TWI703090B - Boride particles, boride particle dispersion, infrared shielding transparent substrate, infrared shielding optical member, infrared shielding particle dispersion, infrared shielding interlayer transparent substrate, infrared shielding particle dispersion powder, and master batch - Google Patents

Abstract

Provided is a boride particle, which has the general formula XB _m (where X is selected from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr One or more metal elements of Ca, where m is a number representing the content of boron in the general formula) means that the carbon content contained in the boride particles when measured by the combustion infrared absorption method is 0.2% by mass or less.

Description

Boride particles, boride particle dispersion, infrared shielding transparent substrate, infrared shielding optical member, infrared shielding particle dispersion, infrared shielding interlayer transparent substrate, infrared shielding particle dispersion powder, and master batch

The present invention relates to a boride particle, a boride particle dispersion, an infrared shielding transparent substrate, an infrared shielding optical member, an infrared shielding particle dispersion, an infrared shielding interlayer transparent substrate, an infrared shielding particle dispersion powder, and a master batch.

In the past, boride particles of rare earth elements such as La were synthesized by a solid-phase reaction method and then pulverized by a dry pulverization method. In particular, the method of pulverizing the particles by colliding with each other by high-speed airflow of a jet mill is more universal. Among rare earth element boride particles, for example, lanthanum hexaboride is obtained by heating lanthanum oxide and boron oxide to a high temperature in the presence of carbon, and then pulverized by a dry pulverizing device. It should be noted that, for example, Patent Document 1 discloses a method of finely pulverizing powder using a jet mill.

These boride particles have conventionally been used in thick film resistor pastes and the like, and when they become fine particles, they can be used as optical materials for sun-shielding. In other words, since the film in which the boride particles are dispersed transmits visible light and can effectively shield the near-infrared rays acting as heat energy, it is known to be suitable as a solar shielding material for houses or car windows (for example, see Patent Literature 2, 3).

However, since the borides of rare earth elements such as La are hard, it is difficult to pulverize into fine particles by dry pulverization using jet mills, etc., and only about 1 μm to 3 μm can be obtained. The problem of larger particles. In addition, it is difficult to suppress re-aggregation of boride particles obtained by the dry pulverization method.

In subsequent studies, it was found that by processing with a media stirring mill, the average dispersed particle diameter of boride particles can be made 200 nm or less (for example, see Patent Document 4). In this way, boride particles having an average dispersed particle diameter of about 200 nm can be obtained economically. If boride particles with an average dispersed particle diameter of 200 nm or less are used, geometric scattering or Mie scattering caused when the particle diameter is larger than 200 nm can be reduced. Therefore, it is possible to prevent the light scattering in the visible light range of 400 nm to 780 nm from becoming frosted glass-like phenomenon, and thereby it is possible to obtain an optical member that emphasizes transparency.

However, as infrared shielding particles, infrared shielding optical members in which the above-mentioned boride particles are dispersed may change color to blue-white when irradiated with strong light such as sunlight or spotlights (hereinafter, this phenomenon may be described as " "Blue haze" (blue haze)). If this blue haze occurs, there is a problem that the beauty of the infrared shielding optical member may be impaired.

It is known that if the average dispersed particle diameter of the boride particles is 200 nm or less, geometric scattering or Mie scattering is reduced, and the scattering coefficient of most of the scattering follows the Rayleigh scattering defined by the following formula (1).

S=[16 π ⁵ r ⁶ /3 λ ⁴ ]‧[(m ² -1)/(m ² +2)] ² ‧[m] (1)

[Among them, in the above formula (1), S is the scattering coefficient, λ is the wavelength, r is the particle size, m=n ₁ /n ₀ , n ₀ is the refractive index of the substrate, and n ₁ is the refractive index of the dispersed substance]

The aforementioned Rayleigh scattering is the scattering of light due to particles having a size smaller than the wavelength of light. According to the above-mentioned formula (1), since Rayleigh scattering is inversely proportional to the fourth power of the wavelength (λ), it is considered that blue light with a shorter wavelength is scattered and changed to a blue-white color.

In addition, in the Rayleigh scattering region, according to the above formula (1), due to the scattered light and the particle size (r) Is proportional to the sixth power, so it is believed that by reducing the particle size, Rayleigh scattering can be reduced and blue haze can be suppressed.

In addition, for example, Patent Document 5 discloses an example in which the occurrence of blue haze can be suppressed by setting the average dispersed particle diameter to 85 nm or less.

<Prior Technical Literature> <Patent Literature>

Patent Document 1: Japanese Patent Application Publication No. 2001-314776

Patent Document 2: Japanese Patent Application Publication No. 2000-096034

Patent Document 3: Japanese Patent Application Publication No. 11-181336

Patent Document 4: Japanese Patent Application Publication No. 2004-237250

Patent Document 5: Japanese Patent Application Publication No. 2009-150979

<Non-Patent Literature>

Non-Patent Document 1: V. Domnich et al., J. Am. Ceram. Soc., (2011) vol.94, Issue 11, pp.3605-3628

Non-Patent Document 2: X.H. Zhao et al., App. Mech. Mater., (2011) vol.55-57, pp.1436-1440

However, if the pulverization method using a media stirring mill disclosed in Patent Document 4 is used to pulverize conventionally used boride particles to an average dispersed particle size of 85 nm or less, the slurry viscosity will increase and the pulverization process may be difficult. .

Therefore, in order to continue the pulverization process, there is a further reduction in the average dispersion particle size and suppression of To make blue mist, it is necessary to extremely reduce the concentration of boride particles in the slurry to reduce the viscosity, and the pulverization efficiency is poor and uneconomical.

Therefore, in view of the above-mentioned problems in the prior art, an object of one aspect of the present invention is to provide boride particles that can be easily pulverized.

In order to solve the above-mentioned problem, according to an embodiment of the present invention, a boride particle is provided, which has the general formula XB _m (where X is selected from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, One or more metal elements of Dy, Ho, Er, Tm, Yb, Lu, Sr, and Ca, where m is a number representing the content of boron in the general formula), and the boride particles when measured by the combustion infrared absorption method contain The carbon content is 0.2% by mass or less.

According to an embodiment of the present invention, it is possible to provide boride particles that can be easily pulverized.

10: Measuring device

11: light source

12: Determination reagent

13: Receiver

14: Integrating sphere

15: Standard reflector

16: Optical trap components

141: first opening

142: second opening

143: Third opening

Fig. 1 is an explanatory diagram showing the principle of measuring the diffuse transmission curve of an infrared shielding particle dispersion and the like according to an embodiment of the present invention (Part 1).

Fig. 2 is an explanatory diagram showing the principle of measuring a diffuse transmission curve of an infrared shielding particle dispersion and the like according to an embodiment of the present invention (Part 2).

Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention is not limited to the following embodiments, and various modifications and substitutions can be made to the following embodiments without departing from the scope of the present invention.

(Boride particles)

In this embodiment, first, a configuration example of boride particles will be described.

The boride particles of this embodiment relate to the general formula XB _m (where X is selected from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, One or more metal elements of Sr and Ca, and m is a boride particle represented by a number representing the boron content in the general formula). In addition, the carbon content contained in the boride particles when measured by the combustion infrared absorption method can be set to 0.2% by mass or less.

The inventors of the present invention conducted intensive studies on boride particles that can be easily pulverized, that is, can be pulverized into fine particles. In addition, they discovered that by setting the carbon content (carbon concentration) in the boride particles to a predetermined value or less, it is possible to obtain boride particles that can be easily pulverized, and completed the present invention.

The boride particles of this embodiment may be particles of boride represented by the general formula XB _m as described above.

In the boride particles of the present embodiment represented by the above-mentioned general formula XB _{m, m} , which is the element ratio (molar ratio) (B/X) of boron (B) and the metal element X, is not particularly limited. Preferably it is 3.0 or more and 20.0 or less.

Examples of borides constituting the boride particles represented by the general formula XB _m include XB ₄ , XB ₆ , XB ₁₂ and the like. However, from the viewpoint of selectively and effectively reducing the transmittance of light in the near-infrared region near the length of 1000 nm, the boride particles of this embodiment preferably contain XB ₄ or XB ₆ as the main component, and may partially contain XB ₁₂ .

Therefore, _m , which is the element ratio (B/X) of boron (B) to metal element (X) in the general formula XB _m , is more preferably 4.0 or more and 6.2 or less.

It should be noted that when the above-mentioned (B/X) is 4.0 or more, the generation of XB or XB ₂ can be suppressed. Although the reason is not clear, the solar shading characteristics can be improved. In addition, when the aforementioned (B/X) is 6.2 or less, the content ratio of hexaborides having excellent solar shading properties can be increased, and it is preferable because the solar shading properties are improved.

Particularly, since the absorption ability of near-infrared rays is high among borides, it is preferable that the boride particles of this embodiment contain XB ₆ as the main component.

Therefore, in the boride particles represented by the general formula XB _{m, m} , which is the element ratio (B/X) of boron (B) to metal element (X), is more preferably 5.8 or more and 6.2 or less.

It should be noted that in the production of boride particles, the obtained powder including boride particles is not only composed of boride particles of a single composition, but may be particles composed of a plurality of borides. . Specifically, it may be particles of a mixture of borides such as XB ₄ , XB ₆ , XB ₁₂ and the like.

Therefore, when X-ray diffraction measurement is performed on, for example, hexaboride particles, which are representative boride particles, even if the X-ray diffraction analysis is a single phase, it is considered that the other phases are actually contained in a small amount.

Therefore, _m in the general formula XB _m of the boride particles of the present embodiment may be, for example, the use of ICP emission spectroscopy (high frequency inductively coupled ion emission spectroscopy) on a powder containing the obtained boride particles. The atomic ratio of boron (B) to one atom of X element in chemical analysis.

The metal element (X) of the boride particles of this embodiment is not particularly limited as shown in the above general formula. For example, it may be selected from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, One or more metal elements of Ho, Er, Tm, Yb, Lu, Sr, and Ca.

However, since lanthanum hexaboride, which is a hexaboride of lanthanum, has a particularly high near-infrared absorption ability, the boride particles of the present embodiment preferably include lanthanum hexaboride particles.

Furthermore, as described above, according to the research of the inventors of the present invention, by setting the carbon content (carbon concentration) in the boride particles to a predetermined value or less, it is possible to obtain boride particles that can be easily pulverized. The reason will be explained below.

According to the study of the inventor of the present invention, carbon contained in the boride particles and the components of the boride particles form a carbon compound, or the carbon compound contained in the raw material may remain.

Examples of such carbon compounds include LaB ₂ C ₂ , LaB ₂ C ₄ , B ₄ C, B _4.5 C, B _5.6 C, B _6.5 C, B _7.7 C, B ₉ C and the like.

According to Non-Patent Document 1, among the above-mentioned carbon compounds, B ₄ C, B _4.5 C, B _5.6 C, B _6.5 C, B _7.7 C, and B ₉ C are hardness indexes of Young’s modulus of 472 GPa, 463 GPa, High hardness carbon compounds of 462GPa, 446GPa, 352GPa, 348GPa.

On the other hand, in Non-Patent Document 2, for example, it is reported that the Young's modulus of lanthanum hexaboride is 194 GPa. In addition, it is estimated that other boride particles also have the same Young's modulus.

In this way, the Young's modulus of the carbon compound mixed as an impurity may be higher than that of the target boride particle. Therefore, in order to obtain boride particles that can be easily pulverized, it is required to suppress the incorporation of these carbon compounds.

In addition, since the mixing amount (content) of these carbon compounds is related to the carbon content in the boride particles, as described above, it is considered that by setting the carbon content in the boride particles to a predetermined value or less, it is possible to easily obtain Finely pulverized boride particles.

The carbon content contained in the boride particles of the present embodiment can be measured by the combustion infrared absorption method. In addition, the boride particles of this embodiment measured by the combustion infrared absorption method contain The carbon content of is preferably 0.2% by mass or less, more preferably 0.1% by mass or less.

In addition, since B ₄ C (boron carbide) among the above-mentioned carbon compounds is particularly easily produced in the boride particles, the boride particles of the present embodiment preferably also suppress the amount of B ₄ C contained. For example, the content (content ratio) of B ₄ C in the boride particles of the present embodiment is preferably 1.0% by mass or less.

By setting the amount of B ₄ C contained in the boride particles of the present embodiment, that is, the content ratio of B ₄ C to 1.0% by mass or less, the content of other carbon compounds can also be suppressed, and it is possible to obtain particularly easy Finely pulverized boride particles are therefore preferred.

The amount of B ₄ C contained in the boride particles of the present embodiment can be measured by ICP analysis by performing pretreatment of nitric acid dissolution and filtration separation.

It is known that B ₄ C hardly dissolves in nitric acid. On the other hand, it is known that boride particles are dissolved in nitric acid.

Therefore, when evaluating the amount of B ₄ C in the boride particles, by adding the boride particles to nitric acid to dissolve the boride particles, the undissolved residue can be separated by filtration, so that only the boride particles can be extracted B ₄ C particles. In addition, the B ₄ C concentration can be calculated by dissolving the separated B ₄ C particles with sodium carbonate and measuring the boron concentration by ICP analysis.

At this time, in order to confirm that the undissolved residue obtained after filtration separation is B ₄ C, it is desirable to prepare reagents that have been treated in the same way until filtration separation, and to perform the undissolved residues of the reagents obtained after filtration separation. XRD measured and confirmed that it was B ₄ C single phase.

On the other hand, although boride particles such as hexaboride particles are powders colored in dark purple, etc., when they are crushed to a particle size sufficiently smaller than the wavelength of visible light and dispersed in the film, visible light is generated for the film. Transmittance. At the same time, the infrared shielding function was discovered.

The reason for this has not been clarified in detail, but it is considered that these boride materials hold more The free electrons in the near-infrared region have 4f-5d band-to-band migration or absorption due to electron-electron and electron-phonon interaction.

According to experiments, it is confirmed that in a film in which these boride particles are sufficiently fine and uniformly dispersed, the transmittance of the film has a maximum value in a wavelength range from 400 nm to 700 and a minimum value in a wavelength range from 700 nm to 1800 nm. Considering that the wavelength of visible light is 380 nm or more and 780 nm or less, and the photosensitivity is a bell shape with a peak near 550 nm, it can be understood that such a film effectively transmits visible light and effectively absorbs and reflects other sunlight.

