | molding, the solar radiation shielding body shape | molded by the desired shape is obtained. The molding conditions are appropriately selected according to various molding methods so that a desired shape can be obtained.
Preferred examples of the base resin include PET resin, acrylic resin, polyamide resin, vinyl chloride resin, polycarbonate resin, olefin resin, epoxy resin, polyimide resin, and fluororesin.

In order to be able to affix the film of the resin film formed by the method of kneading the dispersion for forming the solar shading body described above to glass or the like, an adhesive layer and a release film layer on one surface of the resin film May be laminated. At that time, it is also preferable to add an organic ultraviolet absorber such as benzophenone or triazole to the adhesive and inorganic oxide fine particles such as CeO ₂ , TiO ₂ , and ZnO to impart an ultraviolet shielding function. It is a configuration.

(C) Weather resistance of the solar shading body according to the present invention The solar shading body obtained by coating and forming the solar shading body forming dispersion according to the present invention on an appropriate substrate, or the solar shading body forming dispersion The liquid is kneaded into a base material for forming a solar shading body, and formed into any shape such as a plate, sheet, film, etc., the weather resistance of the solar shading body, particularly wet heat characteristics, that is, in a moist heat atmosphere The hydrolysis resistance is measured by immersing the sunscreen in warm water at 65 ° C. for 2 days, and measuring the change rate of visible light transmittance before and after the immersion (may be described as “ΔVLT” in the present invention). Can be evaluated. The value of ΔVLT of the solar shading material according to the present invention is smaller than the value of ΔVLT of the solar shading material according to the prior art, and a coating film is formed on the substrate using the solar shading material forming dispersion according to the present invention. The solar shading body obtained in this manner and the solar shading body forming dispersion according to the present invention are kneaded into the solar shading body forming base material and molded into any shape such as a plate, sheet, or film. It was confirmed that the solar shading body obtained in this way was a solar shading body excellent in weather resistance, particularly moisture and heat resistance characteristics (for details, refer to Examples and Comparative Examples described later).

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. However, the present invention is not limited to the following examples.
Example 1
1. Preparation of ATO fine particles 55.74 g of SnCl ₄ .5H ₂ O was dissolved in 340 g of water at 25 ° C. to prepare a solution. To the solution, 12.7 ml of a methanol solution in which 4.2 g of SbCl ₃ was dissolved and a 16% NH ₄ OH aqueous solution were dropped in parallel. The parallel dropping was performed over about 25 minutes until the pH of the solution reached 7.5. And the precipitate was produced | generated by the said parallel dripping, and stirring was further continued for 10 minutes after completion | finish of dripping.
The precipitate was then washed repeatedly by decantation. The decantation was repeated until the conductivity of the supernatant of the cleaning liquid became 1 mS / cm or less. When the decantation was complete, the precipitate was filtered.
The filtered precipitate was then wet treated with anhydrous ethyl alcohol solution. During the wet treatment, the mass ratio of the filtered precipitate: anhydrous ethyl alcohol solution was set to a ratio of 1: 4 (the alcohol ratio was equivalent to 80%), and the filtered precipitate and the anhydrous ethyl alcohol solution were kept at room temperature. The precursor was obtained by wet treatment by stirring for 1 hour.
After completion of the wet treatment, the precursor was dried at 90 ° C. for 10 hours to obtain a dried product. The obtained dried product was fired at 700 ° C. for 1 hour in an air atmosphere to obtain ATO fine particles according to the example.
The tap density of the ATO fine particles is 1.39 g / cm ³ , the powder color is L ^* is 55.0874, a ^* is 3.8119, b ^* is −8.0813, and the specific surface area is 67.1 m. ² / g.

2. Preparation of LaB ₆ particles La ₂ O ₃ particle powder having an average particle diameter of about 10 μm and B ₄ C particle powder having an average particle diameter of about 22 μm are set so that the atomic ratio of La element to B element is 1: 6. Mix to make a uniform mixture. The obtained uniform mixture was fired at 1500 ° C. for 3 hours in a vacuum atmosphere (about 0.02 Pa) to obtain LaB ₆ particle powder having an average particle size of about 1.5 μm.
The LaB ₆ particles had a lattice constant of 0.4157 nm, powder colors of L ^* of 36.3706, a ^* of 2.1309, and b ^* of −4.4973.

  In addition, the powder color of the fine particles (standard light source D65, 10 ° field of view) measured in each of the following Examples and Comparative Examples, and a solar shield-forming dispersion in which each fine particle is dispersed are obtained. The optical characteristics of the solar radiation shield were measured using a spectrophotometer U-4100 manufactured by Hitachi, Ltd.

