JP4487787B2 - Solar-shielding boride fine particles, solar-shielding-body-forming dispersion liquid and solar-light shielding body using the boride-fine particles, method for producing solar-shielding boride fine particles, and method for producing solar-shielding body-forming dispersion liquid - Google Patents

Description

  The present invention relates to a boride fine particle for solar radiation shielding, a dispersion for forming a solar radiation shield using the boride fine particles and a solar radiation shield, a method for producing the boride fine particles for solar radiation shielding, and a dispersion for forming a solar radiation shield. Regarding the method.

As a method for removing and reducing a heat component from an external light source such as sunlight or a light bulb, conventionally, a film made of a material that reflects infrared rays is formed on a glass surface to form a heat ray reflective glass. As the material, metal oxides such as FeOx, CoOx, CrOx, and TiOx and metal materials such as Ag, Au, Cu, Ni, and Al have been selected.

  However, since these materials have the property of reflecting or absorbing visible light at the same time, in addition to infrared rays that greatly contribute to the thermal effect, there is a problem that the visible light transmittance is lowered. In particular, base materials used for building materials, vehicles, telephone boxes, etc. require high transmittance in the visible light region. I had to make it thinner. For this reason, a method of forming a film as a 10 nm level thin film by using a physical film forming method such as spray baking, CVD method, sputtering method or vacuum vapor deposition method 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. In addition, when trying to increase the solar shading characteristics with these materials, the reflectance in the visible light region also tends to increase at the same time, and there is also a disadvantage that it gives a glaring appearance like a mirror and impairs the beauty. It was. Furthermore, the film formed of these materials has a relatively low resistance and high reflection of radio waves. For example, the radio waves of mobile phones, TVs, radios, etc. are reflected and cannot be received, or in the surrounding area. There were also drawbacks such as causing radio interference.

In order to improve such a defect, as the physical properties of the film, the light reflectance in the visible light region is low, the reflectance in the infrared region is high, and the surface resistance value of the film is approximately 10 ⁶ Ω / □ or more. The film must be controllable.

  Note that antimony tin oxide (hereinafter abbreviated as ATO) and indium tin oxide (hereinafter abbreviated as ITO) are known as materials having high visible light transmittance and excellent solar radiation shielding function. And since these materials have a relatively low visible light reflectance, they do not give a glaring appearance. However, since the plasma frequency is in the near infrared region, the reflection / absorption effect is still not sufficient in the near infrared region closer to visible light. Furthermore, since these materials have a low solar shielding power per unit weight, there is a problem that the amount of use increases and the cost becomes high in order to obtain a high shielding function.

  Therefore, the present applicant has previously developed a dispersion for solar radiation shielding using hexaboride fine particles as a solar radiation shielding component, and a solar radiation shielding body using the dispersion, and provided as Patent Document 1. The 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, so that it is in the interlayer film or solar radiation shield When uniformly dispersed therein, visible light permeability can be ensured while keeping the infrared light shielding ability sufficiently strong.

  The reason for this is not known in detail, but these hexaborides have a large amount of free electrons in the particles, and the absorption energy of indirect interband transitions due to free electrons inside and on the surface of the particles is just visible to near red. Since it is in the vicinity of the outer region, it is considered that heat rays in this wavelength region are selectively reflected and absorbed.

According to the experiment, the film in which the specific surface area of the hexaboride fine particles is 10 m ² / g or more and is uniformly dispersed in the solvent has a maximum transmittance between wavelengths of 400 nm and 700 nm, and the wavelength of 700 nm to 700 nm. It was observed that there was a minimum value between 1800 nm and the difference between the maximum value and the minimum value of these transmittances was 15 points or more. That is, considering that the visible light wavelength is 380 nm to 780 nm and the visibility is a bell-shaped peak having a peak near 550 nm, visible light is transmitted through the film and other heat rays are effectively reflected or absorbed. .

  In addition, the solar shading ability per unit weight of the hexaboride fine particles is very high, and, for example, the effect is exhibited with a use amount of 1/10 or less as compared with ITO fine particles and ATO fine particles. It has also been found that by using hexaboride fine particles together with ITO fine particles and / or ATO fine particles, only the solar radiation shielding property can be further improved while maintaining a certain visible light transmittance. As a result, it is possible to reduce the total amount of solar shielding particles used and to reduce production costs.

  In addition, since the hexaboride fine particles have an absorptivity in the visible light region as well, by controlling the amount added to the solar shield, the absorption of the solar shield in the visible light region can be freely controlled. It is also possible to provide additional functions such as brightness adjustment and privacy protection.

Here, as a method of producing the boride fine particles, for example, Non-Patent Documents 1 and 2 it has been proposed, of La ₂ O ₃ by B _{4 C} reduction method, which is a kind of boride fine LaB ₆ The industrial production method is described. Although the methods described in these documents are methods that can produce LaB ₆ at low cost, since the firing temperature is as high as 1600 ° C., the resulting LaB ₆ has coarse particles. However, for example, boride fine particles for use in the field of solar radiation shielding are required to have a sufficiently small particle diameter as compared with the visible light wavelength as described above. However, the coarsened boride fine particles are very hard, and it is very difficult to form fine particles even if a strong pulverization is performed by a mechanical method using a jet mill or the like.

  Therefore, the present applicant first baked the finer raw material particles and controlled the firing temperature when producing the boride fine particles, thereby avoiding the coarsening of the boride fine particles, thereby improving the excellent solar radiation. A method for producing boride fine particles having a particle diameter exhibiting a shielding function was found and proposed as Patent Document 2.

JP 2000-169765 A JP 2004-277274 A Doi, Powder and Industry, 21 (5) 1989 Functional materials, 15 (6) 1995

  However, in Patent Document 2, when the obtained boride fine particles are further formed into a medium stirring mill together with various solvents and beads, the boride fine particles after removing the solvent have high surface activity. Therefore, since there is a possibility of spontaneous ignition when taken out into the atmosphere, there is a restriction that it must be handled in an inert gas atmosphere.

  The present invention has been made paying attention to such problems, and the problem is that, even if the boride fine particles are atomized, the boride fine particles for solar radiation shielding that are in the atmosphere and have no spontaneous ignition, The object is to provide a dispersion for forming a solar shading body and a solar shading body using boride fine particles, a method for producing boride fine particles for solar shading that are not pyrophoric, and a method for producing a dispersion for forming a solar shading body. . In the present invention, “not spontaneously ignitable” means that the substance does not ignite spontaneously even when exposed to the atmosphere at room temperature.

As a result of continuing earnest research to solve the above problems, the present inventor added at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si , The boride obtained by firing can be made non-pyrophoric, and this is put into a medium agitating mill together with beads to make fine particles, and after removing the solvent, it does not ignite spontaneously even if taken out into the atmosphere. The present inventors have found that it can be handled in an inert gas-free atmosphere, and have reached the present invention.

The first configuration for solving the problem is:
The boride fine particles have the general formula XB ₆ (wherein the X element is at least one selected from La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) And a hexaboride fine particle containing at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si. Boride fine particles.

The second configuration is
The content of the additive element described in the first configuration is characterized in that when the additive element is A, the weight ratio represented by A / (A + XB ₆ ) is 0.001 to 0.5. Boride fine particles for solar radiation shielding.

In the third configuration, the average primary particle diameter is 400 nm or less, the powder color L ^* in the L ^* a ^* b ^* color system is 30 to 60, a ^* is −5 to 10, and b ^* is −10. It is the boride fine particle for solar radiation shielding as described in the 1st or 2nd structure characterized by being -2.

The fourth configuration is
Any one of the first to third aspects, wherein the surface of the boric fine particles for sunscreening is coated with an oxide containing at least one element selected from Si, Ti, Zr, and Al . It is the boride fine particle for solar radiation shielding as described in a structure .

The fifth configuration is
In a dispersion for forming a solar shading body, comprising a solvent and solar shading fine particles dispersed in the solvent, and applied to the formation of the solar shading body,
The sunscreening fine particles are composed of the sunscreening boride fine particles described in any one of the first to fourth configurations, and the boride fine particles dispersed in the solvent have a dispersed particle diameter of 800 nm or less. It is a dispersion for forming a solar shading body.

The sixth configuration is
The solar radiation according to the fifth aspect, comprising at least one compound selected from ZrO ₂ , TiO ₂ , Si ₃ N ₄ , SiC, SiO ₂ , Al ₂ O ₃ , and Y ₂ O ₃ This is a dispersion for forming a shield.

The seventh configuration is
It is a solar shading body characterized by being formed using the solar shading body forming dispersion liquid described in the fifth or sixth configuration .

The eighth configuration is
It is a solar shading body formed by applying the solar shading body forming dispersion liquid described in the fifth or 6th structure on a transparent substrate.

