JP2021162636A - Infrared blocking film and core shell fine particle dispersion - Google Patents

Abstract

To provide an infrared blocking film which offers a superior infrared blocking property and infrared reflection property, and suppresses deterioration of solar radiation blocking capability due to heat generation and thermal deterioration associated with infrared blocking.SOLUTION: An infrared blocking film is provided, comprising two-dimensionally arranged core shell fine particles, or conductive particles having surfaces coated with one or more selected from a hydrolysis product of the metal chelate compound, a polymer of the hydrolysis product of the metal chelate compound, a hydrolysis product of a metal cyclic oligomer compound, and a polymer of the hydrolysis product of the metal cyclic oligomer compound, the conductive fine particles having an extinction coefficient of 5 L/g cm or greater per unit weight for 1300 nm-light.SELECTED DRAWING: Figure 1

Description

The present invention relates to an infrared shielding film that reflects and shields infrared rays while maintaining visible light transmittance.

Infrared shielding film with heat ray shielding ability (infrared shielding function) that can block a part of the incident solar energy and reduce the cooling load, the feeling of heat and heat of people, adverse effects on plants, etc. is used for automobiles, buildings, etc. It is required for applications such as window materials and vinyl house films, and various studies have been conducted.

When an infrared shielding film is used, for example, as a window material, an example has been reported in which a laminated glass is formed by arranging it as an intermediate film (intermediate layer) between a plurality of opposing plate glasses.

In Patent Document 1, as an example of the laminated glass, a soft resin layer containing a heat ray-shielding metal oxide having a particle size of 0.1 μm or less, which is either tin oxide or indium oxide, is provided between a pair of glass plates. Laminated glass is disclosed.

Further, in Patent Document 2, Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, are described between at least two transparent glass plates. Mn, Ta, W, V, Mo metal simple substance, metal oxide, metal nitride, metal sulfide, each single substance selected from Sb and F dope, or two or more of these There is disclosed a laminated glass having an interlayer film in which functional ultrafine particles which are a composite obtained by selecting the above are dispersed.

Further, Patent Document 3 discloses an automobile window glass in which a mixed layer of ultrafine particles having an average particle size of 0.1 μm or less and a glass component is formed between transparent plate-shaped members. Examples of the ultrafine particles include _{metal oxides such as TiO 2} , ZrO ₂ , SnO ₂ , and In ₂ O ₃ , or a mixture thereof, and examples of the glass component include organosilicon or an organosilicon compound.

Further, in Patent Document 4, a laminated interlayer film composed of three layers is provided between at least two transparent glass plate-like bodies, and Sn, Ti, Si, Zn, Zr, and Fe are provided in the second layer of the interlayer film. , Al, Cr, Co, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, Mo metals, oxides, nitrides, sulfides, or Sb and F doped products. Alternatively, laminated glass in which functional ultrafine particles, which are two or more kinds of composites selected from these, are dispersed, is disclosed.

However, according to the study by the present inventors, the laminated glass disclosed in Patent Documents 1 to 4 does not have sufficient heat ray shielding ability (infrared shielding function) when high visible light transmittance is required. There was a challenge.

Therefore, the applicant of the present invention describes in Patent Document 5 that an intermediate layer having a solar shading function is interposed between two sheets of glass, and the intermediate layer is an additive liquid (or an additive solution in which hexaboroid fine particles are dispersed in a plasticizer. , An additive liquid in which hexaboroid fine particles, ITO fine particles and / or ATO fine particles are dispersed in a plasticizer), and a laminated glass for shielding sunlight, which is an intermediate film composed of a vinyl resin, have been disclosed.

Further, in Patent Document 5, the applicant of the present invention has an intermediate layer having a solar radiation shielding function interposed between two plate glasses, and the intermediate layer is formed on a surface located inside at least one plate glass. Formed by applying a coating liquid containing hexaborized fine particles as a solar shielding component (or a coating liquid containing hexaborized fine particles and one or more selected from ITO fine particles and ATO fine particles as a solar shielding component). Also disclosed is a laminated glass for shielding sunlight formed by an interlayer film containing a vinyl-based resin interposed between two sheets of glass.