The average dispersed particle diameter of the boride particles of the present embodiment is preferably 100 nm or less, and more preferably 85 nm or less. It should be noted that the average dispersed particle diameter mentioned here can be measured by a particle diameter measuring device based on a dynamic light scattering method.

Although the lower limit of the average dispersed particle diameter of the boride particles is not particularly limited, it is preferably, for example, 1 nm or more. This is because it is industrially difficult to make the average dispersed particle diameter of boride particles smaller than 1 nm.

Since the boride particles of the present embodiment described above have a carbon content of a predetermined value or less, they can be easily pulverized so that the average dispersed particle diameter is 100 nm or less, particularly 85 nm or less, for example. Therefore, the infrared shielding optical member in which the boride particles of the present embodiment are dispersed can suppress the occurrence of blue haze even when irradiated with strong light such as sunlight or spotlights.

(Method of manufacturing boride particles)

Next, a configuration example of the manufacturing method of boride particles of this embodiment will be described.

As the method for producing boride particles in this embodiment, as long as the boride particles obtained have the general formula XB _m (where X is selected from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy , Ho, Er, Tm, Yb, Lu, Sr, Ca and more than one metal element, m is the number representing the boron content in the general formula), and the boride particles are measured by the combustion infrared absorption method The carbon content (carbon concentration) contained in the boride particles is not particularly limited if it is 0.2% by mass or less.

As an example of the configuration of the method for producing boride particles of the present embodiment, for example, a solid phase reaction method using carbon or boron carbide as a reducing agent can be cited. Hereinafter, a case of manufacturing boride particles using lanthanum as a metal element will be described as an example.

For example, boride particles using lanthanum as a metal element can be produced by firing a mixture of a boron source and a reducing agent and a lanthanum source.

Specifically, when boron carbide is used as a boron source and reducing agent, and lanthanum oxide is used as a lanthanum source to produce lanthanum boride particles, first, a raw material mixture of boron carbide and lanthanum oxide is prepared. Next, by firing the raw material mixture at a temperature of 1500° C. or higher in an inert atmosphere, the carbon in the boron carbide is used to reduce the lanthanum oxide to generate carbon monoxide and carbon dioxide and remove the carbon. Then, lanthanum boride is obtained from the remaining lanthanum and boron.

It should be noted that the carbon derived from boron carbide is not completely removed as carbon monoxide and carbon dioxide, but a part of it remains in the lanthanum boride particles as impurity carbon. Therefore, the ratio of boron carbide in the raw material increases, and the impurity carbon concentration in the obtained lanthanum boride particles increases.

As described above, the obtained powder including boride particles is not only composed of boride particles of a single composition, but is a mixture of LaB ₄ , LaB ₆ , LaB ₁₂ and the like. Therefore, when the X-ray diffraction measurement is performed on the obtained powder including boride particles, even if the boride is a single phase in X-ray diffraction analysis, it is considered that the other phase is actually contained in a small amount.

At this time, when manufacturing boride particles using lanthanum as a metal element as described above, the original The element ratio B/La of boron in the boron source of the material and lanthanum in the lanthanum source is not particularly limited, but is preferably 3.0 or more and 20.0 or less.

In particular, when the element ratio B/La of boron in the boron source of the raw material and lanthanum in the lanthanum source is 4.0 or more, the generation of LaB, LaB ₂ and the like can be suppressed. In addition, although the reason is not clear, it is possible to improve solar shading characteristics.

On the other hand, when the element ratio B/La of boron in the boron source of the raw material and lanthanum in the lanthanum source is 6.2 or less, the production of boron oxide other than boride particles is suppressed. Since boron oxide particles are hygroscopic, if boron oxide particles are mixed into a powder containing boride particles, the moisture resistance of the powder containing boride particles will decrease, and the deterioration of solar shading properties over time will increase. Big.

Therefore, it is preferable to make the element ratio B/La of boron in the boron source of the raw material and lanthanum in the lanthanum source 6.2 or less and suppress the generation of boron oxide particles. In addition, when the element ratio B/La is 6.2 or less, it is particularly possible to increase the content ratio of hexaborides having excellent solar shading properties, and it is preferable because the solar shading properties are improved.

In order to further reduce the impurity carbon concentration, it is effective to reduce the ratio of boron carbide in the raw material as much as possible. Therefore, for example, by setting B/La to 6.2 or less to generate lanthanum boride particles, it is possible to more reliably obtain a powder including lanthanum boride particles having an impurity carbon concentration of 0.2% by mass or less.

As described above, when producing boride particles using lanthanum as a metal element, it is preferable that the element ratio (molar ratio) B/La of boron in the boron source and lanthanum in the lanthanum source is 4.0 or more and 6.2 or less. By setting the composition of the raw materials within the above range, the impurity carbon concentration in the obtained powder containing lanthanum boride particles can be suppressed to a low level, and at the same time, it is possible to obtain lanthanum boride particles containing lanthanum boride particles exhibiting high solar shading properties. Powder.

In addition, it is particularly preferable that the obtained lanthanum boride particles have LaB ₆ as the main component.

This is because LaB _{6 has} a particularly high near-infrared absorption capacity.

Therefore, it is more preferable that the element ratio B/La of boron in the boron source of the raw material and lanthanum in the lanthanum source is 5.8 or more and 6.2 or less.

In addition, although a case where boron carbide is used as a boron source and a reducing agent, and lanthanum oxide is used as a lanthanum source to produce a lanthanum boride particle is demonstrated here as an example, it is not limited to this embodiment. For example, boron or boron oxide may be used as the boron source, carbon may be used as the reducing agent, and lanthanum oxide may be used as the lanthanum source. At this time, it is preferable to conduct preliminary tests or the like so that no residual carbon or oxygen remains in the product, and to select the mixing ratio of each component.

In addition, for example, in accordance with the metal element X contained in the boride particles to be produced, a compound containing the metal element X may be used instead of lanthanum oxide. Examples of the compound containing the metal element X include one or more compounds selected from the group consisting of a hydroxide of the metal element X, a hydrate of the metal element X, and an oxide of the metal element X. The method for producing the compound containing the metal element X is not particularly limited. For example, a solution containing the compound containing the metal element X and an alkaline solution can be reacted while stirring to produce a precipitate, which can be obtained from the precipitate.

As described above, even when a compound containing the metal element X is used instead of lanthanum oxide, it is preferable to perform preparation tests and the like so that no residual carbon or oxygen remains in the product, and to select the mixing ratio of each component. For example, the element ratio of boron in the boron source and the metal element X in the metal element X source may be the same ratio as the element ratio of boron in the boron source and the lanthanum element in the lanthanum source.

By subjecting the obtained boride particles to wet pulverization, for example, boride particles having a desired average dispersed particle diameter can be obtained.

(Boride particle dispersion)

Next, a configuration example of the boride particle dispersion liquid of this embodiment will be described.

The boride particle dispersion of the present embodiment may include the above-mentioned boride particles and a liquid medium. It should be noted that the boride particles are preferably dispersed in a liquid medium, for example.

The liquid medium used for the boride particle dispersion may include one or more liquid mediums selected from water, organic solvents, oils and fats, liquid resins, and plasticizers.

The organic solvent preferably has a function of maintaining the dispersibility of boride particles and a function of preventing coating defects when the dispersion liquid is applied. Examples of organic solvents include methanol (MA), ethanol (EA), 1-propanol (NPA), isopropanol (IPA), butanol, pentanol, benzyl alcohol, diacetone alcohol and other alcohol solvents, Acetone, methyl ethyl ketone (MEK), methyl propyl ketone, methyl isobutyl ketone (MIBK), cyclohexanone, isophorone and other ketone solvents, 3-methyl-methoxy-propyl Ester solvents such as esters (MMP), ethylene glycol monomethyl ether (MCS), ethylene glycol monoether (ECS), ethylene glycol isopropyl ether (IPC), propylene glycol methyl ether (PGM), propylene glycol ethyl ether ( PE), propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether acetate (PE-AC) and other glycol derivatives, formamide (FA), N-methyl formamide, dimethyl formamide (DMF) ), amides such as dimethylacetamide, N-methyl-2-pyrrolidone (NMP), aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorinated vinyl, chlorobenzene, etc., and can be used in combination from the above One or two or more selected.

Among the above, as the organic solvent, ketones such as MIBK and MEK, aromatic hydrocarbons such as toluene and xylene, and glycol ether acetates such as PGMEA and PE-AC are particularly highly hydrophobic. Therefore, one or two or more selected from the above can be used in combination.

As fats and oils, for example, dry oils selected from linseed oil, sunflower oil, tung oil, semi-drying oils such as sesame oil, cottonseed oil, rapeseed oil, soybean oil, and rice bran oil, olive oil, coconut oil, etc. can be used. Non-drying oils such as palm oil and dehydrated castor oil, fatty acid monoesters, ethers, Isopar E, Exxsol Hexane, Exxsol Heptane, Exxsol E, Exxsol D30, Exxsol D40, Exxsol that directly esterify the fatty acids of vegetable oils with monoalcohols D60, Exxsol D80, Exxsol D95, Exxsol D110, Exxsol D130 (the above are manufactured by Exxon Mobil Corporation) and other petroleum solvents.

As the liquid resin, for example, one or more selected from the group consisting of liquid acrylic resin, liquid epoxy resin, liquid polyester resin, and liquid polyurethane resin can be used.

As the plasticizer, for example, a plasticizer for liquid plastics can be used. As the plasticizer for liquid plastics, for example, phthalic acid plasticizers such as DEHP and DINP, adipic acid plasticizers such as DINA and DOA, phosphoric acid plasticizers, epoxy plasticizers, and polyester plasticizers can be used. More than one kind.

In addition, the liquid medium used for the boride particle dispersion of the present embodiment may contain, for example, a dispersant, a coupling agent, a surfactant, etc. in addition to the above-mentioned components. The dispersant, coupling agent, and surfactant can be selected according to the application, and those having an amino group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group are preferred. These functional groups can be adsorbed on the surface of the boride particles and prevent agglomeration of the boride particles. For example, in a boride particle dispersion prepared using a boride particle dispersion, the boride particles can be uniformly dispersed.

As dispersants, coupling agents, and surfactants, for example, phosphate compounds, polymer-based dispersants, silane-based coupling agents, titanate-based coupling agents, aluminum-based coupling agents, etc. can be preferably used, but they are not limited. Here. Examples of polymer dispersants include acrylic polymer dispersants, polyurethane polymer dispersants, acrylic-block copolymer polymer dispersants, polyether dispersants, polyester polymer dispersants, etc. .

The addition amount of one or more materials selected from dispersants, coupling agents, and surfactants to the boride particle dispersion is preferably in the range of 10 parts by weight to 1000 parts by weight relative to 100 parts by weight of the boride particles, More preferably, it is a range of 20 parts by weight or more and 200 parts by weight or less. If the addition amount of a dispersant or the like is in the above range, the aggregation of the boride particles in the dispersion liquid can be suppressed and the dispersion stability can be maintained high, which is preferable.

The method for dispersing boride particles in a liquid medium is not particularly limited. For example, a method of dispersing the raw material mixture of the boride particle dispersion liquid using a wet media mill such as a bead mill, a ball mill, or a sand mill can be mentioned. In particular, the boride particle dispersion of the present embodiment preferably has a state in which boride particles having an average dispersed particle diameter of 100 nm or less are dispersed in a liquid medium, and it is more preferable that the average dispersed particle diameter of the boride particles is 85 nm or less. Therefore, it is preferable to disperse boride particles to prepare a dispersion by a wet grinding method using a media stirring mill such as a bead mill.

As the boride particle dispersion, when preparing a boride particle dispersion in which boride particles are dispersed in a dispersion medium (liquid medium), the boride particles or dispersants used as the raw material may be mentioned as described above. A method of adding to water, organic solvents, oils and fats, liquid resins, plasticizers, etc. as a liquid medium, and performing dispersion treatment using a medium stirring mill or the like.

In addition, the boride particle dispersion liquid can also be prepared by the following procedure. Here, the case of preparing a boride particle plasticizer dispersion is described as an example.

Specifically, first, using the above-mentioned organic solvent as a liquid medium, a boride particle dispersion liquid in which boride particles are dispersed in an organic solvent is prepared in advance. Next, a plasticizer is added to the boride particle dispersion, and the organic solvent is removed to obtain the boride particle plasticizer dispersion.

Incidentally, as a method of removing the organic solvent, for example, a method of drying the boride particle dispersion under reduced pressure can be cited.

Specifically, the boride particle dispersion liquid containing an organic solvent as a liquid medium to which a plasticizer has been added is dried under reduced pressure while stirring, and the organic solvent component is separated. As an apparatus used for this reduced-pressure drying, a vacuum stirring type dryer is mentioned, but it does not specifically limit as long as it has the said function. In addition, the pressure value at the time of decompression is appropriately selected.

Since the use of this reduced-pressure drying method can improve the removal efficiency of the organic solvent from the boride particle dispersion in which the plasticizer-added organic solvent is used as the liquid medium, it does not cause any increase in the boride particle plasticizer dispersion. Aggregation of the dispersed boride particles is therefore preferred. Furthermore, the productivity of the boride particle plasticizer dispersion liquid is also improved, and the evaporated organic solvent can be easily recovered, which is also preferable from environmental considerations.

In addition, in order to obtain a uniform boride particle dispersion liquid, various additives or the above-mentioned dispersing agent may be added, or pH may be adjusted.

In addition, although the case where the boride particle plasticizer dispersion liquid using a plasticizer as a dispersant is prepared as an example has been described here, it is not limited to this embodiment, and the use of water, organic solvents, and fats and oils By replacing the plasticizer with other dispersion media (liquid media) such as liquid resin, it is possible to obtain dispersions in which boride particles are dispersed in various dispersion media.

The content of the boride particles in the boride particle dispersion, that is, the concentration is not particularly limited, but for example, it is preferably 0.01% by mass or more and 30% by mass or less.

This is because if the content of the boride particles is 0.01% by mass or more, a dispersion of boride particles having a sufficient infrared shielding function can be obtained.