The ninth configuration is
The solar shielding boride fine particles according to any one of the first to fourth configurations , or the solar shielding body-forming dispersion liquid according to the fifth or sixth configuration are kneaded into the solar shielding body-forming base material. It is a solar shading body characterized by shape | molding in the shape of a plate, a sheet | seat, or a film.

The tenth configuration is
The base material for forming the sunscreen is polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, ethylene vinyl acetate copolymer, polyester resin, polyethylene terephthalate. The solar radiation shield according to the ninth aspect, which is at least one selected from a resin, a fluororesin, a polycarbonate resin, an acrylic resin, and a polyvinyl butyral resin.

The eleventh configuration is
Another substrate is laminated on the solar shield so as to sandwich the solar shield described in the eighth configuration, or the solar shield described in the ninth or tenth configuration is sandwiched by another substrate. The solar shading body is characterized by being laminated.

The twelfth configuration is
General formula XB ₆ containing at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si ( where X element is La, Ce, Pr, Nd, Sm, A method of producing boride fine particles for solar shading represented by Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu ).
A solution of a compound containing an X element and a compound containing at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si is reacted with an alkali solution while stirring. To obtain a precipitate,
The precipitate is dried , and hydroxide particles and / or hydrate particles of element X and at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si And obtaining
Wherein X element and Sb, Zn, and heat-treated Mg, Sn, Zr, Mo, Al, and the hydroxide particles and / or hydrate particles of one additive element even without least selected from Si, Obtaining oxide particles of the element X and at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si ;
The X element is mixed with oxide particles of at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si, and B ₄ C particles, Obtaining a mixture of oxide particles of an element and at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si, and B ₄ C particles;
In general, the mixture is heat-treated at less than 1600 ° C. in a vacuum or an inert gas atmosphere , and contains at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si a method for producing a solar radiation shielding boride particles, characterized by comprising the steps of obtaining a solar radiation shielding boride particles of the formula XB _6, the.

The thirteenth configuration is
General formula XB ₆ containing at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si (where X element is La, Ce, Pr, Nd, Sm, And at least one selected from Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu ).
A solution of a compound containing an X element and a compound containing at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si is reacted with an alkali solution while stirring. To obtain a precipitate,
The precipitate is dried , and hydroxide particles and / or hydrate particles of element X and at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si And obtaining
Hydroxide and / or hydrate particles of the element X and at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si; and B ₄ C particles; A hydroxide particle and / or a hydrate particle of the element X and at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si, and B Obtaining a mixture with ₄ C particles;
In general, the mixture is heat-treated at less than 1600 ° C. in a vacuum or an inert gas atmosphere , and contains at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si a method for producing a solar radiation shielding boride particles, characterized by comprising the steps of obtaining a solar radiation shielding boride particles of the formula XB _6, the.

The fourteenth configuration is
When mixing the hydroxide particles and / or hydrate particles of the X element and the additive element, or the oxide particles of the X element and the additive element, and the B ₄ C particles, mixing them The ratio is mixed so that the atomic ratio of X element: boron is 1: 6. The method for producing solar shading boride fine particles according to the twelfth or thirteenth configuration .

The fifteenth configuration is
The content of the additive element is such that when the additive element is A, the weight ratio represented by A / (A + XB ₆ ) is 0.001 to 0.5 . It is a manufacturing method of the boride fine particle for solar radiation shielding in any one of the structures .

The sixteenth configuration is
Hydroxide particles and / or hydrate particles of the X element and additive element having an average particle size of 0.1 μm or less, or oxides of the X element and additive element having an average particle size of 20 μm or less The method for producing boride fine particles for solar radiation shielding according to any one of the twelfth to fifteenth configurations, wherein the particles and the B ₄ C particles having an average particle diameter of 60 μm or less are mixed. is there.

The seventeenth configuration is
Solar shielding boride fine particles produced by the method for producing solar shading boride fine particles according to any one of the twelfth to sixteenth configurations are crushed by colliding with each other in a jet stream. This is a method for producing boride fine particles for solar radiation shielding.

The eighteenth configuration is
The slurry obtained by mixing the sunscreen boride fine particles according to any one of the twelfth to seventeenth configurations and a solvent is put into a medium stirring mill together with beads, and further pulverized and dispersed. It is a manufacturing method of the dispersion liquid for solar radiation shielding body to make.

As described above in detail, the non-pyrophoric boride fine particle for solar radiation shielding according to the present invention has the general formula XB ₆ (where X element is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, At least one selected from Dy, Ho, Er, Tm, Yb, and Lu ), and at least one selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si. It is a borate fine particle for solar radiation shielding having no spontaneous ignition, characterized by containing an additive element of a seed.
The non-pyrophoric boride fine particles for solar radiation shielding do not ignite spontaneously when taken out into the atmosphere even if they are made fine, so they are excellent in work safety and need not be handled in an inert gas atmosphere. The work is easy.

Further, the present invention relates to a general formula XB ₆ containing at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si (provided that the X element is La, Ce,
( 1) At least one selected from Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu ). A manufacturing method comprising:
A solution of a compound containing an X element and a compound containing at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si is reacted with an alkali solution while stirring. To obtain a precipitate,
The precipitate is dried , and hydroxide particles and / or hydrate particles of element X and at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si And obtaining
Hydroxide particles and / or hydrate particles of the element X and at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si are heat-treated, and the X Obtaining oxide particles of the element and at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si ;
The X element is mixed with oxide particles of at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si, and B ₄ C particles, Obtaining a mixture of oxide particles of an element and at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si, and B ₄ C particles;
In general, the mixture is heat-treated at less than 1600 ° C. in a vacuum or an inert gas atmosphere , and contains at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si pyrophoric no method of manufacturing solar radiation shielding boride particles, characterized by comprising obtaining a pyrophoric no solar radiation shielding boride particles of the formula XB _6, the.

Furthermore, the present invention relates to a general formula XB ₆ containing at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si , where X element is La, Ce, Pr , Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and at least one selected from Lu ).
A solution of a compound containing an X element and a compound containing at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si is reacted with an alkali solution while stirring. To obtain a precipitate,
The precipitate is dried , and hydroxide particles and / or hydrate particles of element X and at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si Obtaining
Wherein X element and Sb, Zn, Mg, Sn, Zr, Mo, Al, and a hydroxide and / or hydrate particles of one additive element even without least selected from Si, the _{B 4} C Particles and a hydroxide particle and / or a hydrate particle of the element X and at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si ; Obtaining a mixture with B ₄ C particles;
In general, the mixture is heat-treated at less than 1600 ° C. in a vacuum or an inert gas atmosphere , and contains at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si pyrophoric no method of manufacturing solar radiation shielding boride particles, characterized by comprising obtaining a pyrophoric no solar radiation shielding boride particles of the formula XB _6, the.

  Boron fine particles for solar radiation shielding that are not pyrophoric and obtained by these production methods do not ignite spontaneously when taken out into the atmosphere even if they are micronized, so they are excellent in work safety and in an inert gas atmosphere. The work is easy because no handling is required.

Hereinafter, a method for producing a solar shielding boride fine particle having no spontaneous ignitability and a method for producing a solar shielding body-forming dispersion in the embodiment of the present invention will be described with reference to FIG.
1, Sb according to the present invention, Zn, Mg, Sn, Zr , Mo, Al, and contains at least one additive element selected from Si, pyrophoric represented by the general formula XB ₆ It is a flowchart which shows the manufacturing process of the boride fine particle for solar radiation shielding which does not have, and the manufacturing process of the dispersion liquid for solar radiation shielding body formation.

In the compound solution of the X element and the additive element represented by the symbol (1), the X element is a metal element selected from rare earth elements, among which La, Ce, Pr, Nd, Sm, Eu, Gd, Tb , Dy, Ho, Er, Tm, Yb, or Lu can be favorably used. As the X element compound, for example, nitrates, sulfates, chlorides, hydroxides, and the like of the X element can be used.

Further, as a compound containing at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si , nitrates, sulfates, chlorides, hydroxides, and the like are the same as described above. Can be used in good shape. The amount of addition of at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si is not particularly limited. When these additive elements are A, A / (A + XB ₆ ) Is preferably from 0.001 to 0.5 from the viewpoint of removal of pyrophoricity from the boride and solar shading characteristics.

  The alkaline solution represented by the symbol (2) is not particularly limited, and for example, various aqueous solutions of ammonium hydrogen carbonate, ammonium hydroxide, sodium hydroxide, potassium hydroxide, and the like can be used favorably. Further, the concentration of the alkaline solution (2) is not less than the chemical equivalent necessary for the salt of the X element compound to be a hydroxide, and is preferably 1.5 times the equivalent to equivalent. Within this range, the compound solution (1) of the X element and the additive element and the alkaline solution (2) are sufficiently reacted, and the time required for the cleaning in the subsequent process can be shortened.