In the film in which the 6-boride fine particles used in the laminated glass for shielding solar radiation disclosed in Patent Document 5 are sufficiently finely and uniformly dispersed, the light transmittance has a maximum value in the wavelength range of 400 nm to 700 nm, and the wavelength is also high. It has a minimum value between 700 nm and 1800 nm. Therefore, according to the laminated glass for shielding solar radiation disclosed in Patent Document 5, even when the visible light transmittance is 77% or 78%, the solar radiation transmittance is about 50% to 60%. The performance was significantly improved as compared with the conventional laminated glass disclosed in 1 to 4.

Further, in Patent Document 6, the applicant of the present invention uses tungsten oxide fine particles and / or composite tungsten oxide fine particles as fine particles having a solar radiation shielding function, and the fine particles having a solar radiation shielding function are made into a synthetic resin such as a vinyl resin. A laminated structure for shielding sunlight is disclosed in which a dispersed intermediate layer is interposed between two laminated plates selected from plate glass and the like.

The laminated structure for shielding solar radiation disclosed in Patent Document 6 has an example in which the solar radiation transmittance is 35.7% when the visible light transmittance is 70.0%, and the conventional structures described in Patent Documents 1 to 5 are described. The performance was further improved compared to laminated glass.

Japanese Unexamined Patent Publication No. 8-217500 Japanese Unexamined Patent Publication No. 8-259279 Japanese Unexamined Patent Publication No. 4-160041 Japanese Unexamined Patent Publication No. 10-297945 Japanese Unexamined Patent Publication No. 2001-89202 International Publication No. 2005/0876880

However, according to a further study by the present inventors, the intermediate layer of the combined structure for solar radiation shielding disclosed in Patent Document 5 and Patent Document 6 generates heat when absorbing and shielding infrared rays, so that infrared rays are shielded. The fine particles having a function may be thermally deteriorated and the infrared shielding function may be deteriorated.

The present invention has been made under the above-mentioned circumstances, has high infrared shielding characteristics (solar shielding characteristics, heat shielding characteristics) and infrared reflection characteristics, and also has solar shielding due to heat generation and thermal deterioration due to infrared shielding. It is an object of the present invention to provide an infrared shielding film in which deterioration of function is suppressed, and a core-shell fine particle dispersion liquid used for producing the infrared shielding film.

In order to solve the above-mentioned problems, the present inventors have come up with an infrared shielding film in which conductive fine particles having an infrared shielding function are two-dimensionally arranged.
That is, one of the inventions for solving the above-mentioned problems is
Select from hydrolysis products of metal chelate compounds, polymers of hydrolysis products of metal chelate compounds, hydrolysis products of metal cyclic oligomer compounds, polymers of hydrolysis products of metal cyclic oligomer compounds, metal oxides. Core-shell fine particles, which are conductive fine particles whose surfaces are coated with one or more of the following compounds, are arranged in two dimensions.
It is an infrared shielding film characterized in that the absorption coefficient of the core-shell fine particles with respect to light having a wavelength of 1300 nm per unit weight is 5 L / (g · cm) or more.
Further, one of the inventions for solving the above-mentioned problems is
Select from hydrolysis products of metal chelate compounds, polymers of hydrolysis products of metal chelate compounds, hydrolysis products of metal cyclic oligomer compounds, polymers of hydrolysis products of metal cyclic oligomer compounds, metal oxides. Core-shell fine particles, which are conductive fine particles whose surfaces are coated with one or more of them,
A core-shell fine particle dispersion containing a sequence control agent.
When the core-shell fine particle dispersion liquid is applied to the surface of an appropriate base material to form a dispersion film, the core-shell fine particles are arranged two-dimensionally to form an infrared shielding film.
The infrared shielding film is a core-shell fine particle dispersion having an extinction coefficient of 5 L / (g · cm) or more per unit weight of the core-shell fine particles with respect to light having a wavelength of 1300 nm.

According to the present invention, since the conductive fine particles having an infrared ray shielding function arranged in two dimensions reflect infrared rays, heat generation due to infrared ray shielding and deterioration of the solar radiation shielding function due to thermal deterioration are suppressed while maintaining visible light transmittance. It was possible to provide an infrared shielding film.