3. Manufacture of solar radiation shield 1) In order to prepare dispersion liquid (A liquid) obtained by mixing and grinding ATO fine particle powder, LaB ₆ particle powder, dispersant, and toluene, the above-mentioned 1. ATO fine particle powder 20% by mass and LaB ₆ particle powder 3.5% by mass according to the example obtained in the above were prepared.
2) Dispersant (amine value 18 mgKOH / g, acid value 0 mgKOH / g: hereinafter, amine value, acid value unit “mgKOH / g” is omitted.) Product name: DISPERBYK-164 (manufactured by BYK-Chemie Japan) 15 A mass% was prepared.
3) 61.5% by mass of toluene was prepared.
4) 1) to 3) were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads, and the mixture was pulverized and dispersed for 6.5 hours to prepare a dispersion (solution A).
The average primary particle diameter of ATO fine particles and LaB ₆ fine particles in the liquid A was measured by TEM-EDS analysis. It was confirmed that the ATO fine particles were 25 nm and the LaB ₆ fine particles were 80 nm.
5) In order to prepare the dispersion liquid a for forming a solar shading body, 55.45% by mass of the liquid A was prepared.
6) 20.79% by mass of toluene was prepared.
7) 23.76 mass% of ultraviolet curable resin was prepared.
8) 5) to 7) were mixed to prepare a dispersion a for forming a sunscreen.
9) After applying the solar shield-forming dispersion a onto a PET (polyethylene terephthalate) film having a film thickness of 50 μm using a No. 8 bar, the ultraviolet rays of a high-pressure mercury lamp are used at 70 ° C. for 1 minute. The solar shading body A according to Example 1 was obtained.

4). Measurement of characteristics of solar shield The optical characteristics of the solar shield A according to Example 1 were measured using a spectrophotometer U-4100 manufactured by Hitachi, Ltd. The visible light transmittance was 68.1%, the solar radiation transmittance was 44.2%, and the haze was 1.0%.
Next, as an accelerated deterioration test of the solar radiation shielding body according to Example 1, the solar radiation shielding body was immersed in 65 ° C. hot water for 2 days, and ΔVLT before and after immersion was measured. As a result of the accelerated deterioration test, ΔVLT was 5.1%.
The above results are shown in Table 1.

(Example 2)
Instead of the dispersant having an amine value of 18 and an acid value of 0 according to Example 1, a dispersant having an amine value of 29 and an acid value of 19 and a trade name (DISPERBYK-2001, manufactured by Big Chemi Japan Co., Ltd.) were used. The same operation as in Example 1 was performed to obtain a solar radiation shield B according to Example 2.
The optical characteristic measurement and the accelerated deterioration test of the solar radiation shielding body B according to Example 2 were performed.
The above results are shown in Table 1.

(Example 3)
Instead of the dispersant having an amine value of 18 and an acid value of 0 according to Example 1, a dispersant having an amine value of 10, an acid value of 0 and a trade name (DISPERBYK-163, manufactured by Big Chemi Japan) was used. The same operation as in Example 1 was performed to obtain a solar radiation shield C according to Example 3.
An optical characteristic measurement and an accelerated deterioration test of the solar radiation shielding body C according to Example 3 were performed.
The above results are shown in Table 1.

Example 4
Implemented except that the amine value 13, the acid value 0 dispersant, and the trade name (DISPERBYK-162, manufactured by Big Chemi Japan) were used instead of the amine value 18 and acid value 0 dispersant according to Example 1. The same operation as in Example 1 was performed to obtain a solar radiation shield D according to Example 4.
An optical characteristic measurement and an accelerated deterioration test of the solar shading body D according to Example 4 were performed.
The above results are shown in Table 1.

(Comparative Example 1)
Implemented except that the dispersant having an amine value of 44 and an acid value of 38 and a trade name (BYK-9076, manufactured by BYK-Chemical Japan Co., Ltd.) were used instead of the dispersant having an amine value of 18 and an acid value of 0 according to Example 1. The same operation as in Example 1 was performed to obtain a solar radiation shield E according to Comparative Example 1.
The optical characteristic measurement and the accelerated deterioration test of the solar radiation shield E according to Comparative Example 1 were performed.
The above results are shown in Table 1.

(Comparative Example 2)
Instead of the dispersant having an amine value of 18 and an acid value of 0 according to Example 1, a dispersant having an amine value of 43, an acid value of 46, and a trade name (DISPERBYK-142, manufactured by Big Chemi Japan) were used. The same operation as in Example 1 was performed. However, the dispersion for forming the solar shading body became cloudy, and the solar shading body was not formed.