A compound solution (1) containing the X element as described above, at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si, and an alkaline solution (2) Mixing is performed, and continuous stirring (11) is performed, and both are neutralized to form a precipitate (12). Although the upper limit of the solution temperature at this time is not specifically limited, Usually, it shall be 100 degrees C or less. On the other hand, the lower limit of the solution temperature is not particularly limited, but if it is set too low, a new cooling device or the like is required, which causes an increase in production cost. The time for the neutralization reaction is not particularly limited, but is less than 30 minutes, preferably 25 minutes or less from the viewpoint of productivity. After the neutralization reaction is completed, in order to homogenize the system, precipitation is matured while continuing stirring, and the temperature at that time is the same as the neutralization temperature. The duration of stirring is not particularly limited, but may be 30 minutes or less, preferably about 15 minutes or less from the viewpoint of productivity.

  The precipitate produced by the precipitation (12) is thoroughly washed (13) to remove the remaining alkali content and the like. As a cleaning method, decantation with pure water can be used in an excellent manner.

When the precipitate that has been washed (13) is dried (14), hydroxylated containing element X and at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si And / or hydrate (3) particles are obtained. In drying (14), the temperature and time are not particularly limited.

Hydroxide and / or hydrate (3) particles of the obtained X element and at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si It is possible to proceed to the post-process as it is, but this element X and a hydroxide of at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si and / or The particles of the hydrate (3) may be further heat-treated (15) to form an oxide (5) of the X element and the additional element before proceeding to the subsequent step.

And X element, Sb, heat treatment Zn, Mg, Sn, Zr, Mo, Al, and hydroxides and / or hydrates of the one additional element even without least selected from Si particles (3) In the case of (15), the heat treatment temperature is set to 400 ° C. to 1000 ° C. and the heat treatment time is 30 minutes from the viewpoint of avoiding the coarsening of the oxide (5) particles of the generated X element and the above additive element. Although it will not specifically limit if it is above, it is preferable to set it as 30 minutes-4 hours from a viewpoint of productivity.

Hydroxides and / or hydrates of element X and at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si by heat treatment (15) Is an oxide (5) particle of element X and at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si, and an aggregate in which the particles are aggregated It becomes.

By taking the above-described production process, the obtained X element and a hydroxide and / or of at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si, and / or The particle size of the hydrate (3) and the particle size of the oxide (5) particles are in the range required for producing boride fine particles exhibiting an excellent solar radiation shielding function, for example. It can be.

Hydroxide and / or hydrate (3) particles of the obtained X element and at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si ; Alternatively, an oxide (5) particle of an X element and at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si, and B ₄ C (4) Mix (16) with the particles.

In this mixing (16), the X element and B atoms are mixed uniformly so that the atomic ratio is 1: 4 to 6.3. At this time, the average particle diameter of the B ₄ C (4) particles is preferably 60 μm or less, preferably 40 μm or less, and more preferably 30 μm or less, from the viewpoint of generation of fine particles such as XB ₄ and XB _6. . The average particle size of the hydroxide particles and / or hydrate particles of the X element and the additive element is 0.1 μm or less, and the average particle size of the oxide of the X element and the additive element is 20 μm or less. preferable. This is because by specifying the particle diameter of each raw material powder, boride fine particles (6) having a dispersed particle diameter of 800 nm or less in a solvent can be easily produced at low cost.

Then, the obtained uniform mixture is heat-treated (17) under a vacuum or an inert gas atmosphere at less than 1600 ° C. , and at least one selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si The boride fine particles (6) represented by the general formula XB _m (where 4 ≦ m <6.3, the same shall apply hereinafter) are obtained.

Here, the boride fine particles (6) will be described.
Boride particles (6) is represented by the general formula XB _m, XB _4, XB 6, but boride represented by _{XB 12} and the like, as the material of the solar radiation-shielding body, 4 ≦ m <6.3 It is preferable that That is, the boride fine particles are preferably mainly composed of XB ₄ and XB ₆ among the borides, and may further contain a part of XB ₁₂ . Here, m is a chemical analysis of the obtained powder containing boride fine particles (6), and indicates the atomic ratio of B to one atom of X element.

The produced powder containing the boride fine particles (6) is actually a mixture of XB ₄ , XB ₆ , XB _{12, and the} like. For example, in the case of hexaboride fine particles, which are typical boride fine particles, even if it is a single phase in X-ray diffraction, 5.8 <m <6.2 is actually obtained, and a small amount of other phases are contained. It is thought that 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 in addition to the boride fine particles (6) is suppressed. Since boron oxide particles are hygroscopic, when boron oxide particles are mixed in boride powder, the hygroscopic property of the boride powder is lowered, and the solar radiation shielding characteristics are deteriorated with time. Therefore, it is preferable to suppress the generation of boron oxide particles by setting m ≦ 6.3.

From the above, the hydroxide and / or hydrate (3) particles of the X element and the additive element, or the oxide (5) particles of the X element and the additive element, and B ₄ C In the mixing (16) with the particles of (4), it is preferable to make a uniform mixture so that the atomic ratio of the X element and the B element is 1: 4 to 1: 6.3. Is more preferably a 1: 6 homogeneous mixture.

Particles of hydroxide and / or hydrate (3) of element X and at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si , or X The atmosphere when heat-treating (17) the uniform mixture of the oxide (5) particles of the element and the additive element and the B ₄ C (4) particles may be a vacuum or an inert gas atmosphere. preferable. If the atmosphere is a vacuum, a higher degree of vacuum is preferable from the viewpoint of the stability of the boride fine particles. If the atmosphere is an inert gas, it is preferable to use an inert gas other than nitrogen from the viewpoint of avoiding the formation of boron nitride.

  The heat treatment temperature is preferably less than 1600 ° C. This is because if it is less than 1600 ° C., coarsening of the boride fine particles (6) can be avoided. Moreover, what is necessary is just to select baking time suitably so that a desired average particle diameter etc. may be obtained in the boride fine particle (6).

In this way, Sb, Zn, Mg, boric suitable to Sn, Zr, Mo, represented by the general formula XB ₆ containing at least one additive element selected Al, and from Si, for example solar radiation shielding Compound fine particles (6) are obtained. It is preferable that the surface of the boride fine particles (6) is not oxidized. However, in general, the obtained boride fine particles (6) are slightly oxidized, and surface oxidation occurs to some extent in the particle dispersion process. Inevitable. Further, the boride fine particles (6) exhibit a greater solar shielding effect as the crystal completeness is higher, but the crystallinity is low and an extremely broad diffraction peak is generated by X-ray diffraction. Even if it exists, if the fundamental coupling | bonding inside particle | grains consists of the coupling | bonding of X elements including lanthanum and boron, a desired solar radiation shielding effect will be expressed.

  Here, if necessary, the boride fine particles (6) collide with each other in a jet stream and pulverize (8) to further finely pulverize them. The type of jet mill at this time is not particularly limited, and a known one can be used. Also, the jet mill conditions are not particularly limited.

  Next, the dispersion for solar radiation shielding body (10) in the present embodiment is prepared by pulverizing the boride fine particles (6) directly in the solvent (7) or in the jet stream (8) and then in the solvent (7). The slurry (18) mixed therein was put into a medium stirring mill (9) together with beads and further pulverized and dispersed (19).

The medium agitation mill (9) is a slurry of spherical beads and powder to be crushed into a pulverization vessel to forcibly agitate the particles in the slurry mainly using the shear stress of the beads. It is a method of pulverizing and dispersing. The stirring mechanism of the medium stirring mill (9) is not particularly limited as long as the shear stress of the beads is efficiently transmitted to the slurry.

  The bead diameter is generally selected according to the final particle diameter of the target slurry, but is preferably 1 mm or less in diameter. If it is 1 mm or less, the efficiency which crushes particle | grains finely will improve. Further, the smaller the bead diameter, the faster the grinding speed and the smaller the particle size of the boride to be ground. In particular, when pulverizing and dispersing fine boride fine particles of 800 nm or less, further 100 nm or less, beads having a diameter of 0.3 mm or less are preferable.

As for the bead material, it is preferable to use beads of the same quality as the slurry in order to prevent mixing of impurities with respect to a slurry containing an object to be crushed having a high hardness such as boride. In addition, ceramic beads are preferable among beads that are generally available on the market. Specific examples include ZrO ₂ beads and YSZ beads. These have a high specific gravity, high grinding efficiency, little wear, and the worn components are transparent, so that the ground product is preferable for use in optical applications. Beads with low specific gravity, such as glass beads, are not suitable for grinding high hardness materials such as borides.

  In the process of pulverization and dispersion, various dispersants are preferably used in order to prevent dispersion inhibition due to reaggregation or the like. As the dispersant, a compound having an alkoxide group in the molecular structure, a compound having an amino group, various surfactants, and the like are used. These adsorb on the surface of borides that have been pulverized and dispersed, and prevent reaggregation by utilizing structural disturbances or electrostatic repulsion.