In addition, if the content of boride particles is 30% by mass or less, the boride particles are The viscosity of the dispersion is not too high and the dispersion stability can be maintained, which is preferable. In particular, the content of the boride particles in the boride particle dispersion is more preferably 1% by mass or more and 30% by mass or less.

In addition, as for the boride particles in the boride particle dispersion, the average dispersed particle diameter measured by the dynamic light scattering method is preferably dispersed at 100 nm or less, and more preferably at 85 nm or less. This is because if the average dispersed particle diameter of the boride particles is 100 nm or less, the occurrence of blue haze in the infrared shielding film manufactured using the boride particle dispersion of the present embodiment can be suppressed, and the optical characteristics can be improved. In addition, when the average dispersed particle diameter is 85 nm or less, the occurrence of blue haze in the infrared shielding film can be particularly suppressed.

It should be noted that when the above-mentioned boride particles are used to prepare a boride particle dispersion, there will be no problems such as gelation of the boride particle dispersion (slurry), and the average dispersed particle size can be effectively pulverized to 100nm. Hereinafter, the inventors of the present invention have made the following guesses for the reason, especially for 85 nm or less.

Since the boride particles are hard, when a wet media stirring mill is used for pulverization, abrasion residues such as fine powder abraded by the media beads or fine beads after the media beads are broken will be mixed into the slurry. At this time, as the carbon concentration increases, the hardness of the boride particles increases. Therefore, when boride particles with a carbon concentration higher than 0.2% by mass are used as raw materials, a large amount of wear slag of the media beads will be mixed into the slurry. In material. The mixing of the wear slag of the media beads is the cause of the increase in the slurry concentration.

The concentration ratio of the wear slag to the boride of the media beads in the slurry can be used as an indicator of the wear volume of the media beads. For example, when using yttria-stabilized zirconia beads (also only described as "zirconia beads"), which are well-known for their high wear resistance, as the media beads, the Zr from the zirconia beads in the slurry can be combined with the formula XB The concentration ratio Zr/X of the weight concentration (mass %) of the metal element X in the boride represented by _m is used as an index of the wear amount of the media beads.

And, when the carbon concentration contained in the boride particles is higher than 0.2% by mass, the concentration ratio of zirconium from the zirconia beads to the metal element X in the boride represented by the general formula XB _m in the resulting slurry is Zr /X is greater than 1.5. In other words, it was shown that the amount of wear of the media beads became very large. The mixing of the wear slag of the media beads is the cause of the increase in the viscosity of the slurry.

In contrast, by using boride particles with a carbon concentration of 0.2% by mass or less as a raw material, when yttria-stabilized zirconia beads are used as media beads, they are crushed to an average dispersed particle size of 100 nm or less, especially When it is 85 nm or less, the concentration ratio Zr/X in the obtained slurry can be 1.5 or less. In other words, since the mixing amount of the wear slag of the media beads is greatly reduced, it is estimated that the pulverization can be effectively performed without deteriorating the viscosity of the slurry. However, there are still many unexplained parts regarding the increase in the viscosity of the slurry, and it may play a role other than the above, so it is not limited to the above.

It should be noted that when zirconia beads are used as media beads to perform the dispersion treatment of the boride particle dispersion, it is preferable that the Zr derived from the zirconia beads in the boride particle dispersion and the boride represented by the general formula XB _m The concentration ratio Zr/X of the metal element X is 1.5 or less. In other words, the boride particle dispersion may contain zirconia derived from the media beads used in the pulverization, and the weight concentration of Zr relative to the weight concentration of the metal element X in the boride particle dispersion is preferably 1.5 times or less. This is because when the concentration ratio Zr/X in the boride particle dispersion liquid obtained as described above is 1.5 or less, the increase in the viscosity of the boride particles can be sufficiently suppressed.

The boride particle dispersion of the present embodiment described above can be used for various applications as an infrared shielding particle dispersion. In addition, the boride particle dispersion of the present embodiment contains the above-mentioned boride particles, and can easily make the average dispersed particle diameter be 100 nm or less, particularly 85 nm or less. Therefore, the occurrence of blue haze can be suppressed.

(Infrared shielding transparent substrate, infrared shielding optical member)

A configuration example of the infrared-shielding transparent substrate of the present embodiment will be described.

The infrared shielding transparent substrate of this embodiment has a coating on at least one surface of the transparent substrate, and the coating includes infrared shielding particles and a binder.

In addition, infrared shielding particles can be used by the general formula XB _m (where X is selected from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr One or more metal elements of Ca, where m is a number representing the boron content in the general formula), and the carbon content measured by the combustion infrared absorption method is 0.2% by mass or less of boride particles.

As described above, the infrared shielding transparent substrate of this embodiment may have a transparent substrate and a coating layer arranged on at least one surface of the transparent substrate. Also, the coating may include infrared shielding particles and a binder.

The components are explained below.

(1) About infrared shielding particles and their manufacturing method

Since the above-mentioned boride particles can be used as the infrared shielding particles, the description is omitted here.

(2) Adhesive

Since the coating layer contains a binder as described above, the binder will be described below.

As the binder, for example, ultraviolet (UV) curing resin, thermoplastic resin, thermosetting resin, electron beam curing resin, room temperature curing resin, etc. can be selected according to the purpose. In particular, as the adhesive, it is preferable to include one or more adhesives selected from ultraviolet curable resins, thermoplastic resins, thermosetting resins, and room temperature curable resins.

Specific examples of the binder include polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, ethylene vinyl acetate copolymer, polyester Resin, polyethylene terephthalate resin, fluororesin, polycarbonate resin, acrylic resin, polyvinyl butyral resin, etc.

As the binder, for example, one or two or more selected from the above-mentioned resin group can be used in combination. However, as a binder for coating, among the above-mentioned resin groups, it is particularly preferable to use a UV curable resin from the viewpoint of productivity, equipment cost, and the like.

In addition, an inorganic binder using a metal alkoxide may be used instead of the aforementioned resin-based binder. As the metal alkoxide, alkoxides such as Si, Ti, Al, and Zr can be cited as representative materials. The inorganic resin using these metal alkoxides can be hydrolyzed and polycondensed by heating or the like to form an oxide film coating.

In addition, the above-mentioned resin-based binder and the above-mentioned inorganic binder may be mixed and used.

(3) Transparent substrate

The infrared-shielding transparent substrate of this embodiment may have a coating on at least one surface of the transparent substrate. Therefore, a configuration example of the transparent substrate will be described below.

As the transparent substrate, for example, a transparent film substrate or a transparent glass substrate can be preferably used.

The transparent film substrate is not limited to the film shape, and may be, for example, a plate shape or a sheet shape. The material of the transparent film substrate is not particularly limited. For example, one or more selected from polyester, acrylic, polyurethane, polycarbonate, polyethylene, ethylene vinyl acetate copolymer, vinyl chloride, fluororesin, etc. can be used. The transparent film substrate is preferably a polyester film, and more preferably a polyethylene terephthalate (PET) film.

In addition, the transparent glass substrate is not particularly limited, and quartz glass and soda glass can be used. And other transparent glass substrates.

In addition, it is preferable to perform surface treatment on the surface of the transparent substrate in order to improve the coatability of the infrared shielding particle dispersion or the adhesion with the coating. In addition, in order to improve the adhesion between the transparent substrate and the coating, an intermediate layer can also be formed on the transparent substrate, and a coating can be formed on the intermediate layer. The composition of the intermediate layer is not particularly limited. For example, a polymer film, a metal layer, an inorganic layer (for example, an inorganic oxide layer such as silicon dioxide, titanium dioxide, and zirconium oxide), an organic/inorganic composite layer, etc. can be used.

As described above, the infrared-shielding transparent substrate of this embodiment has a coating on at least one surface of the transparent substrate, and the coating includes infrared-shielding particles and a binder.

The coating may consist of only infrared shielding particles and a binder, or may contain other components. For example, as described above, an infrared shielding particle dispersion can be used to produce a coating, and a solvent, a dispersant, a coupling agent, or a surfactant can be added to the infrared shielding particle dispersion. Therefore, the coating layer may contain an additive component added to the infrared shielding particle dispersion, or a component derived from the additive component.

In addition, in order to further impart an ultraviolet shielding function to the infrared shielding transparent substrate of this embodiment, particles selected from inorganic titanium oxide, zinc oxide, or cerium oxide, organic benzophenone or benzene may be added to the coating. At least one ultraviolet shielding material such as triazole.

It should be noted that the above-mentioned ultraviolet shielding material is not limited to the form added to the coating, and a layer containing the ultraviolet shielding material may be formed separately. When a layer containing an ultraviolet shielding material is formed, the arrangement of the layer is not particularly limited. For example, it may be formed on a coating layer.

In addition, in order to increase the visible light transmittance of the infrared shielding transparent substrate of the present embodiment, the coating layer may be further mixed with ATO, ITO, aluminum-added zinc oxide, and indium tin composite oxide. More than one kind of particles. By adding these transparent particles to the coating layer, the transmittance around 750nm is increased and the infrared light with a wavelength longer than 1200nm is blocked at the same time. Therefore, the transmittance of near-infrared light is higher and the heat ray shielding characteristics can be obtained. Higher heat ray shielding body. It should be noted that the above-mentioned one or more particles selected from ATO and the like are not limited to the form added to the coating, and a layer containing the particles may be formed in addition to the coating.

The thickness of the coating on the transparent substrate is not particularly limited. In practice, it is preferably 20 μm or less, and more preferably 6 μm or less. This is because if the thickness of the coating is 20μm or less, in addition to exhibiting sufficient pencil hardness and scratch resistance, the substrate film can be prevented from warping when the solvent in the coating is volatilized and the adhesive is cured. An abnormal step occurred.

It should be noted that the lower limit of the thickness of the coating layer is not particularly limited. For example, it is preferably 10 nm or more, and more preferably 50 nm or more.

The content of infrared shielding particles contained in the coating is not particularly limited, but the content per unit projected area of the transparent substrate/coating is preferably 0.01 g/m ² or more and 1.0 g/m ² or less. This is because if the content is 0.01g/m ² or more, the heat ray shielding properties can be deliberately exhibited compared to the case without infrared shielding particles, and if the content is 1.0g/m ² or less, the infrared shielding transparent substrate It can sufficiently maintain the transmittance of visible light.

In addition, for the infrared-shielding transparent substrate of the present embodiment, it is preferable that when the visible light (wavelength 400nm or more and 780nm or less) transmittance of the coating is set to a range of 45% or more and 55% or less, the region having a wavelength of 360nm or more and 500nm or less The maximum value of the diffuse transmission curve is 1.5% or less.

It should be noted that when a transparent substrate with sufficient visible light transmittance is used and the transparent substrate has almost no effect on the visible light transmittance of the infrared-shielding transparent substrate, that is, for example, When a transparent substrate having a visible light transmittance of 90% or more is used, the visible light transmittance of the coating can be regarded as the visible light transmittance of the infrared shielding transparent substrate.

Here, the evaluation method of the blue haze will be described.

I don't know how to directly measure the blue haze. However, the applicant of the present invention has proposed focusing on the linear incident light and scattered light as components of the transmitted light when light is irradiated with an infrared shielding particle dispersion or the like as a reagent, and by calculating the diffuse transmission for each wavelength The method of evaluating "blue haze" based on the rate (see Patent Document 5). Hereinafter, the measurement principle of the diffuse transmittance for each wavelength, that is, the diffuse transmittance curve, will be described using FIGS. 1 and 2.

First, the measuring device for measuring the diffuse transmission curve will be described using FIGS. 1 and 2.

As shown in FIGS. 1 and 2, the measuring device 10 has an integrating sphere 14. In addition, the integrating sphere 14 has diffuse reflectivity on the inner surface of the spherical body, and the integrating sphere 14 has a first opening 141 where the measuring reagent 12 (see FIG. 2) is installed, and a standard reflector 15 or light trap member 16 is installed. The second opening 142 and the third opening 143 to which the light receiver 13 is attached.

In addition, it has a light source 11 that emits linear light to be incident into the spherical space through the first opening 141, a spectroscope, not shown, which is mounted on the light receiver 13 and splits the received reflected light or scattered light, An unshown data storage unit that is connected to the above spectroscope and stores the spectroscopic data of the reflected light or scattered light to be split, and calculates the diffuse transmission separately based on the stored blank transmitted light intensity and diffuse transmitted light intensity of each spectroscopic data An unshown arithmetic unit that obtains the ratio of the light intensity and the blank transmitted light intensity for each wavelength and the diffuse transmittance of each wavelength.

Here, the integrating sphere 14 is coated with barium sulfate or barium sulfate on the inner surface of the spherical body. SPECTRALON (registered trademark) and the like have diffuse reflectivity, and the incident angle to the standard reflector 15 can be, for example, 10° on both the standard side and the contrast side. In addition, as the aforementioned light receiver 13, for example Either a photomultiplier tube (in the ultraviolet, visible region) or cooled lead sulfide (in the near infrared region) can be used. In addition, for an unshown spectroscope mounted on the light receiver 13, the wavelength measurement range of the ultraviolet and visible light regions and the photometry accuracy (±0.002 Abs) are necessary.

In addition, as the light source 11 that emits and enters the spherical space, for example, a deuterium lamp can be used in the ultraviolet region, and a 50W halogen lamp can be used in the visible light and near-infrared region.

In addition, for the standard reflector 15, for example, a whiteboard made of SPECTRALON can be used. For the light trap member 16, the function of capturing the incident linear light without reflecting is necessary, for example, it can be used to almost Fully absorbing black box.

In addition, the above-mentioned diffuse transmission curve measuring device can be used to evaluate the diffuse transmission of the infrared shielding transparent substrate as a measuring reagent through the blank transmitted light intensity measurement step, the diffuse transmitted light intensity measurement step, and the diffuse transmission calculation step. The maximum value of the curve.

First, in the blank transmitted light intensity measurement step, as shown in FIG. 1, the standard reflector 15 is mounted on the second opening 142 of the integrating sphere 14, and the measurement reagent is not mounted on the first opening 141. The linear light from the light source 11 enters the spherical space through the first opening 141. Next, the reflected light reflected by the standard reflector 15 is received by the light receiver 13, and the light is split by an unshown spectroscope mounted on the light receiver 13 to obtain spectroscopic data of the reflected light. The spectroscopic data at this time is the blank transmitted light intensity.