It is a schematic plan view of the crystal structure of a hexagonal crystal.

The infrared shielding film according to the present invention has a surface of conductive fine particles as a core, which is a hydrolysis product of a metal chelate compound, a polymer of a hydrolysis product of a metal chelate compound, a hydrolysis product of a metal cyclic oligomer compound, and the like. Fine particles coated with one or more selected from a polymer of a hydrolysis product of a metal cyclic oligomer compound, a hydrate of a metal oxide, and a metal oxide as a shell (referred to as "core-shell fine particles" in the present invention). It may be described.) Is a two-dimensional arrangement. The interval in the two-dimensional arrangement of the core-shell fine particles is 0.5 nm or more and 10 nm or less, and the extinction coefficient per unit weight of the core-shell fine particles at a wavelength of 1300 nm is 5 L / (g · cm) or more.
Then, the infrared shielding film according to the present invention produces core-shell fine particles in which the surface of the conductive fine particles as the core is coated with a metal chelate compound or the like as a shell, and then the core-shell fine particles and an arrangement control agent described later are used. After producing a dispersion liquid containing a solvent (may be referred to as "core-shell fine particle dispersion liquid" in the present invention), an infrared shielding film is formed on a predetermined substrate or the like using the core-shell fine particle dispersion liquid. It forms a film.
Hereinafter, the present invention will be described as 1. Core-shell fine particles and their manufacturing method 2. 2. Core-shell fine particle dispersion and its manufacturing method. The infrared shielding film and its manufacturing method will be described in this order.

1. 1. Core-shell fine particles and method for producing them The following describes the core-shell fine particles and the method for producing the same according to the present invention: [1] conductive fine particles, [2] raw material for core-shell fine particle forming agent, [3] method for producing core-shell fine particles, and [4] core-shell fine particles. The powder containing the above will be described in this order.

[1] Conductive fine particles Generally, it is known that a material containing free electrons, that is, a conductive material, exhibits a reflection absorption response to electromagnetic waves (light) around a region of sunlight having a wavelength of 200 nm to 2600 nm due to plasma oscillation. Has been done. It is known that when the powder of such a material is made into particles smaller than the wavelength of light, geometrical scattering in the visible light region (wavelength 380 nm to 780 nm) is reduced and transparency in the visible light region can be obtained. In the present invention, "transparency" is used to mean "less scattering and high transparency with respect to light in the visible light region". Further, it is known that when the powder of such a material is made into small particles until it becomes conductive fine particles having a diameter of 500 nm or less, it exhibits a light reflection / absorption response based on the principle of localized surface plasmon resonance by free electrons. In particular, the conductive fine particles according to the present invention show a strong reflection / absorption response in the near-infrared region having a wavelength of 780 nm to 2600 nm, and are useful as a solar radiation shielding function. The conductive fine particles preferably have a diameter of 200 nm or less, and more preferably 100 nm or less.

The conductive fine particles used in the infrared shielding film according to the present invention are one or more selected from hexaboride fine particles, tungsten oxide fine particles, and composite tungsten fine particles. These conductive fine particles have a high absorption coefficient per unit weight, and when an infrared shielding film is produced by the method described later, the absorption coefficient of the conductive fine particles at a wavelength of 1300 nm is 5 L / (g · cm) or more. Become.
Regarding these conductive fine particles, (1) hexaboride, (2) optical properties of hexaboride fine particles, (3) tungsten oxide, (4) composite tungsten oxide, (5) tungsten oxide fine particles and composite tungsten. The optical characteristics of the oxide fine particles will be described in this order.

(1) Hexoboride Boride is a general formula XB _m (where X is Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, One or more metal elements selected from Sr and Ca, m is a numerical value indicating the amount of boron in the general formula), and _{borides represented by XB 4} , XB ₆ , XB _12, etc. can be mentioned. However, when used as a material for an infrared shield, _{it is preferable that XB 4} and XB ₆ are the main constituents of the above-mentioned borides, and a part of XB ₁₂ may be contained.