  The medium agitating mill (9) is not particularly limited as long as it is a method of uniformly dispersing boride fine particles in a dispersion, and examples thereof include a bead mill, a ball mill, a sand mill, a paint shaker, and an ultrasonic wave. A homogenizer etc. are mentioned. Depending on the dispersion treatment conditions using these equipments, the boride fine particles (6) are dispersed in the solvent (7) and at the same time, micronization due to collision between the boride fine particles (6) proceeds. ) Can be made finer and dispersed (that is, pulverized and dispersed).

  The solvent (7) is not particularly limited, and may be selected according to the coating conditions, the coating environment, and the inorganic binder or resin binder to be added as appropriate, of the dispersion for solar radiation shielding body (10). That's fine. Examples of the solvent (7) include water, ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol, diacetone alcohol, methyl ether, and ethyl ether. Various organic solvents such as ethers such as tellurium and propyl ether, esters, acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, isobutyl ketone and other organic solvents can be used. It may be added to adjust the pH.

Here, when it is desired to add a new function, for example, a weather resistance function, to the boride fine particles (6), a step of removing the dispersion solvent is required after the treatment by the medium stirring mill (9). At this time, since the boride fine particles (6) after the solvent (7) is removed are stable without spontaneous ignition, handling becomes safe and easy.
Further, in order to further improve the dispersion stability of the boride fine particles (6) in the dispersion for solar radiation shielding body (10), it is of course possible to add various surfactants and coupling agents.

The dispersion for solar radiation shielding body (10) according to the present embodiment is specified by measuring the dispersion state of the boride fine particles (6) when the boride fine particles (6) are dispersed in the solvent (7). Is done. The particle size of the boride can be determined depending on the purpose of use, but when maintaining transparency and applying to optical applications, a particle size of 800 nm or less is preferable. If it is 800 nm or less, the light is not completely blocked, so that the visibility in the visible light region can be maintained, and at the same time, the transparency can be efficiently maintained.

  In particular, when importance is attached to the transparency in the visible light region, it is necessary to consider scattering by particles. When importance is attached to transparency, the particle diameter is 200 nm or less, preferably 100 nm or less. When the particle diameter of the particles is larger than the above, light in the visible light region of 400 nm to 780 nm is scattered by geometrical scattering or Mie scattering, and it becomes like a frosted glass, and does not allow clear transparency. When the particle diameter is 200 nm or less, the scattering is 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 particle diameter decreases. Furthermore, when the thickness is 100 nm or less, the scattered light is very small and the transparency is further increased.

  As described above, the dispersion (10) for forming a solar shading material, in which the dispersed particle diameter of the boride fine particles (6) dispersed in the solvent (7) is sufficiently fine and uniformly dispersed to 800 nm or less, is applied. Thus, an excellent solar shading body can be obtained.

Here, the dispersed particle size means the aggregated particle size of the boride fine particles (6) in the solvent (7), and can be measured with various commercially available particle size distribution analyzers. For example, in a state where aggregates of boride fine particles (6) are also present, sampling is performed from a dispersion (10) for forming a solar shield in which boride fine particles (6) are dispersed in a solvent (7), and dynamic It can be measured using ELS-800 manufactured by Otsuka Electronics Co., Ltd. based on the light scattering method. An apparatus that analyzes laser light scattering can be used. The dispersed particle size of the boride fine particles is desirably 800 nm or less. This is because when the thickness is 800 nm or less, it is possible to avoid a case where a gray film or a molded body (a plate, a sheet, or the like) whose transmittance is monotonously decreased is formed.
In addition, if a large number of aggregated coarse particles are included, it becomes a light scattering source, and when it is made into a film or molded body (plate, sheet, etc.), haze increases and the visible light transmittance decreases. This is not preferable.

  In a solar radiation shield in which the boride fine particles (6) have a dispersed particle size of 800 nm or less and are sufficiently fine and uniformly dispersed, the light transmittance has a maximum value at a wavelength of 400 to 700 nm and a minimum value at a wavelength of 700 to 1800 nm. A solar shading body is obtained.

  The larger the difference between the maximum value and the minimum value of the film transmittance in this solar radiation shielding body, the better the solar radiation shielding characteristics. This is because the boride fine particle transmission profile has a maximum value at a wavelength of 400 nm to 700 nm, a minimum value at a wavelength of 700 to 1800 nm, a visible light wavelength range of 380 nm to 780 nm, and a visibility of about 550 nm. In view of the bell-shaped shape, it is understood from this transmission characteristic that visible light is effectively transmitted and other heat rays are effectively reflected and absorbed.

  In the solar shield formed from the boride fine particles (6) in the present embodiment, or the solar shield forming dispersion (10) in which the boride fine particles (6) are dispersed in the solvent (7), In order to impart an ultraviolet shielding function, particles such as inorganic titanium oxide, zinc oxide and cerium oxide, or one or more of organic benzophenone and benzotriazole may be added.

Moreover, in order to improve the light transmittance of the solar shading body, particles such as ATO, ITO, and aluminum-added zinc oxide may be further mixed. When these transparent particles are added to the dispersion (10) for forming a sunscreen, the transmittance in the vicinity of 750 nm increases and the near infrared rays are shielded, so that the visible light transmittance is high and the sunscreen properties. A higher solar shading body is obtained.

On the contrary, if the dispersion for solar radiation shielding body (10) in this embodiment is added to a dispersion in which particles of ATO, ITO, aluminum-added zinc oxide and the like are dispersed, for example, the above LaB ₆ (lanthanum boride) ) Is green, the film can be colored, and at the same time, the solar radiation shielding effect can be assisted. In this case, it is possible to assist the solar radiation shielding effect with only a slight addition amount to the main ATO, ITO, etc., the required amount of ATO or ITO can be greatly reduced, and the cost of the dispersion liquid is reduced. be able to.

  In addition, the dispersion for solar radiation shielding body (10) in the present embodiment does not form the desired solar radiation shielding body by utilizing the decomposition of the liquid component or the chemical reaction due to the heat at the time of firing. It is possible to form a stable solar shading body.

  Furthermore, since the boride fine particles (6) exhibiting such excellent solar radiation shielding effect are inorganic materials, they are superior in weather resistance as compared with organic materials, and are used, for example, in parts exposed to sunlight (ultraviolet rays). However, there is almost no deterioration of color and various functions. As a result, windows, telephone boxes, show windows, lighting lamps, transparent cases, etc. for vehicles, buildings, offices, ordinary houses, etc., such as single glass, laminated glass, plastics, and other transparent solar shielding functions are required. It can be used in a wide range of fields such as substrates.

Hereinafter, the above-described boride fine particles for solar radiation shielding that are not pyrophoric, the dispersion liquid for forming the solar radiation shield and the solar radiation shield using the boride fine particles will be described in more detail.
[1] Boride fine particles As boride fine particles, the general formula XB _m (where X element is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and And at least one selected from Lu , 4 ≦ m ≦ 6.3), and at least one selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si It is characterized by containing elements.

In particular, XB ₆ (where X element is at least one selected from La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu ) And hexaboride fine particles containing at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si .

The boride fine particles are represented by the general formula XB _m , and boride compounds represented by XB ₄ , XB ₆ , XB _{12 and the} like can be mentioned, but the material of the solar radiation shield is 4 ≦ m <6.3. It is preferable. That is, the boride fine particles are preferably mainly composed of XB ₄ and XB ₆ among the borides, and may further contain a part of 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.

As described above, the produced powder containing boride fine particles is actually a mixture of XB ₄ , XB ₆ , XB _{12 and the} like. For example, in the case of hexaboride which is a typical boride fine particle, even if it is a single phase by X-ray diffraction, 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 in addition to the boride fine particles is suppressed. Since boron oxide particles are hygroscopic, if boron oxide particles are mixed in the boride powder, the moisture resistance of the boride powder is lowered, and the deterioration of solar radiation shielding characteristics with time is increased. Therefore, it is preferable to suppress the generation of boron oxide particles when m <6.3.
From the above, it is preferable to make a uniform mixture so that the atomic ratio of the X element and B is 1: 4 to 1: 6.3, more preferably about 1: 6.

Further, the solar shading fine particles applied in the present embodiment have an average primary particle diameter of 400 nm or less, and a powder color L ^* in the L ^* a ^* b ^* color system of 30 to 60, This can be composed of boride fine particles having a ^* of −5 to 10 and b ^* of −10 to 2.

The average primary particle diameter is a value calculated as follows. In other words, the above-mentioned solar shading fine particles having no pyrophoric properties are pulverized / dispersed in, for example, a paint shaker in which solar shading particles such as boride fine particles, a dispersing agent, beads, etc. are placed in a solvent. After the treatment, the solvent is evaporated, and the dispersant is removed by thermal decomposition. Then, the specific surface area (N ₂ adsorption method, etc.) of the non-pyrophoric boride fine particles for solar radiation is measured. It is a value calculated by an equation.
d = 6 / ρ × SA (where d is the average primary particle size, ρ is the boride density, and SA is the specific surface area)

  The reason why the average primary particle size of the solar shading fine particles is set to 400 nm or less as described above is to ensure transparency by setting the particle size to the Rayleigh scattering region.