Next, in the diffuse transmission light intensity measurement step, as shown in FIG. 2, the optical trap member 16 is attached to the second opening 142 of the integrating sphere 14. Next, with the measuring reagent installed in the first opening 141, the linear light from the light source 11 is incident into the spherical space through the measuring reagent 12 and the first opening 141, and the light trap member is received by the light receiver 13 16 Scattered light other than captured light. At this time, an unshown spectroscope mounted on the light receiver 13 is used to split the light and obtain the scattered light Spectroscopic data. The spectroscopic data at this time is the intensity of diffuse transmitted light.

Next, in the diffuse transmission calculation step, based on the respective data of the blank transmitted light intensity and the diffuse transmitted light intensity stored by an unshown data storage unit (not shown), an unshown arithmetic unit may be used to calculate the diffuse transmission respectively. The ratio of the transmitted light intensity and the blank transmitted light intensity for each wavelength and the diffuse transmittance of each wavelength is obtained, and the wavelength in the diffuse transmittance curve of the measurement reagent 12 is obtained from the obtained diffuse transmittance of each wavelength The maximum value in the region of 360nm~500nm.

Here, in the measurement device that measures the diffuse transmission curve, an optical system for adjusting light may be provided between the light source 11 and the measurement reagent 12. In addition, in this optical system, for example, a plurality of lenses are combined to adjust parallel light, and an aperture is used to adjust the amount of light. Sometimes filters can be used to remove specific wavelengths.

In addition, for the infrared-shielding transparent substrate of the present embodiment, it is preferable that the visible light (wavelength 400nm or more and 780nm or less) transmittance of the coating is set to any of 45% or more and 55% or less, as described above, with a wavelength of 360nm or more and 500nm or less. The maximum value of the diffuse transmission curve at the area is 1.5% or less. This is because it was confirmed that almost no blue haze was observed on the infrared-shielding transparent substrate that satisfies the above conditions.

It should be noted that setting the visible light transmittance of the coating to 45% or more and 55% or less is to limit the measurement conditions of the diffuse transmittance (diffuse transmittance curve). Since the diffuse transmittance is proportional to the visible light transmittance, the range is set. In addition, the measurement of the diffuse transmittance (diffuse transmittance curve) in the region with a wavelength of 360 nm or more and 500 nm or less is because the scattering in this region is the cause of the blue haze. If the maximum value of the diffuse transmittance in the above range is 1.5% or less, the blue haze cannot be observed with the naked eye experimentally.

The infrared-shielding transparent substrate of this embodiment can be used for various optical members, for example, An infrared-shielding optical member including the infrared-shielding transparent substrate of the present embodiment.

Examples of the infrared shielding optical member referred to here include windows of buildings, windows of automobiles, and the like.

According to the infrared-shielding transparent substrate of the present embodiment described above and the infrared-shielding optical member including the infrared-shielding transparent substrate, it is possible to obtain an infrared-shielding transparent substrate using boride particles that can be easily pulverized. Therefore, it is possible to sufficiently reduce the average dispersed particle diameter of the infrared shielding particles contained in the coating layer, and it is possible to suppress the occurrence of blue haze.

(Manufacturing method of infrared shielding transparent substrate)

The infrared-shielding transparent base material of this embodiment can be manufactured using an infrared-shielding particle dispersion liquid, for example. Therefore, first, the infrared shielding particle dispersion liquid and its manufacturing method will be described here.

(1) Infrared shielding particle dispersion and its manufacturing method

As described above, the infrared-shielding transparent substrate of the present embodiment can be produced using an infrared-shielding particle dispersion containing boride particles as the infrared-shielding particles described above. Therefore, an example of the configuration of the infrared shielding particle dispersion and its manufacturing method will be described here.

The infrared-shielding particle dispersion is a dispersion liquid in which the above-mentioned infrared-shielding particles are dispersed in a solvent. The infrared-shielding particle dispersion liquid is obtained by adding the above-mentioned infrared-shielding particles, a dispersant, coupling agent, surfactant, etc., if necessary, to a solvent and performing a dispersion treatment to disperse the infrared-shielding particles in the solvent.

For the solvent of the infrared shielding particle dispersion liquid, the function of maintaining the dispersibility of the infrared shielding particle and the function of not causing coating defects when used for coating the dispersion are required.

Specifically, alcohol solvents such as methanol (MA), ethanol (EA), 1-propanol (NPA), isopropanol (IPA), butanol, pentanol, benzyl alcohol, diacetone alcohol, acetone , Methyl ethyl ketone (MEK), Methyl propyl ketone, methyl isobutyl ketone (MIBK), cyclohexanone, isophorone and other ketone solvents, 3-methyl-methoxy-propionate (MMP) and other ester solvents, ethyl Glycol monomethyl ether (MCS), ethylene glycol monoether (ECS), ethylene glycol isopropyl ether (IPC), propylene glycol methyl ether (PGM), propylene glycol ethyl ether (PE), propylene glycol methyl ether acetate ( PGMEA), propylene glycol ethyl ether acetate (PE-AC) and other glycol derivatives, formamide (FA), N-methylformamide, dimethylformamide (DMF), dimethylacetamide, N-formamide Amides such as nyl-2-pyrrolidone (NMP), aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorinated vinyl and chlorobenzene, etc., and one or two or more selected from the above can be used in combination.

Among the above, as the solvent, ketones such as MIBK and MEK, aromatic hydrocarbons such as toluene and xylene, and glycol ether acetates such as PGMEA and PE-AC are particularly highly hydrophobic. Therefore, one or two or more selected from the above can be used in combination.

In addition, in order to form a coating on a transparent substrate such as a transparent film substrate or a transparent glass substrate, it is preferable to select an organic solvent with a low boiling point as the solvent. This is because if the solvent is an organic solvent with a low boiling point, the solvent can be easily removed in the drying step after coating without impairing the characteristics of the coating layer, such as hardness or transparency.

Specifically, for example, it is preferable to use one or two or more selected from ketones such as methyl isobutyl ketone and methyl ethyl ketone, and aromatic hydrocarbons such as toluene and xylene in combination.

The dispersant, coupling agent, and surfactant can be selected according to the application, and those having an amino group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group are preferred. These functional groups are adsorbed on the surface of the infrared shielding particles and prevent aggregation of the infrared shielding particles, so that when the coating is formed on the transparent substrate or the following infrared shielding particle dispersion is formed, the coating or the In the infrared shielding particle dispersion, the effect of uniformly dispersing the infrared shielding particles is exerted.

As the dispersant, coupling agent, and surfactant, for example, phosphate compounds, polymer-based dispersants, silane-based coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and the like can be preferably used.

It should be noted that, as the polymer dispersant, acrylic polymer dispersant, polyurethane polymer dispersant, acrylic-block copolymer polymer dispersant, polyether dispersant, polyester Polymer dispersant, etc.

However, the dispersant, coupling agent, and surfactant are not limited to these, and various dispersants, coupling agents, and surfactants can be used.

The amount of one or more materials selected from the group consisting of dispersants, coupling agents, and surfactants added to the infrared shielding particle dispersion is preferably 10 parts by weight or more relative to 100 parts by weight of the boride particles as infrared shielding particles The range of 1000 parts by weight or less is more preferably the range of 20 parts by weight or more and 200 parts by weight or less.

If the addition amount of a dispersant or the like is in the above range, it is possible to suppress the aggregation of the infrared shielding particles in the dispersion liquid and maintain high dispersion stability.

The method of dispersing boride particles as infrared shielding particles in a solvent (liquid medium) is not particularly limited. For example, a method of dispersing the raw material mixture of the infrared shielding particle dispersion liquid using a wet media grinder such as a bead mill, a ball mill, or a sand mill can be mentioned. In particular, the infrared shielding particle dispersion of the present embodiment preferably has a state in which infrared shielding particles having an average dispersed particle diameter of 100 nm or less are dispersed in a solvent (liquid medium), and it is more preferable that the average dispersed particle diameter of the infrared shielding particles is 85 nm the following. Therefore, it is preferable to disperse boride particles to prepare a dispersion by a wet grinding method using a media stirring mill such as a bead mill.

In order to obtain a uniform dispersion of infrared shielding particles, various additives or the above-mentioned dispersants may be added, or pH may be adjusted.

The content of the infrared shielding particles in the above-mentioned infrared shielding particle dispersion is preferably 0.01% by mass to 30% by mass. This is because if the content of the infrared shielding particles is 0.01% by mass or more, a coating having an infrared shielding function can be formed on the transparent substrate. It is also because if the content of the infrared shielding particles is 30% by mass or less, the infrared shielding particles can be easily coated on the transparent substrate, and the productivity of the coating can be improved.

In addition, the infrared-shielding particles in the infrared-shielding particle dispersion are preferably dispersed so that the average dispersed particle diameter is 100 nm or less, and more preferably 85 nm or less. This is because if the average dispersed particle diameter of the infrared shielding particles is 100 nm or less, the occurrence of blue haze in the infrared shielding transparent substrate manufactured using the infrared shielding particle dispersion of this embodiment can be suppressed, and the optical characteristics can be improved. . In addition, when the average dispersed particle diameter is 85 nm or less, the occurrence of blue haze in the infrared-shielding transparent substrate can be particularly suppressed.

It should be noted that when the above-mentioned boride particles are used to produce an infrared shielding particle dispersion, there will be no problems such as gelation of the infrared shielding particle dispersion (slurry), and the average dispersed particle size can be effectively pulverized to 100nm Hereinafter, the inventors of the present invention have made the following guesses for the reason, especially for 85 nm or less.

Since the boride particles are hard, when a wet media stirring mill is used for pulverization, abrasion residues such as fine powder abraded by the media beads or fine beads after the media beads are broken will be mixed into the slurry. At this time, as the carbon concentration increases, the hardness of the boride particles increases. Therefore, when boride particles with a carbon concentration higher than 0.2% by mass are used as raw materials, a large amount of wear slag of the media beads will be mixed into the slurry. In material. The mixing of the wear slag of the media beads is the cause of the increase in the slurry concentration.

In contrast, by using boride particles having a carbon concentration of 0.2% by mass or less as a raw material, when pulverized to an average dispersed particle diameter of 100 nm or less, particularly 85 nm or less, The mixing amount of the wear slag of the media beads can be greatly reduced, so it is presumed that the grinding can be effectively carried out without deteriorating the viscosity of the slurry. However, there are still many unexplained parts regarding the increase in the viscosity of the slurry, and it may play a role other than the above, so it is not limited to the above.

(2) Manufacturing method of infrared shielding transparent substrate

Next, a configuration example of the method of manufacturing an infrared shielding transparent substrate of this embodiment will be described.

The infrared-shielding transparent substrate of the present embodiment uses the above-mentioned infrared-shielding particle dispersion liquid and is manufactured by forming a coating layer containing infrared-shielding particles on the transparent substrate. The following is an example of specific steps

A binder is added to the infrared shielding particle dispersion liquid to obtain a coating liquid.

After coating the obtained coating liquid on the surface of the transparent substrate, evaporating the solvent and curing the binder by a predetermined method, a coating layer in which the infrared shielding particles are dispersed in the medium can be formed.

In addition, by not adding a binder to the infrared shielding particle dispersion liquid, a coating liquid with adjusted concentration can be prepared, and after coating on a transparent substrate, the solvent is evaporated, and then the coating liquid containing the binder is covered and coated. The solvent is evaporated to form a coating.

Since the adhesive and transparent substrate that can be preferably applied to the coating have already been described, the description is omitted here.

In addition, for the surface of the transparent substrate, in order to improve the coatability of the infrared shielding particle dispersion liquid or the adhesion with the coating, it is preferable to perform surface treatment. In addition, in order to improve the adhesion between the transparent substrate and the coating, an intermediate layer can also be formed on the transparent substrate, and a coating can be formed on the intermediate layer. The composition of the intermediate layer is not particularly limited. For example, polymer films, metal layers, inorganic layers (such as inorganic oxide layers such as silicon dioxide, titanium dioxide, and zirconium oxide), organic /Inorganic composite layer.

The method of providing a coating on the transparent substrate is not particularly limited as long as it can uniformly apply the infrared shielding particle dispersion to the surface of the transparent substrate. For example, a bar coating method, a gravure coating method, a spray coating method, a dip coating method, etc. can be mentioned.

For example, when a UV curable resin is used as the binder contained in the infrared shielding particles, and the coating is formed by the bar coating method, it is preferable to appropriately adjust the liquid concentration and additives to the infrared shielding particle dispersion in advance to have an appropriate balance ( leveling). In addition, a wire bar of bar size can be selected to form a coating film on the transparent substrate, so that the thickness of the coating and the content of infrared shielding particles can reach the target of the infrared shielding transparent substrate to be obtained.

Next, after the organic solvent contained in the coating film is removed by drying, it is cured by irradiating ultraviolet rays, so that a coating layer can be formed on the transparent substrate. At this time, the drying conditions of the coating film vary depending on the types or usage ratios of the respective components and solvents. For example, it can be implemented by heating at a temperature of 60°C to 140°C for about 20 seconds to 10 minutes. The ultraviolet irradiation method is not particularly limited. For example, a UV exposure machine such as an ultra-high pressure mercury lamp can be preferably used.

In addition, it is also possible to perform operations on the adhesion between the transparent substrate and the coating, the smoothness of the coating film at the time of coating, the drying property of the organic solvent, etc., using the steps before and after the coating is formed. As the preceding and following steps, for example, a surface treatment step of a transparent substrate, a pre-baking (pre-heating of the substrate) step, a post-baking (post-heating of the substrate) step, etc. can be appropriately selected. The heating temperature in the pre-baking step and/or the post-baking step is preferably 80°C or more and 200°C or less, and the heating time is preferably 30 seconds or more and 240 seconds or less.

The thickness of the coating formed or the preferred range of the content of the infrared shielding particles in the coating has already been described, so the description is omitted here.

It should be noted that, in order to further impart an ultraviolet shielding function to the infrared shielding transparent substrate of the present embodiment, particles selected from inorganic titanium oxide, zinc oxide, cerium oxide, etc., and organic diphenylmethyl can be added to the coating. At least one ultraviolet shielding material such as ketone or benzotriazole.