(Comparative Example 3)
Instead of the dispersant having an amine value of 18 and an acid value of 0 according to Example 1, a dispersant having an amine value of 0 and an acid value of 22 and a trade name (DISPERBYK-174, manufactured by Big Chemi Japan) were used. The same operation as in Example 1 was performed. However, since sedimentation due to the aggregation of the filler was observed, the formation of the solar radiation shield was not achieved.
The above results are shown in Table 1.

(Summary)
When the optical characteristics of the solar shields B to E were measured, the solar shield B had a visible light transmittance of 67.9%, a solar transmittance of 44.0%, a haze of 1.0%, and ΔVLT of 3.9%. Yes, the solar shield C has a visible light transmittance of 68.4%, a solar transmittance of 45.2%, a haze of 1.2%, and ΔVLT of 4.6%, and the solar shield D has a visible light transmittance of 68.1%, solar transmittance 44.5%, haze 1.0%, ΔVLT is 4.8%, and the solar shield E has a visible light transmittance of 67.5% and a solar transmittance of 43.3%. The haze was 1.0% and ΔVLT was 7.5%, and the dispersion for forming a solar shading body according to Comparative Example 2 became cloudy, and the solar shading body was not formed.

  As described above, the solar radiation transmittances of the solar shields A to D of Examples 1 to 4 were 46% or less, the haze was 1.2% or less, and ΔVLT was 5.1% or less. . On the other hand, the solar radiation transmittance and haze of the solar shield E of Comparative Example 1 are the same as those of the above example, but ΔVLT exceeds 7%, compared with the solar shields A to D of this example. It was found that the weather resistance (wet heat characteristics) was inferior. This result is considered because the acid value of the dispersant used in Comparative Example 1 was as large as 38. Moreover, the dispersion for solar radiation shielding body which concerns on the comparative example 2 becomes cloudy, and also the dispersion liquid for solar radiation shielding body which concerns on the comparative example 3 aggregates a filler, and does not result in formation of a solar radiation shielding body in any case. It was. This is probably because the acid value of the dispersant used in Comparative Example 2 was as large as 46. Further, in Comparative Example 3, it is considered that the amine value of the dispersant used was 0 and did not have an amine value.

Claims (7)

A dispersion for forming a sunscreen, in which sunscreen particles and a dispersant are dispersed in a solvent,
The solar shading fine particles have the general formula XB ₆ (where X is La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr, Ca 1 or more selected from the group of the above) and antimony-containing tin oxide ( ATO ) fine particles, and the average primary particle size of the hexaboride fine particles and the ATO fine particles is It is 200 nm or less, the content of the hexaboride fine particles in the dispersion for forming the sunscreen is 0.01% by mass to 3.0% by mass, and the content of the ATO fine particles is 10.0% by mass. % To 30.0% by mass, and the hexaboride fine particles and the ATO fine particles are blended in a mass ratio of 0.1: 99.9 to 13.8: 86.2,
The dispersion for forming a solar shading body, wherein the dispersant has an amine value of 10 mgKOH / g or more and 29 mgKOH / g or less and an acid value of 19 mgKOH / g or less. The ATO fine particles have a tap density of 1.85 g / cm ³ or less, a specific surface area of 5 to 110 m ² / g, and a powder color L ^* of 40 to 65 according to the L ^* a ^* b ^* color system. Yes, a ^* is -5 to -1, b ^* is -11 to -1,
The hexaboride fine particles have a lattice constant of 0.4100 to 0.4160 nm, a powder color L ^* according to L ^* a ^* b ^* color system of 30 to 60, and a ^* of −5 to 10. The dispersion for forming a solar radiation shielding body according to claim 1, wherein b ^* is −10 to 2. The dispersion for forming the sunscreen further comprises ZrO ₂ , TiO ₂ , Si ₃ N ₄ , SiC, SiO ₂ , Al ₂ O ₃ , Y ₂ O ₃ , ZnO, CeO ₂ , Fe (OH) ₃ , FeOOH. The dispersion for forming a solar shading body according to claim 1, comprising at least one compound selected from the group consisting of:   The solar radiation shielding body characterized by the film | membrane containing the dispersion liquid for solar radiation shielding body formation in any one of Claims 1-3 being formed into a film on the base material.   The solar radiation shielding body according to claim 4, wherein the base material is a transparent base material.   The solar radiation shielding body according to claim 5, wherein the transparent substrate is one selected from glass, a resin film, and a resin board.   A solar shading body forming base material into which the solar shading body forming dispersion according to any one of claims 1 to 3 is kneaded is formed into a shape selected from a plate shape, a sheet shape, and a film shape. A solar shading body characterized by that.