  Furthermore, it is weather resistance that the surface of the boric fine particles for solar radiation shielding that are not pyrophoric is coated with an oxide containing at least one additive element selected from Si, Ti, Zr, and Al. From the viewpoint of

The solar-shielding boride fine particles having no spontaneous ignition can be produced by, for example, a gas phase method such as a solid phase reaction method, an evaporation quenching method, or a plasma CVD method. In addition, although a solid-phase reaction method is demonstrated as an example, if it has the said powder characteristic, a manufacturing method will not be limited. An example of a method for producing solar radiation-shielding LaB ₆ (lanthanum boride) having no spontaneous ignition by the solid phase reaction method will be briefly described.

After mixing a lanthanum compound and a compound containing at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si, and firing at 600 ° C. to 1000 ° C. in the atmosphere The fired product is sufficiently mixed with a boron compound, and these are subjected to a solid phase reaction at a temperature of less than 1600 ° C. in a vacuum or an inert gas atmosphere to produce lanthanum boride having no spontaneous ignition. It is preferable that the additive containing the above additive element for removing pyrophoric properties is dissolved in LaB ₆ from the viewpoint of optical properties.

The hexaboride fine particles have a powder color L ^* of 30 to 60 and an a ^* of −5 in the L ^* a ^* b ^* color system (JIS Z8729) recommended by the International Commission on Illumination (CIE). -10, b ^* is preferably in the range of -10-2.

Further, as an example, the solar shielding hexaboride fine particles (XB ₆ ) having no pyrophoric properties added with Zn can give a larger solar shielding effect as the crystal completeness is higher. 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 average primary grains If the diameter is 400 nm or less, the powder color L ^* is 30 to 60, a ^* is -5 to 10, and b ^* is -10 to 2, the desired solar radiation shielding effect is exhibited. Is possible. The state of Zn at this time is considered to be solid solution.

Further, the obtained boride fine particles were preliminarily pulverized with a jet mill (average particle diameter by Microtrac is 0.5 to 1.5 μm), and the pulverized boride fine particles were put together with beads into a medium stirring mill. Crush and disperse. The average particle size of the boride fine particles at this time is 0.1 to 0.03 μm. Even if the particles are made fine to such a level, the boride fine particles after removing the solvent do not ignite spontaneously. Therefore, it is easy to handle without using an inert gas. Further, although it is presumed that spontaneous combustion does not occur even when the particles are made fine, the average particle diameter is limited to 0.03 μm in terms of the ability of a commercially available grinder.

[2] Dispersion for forming a solar shading body The dispersion for forming a solar shading body is composed of a solvent and boride fine particles for solar shading that are not pyrophoric and dispersed in the solvent. Further, by applying a dispersion for forming a solar shading material, the dispersion particle diameter of the boric fine particles for sun shading dispersed in the solvent is sufficiently fine and uniformly dispersed to 800 nm or less, and excellent solar shading is applied. A solar shading body having characteristics can be obtained.

  Here, the dispersed particle diameter means an aggregated particle diameter obtained by agglomerating boride fine particles for solar radiation shielding that are not pyrophoric in a solvent, and can be measured with various commercially available particle size distribution analyzers. it can. For example, in a state where there are aggregates of irradiating boride fine particles for non-pyrophoric radiation, sampling is performed from a dispersion in which the irradiating boride fine particles are dispersed in a solvent, and the principle of dynamic light scattering is used. Otsuka Electronics Co., Ltd. ELS-800 can be used. Further, an apparatus for measuring the particle diameter by analyzing the light scattering of the laser can be used.

  The dispersion particle size of the sunscreen boride fine particles having no spontaneous ignition is desirably 800 nm or less. If this dispersed particle size is 800 nm or less, the desired solar shading characteristics can be obtained, resulting in a gray film or molded body (plate, sheet, etc.) having a monotonously reduced transmittance. This is because it can be avoided. In addition, if a large amount of aggregated coarse particles are contained, it becomes a light scattering source, and when it is made into a film or molded body (plate, sheet, etc.), haze increases and the visible light transmittance decreases. This is not preferable.

  In addition, the dispersion method of the non-pyrophoric sunscreen boride fine particles in the solvent is not particularly limited as long as it is a method of uniformly dispersing in the dispersion, for example, a bead mill, a ball mill, a sand mill, Examples thereof include a paint shaker and an ultrasonic homogenizer. Depending on the dispersion treatment conditions using these equipment, the dispersion of boric acid particles for non-pyrophoric solar shielding into a solvent and the formation of fine particles due to collisions between the boric fine particles for solar shading proceed. It is possible to further disperse the fine particles of boride for solar radiation shielding.

  Next, the solar shielding body-forming dispersion liquid is obtained by dispersing the solar shielding boride fine particles having no spontaneous ignition as described above in a solvent, but the solvent is not particularly limited, and It may be selected according to conditions and application environment, and when an inorganic binder or resin binder is further contained, it may be selected appropriately according to the binder. Examples of the solvent include water, alcohols such as ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol, diacetone alcohol, methyl ether, and ethyl ether. Various organic solvents such as ethers such as propyl ether, esters, acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, and isobutyl ketone can be used, and acids and alkalis can be added as necessary. Then, the pH may be adjusted. Furthermore, in order to further improve the dispersion stability of the fine particles in the dispersion, various surfactants, coupling agents and the like can of course be added.

Moreover, when mix | blending a binder, the kind of the inorganic binder and the resin binder is not specifically limited. For example, examples of the inorganic binder include metal alkoxides of silicon, zirconium, titanium, or aluminum, and their partial hydrolysis-condensation polymers or organosilazanes. As the resin binder, a thermoplastic resin such as an acrylic resin, a thermosetting resin such as an epoxy resin, or the like can be used.

In addition, when the coating film is formed on the transparent substrate using the above-mentioned dispersion for forming a solar shielding body, the conductivity of the film is a conductive path that passes through contact points of the solar shielding boride fine particles that are not pyrophoric. Therefore, for example, the conductive path can be partially cut by adjusting the amount of the surfactant or the coupling agent, so that the surface resistance is 10 ⁶ Ω / □ or more and the conductivity of the film is reduced. Is easy to reduce. The conductivity can also be controlled by adjusting the content of the inorganic binder or the resin binder.

Further, the dispersion for forming a solar shield was selected from ZrO ₂ , TiO ₂ , Si ₃ N ₄ , SiC, SiO ₂ , Al ₂ O ₃ , Y ₂ O ₃ for the purpose of increasing the film strength. At least one compound can be contained. The content of the compound selected from ZrO ₂ , TiO ₂ , Si ₃ N ₄ , SiC, SiO ₂ , Al ₂ O ₃ , and Y ₂ O ₃ includes (weight of the above compound / boride fine particles for solar radiation shielding) It is desirable that the value of (weight) × 100 is set in the range of 0.1 to 250%. This is because if 0.1% or more, the effect of addition (film strength) increases, and if it is 250% or less, the ratio of boride fine particles is not reduced, and a good solar shading function can be secured.

[3] Solar shield The solar shield is applied to a transparent substrate (such as glass or plastic) as appropriate to form a coating as described above. Alternatively, the solar shield is dispersed as described above. The liquid is kneaded into a base material for forming a solar shading body to produce a plate, plate, sheet or film.

  When the solar shading body is composed of a transparent substrate and a film formed thereon, the resin binder or inorganic binder contained in the solar shading body-forming dispersion is applied after curing and then the above There is an effect of improving the adhesion of the solar shielding boride fine particles having no spontaneous ignition to the base material and further improving the hardness of the film. Further, on the coating thus obtained, a coating made of a metal alkoxide of silicon, zirconium, titanium, or aluminum, or a partially hydrolyzed polycondensation product thereof is applied as a second layer, and silicon, zirconium, By forming an oxide film of titanium or aluminum, it is possible to further improve the binding force, the hardness of the film, and the weather resistance of the film mainly composed of boride fine particles for solar radiation shielding that are not pyrophoric. it can.

  In addition, the coating obtained when the dispersion for forming the solar radiation shielding body does not contain a resin binder or an inorganic binder is a film in which only the above-described solar radiation boride fine particles having no spontaneous ignition are deposited on the base material. Become a structure. And although it shows the solar radiation shielding effect as it is, the coating liquid further contains an inorganic binder or a resin binder such as a metal alkoxide of silicon, zirconium, titanium, or aluminum or a partially hydrolyzed polycondensate thereof on this film. It is good to apply | coat and form a film to make a multilayer film. By doing so, the coating liquid component is formed to fill the gap where the boride fine particles of the first layer are deposited, so that the haze of the film is reduced and the visible light transmittance is improved. The binding property to the base material is improved.