In addition, in order to increase the visible light transmittance of the infrared shielding transparent substrate of the present embodiment, one or more particles selected from ATO, ITO, aluminum-added zinc oxide, and indium tin composite oxide may be further mixed into the coating layer. By adding these transparent particles to the coating layer, the transmittance around 750nm is increased and the infrared light with a wavelength longer than 1200nm is blocked at the same time. Therefore, the transmittance of near-infrared light is higher and the heat ray shielding characteristics can be obtained. Higher heat ray shielding body.

According to the method for producing an infrared-shielding transparent substrate of the present embodiment described above, it is possible to produce an infrared-shielding transparent substrate using boride particles that can be easily pulverized. According to this infrared-shielding transparent substrate, the average dispersed particle diameter of the infrared-shielding particles contained in the coating layer can be sufficiently reduced, and the occurrence of blue haze can be suppressed.

(Infrared shielding particle dispersion)

A configuration example of the infrared shielding particle dispersion of this embodiment will be described.

The infrared shielding particle dispersion of this embodiment may include boride particles and a thermoplastic resin. Here, as the boride particles, the general formula XB _m (where X is selected from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu , Sr, Ca, one or more metal elements, m is a number representing the boron content in the general formula), and the carbon content when measured by the combustion infrared absorption method is 0.2% by mass or less.

The components are explained below.

(1) Regarding boride particles (infrared shielding particles) and their manufacturing methods

Since the above-mentioned boride particles can be used, the description is omitted here.

(2) Thermoplastic resin

As described above, the infrared shielding particle dispersion of this embodiment may have a thermoplastic resin. The thermoplastic resin is not particularly limited, and various thermoplastic resins can be used according to the use and the like.

For example, when the infrared shielding particle dispersion of the present embodiment is used for various window materials, it is preferably a thermoplastic resin having sufficient transparency.

Specifically, the thermoplastic resin is preferably one or more thermoplastic resins selected from the group consisting of polyethylene terephthalate resin, polycarbonate resin, acrylic resin, styrene resin, polyamide resin, polyethylene resin, Resin group consisting of vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluororesin, ethylene-vinyl acetate copolymer, ionomer resin, polyvinyl butyral resin, and polyvinyl acetal resin A resin; a mixture of two or more resins selected from the above resin group; or a copolymer of two or more resins selected from the resin group.

In addition, for example, when the infrared shielding particle dispersion of the present embodiment is used as a window material of the original plate shape, as a thermoplastic resin, it is preferable to satisfy high transparency and general characteristics required as a window material, namely rigidity and light weight. , Long-term durability and low cost. In this case, the thermoplastic resin is preferably one or more selected from polyethylene terephthalate resin, polycarbonate resin, ionomer resin, and acrylic resin, and more preferably polycarbonate resin.

On the other hand, when the infrared-shielding particle dispersion of the present embodiment is used as an intermediate layer of an infrared-shielding interlayer transparent substrate to be described later, from the viewpoint of adhesion to the transparent substrate, weather resistance, penetration resistance, etc. In view, as the thermoplastic resin, polyvinyl acetal resin or ethylene-vinyl acetate copolymer can be preferably used. In particular, in this case, the thermoplastic resin is more preferably a polyvinyl acetal resin.

In addition, when the infrared-shielding particle dispersion of this embodiment is used as an intermediate layer, and the thermoplastic resin constituting the infrared-shielding particle dispersion alone does not have sufficient flexibility or adhesion to a transparent substrate, for example When the thermoplastic resin is polyvinyl acetal, it is preferable to further add a plasticizer.

The plasticizer is not particularly limited, and a substance that functions as a plasticizer with respect to the thermoplastic resin used can be used. For example, plasticizers used for polyvinyl acetal resins include plasticizers that are compounds of monohydric alcohols and organic acid esters, plasticizers that are esters such as polyol organic acid ester compounds, and organic phosphoric acid plasticizers. And other phosphoric acid plasticizers. Each plasticizer is preferably liquid at room temperature. Among them, it is preferable as a plasticizer for ester compounds synthesized from polyhydric alcohols and fatty acids.

As described above, the infrared shielding particle dispersion of the present embodiment may contain boride particles and a thermoplastic resin, and for example, may have a form in which the boride particles are dispersed in the thermoplastic resin.

In addition, the infrared shielding particle dispersion of this embodiment may contain arbitrary components as needed in addition to boride particles and a thermoplastic resin. For example, as described above, a plasticizer, or any additional component added in the process of producing the infrared shielding particle dispersion, or a component derived from the additional component may be contained.

In addition, in order to further impart an ultraviolet shielding function to the infrared shielding particle dispersion of the present embodiment, particles of inorganic titanium oxide, zinc oxide, or cerium oxide, organic benzophenone, or benzophenone may be added to the infrared shielding particle dispersion. At least one of benzotriazole and the like.

In addition, in order to increase the visible light transmittance of the infrared shielding particle dispersion of the present embodiment, it is possible to further mix in the coating layer selected from ATO, ITO, aluminum-added zinc oxide, and indium tin composite oxygen. More than one kind of particles. Since these transparent particles are added to the infrared shielding particle dispersion, the transmittance around 750nm is increased, and the infrared light with a wavelength longer than 1200nm can be shielded. Therefore, it is possible to obtain high transmittance of near-infrared light and heat Infrared shielding particle dispersion with high radiation shielding properties.

The content of boride particles as infrared-shielding particles contained in the infrared-shielding particle dispersion is not particularly limited, but the content of boride particles per unit projected area is preferably 0.01 g/m ² or more and 1.0 g/m ² or less. This is because if the content is 0.01 g/m ² or more, the heat ray shielding properties can be deliberately exhibited compared to the case where the boride particles as infrared shielding particles are not contained, and if the content is 1.0 g/m ² or less, then The infrared shielding particle dispersion can sufficiently maintain the transmittance of visible light.

The optical properties of the infrared shielding particle dispersion of the present embodiment are not particularly limited. Preferably, when the maximum transmittance in the visible light wavelength region is 70%, the transmittance of near-infrared light at a wavelength of 850 nm is 23% to 45%, In addition, the minimum transmittance of heat rays having a wavelength of 1200 nm or more and 1800 nm or less is 15% or less.

Here, as a method of adjusting the maximum transmittance in the visible light wavelength region to 70%, the content of boride particles as infrared-shielding particles for the dispersion of infrared-shielding particles or the thickness of the dispersion of infrared-shielding particles, etc. Method of adjustment.

Specifically, the concentration of infrared shielding particles contained in the infrared shielding particle dispersion powder, the infrared shielding particle plasticizer dispersion or the master batch described later, the above-mentioned infrared shielding particle dispersion powder when preparing the resin composition, The addition amount of the infrared-shielding particle plasticizer dispersion or the master batch, the thickness of the film or sheet, etc. can be adjusted easily.

The shape of the infrared shielding particle dispersion of this embodiment is not particularly limited, for example It may have a plate shape, specifically, a sheet shape, a plate shape, or a film shape. In addition, the infrared shielding particle dispersion of this embodiment can also be called an infrared shielding film or an infrared shielding sheet according to its shape, for example.

In addition, for the infrared shielding particle dispersion of the present embodiment, when the visible light (wavelength 400nm or more and 780nm or less) transmittance is set to 45% or more and 55% or less, the diffuse transmission curve at the wavelength of 360nm or more and 500nm or less is The maximum value is 1.5% or less.

Since the evaluation method of the blue haze has already been described, the description is omitted here. It should be noted that although the method for directly measuring the blue haze is not known as described above, the applicant of the present invention focused on the linear incidence of the transmitted light component when the infrared shielding particle dispersion as a reagent is irradiated with light. For light and scattered light, a method for evaluating the "blue haze" by finding the diffuse transmittance of each wavelength has been proposed, and it is described in this specification.

In addition, for the infrared shielding particle dispersion of the present embodiment, it is preferable that the wavelength of 360 nm or more when the visible light (wavelength 400 nm or more and 780 nm or less) transmittance of the infrared shielding particle dispersion is set to any of 45% or more and 55% or less as described above The maximum value of the diffuse transmission curve in the region below 500 nm is 1.5% or less. This is because it was confirmed that almost no blue haze was observed on the infrared shielding particle dispersion satisfying the above-mentioned conditions.

It should be noted that setting the visible light transmittance of the infrared shielding particle dispersion to 45% or more and 55% or less is to limit the measurement conditions of the diffuse transmittance (diffuse transmittance curve). Since the diffuse transmittance is proportional to the visible light transmittance, Predetermined area. In addition, the measurement of the diffuse transmittance (diffuse transmittance curve) in the region with a wavelength of 360 nm or more and 500 nm or less is because the scattering in this region is the cause of the blue haze. If the maximum value of the diffuse transmittance in the above range is 1.5% or less, the blue haze cannot be observed with the naked eye experimentally.

According to the infrared-shielding particle dispersion of the present embodiment described above, it is possible to obtain an infrared-shielding particle dispersion using boride particles that can be easily pulverized. Therefore, the average dispersed particle diameter of the boride particles contained as infrared shielding particles can be sufficiently reduced, and the occurrence of blue haze can be suppressed.

(Method for manufacturing infrared shielding particle dispersion powder, master batch, and infrared shielding particle dispersion)

(1) Infrared shielding particle dispersion and its manufacturing method

In addition, the infrared-shielding particle dispersion of the present embodiment can be produced using the above-mentioned infrared-shielding particle dispersion containing boride particles as infrared-shielding particles. Therefore, an example of the configuration of the infrared shielding particle dispersion and its manufacturing method will be described here.

The infrared shielding particle dispersion is a dispersion in which the above-mentioned boride particles are dispersed in a solvent. Infrared shielding particle dispersion liquid, by adding the above-mentioned boride particles as infrared shielding particles, an appropriate amount of dispersing agent, coupling agent, surfactant, etc. as necessary, to a solvent and performing dispersion treatment, the boride particles are dispersed in Obtained in solvent.

Since the infrared-shielding particle dispersion liquid can use the same thing as the dispersion liquid demonstrated in the manufacturing method of an infrared-shielding transparent base material, description is abbreviate|omitted here.

The content of the infrared shielding particles in the infrared shielding particle dispersion is preferably 0.01% by mass or more and 30% by mass or less. This is because if the content of the infrared shielding particles is 0.01% by mass or more, it is possible to form an infrared shielding particle dispersion having a sufficient infrared shielding function. In addition, if the content of the infrared shielding particles is 30% by mass or less, the Hirowai Line shielding particle dispersion can be easily formed, and the productivity of the infrared shielding particle dispersion can be improved.

In addition, the infrared shielding particles in the dispersion of infrared shielding particles are preferably The dispersion particle size is 100 nm or less for dispersion, more preferably 85 nm or less for dispersion. This is because if the average dispersed particle diameter of the infrared shielding particles is 100 nm or less, the occurrence of blue haze in the infrared shielding particle dispersion produced using the infrared shielding particle dispersion of this embodiment can be suppressed, and the optical characteristics can be improved. . In addition, when the average dispersed particle diameter is 85 nm or less, it is possible to particularly suppress the occurrence of blue haze in the infrared shielding particle dispersion.

(2) Infrared shielding particle dispersion powder, infrared shielding particle plasticizer dispersion, master batch, and manufacturing method thereof

The above-mentioned boride particles as infrared shielding particles can be dispersed in a solvent together with a dispersant, a coupling agent and/or a surfactant as necessary to obtain an infrared shielding particle dispersion.

In addition, by removing the solvent from the infrared-shielding particle dispersion, for example, the infrared-shielding particle dispersion powder of the present embodiment in which the infrared-shielding particles are dispersed in a dispersant can be obtained.

At this time, the infrared shielding particle dispersion powder may include boride particles and a dispersant. The boride particles have the general formula XB _m (where X is selected from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb , Dy, Ho, Er, Tm, Yb, Lu, Sr, Ca, more than one metal element, m is a number representing the boron content in the general formula), and the carbon content when measured by the combustion infrared absorption method is 0.2 Less than mass%.

As a method of removing the solvent from the infrared-shielding particle dispersion, it is preferable to dry the infrared-shielding particle dispersion under reduced pressure. Specifically, the infrared-shielding particle dispersion is dried under reduced pressure while stirring, and the infrared-shielding particle containing composition is separated from the solvent component. As a device used for this reduced pressure drying, a vacuum stirring type dryer can be mentioned, but as long as it is A device having the above-mentioned functions is sufficient, and it is not particularly limited. In addition, the pressure value at the time of pressure reduction in the drying step is appropriately selected.

Since the use of this reduced-pressure drying method can improve the removal efficiency of the solvent from the infrared-shielding particle dispersion, and does not expose the infrared-shielding particle dispersion of this embodiment to high temperatures for a long time, it does not cause any damage to the The agglomeration of the infrared shielding particles dispersed in the dispersion powder or the plasticizer dispersion liquid is therefore preferable. In addition, the productivity of the infrared shielding particle dispersion powder and the like is also improved, and the evaporated solvent can be easily recovered, which is also preferable from environmental considerations.

In the infrared shielding particle dispersion powder of the present embodiment obtained after the drying step, the residual organic solvent is preferably 5% by mass or less. The reason is that if the residual organic solvent is 5% by mass or less, no bubbles are generated when the infrared shielding particle dispersion powder is processed into an infrared shielding interlayer transparent substrate, and the appearance or optical properties are maintained well.

In addition, infrared shielding particles may be dispersed in a plasticizer together with a dispersant, coupling agent, and/or surfactant to obtain an infrared shielding particle plasticizer dispersion.

It should be noted that the infrared shielding particle plasticizer dispersion is not limited to the above method, and it can be obtained by adding a plasticizer to the infrared shielding particle dispersion and removing the solvent. The removal of the solvent is preferably performed by drying under reduced pressure in the same manner as the process of producing the infrared shielding particle dispersion powder.

As an infrared shielding particle plasticizer dispersion, it may include boride particles and a plasticizer. The boride particles have the general formula XB _m (where X is selected from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr, Ca, more than one metal element, m is a number representing the boron content in the general formula), the carbon content when measured by the combustion infrared absorption method is 0.2 Less than mass%.