  The coating method in the case of forming a film by appropriately applying the dispersion for forming a solar shielding body on a transparent substrate is not particularly limited. For example, spin coating method, bar coating method, spray coating method, dip coating method, screen printing method, roll coating method, flow coating, etc. Any method can be used as long as it can be applied.

The substrate heating temperature after the application of the dispersion containing the metal alkoxide of silicon, zirconium, titanium, or aluminum and its hydrolysis polymer as the inorganic binder is less than 100 ° C., and the alkoxide contained in the coating film. Alternatively, the polymerization reaction of the hydrolyzed polymer is often left unfinished, and water and organic solvents remain in the film, causing a reduction in the visible light transmittance of the film after heating. It is preferable to perform heating at a temperature equal to or higher than the boiling point of the solvent in the dispersion. Moreover, what is necessary is just to harden | cure according to each hardening method, when a resin binder is used. 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. For this reason, the application | coating in the field to the existing window glass etc. is possible.

And, for example, the solar shading body according to the present embodiment composed of a transparent base material and a film formed thereon has moderately dispersed solar shading boride fine particles that are not pyrophoric in the film. Therefore, as compared with an oxide thin film formed by a physical film forming method having a mirror-like surface in which crystals are densely filled in the film, reflection in the visible light region is less and it is possible to avoid a glare appearance. On the other hand, since there is a plasma frequency from the visible region to the near infrared region, the plasma reflection associated therewith increases in the near infrared region. In order to further suppress the reflection in the visible light region, a low refractive index film such as SiO ₂ or MgF ₂ is formed on the film in which the boride particles for solar radiation shielding that are not pyrophoric are dispersed. By forming the film, a multilayer film having a luminous reflectance of 1% or less can be easily obtained.

  Moreover, in order to form a solar shading body, the solar shading body forming matrix into which the dispersion for forming the sun shading body is kneaded is polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene. At least one selected from resin, polypropylene resin, ethylene vinyl acetate copolymer, polyester resin, polyethylene terephthalate resin, fluorine resin, polycarbonate resin, acrylic resin, polyvinyl butyral resin Resins are preferred.

Further, the solar shield applied as a coating by applying to the dispersion for forming the solar shield, or the dispersion for forming the solar shield is kneaded into the base material for forming the solar shield to form a plate, sheet or film. The solar shading body may be laminated by sandwiching the solar shading body from both sides with another base material.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples.
Incidentally, the powder color (standard light source D65, 10, field of view) of the fine particles e to l applied in each of the following examples and comparative examples, and solar shading obtained using a dispersion liquid in which each fine particle is dispersed ^. The optical characteristics of the bodies A to L were measured using a spectrophotometer U-4000 manufactured by Hitachi, Ltd. Moreover, regarding the solar radiation shielding characteristics, the maximum value P, the minimum value B, and the visible light transmittance VLT of the transmittance were obtained from the transmission profile of each solar shield. The dispersed particle size was measured using ELS-800 manufactured by Otsuka Electronics Co., Ltd.

Example 1
To a mixed solution of 104.8 g of 10% La (NO ₃ ) ₃ 6H ₂ O aqueous solution (424.8 g) and 10% Zn (NO ₃ ) ₂ 6H ₂ O aqueous solution (109.6 g), a 15% NH ₄ OH solution at pH 8. 6 was added dropwise over 25 minutes to form a precipitate, and stirring was continued for 10 minutes after the addition.
Next, using pure water, the precipitate produced by decantation was washed, and this was repeated until the conductivity of the supernatant was 1 mS / cm or less. The washed precipitate was dried at 105 ° C. and calcined at 600 ° C. for 1 hour in the air.
The obtained La and Zn hydroxide and B ₄ C particles having an average particle diameter of about 22 μm were mixed so that the atomic ratio of La element to B element was 1: 6 to obtain a uniform mixture. Thereafter, this uniform mixture was fired at 1350 ° C. for 3 hours in a vacuum atmosphere (about 0.02 Pa) to obtain Zn-containing LaB ₆ particles.

The Zn-containing LaB ₆ particles were pulverized using a jet mill under conditions of a gas pressure of 0.6 MPa / cm ² and a used air amount of 0.8 m ³ / min to obtain the Zn-containing LaB ₆ particles a.
The container was filled with the Zn-containing LaB ₆ particles a13 wt%, isopropyl alcohol 87 wt%, 0.3 mmφZrO ₂ beads, and subjected to a 4-hour bead mill dispersion treatment to obtain a Zn-containing LaB ₆ particle dispersion. Prepared. After removing isopropyl alcohol from the dispersion under conditions of 80 ° C. under vacuum, Zn-containing LaB ₆ fine particles were taken out into the atmosphere, but were not spontaneously ignited and stable. This is represented by a circle in FIG.

Next, a mixture of Zn-containing LaB ₆ particles a 40% by weight, polymer dispersant 12% by weight, isopropyl alcohol 48% by weight is filled into a container together with 0.3 mmφZrO ₂ beads, and pulverized for 24 hours. A Zn-containing LaB ₆ dispersion was prepared by dispersion treatment (solution A). Here, the dispersed particle diameter of the LaB ₆ particles in the Zn-containing LaB ₆ dispersion (liquid A) was 81 nm.
Next, bar NO. 24 (JIS K5400) bar coater, film thickness 50μm
After applying the above-mentioned dispersion for forming a sunscreen (Liquid A) on a PET (polyethylene terephthalate) film, irradiation with a high-pressure mercury lamp was performed at 70 ° C. for 1 minute, and solar radiation according to Example 1 A shield A was obtained.

  Here, using a spectrophotometer U-4000 manufactured by Hitachi, Ltd., the visible light transmittance and the solar shading characteristics were measured as the optical characteristics of the solar shading body A. In addition, the solar shading characteristics evaluation in the measurement is to measure the light transmittance of the solar shading body in the wavelength range of 300 to 2100 nm and express it as a percentage, and point the difference between the maximum value P and the minimum value B of the percentage. This is what I asked for. As shown in FIG. 2, as a result of measuring the visible light transmittance and the solar radiation shielding characteristic of the solar shading body A, the visible light transmittance is 69.1%, and the difference between the local maximum value P and the minimum value B of the transmittance is 51. A value of 6 points was obtained.

(Example 2)
A Zn-containing LaB ₆ particle b, a Zn-containing LaB ₆ dispersion B and a solar shading body B according to Example 2 were obtained in the same manner as in Example 1 except that baking was not performed for 1 hour at 600 ° C. in the air. .
After removing isopropyl alcohol from the dispersion B under conditions of 80 ° C. under vacuum, LaB ₆ particles were taken out into the atmosphere, but were not spontaneously ignited and stable. This is represented by a circle in FIG.
As shown in FIG. 2, as in Example 1, the solar light shielding body B was measured for the visible light transmittance and the solar light shielding characteristics. As a result, the solar light shielding body B had a visible light transmittance of 69.1% and a transmittance. The difference between the local maximum value P and the local minimum value B was 51.6 points.

(Example 3)
In Example 1, instead of La (NO ₃ ) ₃ 6H ₂ O, Ce (NO ₃ ) ₃ 6H ₂ O
Except that 10% Ce (NO ₃ ) ₃ 6H ₂ O 12.36 kg, 10% Zn (NO ₃ ) ₂ 6H ₂ O aqueous solution 1.02 kg, and 15% NH ₄ OH solution 4.91 kg were used. In the same manner as in Example 1, Zn-containing Ce B ₆ particles c, Zn-containing Ce B ₆ dispersion C, and solar shield C according to Example 3 were obtained. The dispersion particle diameter of the Zn-containing Ce B ₆ particles c in the dispersion C was 85 nm.
After removing isopropyl alcohol from the dispersion C under conditions of 80 ° C. under vacuum, LaB ₆ particles were taken out into the atmosphere, but were not spontaneously ignited and stable. This is represented by a circle in FIG.
As shown in FIG. 2, the visible light transmittance and the solar light shielding characteristics of the solar shield C were measured in the same manner as in Example 1. As a result, the solar shield C was found to have a visible light transmittance of 69.5% and a transmittance. The difference between the local maximum value P and the local minimum value B was 43.7 points.

(Comparative Example 1)
In Example 1, LaB ₆ particles d, LaB ₆ dispersion D and solar radiation shield D according to Comparative Example 1 were obtained in the same manner as Example 1 except that Zn (OH) ₂ was not used. The dispersion particle diameter of the LaB ₆ particles d in the dispersion D was 85 nm.
After removing isopropyl alcohol from the dispersion D under the condition of 80 ° C. under vacuum, it spontaneously ignited as soon as the LaB ₆ particles were taken out into the atmosphere. This is represented by a cross in FIG.
As shown in FIG. 2, the visible light transmittance and the solar light shielding characteristics of the solar shading body D were measured in the same manner as in Example 1. As a result, the solar shading body D had a visible light transmittance of 51.5% and a transmissivity. The difference between the local maximum value P and the local minimum value B was 48.8 points.

(Evaluation of Examples 1 to 3 and Comparative Example 1)
As is clear from the results of Examples 1 to 3 and Comparative Example 1 (FIG. 2), all the particles according to Examples 1 to 3 did not spontaneously ignite even when taken out into the atmosphere, and transmitted through the solar radiation shield. The difference between the local maximum value P and the local minimum value B was 40 points or more. On the other hand, the difference between the maximum value P and the minimum value B of the transmittance of the solar shield D of Comparative Example 1 was 40 points or more, but the LaB ₆ particles d spontaneously ignited as soon as they were taken out into the atmosphere.
From the above, the borate fine particles for solar shading obtained by the production method according to this example do not spontaneously ignite, and the solar shading body prepared from the particles has a maximum value P and a minimum value B of transmittance. It was found that the optical characteristics were excellent with a difference of 40 points or more.

Example 4
After thoroughly mixing 540.5 g of La (OH) _{3 and} 31.6 g of Zn (OH) _2, it was fired at 600 ° C. for 1 hour in the atmosphere. After mixing the obtained oxides of La and Zn and B ₄ C particles having an average particle diameter of about 22 μm so that the atomic ratio of La element to B element is 1: 6, a uniform mixture is obtained. The homogeneous mixture was calcined at 1400 ° C. for 2 hours in a vacuum atmosphere (about 0.02 Pa) to obtain LaB ₆ particles e containing 3.5% Zn. The powder color of the Zn-containing LaB ₆ particles e in the L ^* a ^* b ^* color system was measured and is shown in FIG. This Zn-containing LaB ₆ particle e13% by weight, isopropyl alcohol 87% by weight, 0.3 mmφZrO ₂ beads were filled in a container, and subjected to a beads mill dispersion treatment for 4 hours to obtain a Zn-containing LaB ₆ particle dispersion. Prepared.
After removing isopropyl alcohol from the dispersion under conditions of 80 ° C. under vacuum, Zn-containing LaB ₆ fine particles were taken out into the atmosphere, but were not spontaneously ignited and stable. This is represented by a circle in FIG.

Next, a mixture of 40 wt% Zn-containing LaB ₆ particles e, 12 wt% polymer dispersant and 48 wt% isopropyl alcohol was filled into a container together with 0.3 mmφZrO ₂ beads, and the mixture was mixed for 8 hours. - to prepare a Zn-containing LaB ₆ dispersion by the Zumiru distributed processing (E solution). Here, the Zn-containing LaB ₆ particles have an average primary particle diameter of 35 nm by the pulverization / classification treatment. Moreover, the dispersed particle diameter of the LaB ₆ particles in the Zn-containing LaB ₆ dispersion (E liquid) was 83 nm. The ZrO ₂ content in the dispersion (liquid E) was 137%.
Next, bar NO. 8 (JIS K5400) bar coater with a thickness of 50 μm
After applying the above-mentioned dispersion for forming a solar shielding body (E liquid) on an ET (polyethylene terephthalate) film, the solar radiation shielding according to Example 1 was irradiated with a high-pressure mercury lamp at 70 ° C. for 1 minute. Body E was obtained.

Here, using a spectrophotometer U-4000 manufactured by Hitachi, Ltd., the visible light transmittance and the solar radiation shielding characteristic were measured as the optical characteristics of the solar radiation shielding body E. The solar shading characteristic evaluation in the measurement is obtained by expressing the transmittance of the solar shading body as a percentage and calculating the difference between the maximum value P and the minimum value B of the percentage as a point. And as a result of measuring the visible light transmittance and the solar radiation shielding characteristic of the solar shading body E, the visible light transmittance is 71.7%, and the difference between the maximum value P and the minimum value B of the transmittance is 51.8 points. Obtained. This value is shown in FIG.

(Example 5 to Example 7)
Zn _{(OH) 2} except that the 66.8g of got solar radiation-shielding body F according to the Zn-containing LaB ₆ particles f, Zn-containing LaB ₆ dispersion F and Example 5 in the same manner as in Example 4.
Further, in the same manner as in Example 4 except that 60.1 g of Al (OH) ₃ was used instead of Zn (OH) ₂ , Al-containing LaB ₆ particles g, Al-containing LaB ₆ dispersion G and Example 6 were used. Such solar radiation shield G was obtained.
Except for using 49.9 g of Mg (OH) ₂ instead of Zn (OH) ₂ , the Mg-containing LaB ₆ particles h, the Mg-containing LaB ₆ dispersion H and the solar radiation according to Example 7 are the same as in Example 4. A shield H was obtained.

Here, the dispersion particle diameter of the Zn-containing LaB ₆ particles f in the dispersion liquid F is 110.6 nm, the dispersion particle diameter of the Al-containing LaB ₆ particles g in the dispersion liquid G is 83 nm, and the Mg content in the dispersion liquid H is The dispersed particle diameter h of LaB ₆ particles was 81 nm. The average primary particle size was 36 nm for Zn-containing LaB ₆ particles f, 36 nm for Al-containing LaB ₆ particles g, and 37 nm for Mg-containing LaB ₆ particles h. Then, the powder color in the L ^* a ^* b ^* color system of each particle f to h was measured and shown in FIG.
In addition, the ZrO ₂ content in the dispersions F to H was 137%.
From each of the dispersions F to H, isopropyl alcohol was removed under conditions of 80 ° C. under vacuum, and then Zn-containing LaB ₆ particles f, Al-containing LaB ₆ particles g, and Mg-containing LaB ₆ particles h were taken out into the atmosphere. However, they did not ignite spontaneously and were stable. This is represented by a circle in FIG.

  And as in Example 4, as a result of measuring the visible light transmittance and the solar radiation shielding characteristics of each solar radiation shielding body, the solar radiation shielding body F has a visible light transmittance of 68.9%, and a maximum value P of the transmittance. The difference of 51.8 points from the minimum value B is obtained, and the solar shading body G has a visible light transmittance of 71.5% and a difference of 52.0 points between the maximum value P and the minimum value B of the transmittance. The solar shading body H obtained a visible light transmittance of 71.8% and a difference of 52.3 points between the maximum value P and the minimum value B of the transmittance.

(Example 8)
A Zn-containing CeB ₆ dispersion I (Example 8) was obtained in the same manner as in Example 4, except that 30.9 g of Ce (OH) ₄ was used instead of La (OH) ₃ in Example 4. The dispersion particle diameter of the Zn-containing CeB ₆ particles i in the dispersion I was 85 nm. The average primary particle diameter of the Zn-containing CeB ₆ particles i was 38 nm. The powder color of the Zn-containing CeB ₆ particles i in the L ^* a ^* b ^* color system was measured and is shown in FIG. The ZrO ₂ content in the dispersion I liquid was 139%.
After removing isopropyl alcohol from the dispersion I under the condition of 80 ° C. under vacuum, the Zn-containing CeB ₆ particles i were taken out into the atmosphere, but were not spontaneously ignited and stable. This is represented by a circle in FIG.
And as in Example 4, as a result of measuring the visible light transmittance and solar radiation shielding characteristics of the solar radiation shield I, the solar radiation shield I has a visible light transmittance of 71.9% and a maximum value P of the transmittance. A difference of 43.9 points from the minimum value B was obtained.

Example 9
Disperse the Zn-containing LaB ₆ particles e of 20% by weight, the polymer dispersant 5% by weight and toluene 75% by weight with a paint shaker containing 0.3 mmφZrO ₂ beads for 24 hours. Thus, a Zn-containing LaB ₆ dispersion liquid J having an average dispersed particle diameter of 82 nm was prepared. The ZrO ₂ content in the dispersion liquid J was 137%.
Next, the obtained dispersion liquid J is added to polyvinyl butyral, to which triethylene glycol-di-2-ethylbutyrate is added as a plasticizer, and the concentration of Zn-containing LaB ₆ particles e is 0.02. The composition for an interlayer film was prepared so that the weight percent and the polyvinyl butyral concentration would be 71.1 weight percent. The prepared composition was kneaded with a roll and formed into a 0.76 mm thick sheet to produce an interlayer film. The prepared intermediate film is sandwiched between two green glass substrates of 100 mm × 100 mm × about 2 mm thickness, heated to 80 ° C. and temporarily bonded, and then finally bonded by 140 ° C. and 14 kg / cm ² autoclave. The solar radiation shield J was made.
And as in Example 4, as a result of measuring the visible light transmittance and the solar shading characteristics of the solar shading body J, the solar shading body J has a visible light transmittance of 73.0%, a maximum value P of transmittance, and A value of 50.9 points different from the minimum value B was obtained.