In addition, by dispersing boride particles or dispersed powder in a resin, the resin is pelletized to obtain a master batch of the present embodiment.

In addition, by uniformly mixing boride particles or infrared shielding particles dispersed powder, thermoplastic resin powder or pellets, and other additives as needed, a vented single-rod or double-rod extruder is used Kneading and cutting the melt-extruded filaments into pellet shapes can also obtain a masterbatch.

The shape of the master batch is not particularly limited, and examples include cylindrical or prismatic shapes. In addition, a so-called thermal cutting method in which the molten extrudate is directly cut can be used. At this time, it is common to obtain a nearly spherical shape.

It should be noted that the masterbatch of this embodiment is an infrared shielding particle dispersion including boride particles and a thermoplastic resin, and has a particle shape. The boride particles are represented by the general formula XB _m (where X is selected from Y, La , Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr, Ca, more than one metal element, m is the number representing the boron content in the general formula) And the carbon content when measured by the combustion infrared absorption method is 0.2% by mass or less.

(3) Manufacturing method of infrared shielding particle dispersion

By uniformly mixing the infrared-shielding particle dispersion powder, the infrared-shielding particle plasticizer dispersion, or the master batch of the above-mentioned present embodiment into a thermoplastic resin as a transparent resin, the infrared-shielding particle dispersion of the present embodiment can be manufactured.

According to the infrared shielding particle dispersion of the present embodiment, for example, the infrared shielding characteristics of the composite tungsten oxide of the prior art can be ensured, and the transmittance of near-infrared light in the wavelength range from 700 nm to 1200 nm can be improved.

Since the thermoplastic resin that can be preferably used in the infrared shielding particle dispersion of this embodiment Grease has already been explained, so the explanation is omitted here.

In addition, by kneading the dispersed powder or plasticizer dispersion or masterbatch, thermoplastic resin, and other additives such as plasticizers as necessary, the kneaded product is made by known methods such as extrusion molding and injection molding. It is formed into a flat or curved sheet to produce an infrared shielding particle dispersion.

For the method of forming the infrared shielding particle dispersion, a known method can be used. For example, a calender roll method, extrusion method, casting method, inflation method, etc. can be used.

(Infrared shielding laminated transparent substrate)

The infrared-shielding interlayer transparent substrate of the present embodiment may have a plurality of transparent substrates and the aforementioned infrared-shielding particle dispersion. In addition, it may have a structure in which the infrared shielding particle dispersion is provided between a plurality of transparent substrates.

The infrared shielding interlayer transparent substrate is a transparent substrate that uses a transparent substrate sandwiched from both sides to form an intermediate layer of an infrared shielding particle dispersion.

As the transparent substrate, a glass plate, plate-shaped plastic, or film-shaped plastic that is transparent in the visible light region can be used. In other words, a transparent glass substrate or a transparent plastic substrate can be used.

The material of the plastic is not particularly limited and can be selected according to the application. For example, when used in transportation equipment such as automobiles, from the viewpoint of ensuring the visibility of the driver or occupant of the transportation equipment, polycarbonate resin and acrylic are preferred. Transparent resin such as resin and polyethylene terephthalate resin. In addition to this, polyamide resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluororesin, etc. can be used.

It should be noted that for the infrared shielding interlayer transparent substrate of the present embodiment, it is preferable to use the infrared shielding particle dispersion contained in the visible light (wavelength 400nm or more and 780nm or less) When the transmittance is set to any of 45% or more and 55% or less, the maximum value of the diffuse transmission curve in the region with a wavelength of 360 nm or more and 500 nm or less is 1.5% or less. This is because when the maximum value of the diffuse transmission curve is in the above range, the blue haze can be reliably suppressed.

The infrared-shielding interlayer transparent substrate of the present embodiment can also be obtained by laminating and integrating a plurality of opposing inorganic glasses sandwiching the infrared-shielding particle dispersion by a known method. The obtained infrared-shielding laminated inorganic glass can be preferably used mainly as inorganic glass for the front side of automobiles or glass for buildings.

<Example>

Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to the following examples.

First, the evaluation method of the reagent in the following Examples and Comparative Examples will be described.

(Composition of boride particles)

The boride particles obtained in the following Examples and Comparative Examples were analyzed using ICP (manufactured by Shimadzu Corporation. Model: ICPE9000), and the ratio of boron (B) and metal element X expressed by the general formula XB _{m was} calculated. The element ratio (molar ratio), that is, the value of m, which is the element ratio (B/X) of boron (B) and the metal element X in the boride particles.

(Carbon concentration in boride particles)

The carbon content (carbon concentration) in the boride particles produced in the following examples and comparative examples was measured by the combustion infrared absorption method.

(B ₄ C concentration in boride particles)

Among the obtained boride particles, the reagent for measuring the B ₄ C concentration was divided into two, weighed in a platinum crucible, and 7N nitric acid was added and heated to 50° C. to dissolve the boride particles. After cooling, after adding pure water, the undissolved residue (B ₄ C) was separated by filtration with a membrane filter made of cellulose acetate with a pore size of 0.2 μm.

A part of the obtained undissolved residue was put into an original platinum crucible, and then wetted with a saturated aqueous solution of calcium hydroxide in order to prevent boron volatilization, and then dried in a dryer at about 80°C. After drying, add sodium carbonate and mix well and heat to melt. After cooling, the molten salt in the crucible was dissolved in warm water and transferred to a Teflon (registered trademark) beaker. After adding nitric acid, it is heated and boiled to remove carbon dioxide gas and used as a reagent solution for ICP. The boron concentration of the obtained reagent solution was analyzed by ICP.

In addition, the other part of the obtained undissolved residue was subjected to XRD measurement to confirm whether the undissolved residue was a B ₄ C single phase. In the case of a B ₄ C single phase, the B ₄ C concentration is calculated from the boron concentration analyzed by ICP.

(Average dispersion particle size)

For the average dispersed particle diameter of the boride particles in the infrared shielding particle dispersion (boride particle dispersion) prepared in the following examples and comparative examples, a particle diameter measuring device based on the dynamic light scattering method (Otsuka Electronics Co., Ltd. ) Manufacturing. Model: ELS-8000) for measurement. The refractive index of the particles was set to 1.81, and the particle shape was non-spherical. The background was measured with toluene, and the solvent refractive index was set to 1.50.

(The weight concentration ratio of Zr in the boride particle dispersion to the metal element X (Zr/X))

The weight concentration ratio (Zr/X) of Zr to the metal element X in the boride particle dispersion liquid was measured by ICP (manufactured by Shimadzu Corporation. Model ICPE9000) and calculated from the measured value.

(Visible light transmittance)

The visible light transmittance in the following Examples and Comparative Examples refers to the ratio of the transmitted light beam to the incident light beam of the sunlight beam perpendicularly incident on the reagent. Here, the so-called daylight mentioned above refers to CIE daylight specified by the International Commission of Illumination. For this CIE daylight, the spectral illuminance distribution of daylight at the same color temperature as the color temperature of black body radiation is expressed as a relative value with respect to a value at a wavelength of 560 nm based on observation data. In addition, the light beam refers to a value obtained by integrating the value of the product of the radiation beam for each radiation wavelength and the value of the photosensitivity (the sensitivity of the human eye to light) by the wavelength. In other words, the so-called visible light transmittance is a value indicating the brightness perceived by the human eye using the integrated value of the transmitted light amount normalized to the light sensitivity of the human eye by the light transmittance in the region having a wavelength of 380 nm or more and 780 nm or less.

For the measurement of visible light transmittance, a spectrophotometer (manufactured by Hitachi, Ltd. Model: U-4100) was used for the infrared shielding particle dispersions or infrared shielding interlayer transparent substrates produced in the following examples and comparative examples at a wavelength of 300nm The above range of 2600 nm or less is measured at 1 nm intervals.

(Maximum value of diffuse transmission curve)

For the boride particle dispersions prepared in the following Examples and Comparative Examples, the visible light (wavelength 400nm or more and 780nm or less) transmittance was adjusted to 50%, and a spectrophotometer (manufactured by Hitachi, Ltd., model: U-) was used. 4100) As a spectroscope, the maximum value of the diffuse transmission curve in the region with a wavelength of 360 nm or more and 500 or less was measured by the method described using FIGS. 1 and 2.

For the measurement reagent, the boride particle dispersion prepared in each of the Examples and Comparative Examples was diluted with a main solvent so as to obtain the above-mentioned visible light transmittance, and placed in a 10 mm rectangular glass cell for measurement.

When the maximum value of the measured diffuse transmission curve is 1.5% or less, it is confirmed that the boride is used In the infrared shielding particle dispersion produced by the particle dispersion, almost no blue haze was observed.

In the measurement, the visible light transmittance of the boride particle dispersion is set to 50% or less in order to limit the measurement conditions of the diffuse transmittance (diffuse transmittance curve). Since the diffuse transmittance is proportional to the visible light transmittance, the range is set. In addition, the measurement of the diffuse transmittance (diffuse transmittance curve) in the region with a wavelength of 360 nm or more and 500 nm or less is because the scattering in this region is the cause of the blue haze.

In addition, for the infrared-shielding transparent substrates, infrared-shielding particle dispersions, or infrared-shielding interlayer transparent substrates produced in the following examples and comparative examples, a spectrophotometer (manufactured by Hitachi, Ltd., model: U-4100) was used as the spectrometer The diffuser was measured at intervals of 1 nm in the range of 300 nm or more and 800 nm or less in wavelength by the method described using FIGS. 1 and 2. In addition, the maximum value is obtained from the obtained diffuse transmission curve.

It should be noted that when evaluating the maximum value of the diffuse transmission curve of the infrared-shielding particle dispersion and the infrared-shielding interlayer transparent substrate, except for the examples and comparative examples, the visible light transmittance is 50%. Except for adjusting the thickness of the infrared shielding particle dispersion, under the same conditions as in the respective examples and comparative examples, an infrared shielding ratio dispersion and an infrared shielding interlayer transparent substrate for diffuse transmission curve measurement were prepared and evaluated.

(Haze)

For the haze values of the infrared-shielding transparent substrates, infrared-shielding particle dispersions, or infrared-shielding interlayer transparent substrates produced in the following examples and comparative examples, a haze meter (manufactured by Murakami Color Technology Laboratory. Model: HM) -150), measured based on JIS K 7105-1981.

(Blue mist)

For the blue haze, the infrared shielding transparent substrate made in the following examples and comparative examples, The infrared-shielding particle dispersion or the infrared-shielding interlayer transparent substrate is irradiated with an artificial solar lamp (XC-100 manufactured by Seric Co., Ltd.) and confirmed by visual inspection.

The preparation conditions and evaluation results of the reagents in the respective examples and comparative examples will be described below.

[Example 1]

Boron carbide was used as a boron source and reducing agent, lanthanum oxide was used as a lanthanum source, and lanthanum and boron were weighed and mixed so that the element ratio of B/La was 5.90. After that, it was fired in an argon atmosphere at a temperature of 1600±50°C for 6 hours to obtain a powder containing lanthanum hexaboride particles.

The carbon content of the obtained powder containing lanthanum hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.05% by mass. In addition, the composition of the obtained lanthanum hexaboride particles was evaluated by ICP, and it was confirmed that _m , which is the element ratio (B/La) of boron (B) to lanthanum (La) in the general formula LaB _m , was 5.8.

Furthermore, for powder containing lanthanum hexaboride particles to be obtained using the evaluation method described above B ₄ C concentration boride particles, the concentration of B ₄ C powder containing lanthanum hexaboride particles was measured as 0.2% by mass.

Then, the ratio of 10 parts by weight of the prepared powder containing lanthanum hexaboride particles (infrared shielding material), 80 parts by weight of toluene, and 10 parts by weight of dispersant (acrylic polymer dispersant with amino group) Weigh and mix to prepare 3kg slurry. The slurry and the beads were put into a media stirring mill, the slurry was circulated, and the pulverization and dispersion treatment was performed for 20 hours.

The media stirring mill used was a horizontal cylindrical Annular-type (manufactured by Ashizawa Co., Ltd.), and the material of the inside of the container and the rotor (rotating stirring part) was ZrO ₂ . In addition, for the above-mentioned beads, beads made of YSZ (Yttria-Stabilized Zirconia) with a diameter of 0.3 mm were used. The rotation speed of the rotor was 13 m/sec, and the pulverization was performed at a slurry flow rate of 1 kg/min. The average dispersed particle diameter of the boride particles in the obtained boride particle dispersion was measured to be 70 nm.

Furthermore, for the dispersion liquid, the weight concentration ratio (Zr/La) of Zr to La in the boride particle dispersion liquid and the maximum value of the diffuse transmission curve were evaluated as described above.

The results are shown in Table 1.

In addition, the obtained dispersion liquid, the ultraviolet curable resin, and toluene were mixed in a ratio of dispersion liquid: ultraviolet curable resin: toluene = 2:1:1 in a weight ratio to prepare a coating liquid. It is coated on a transparent glass substrate with a bar coater to form a coating film. At this time, the rod used for coating is selected so that the visible light transmittance of the coating obtained is about 50%. It should be noted that the IMC-700 manufactured by Imoto Seisakusho was used as a bar coater, and the thickness of the coating obtained was approximately 10 μm.

Next, the solvent was evaporated from the coating film by maintaining at 70°C for 1 minute, and ultraviolet rays were irradiated to cure the coating film. In addition, the optical properties of the obtained infrared shielding transparent substrate were measured. The measurement results are shown in Table 1 below.

The haze of the obtained transparent infrared shielding substrate was 0.2%, and it was confirmed that the transparency was extremely high. In addition, the maximum value of the diffuse transmission curve in the region with a wavelength of 360 nm or more and 500 nm or less is 0.6%. In addition, blue haze when irradiated with artificial sunlight was not observed.

Furthermore, by adding the same amount of dispersant (acrylic polymer dispersant with amino group) to the obtained dispersion, the resulting mixed liquid is kept in a dryer to remove the solvent component and then pulverize to obtain infrared rays. Masking particle dispersant powder.

The obtained infrared shielding particle dispersion powder was mixed with a polycarbonate resin, and an extrusion machine was used to prepare a pellet-shaped masterbatch.

In addition, the above masterbatch is mixed with polycarbonate resin, and the infrared ray is formed by an extrusion machine Mask the particle dispersion. At this time, the mixing ratio of the polycarbonate resin and the master batch was adjusted so that the visible light transmittance of the obtained infrared shielding particle dispersion was about 70%. The measurement results of the optical properties of the obtained infrared shielding particle dispersion are shown in Table 1 below.

The visible light transmittance was about 70%, and it was confirmed that light in the visible light region was sufficiently transmitted. Furthermore, the haze was 0.3%, which confirmed that the transparency was extremely high. In addition, the maximum value of the diffuse transmission curve in the wavelength range of 360 nm to 500 nm is 0.8%, and blue haze (coloring) when irradiated with artificial sunlight is not observed.

It should be noted that when evaluating the maximum value of the diffuse transmission curve of the infrared-shielding particle dispersion or the infrared-shielding interlayer transparent substrate, the above-mentioned infrared-shielding particle dispersion or the infrared-shielding interlayer transparent substrate for the measurement of the diffuse transmission curve is produced Materials and evaluate them. The same applies to the following other Examples and Comparative Examples.

[Example 2]

Except that the boron carbide and lanthanum oxide were weighed and mixed so that the element ratio of lanthanum and boron was 5.95, B/La, a powder containing lanthanum hexaboride particles was obtained in the same manner as in Example 1.

The carbon content of the obtained powder containing lanthanum hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.1% by mass. In addition, the composition of the obtained lanthanum hexaboride particles was evaluated by ICP, and it was confirmed that _m , which is the element ratio (B/La) of boron (B) to lanthanum (La) in the general formula LaB _m , was 5.9.

Furthermore, for powder containing lanthanum hexaboride particles to be obtained using the evaluation method described above B ₄ C concentration boride particles, the concentration of B ₄ C powder containing lanthanum hexaboride particles was measured as 0.5% by mass.

Next, in the same manner as in Example 1, except that the powder containing lanthanum hexaboride particles was used, Prepare a dispersion of boride particles. In addition, using the obtained dispersion liquid, an infrared-shielding transparent substrate, an infrared-shielding particle dispersion powder, a master batch, and an infrared-shielding particle dispersion were produced in the same manner as in Example 1.

The same evaluations as in Example 1 were performed for the obtained dispersion liquid, the infrared-shielding transparent substrate, and the infrared-shielding particle dispersion. The results are shown in Table 1.

[Example 3]

Except that the boron carbide and lanthanum oxide were weighed and mixed so that the element ratio of lanthanum and boron was 6.00 B/La, a powder containing lanthanum hexaboride particles was obtained in the same manner as in Example 1.

The carbon content of the obtained powder containing lanthanum hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.2% by mass. In addition, the composition of the obtained lanthanum hexaboride particles was evaluated by ICP, and it was confirmed that _m , which is the element ratio (B/La) of boron (B) to lanthanum (La) in the general formula LaB _m , was 5.9.

Furthermore, for powder containing lanthanum hexaboride particles to be obtained using the evaluation method described above B ₄ C concentration boride particles, the concentration of B ₄ C powder containing lanthanum hexaboride particles was measured as 0.9% by mass.

Next, except that the powder containing the lanthanum hexaboride particles was used, the boride particle dispersion was prepared in the same manner as in Example 1. In addition, using the obtained dispersion liquid, an infrared-shielding transparent substrate, an infrared-shielding particle dispersion powder, a master batch, and an infrared-shielding particle dispersion were produced in the same manner as in Example 1.

The same evaluations as in Example 1 were performed for the obtained dispersion liquid, the infrared-shielding transparent substrate, and the infrared-shielding particle dispersion. The results are shown in Table 1.

[Example 4]

Except that the boron carbide and lanthanum oxide were weighed and mixed so that the element ratio of lanthanum to boron was 6.10, B/La, a powder containing lanthanum hexaboride particles was obtained in the same manner as in Example 1.

The carbon content of the obtained powder containing lanthanum hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.2% by mass. In addition, the composition of the obtained lanthanum hexaboride particles was evaluated by ICP, and it was confirmed that _m , which is the element ratio (B/La) of boron (B) to lanthanum (La) in the general formula LaB _m , was 6.0.

Furthermore, for powder containing lanthanum hexaboride particles to be obtained using the evaluation method described above B ₄ C concentration boride particles, the concentration of B ₄ C powder containing lanthanum hexaboride particles was measured as 0.9% by mass.

Next, except that the powder containing the lanthanum hexaboride particles was used, the boride particle dispersion was prepared in the same manner as in Example 1. In addition, using the obtained dispersion liquid, an infrared-shielding transparent substrate, an infrared-shielding particle dispersion powder, a master batch, and an infrared-shielding particle dispersion were produced in the same manner as in Example 1.

The same evaluations as in Example 1 were performed for the obtained dispersion liquid, the infrared-shielding transparent substrate, and the infrared-shielding particle dispersion. The results are shown in Table 1.

[Example 5]

Except that boron carbide and lanthanum oxide were weighed and mixed so that B/La, which is the element ratio of lanthanum to boron, was 6.20, and then fired under the temperature condition of 1650±50°C, it was the same as in Example 1. A powder containing lanthanum hexaboride particles was obtained.

The carbon content of the obtained powder containing lanthanum hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.2% by mass. In addition, the composition of the obtained lanthanum hexaboride particles was evaluated by ICP, and it was confirmed that _m , which is the element ratio (B/La) of boron (B) to lanthanum (La) in the general formula LaB _m , was 6.0.

Furthermore, for powder containing lanthanum hexaboride particles to be obtained using the evaluation method described above B ₄ C concentration boride particles, the concentration of B ₄ C powder containing lanthanum hexaboride particles was measured as 0.9% by mass.

Next, except that the powder containing the lanthanum hexaboride particles was used, the boride particle dispersion was prepared in the same manner as in Example 1. In addition, using the obtained dispersion liquid, an infrared-shielding transparent substrate, an infrared-shielding particle dispersion powder, a master batch, and an infrared-shielding particle dispersion were produced in the same manner as in Example 1.

The same evaluations as in Example 1 were performed for the obtained dispersion liquid, the infrared-shielding transparent substrate, and the infrared-shielding particle dispersion. The results are shown in Table 1.

[Example 6]

Except that boron oxide is used as a boron source, lanthanum oxide is used as a lanthanum source, carbon (graphite) is used as a reducing agent, and the element ratio of lanthanum to boron is B/La of 6.10, the measurement and mixing are carried out in accordance with the examples. 1 In the same manner, a powder containing lanthanum hexaboride particles was obtained. However, 60 parts by weight of carbon were weighed and mixed with respect to 100 parts by weight of boron oxide.

The carbon content of the obtained powder containing lanthanum hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.1% by mass. In addition, the composition of the obtained lanthanum hexaboride particles was evaluated by ICP, and it was confirmed that _m , which is the element ratio (B/La) of boron (B) to lanthanum (La) in the general formula LaB _m , was 6.0.

Furthermore, for powder containing lanthanum hexaboride particles to be obtained using the evaluation method described above B ₄ C concentration boride particles, the concentration of B ₄ C powder containing lanthanum hexaboride particles was measured as 0.4% by mass.

Next, except that the powder containing the lanthanum hexaboride particles was used, the boride particle dispersion was prepared in the same manner as in Example 1. In addition, using the obtained dispersion liquid, an infrared-shielding transparent substrate, an infrared-shielding particle dispersion powder, a master batch, and an infrared-shielding particle dispersion were produced in the same manner as in Example 1.

The same evaluations as in Example 1 were performed for the obtained dispersion liquid, the infrared-shielding transparent substrate, and the infrared-shielding particle dispersion. The results are shown in Table 1.

[Example 7]

A powder containing cerium hexaboride particles was obtained in the same manner as in Example 1, except that cerium oxide was used instead of lanthanum oxide so that the element ratio of cerium to boron B/Ce was 6.10.

The carbon content of the obtained powder containing cerium hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.2% by mass. In addition, it was confirmed that _m , which is the element ratio (B/Ce) of boron (B) to cerium (Ce) in the general formula CeB _m , of the obtained cerium hexaboride contained by ICP was 6.0.

Furthermore, for powder containing cerium hexaboride particles to be obtained using the evaluation method described above B ₄ C concentration boride particles, the concentration of B ₄ C powder containing cerium hexaboride particles was measured as 0.9% by mass.

Next, except for using the powder containing the cerium hexaboride particles, a dispersion of boride particles was prepared in the same manner as in Example 1. In addition, using the obtained dispersion liquid, an infrared-shielding transparent substrate, an infrared-shielding particle dispersion powder, a master batch, and an infrared-shielding particle dispersion were produced in the same manner as in Example 1.

The same evaluations as in Example 1 were performed for the obtained dispersion liquid, the infrared-shielding transparent substrate, and the infrared-shielding particle dispersion. The results are shown in Table 1.

[Example 8]

By adding a dispersant (fatty acid amine dispersant) and a plasticizer to the infrared shielding particle dispersion (boride particle dispersion) prepared in Example 1 in a weight ratio of 4:1:10, the reduction The solvent component is removed in a press dryer to obtain an infrared shielding particle plasticizer dispersion.

The obtained infrared-shielding particle plasticizer dispersion is mixed with polyvinyl butyral resin, and a sheet-shaped infrared-shielding particle dispersion is obtained by an extrusion machine.

At this time, the mixing ratio is adjusted so that the visible light transmittance of the finally obtained infrared shielding interlayer transparent substrate is about 70%.

The obtained sheet-shaped infrared shielding particle dispersion was sandwiched between two glass substrates (thickness: 3 mm), and a laminated glass-shaped infrared shielding interlayer transparent substrate was produced using a heating press.

The obtained wire-shielding interlayer transparent substrate was evaluated in the same manner as in the case of the infrared-shielding particle dispersion of Example 1. The results are shown in Table 1.

[Comparative Example 1]

Boron carbide was used as the boron source and reducing agent, and lanthanum oxide was used as the lanthanum source, and the lanthanum and boron element ratio B/La was weighed and mixed. After that, it was fired in an argon atmosphere at a temperature of 1480±50°C for 6 hours to obtain a powder containing lanthanum hexaboride particles.

The carbon content of the obtained powder containing lanthanum hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.6% by mass. In addition, the composition of the obtained lanthanum hexaboride particles was evaluated by ICP, and it was confirmed that _m , which is the element ratio (B/La) of boron (B) to lanthanum (La) in the general formula LaB _m , was 6.0.

Furthermore, for powder containing lanthanum hexaboride particles to be obtained using the evaluation method described above B ₄ C concentration boride particles, the concentration of B ₄ C powder containing lanthanum hexaboride particles was measured as 2.6 mass%.

Next, except that the powder containing the lanthanum hexaboride particles was used, the boride particle dispersion was prepared in the same manner as in Example 1.

The same evaluation as in Example 1 was performed on the obtained dispersion liquid. The results are shown in Table 2.

It should be noted that in order to prepare the dispersion, even though the average dispersed particle size was 105nm larger than 100nm at the time of the pulverization treatment for 20 hours, the pulverization effect was significantly reduced due to the increase in the slurry viscosity, so it was judged that The above pulverization treatment is also difficult to obtain a particle size of 100 nm or less.

In addition, Zr/La in the obtained boride particle dispersion was 1.8, which was high compared to the cases of Examples 1 to 8, and it was found that a large amount of media beads were abraded and mixed in the slurry.

In addition, the diffuse transmittance peak value of 1.8% is higher than in the cases of Examples 1 to 8, and it is feared that blue haze may be strongly observed when optical members are produced using this.

Using the obtained dispersion liquid, as in the case of Example 1, a coating layer was formed on a transparent glass substrate as an infrared shielding transparent substrate. In addition, the optical properties of the obtained infrared shielding transparent substrate were measured. The measurement results are shown in Table 2 below.

The haze of the obtained transparent infrared shielding substrate was 1.6%, and it was confirmed that the transparency was very low. In addition, the maximum value of the diffuse transmission curve in the region having a wavelength of 360 nm or more and 500 nm or less was 1.9%, and the blue haze was clearly confirmed visually when artificial sunlight was irradiated.

Furthermore, by adding the same amount of dispersant (acrylic polymer dispersant with amino group) to the obtained dispersion, the resulting mixed liquid is kept in a dryer to remove the solvent component and then pulverize to obtain infrared rays. Masking particle dispersant powder.

The obtained infrared shielding particle dispersion powder was mixed with a polycarbonate resin, and an extrusion machine was used to prepare a pellet-shaped masterbatch.

Furthermore, the above-mentioned master batch is mixed with a polycarbonate resin, and an infrared shielding particle dispersion is formed by an extrusion processing machine. At this time, the mixing ratio of the polycarbonate resin and the master batch was adjusted so that the visible light transmittance of the obtained infrared shielding particle dispersion was about 70%. The measurement results of the optical properties of the obtained infrared shielding particle dispersion are shown in Table 2 below.

The visible light transmittance was about 70%, and it was confirmed that light in the visible light region was sufficiently transmitted. However, the haze was 1.6%, confirming that the transparency was very low. In addition, the maximum value of the diffuse transmission curve in the wavelength range of 360nm to 500nm is 2.0%, and the blue haze is clearly confirmed visually when irradiated with artificial sunlight.

[Comparative Example 2]

Except that the boron carbide and lanthanum oxide were weighed and mixed so that the element ratio of lanthanum to boron B/La was 6.20, a powder containing lanthanum hexaboride particles was obtained in the same manner as in Comparative Example 1.

The carbon content of the obtained powder containing lanthanum hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.8% by mass. In addition, the composition of the obtained lanthanum hexaboride particles was evaluated by ICP, and it was confirmed that _m , which is the element ratio (B/La) of boron (B) to lanthanum (La) in the general formula LaB _m , was 6.1.

Furthermore, for powder containing lanthanum hexaboride particles to be obtained using the evaluation method described above B ₄ C concentration boride particles, the concentration of B ₄ C powder containing lanthanum hexaboride particles was measured as 3.7 mass%.

Next, except that the powder containing the lanthanum hexaboride particles was used, the boride particle dispersion was prepared in the same manner as in Example 1. In addition, the obtained dispersion liquid was prepared in the same manner as in Example 1. Used as infrared shielding transparent substrate, infrared shielding particle dispersion powder, master batch, and infrared shielding particle dispersion.