(Example 10)
The Zn-containing LaB ₆ dispersion (E liquid) of Example 4 was added to the polycarbonate resin so that the LaB ₆ concentration was 0.005 wt%, and melted and mixed uniformly with a blender and a twin screw extruder. After that, extrusion was performed to a thickness of 2 mm using a T-die to obtain a solar radiation shielding body (heat ray shielding polycarbonate sheet) in which LaB ₆ fine particles were uniformly dispersed throughout the resin. A solar shading body K is produced in the same manner as in Example 4 except that the solar shading body and the other green glass substrate are sandwiched by a polyvinyl butyral sheet for interlayer film having a thickness of 0.76 mm. did.
And as in Example 4, as a result of measuring the visible light transmittance and the solar radiation shielding characteristics of the solar radiation shield K, the solar radiation shield K has a visible light transmittance of 74.0%, a maximum transmittance value P, and A difference of 51.3 points from the minimum value B was obtained.

(Comparative Example 2)
A LaB ₆ dispersion L was prepared in the same manner as in Example 4 except that Zn (OH) ₂ in Example 4 was not added. And the powder color in the L ^* a ^* b ^* color system of this LaB ₆ particle | grains 1 was measured, and it described in FIG.
The dispersion particle diameter of the LaB ₆ particles 1 in the dispersion L was 85 nm.
After isopropyl alcohol was removed from the dispersion L at 80 ° C. under vacuum, the LaB ₆ particles were spontaneously ignited as soon as they were taken out into the atmosphere. This is represented by a cross in FIG.
And as in Example 4, as a result of measuring the visible light transmittance and the solar radiation shielding characteristics of the solar radiation shield L, the solar radiation shield L has a visible light transmittance of 71.7% and a maximum value P of the transmittance. A difference of 49.0 points from the minimum value B was obtained.

(Evaluation of Examples 4 to 10 and Comparative Example 2)
As is clear from the results shown in FIG. 3, all particles according to Examples 4 to 10 do not ignite spontaneously when taken out into the atmosphere, and the maximum value P and the minimum value B of the transmittance of the solar shield. The difference was 40 points or more.
On the other hand, the difference between the maximum value P and the minimum value B of the transmittance of the solar shield L of Comparative Example 2 was 40 points or more, but the LaB ₆ particles l spontaneously ignited as soon as they were taken out into the atmosphere.
From the above, the boride fine particles according to the present invention do not ignite spontaneously, and the solar shield prepared from the particles is excellent in that the difference between the maximum value P and the minimum value B of the transmittance is 40 points or more. It was found to have optical properties.

It is a flowchart which shows the manufacturing process of one Embodiment in the manufacturing method of the boride microparticles | fine-particles for solar shading which do not have spontaneous ignition based on this invention, and the manufacturing method of the dispersion liquid for solar shading formation. It is a table | surface which shows the measurement result of the physical characteristic of the boride fine particle for solar radiation shielding in Examples 1-3 grade | etc., Which has no spontaneous ignition property, and the optical characteristic of a solar radiation shield. It is a table | surface which shows the measurement result of the physical characteristic of solar boride fine particle for solar radiation shielding in Examples 4-10 grade | etc., And the optical characteristic of a solar radiation shield.

Claims (18)

The boride fine particles have the general formula XB ₆ (wherein the X element is at least one selected from La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) And a hexaboride fine particle containing at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si. Boride fine particles. The content of the additive element, the additional element when the A, according to claim 1, the weight ratio expressed by A / (A + XB ₆₎ is characterized in that 0.001 to 0.5 Boride fine particles for solar radiation shielding. The average primary particle diameter is 400 nm or less, the powder color L ^* in the L ^* a ^* b ^* color system is 30 to 60, a ^* is −5 to 10, and b ^* is −10 to 2. The boride fine particles for solar radiation shielding according to claim 1, wherein: 4. The surface of the solar shading boride fine particles is coated with an oxide containing at least one element selected from Si, Ti, Zr, and Al . Boride fine particles for solar radiation shielding as described in 1. In a dispersion for forming a solar shading body, comprising a solvent and solar shading fine particles dispersed in the solvent, and applied to the formation of the solar shading body,
The solar shading fine particles are composed of the solar shading boride fine particles according to any one of claims 1 to 4 , and the boride fine particles dispersed in a solvent have a dispersed particle diameter of 800 nm or less. A dispersion for forming a solar shading material. 6. The solar radiation shield according to claim 5 , comprising at least one compound selected from ZrO ₂ , TiO ₂ , Si ₃ N ₄ , SiC, SiO ₂ , Al ₂ O ₃ , and Y ₂ O _3. Forming dispersion. A solar shading body, characterized by being formed using the solar shading body-forming dispersion liquid according to claim 5 or 6 . A solar shading body formed by applying the solar shading body-forming dispersion liquid according to claim 5 or 6 on a transparent substrate. The solar shading boride fine particles according to any one of claims 1 to 4 , or the solar shading body forming dispersion according to claim 5 or 6 , is kneaded into a solar shading body forming base material, A solar shading body characterized by being formed into a sheet or film. The base material for forming the sunscreen is polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, ethylene vinyl acetate copolymer, polyester resin, polyethylene terephthalate. 10. The solar radiation shielding body according to claim 9 , wherein the solar radiation shielding body is at least one selected from a resin, a fluororesin, a polycarbonate resin, an acrylic resin, and a polyvinyl butyral resin. Another substrate is laminated on the solar shield so as to sandwich the solar shield according to claim 8 , or the solar shield according to claim 9 or 10 is sandwiched between other substrates and laminated. A solar shading body characterized by that. General formula XB ₆ containing at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si ( where X element is La, Ce, Pr, Nd, Sm, A method for producing boride fine particles for solar radiation shielding represented by at least one selected from Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu ,
A solution of a compound containing an X element and a compound containing at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si is reacted with an alkali solution while stirring. To obtain a precipitate,
The precipitate is dried , and hydroxide particles and / or hydrate particles of element X and at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si Obtaining
Wherein X element and Sb, Zn, and heat-treated Mg, Sn, Zr, Mo, Al, and the hydroxide particles and / or hydrate particles of one additive element even without least selected from Si, Obtaining oxide particles of the element X and at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si ;
The X element is mixed with oxide particles of at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si, and B ₄ C particles, Obtaining a mixture of oxide particles of an element and at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si, and B ₄ C particles;
In general, the mixture is heat-treated at less than 1600 ° C. in a vacuum or an inert gas atmosphere , and contains at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si method of manufacturing a solar radiation shielding boride particles, characterized by comprising the steps of obtaining a solar radiation shielding boride particles of the formula XB _6, the. General formula XB ₆ containing at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si (where X element is La, Ce, Pr, Nd, Sm, At least one selected from Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu ).
A solution of a compound containing an X element and a compound containing at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si is reacted with an alkali solution while stirring. To obtain a precipitate,
The precipitate is dried , and hydroxide particles and / or hydrate particles of element X and at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si Obtaining
Hydroxide and / or hydrate particles of the element X and at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si; and B ₄ C particles; A hydroxide particle and / or a hydrate particle of the element X and at least one additional element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si, and B Obtaining a mixture with ₄ C particles;
In general, the mixture is heat-treated at less than 1600 ° C. in a vacuum or an inert gas atmosphere , and contains at least one additive element selected from Sb, Zn, Mg, Sn, Zr, Mo, Al, and Si method of manufacturing a solar radiation shielding boride particles, characterized by comprising the steps of obtaining a solar radiation shielding boride particles of the formula XB _6, the. When mixing the hydroxide particles and / or hydrate particles of the X element and the additive element, or the oxide particles of the X element and the additive element, and the B ₄ C particles, mixing them 14. The method for producing solar shading boride fine particles according to claim 12 or 13 , wherein the ratio is mixed so that the atomic ratio of X element: boron is 1: 6 . The content of the additive element is such that when the additive element is A, the weight ratio represented by A / (A + XB ₆ ) is 0.001 to 0.5 . The manufacturing method of the boride fine particle for solar radiation shielding in any one . Hydroxide particles and / or hydrate particles of the X element and additive element having an average particle size of 0.1 μm or less, or oxides of the X element and additive element having an average particle size of 20 μm or less The method for producing boride fine particles for solar shading according to claim 12, wherein the B ₄ C particles having an average particle diameter of 60 μm or less are mixed. Solar radiation shielding boride fine particles produced by the method for producing solar radiation shielding boride fine particles according to any one of claims 12 to 16 are collided with each other in a jet stream and pulverized. A method for producing boride fine particles for shielding. The slurry obtained by mixing the sunscreen boride fine particles according to any one of claims 12 to 17 and a solvent is put into a medium stirring mill together with beads, and further pulverized and dispersed. A method for producing a dispersion for forming a sunscreen.

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