The same evaluations as in Example 1 were performed for the obtained dispersion liquid, the infrared-shielding transparent substrate, and the infrared-shielding particle dispersion. The results are shown in Table 2.

It should be noted that in order to prepare the dispersion, even though the average dispersed particle size was 111nm larger than 100nm at the time of the pulverization treatment for 20 hours, the pulverization effect was significantly reduced due to the increase in slurry viscosity, so it was judged that The above pulverization treatment is also difficult to obtain a particle size of 100 nm or less.

In addition, Zr/La in the obtained boride particle dispersion was 2.0, which was high compared to the cases of Examples 1 to 8, and it was found that a large amount of media beads were worn and mixed in the slurry.

In addition, the diffuse transmittance peak value of 2.4% is higher than in the cases of Examples 1 to 8, and it is feared that blue haze may be strongly observed when an optical member is produced using this.

In addition, the obtained dispersion liquid was used to form a coating layer on the transparent glass substrate in the same manner as in the case of Example 1. In addition, the optical properties of the obtained infrared shielding transparent substrate were measured. The measurement results are shown in Table 2 below.

The haze of the obtained transparent infrared shielding substrate was 1.8%, and it was confirmed that the transparency was very low. In addition, the maximum value of the diffuse transmission curve in the region having a wavelength of 360 nm or more and 500 nm or less was 2.4%, and when artificial sunlight was irradiated, the blue haze was clearly confirmed visually as in Comparative Example 1.

[Comparative Example 3]

In addition to using boron oxide as a boron source, lanthanum oxide as a lanthanum source, carbon (graphite) as a reducing agent, and weighing and mixing so that the element ratio of lanthanum to boron is B/La of 6.10, the comparison example 1 In the same manner, a powder containing lanthanum hexaboride particles was obtained. However, relative to 100 parts by weight of boron oxide are weighed and mixed with 60 parts by weight of carbon.

The carbon content of the obtained powder containing lanthanum hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.7% by mass. In addition, the composition of the obtained lanthanum hexaboride particles was evaluated by ICP, and it was confirmed that _m , which is the element ratio (B/La) of boron (B) to lanthanum (La) in the general formula LaB _m , was 6.0.

Furthermore, for powder containing lanthanum hexaboride particles to be obtained using the evaluation method described above B ₄ C concentration boride particles, the concentration of B ₄ C powder containing lanthanum hexaboride particles was measured as 3.4% by mass.

Next, except that the powder containing the lanthanum hexaboride particles was used, the boride particle dispersion was prepared in the same manner as in Example 1. In addition, the obtained dispersion liquid was used in the same manner as in Example 1 to produce an infrared-shielding transparent substrate, an infrared-shielding particle dispersion powder, a master batch, and an infrared-shielding particle dispersion.

The same evaluations as in Example 1 were performed for the obtained dispersion liquid, the infrared-shielding transparent substrate, and the infrared-shielding particle dispersion. The results are shown in Table 2.

The haze of the obtained transparent infrared shielding substrate was 1.7%, and it was confirmed that the transparency was very low. In addition, the maximum value of the diffuse transmission curve in the region with a wavelength of 360 nm or more and 500 nm or less was 2.2%. In addition, when artificial sunlight was irradiated, the blue haze was clearly confirmed visually as in Comparative Example 1.

[Comparative Example 4]

A powder containing cerium hexaboride particles was obtained in the same manner as in Comparative Example 1, except that cerium oxide was further used instead of lanthanum oxide so that the element ratio of cerium to boron B/Ce was 6.10.

The carbon content of the obtained powder containing cerium hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.9% by mass. In addition, the composition of the obtained cerium hexaboride particles was evaluated by ICP, and it was confirmed that _m , which is the element ratio (B/Ce) of boron (B) to lanthanum (Ce) in the general formula CeB _m , was 6.0.

Furthermore, for powder containing cerium hexaboride particles to be obtained using the evaluation method described above B ₄ C concentration boride particles, the concentration of B ₄ C powder containing cerium hexaboride particles was measured as 4.4% by mass.

Next, except for using the powder containing the cerium hexaboride particles, a dispersion of boride particles was prepared in the same manner as in Example 1. In addition, the obtained dispersion liquid was used in the same manner as in Example 1 to produce an infrared-shielding transparent substrate, an infrared-shielding particle dispersion powder, a master batch, and an infrared-shielding particle dispersion.

The same evaluations as in Example 1 were performed for the obtained dispersion liquid, the infrared-shielding transparent substrate, and the infrared-shielding particle dispersion. The results are shown in Table 2.

The haze of the obtained transparent infrared shielding substrate was 1.9%, and it was confirmed that the transparency was very low. In addition, the maximum value of the diffuse transmission curve in the region having a wavelength of 360 nm or more and 500 nm or less was 2.5%, and when artificial sunlight was irradiated, the blue haze was clearly confirmed visually as in Comparative Example 1.

In Examples 1 to 8, it can be confirmed that the average dispersed particle size can be pulverized and made fine to 100 nm or less, particularly to 85 nm or less, relatively simply and economically, for boride particles obtained by solid phase reaction or the like. In addition, in Examples 1 to 8, the boride particles obtained The average dispersed particle size is 100nm or less, especially 85nm or less, so even if the infrared shielding film made using the particles or dispersion, the infrared shielding transparent substrate with coating, or the infrared shielding particle dispersion is irradiated with artificial sunlight Will not be colored blue-white. In other words, it is confirmed that the blue haze is suppressed.

Therefore, it can be confirmed that the infrared shielding film, the infrared shielding transparent substrate, the infrared shielding optical member with the infrared shielding transparent substrate, the infrared shielding particle dispersion, or the infrared ray prepared by using the boride particle dispersions of Examples 1 to 8 The shielding laminated transparent substrate and the like can be preferably used for window glass or vehicle window glass for building materials.

It should be noted that in Example 1 to Example 7, the thickness of the coating is about 10 μm, which is 20 μm or less.

On the other hand, for Comparative Examples 1 to 4 using powders containing boride particles with a carbon concentration higher than 0.2% by mass as raw materials, it can be confirmed that the average dispersed particle size is greater than 100 nm after 20 hours of pulverization. Even if the viscosity increases, it is difficult to form a particle size of 100 nm or less even if it is further crushed. Furthermore, the maximum value of the diffuse transmission curve of the boride particle dispersion is also higher than 1.5%. Therefore, it can be confirmed that there is a concern that blue haze may occur in the infrared-shielding transparent substrate and the like produced using the boride particle dispersion. In addition, there are problems with window glass or vehicle window glass used for building materials.

In the above, through the embodiments and examples, the boride particles, boride particle dispersions, infrared shielding transparent substrates, infrared shielding optical members, infrared shielding particle dispersions, infrared shielding interlayer transparent substrates, infrared shielding particle dispersion powder, And the master batch has been described, but the present invention is not limited to the above-mentioned embodiments and examples. Various modifications and changes can be made within the scope of the gist of the present invention described in the scope of the patent application.

This application is based on the Japanese Patent Application No. 2016-000298 filed with the Japan Patent Office on January 4, 2016, and the Japanese Patent Application No. 2016-000300 filed with the Japan Patent Office on January 4, 2016. The Japanese Patent Application No. 2016-000301 filed with the Japan Patent Office on January 4, 2016, the Japanese Patent Application No. 2016-254433 filed with the Japan Patent Office on December 27, 2016, and the Japanese Patent Application No. 2016-254433 filed with the Japan Patent Office on December 27, 2016. Priority of the Japanese Patent Application No. 2016-254437 filed by the Japan Patent Office and the Japanese Patent Application No. 2016-254440 filed with the Japan Patent Office on December 27, 2016, the Japanese Patent Application No. 2016-000298 No., Japanese Patent Application No. 2016-000300, Japanese Patent Application No. 2016-000301, Japanese Patent Application No. 2016-254433, Japanese Patent Application No. 2016-254437, Japanese Patent Application No. 2016-254440 The entire content of the number is incorporated into this international application by reference.

10‧‧‧Measurement device

11‧‧‧Light source

13‧‧‧Receiver

14‧‧‧Integrating Sphere

15‧‧‧Standard reflector

141‧‧‧First opening

142‧‧‧Second opening

143‧‧‧The third opening

Claims (26)

A kind of boride particles, which are represented by the general formula XB _m (where X is selected from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr, One or more metal elements of Ca, where m is a number representing the content of boron in the general formula) means that the carbon content contained in the boride particles when measured by the combustion infrared absorption method is 0.2% by mass or less, and the content of B ₄ C The content is 1.0% by mass or less. For example, the boride particle of item 1 in the scope of patent application, wherein _m in the general formula XB m is 4.0 or more and 6.2 or less. Such as the boride particles of item 1 or 2 in the scope of patent application, wherein the boride particles include lanthanum hexaboride particles. A dispersion of boride particles, which includes the boride particles of any one of items 1 to 3 in the scope of patent application, and a liquid medium. For example, the boride particle dispersion of item 4 in the scope of the patent application, wherein the liquid medium includes one or more selected from the group consisting of water, organic solvents, grease, liquid resins, and plasticizers. For example, the boride particle dispersion liquid of item 4 or 5 of the scope of patent application, wherein the average dispersed particle diameter of the boride particles measured by the dynamic light scattering method is 85 nm or less. For example, the boride particle dispersion of item 4 or 5 in the scope of patent application, wherein the concentration of the boride particles is 0.01% by mass to 30% by mass. Such as the boride particle dispersion liquid of any one of the 4th or 5th item of the scope of patent application, wherein the weight concentration of Zr relative to the weight concentration of the metal element X is 1.5 times or less. An infrared shielding transparent substrate, which has a coating on at least one surface of the transparent substrate. The coating includes infrared shielding particles and a binder. The infrared shielding particles are composed of the general formula XB _m (where X is selected from One or more metal elements of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr, Ca, and m represents the boron content in the general formula The number) represents boride particles with a carbon content of 0.2% by mass or less when measured by the combustion infrared absorption method, and the amount of B ₄ C contained in the boride particles is 1.0% by mass or less. For example, the infrared-shielding transparent substrate of item 9 in the scope of patent application, wherein _m in the general formula XB m is 4.0 or more and 6.2 or less. For example, the infrared-shielding transparent substrate of item 9 or 10 in the scope of patent application, wherein the average dispersed particle diameter of the boride particles is 1 nm or more and 100 nm or less. For example, the infrared shielding transparent substrate of item 9 or 10 of the scope of patent application, wherein the adhesive includes one or more selected from the group consisting of ultraviolet curable resin, thermoplastic resin, thermosetting resin, and room temperature curable resin. For example, the infrared shielding transparent substrate of item 9 or 10 of the scope of patent application, wherein the thickness of the coating is 20 μm or less. For example, the infrared shielding transparent substrate of the 9th or 10th item of the scope of patent application, wherein when the visible light transmittance of the coating is set to the range of 45% to 55%, the diffuse transmission at the wavelength of 360nm to 500nm The maximum value of the curve is 1.5% or less. For example, the infrared-shielding transparent substrate of item 9 or 10 in the scope of patent application, wherein the transparent substrate is a transparent film substrate or a transparent glass substrate. An infrared shielding optical component, which includes the infrared shielding transparent substrate of any one of the 9th to 15th patent applications. An infrared shielding particle dispersion, which includes boride particles and a thermoplastic resin, wherein the boride particles have the general formula XB _m (wherein X is selected from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr, Ca, more than one metal element, m is a number representing the boron content in the general formula), and the carbon content when measured by the combustion infrared absorption method is 0.2% by mass or less, and the amount of B ₄ C contained in the boride particles is 1.0% by mass or less. For example, the infrared shielding particle dispersion of item 17 in the scope of patent application, wherein _m in the general formula XB m is 4.0 or more and 6.2 or less. For example, the infrared shielding particle dispersion of item 17 or 18 in the scope of patent application, wherein the average dispersed particle diameter of the boride particles is 1 nm or more and 100 nm or less. For example, the infrared shielding particle dispersion of item 17 or 18 in the scope of the patent application, wherein the thermoplastic resin is one or more selected from the group consisting of polyethylene terephthalate resin, polycarbonate resin, acrylic resin, benzene Vinyl resin, polyamide resin, polyethylene resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluororesin, ethylene-vinyl acetate copolymer, ionomer resin, polyvinyl butyral resin 1. One resin of the resin group consisting of polyvinyl acetal resin; a mixture of two or more resins selected from the resin group; and a copolymer of two or more resins selected from the resin group. For example, the infrared shielding particle dispersion of item 17 or 18 in the scope of patent application, wherein the infrared shielding particle dispersion is in the shape of a sheet, a plate or a film. For example, the infrared shielding particle dispersion of item 17 or 18 in the scope of patent application, wherein the content of the boride particles per unit projected area is 0.01 g/m ² or more and 1.0 g/m ² or less. For example, the infrared shielding particle dispersion of No. 17 or 18 of the scope of patent application, wherein when the visible light transmittance is set to the range of 45% to 55%, the maximum value of the diffuse transmission curve at the wavelength of 360nm to 500nm It is 1.5% or less. An infrared shielding interlayer transparent substrate, which has: a plurality of transparent substrates; and the infrared shielding particle dispersion of any one of the 17 to 23 patent applications, wherein the infrared shielding particle dispersion is arranged on the plurality of sheets Between transparent substrates. An infrared shielding particle dispersion powder, comprising boride particles and a dispersant, wherein the boride particles have the general formula XB _m (where X is selected from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr, Ca, more than one metal element, m is a number representing the boron content in the general formula), and the carbon content when measured by the combustion infrared absorption method is 0.2% by mass or less, and the amount of B ₄ C contained in the boride particles is 1.0% by mass or less. A master batch, which is a dispersion of infrared shielding particles including boride particles and thermoplastic resin, and has a particle shape, wherein the boride particles have the general formula XB _m (where X is selected from Y, La, Ce, Pr , Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr, Ca, more than one metal element, m is the number that represents the boron content in the general formula), and it is expressed by burning The carbon content measured by the infrared absorption method is 0.2% by mass or less, and the amount of B ₄ C contained in the boride particles is 1.0% by mass or less.

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