(2) Optical Characteristics of Hexhooxide Fine Particles Hexhoride fine particles are powders colored in dark bluish purple or the like, but are crushed so that the particle size is sufficiently smaller than the visible light wavelength and dispersed in a predetermined film. In this state, the film is transparent to visible light, and at the same time, an infrared shielding function is exhibited.

Although the reason for this has not been elucidated in detail, these borides have a relatively large number of free electrons, and the interband transition between 4f-5d and absorption by electron-electron and electron-phonone interactions are in the infrared region. It is thought that it is derived from the existence in.

In a film in which boride fine particles are sufficiently finely and uniformly dispersed, the transmittance of the film has a maximum value in the light region having a wavelength of 400 nm or more and 700 nm or less, and is extremely small in a light region having a wavelength of 700 nm or more and 1800 nm or less. Confirmed to have a value. Considering that the visible light wavelength is 380 nm or more and 780 nm or less and the visual sensitivity is a bell type with a peak around 550 nm, the film effectively transmits visible light and effectively absorbs other solar light. Can be reflected.

When the average dispersed particle size of the boride fine particles is 200 nm or less, geometric scattering or Mie scattering is reduced, and the boride fine particles become a Rayleigh scattering region. In the Rayleigh scattering region, since the scattered light is inversely proportional to the fourth power of the particle size, it is understood that a large amount of blue light having a short wavelength is scattered and discolored to bluish white.
Further, in the Rayleigh scattering region, since the scattered light is proportional to the sixth power of the particle size, the Rayleigh scattering can be reduced and the occurrence of blue haze can be suppressed by reducing the particle size. Subsequent studies have shown that blue haze is improved by reducing the average dispersed particle size to 85 nm or less.

From the above, the average dispersed particle size of the boride fine particles according to the present invention is preferably 100 nm or less, and more preferably 85 nm or less.
On the other hand, the lower limit of the average dispersed particles of the boride fine particles is not particularly limited, but is preferably 1 nm or more, for example. This is because industrial production is easy if the average dispersed particle size of the boride fine particles is 1 nm or more. The average dispersed particle size can be measured by a particle size measuring device based on a dynamic light scattering method.

Such boride fine particles may be produced by a known method.
For example, some are synthesized by a solid phase reaction method and then pulverized by a dry pulverization method. As the dry pulverization method, for example, there is a method of colliding particles with each other by a high-speed air flow such as a jet mill to pulverize the particles.
Further, after being synthesized by the solid phase reaction method, the synthesized boride fine particles are dispersed in a solvent to prepare a dispersion liquid, and then pulverized by a wet pulverization method using a wet medium mill such as a bead mill, a ball mill or a sand mill. You may.

(3) Tungsten oxide Generally, since there _{are no effective free electrons in tungsten oxide (WO 3} ), the absorption and reflection characteristics in the infrared region are small, and it is not effective as infrared absorption fine particles.
On the other hand, WO ₃ having an oxygen deficiency and composite tungsten oxide obtained by adding a positive element such as Na to WO _{3 are known to be conductive materials and materials having free electrons.} Analysis of single crystals and the like of materials having these free electrons suggests the response of free electrons to light in the infrared region.

The tungsten oxide according to the present invention is a tungsten oxide represented by the general formula WyOz (where W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999).
In the tungsten oxide represented by the general formula WyOz, the range of the composition of the tungsten and oxygen is that the composition ratio of oxygen to tungsten is less than 3, and further, when the tungsten oxide is described as WyOz, 2 It is preferable that .2 ≦ z / y ≦ 2.999. When the value of z / y is 2.2 or more, it is possible to avoid the appearance of a crystal phase of _{WO 2 other than the intended one in the tungsten oxide, and the chemical stability as a material.} Can be obtained, so that it becomes an effective infrared absorbing fine particle. On the other hand, when the value of z / y is 2.999 or less, a required amount of free electrons are generated to obtain efficient infrared absorbing fine particles.

(4) Composite Tungsten Oxide By adding the element M described later to the _{above-mentioned WO 3 to form a composite tungsten oxide, free electrons are generated in the WO 3} and are derived from free electrons especially in the near infrared region. It exhibits strong absorption characteristics and is effective as near-infrared absorbing fine particles with a wavelength of around 1000 nm.
That is, by using the control of the amount of oxygen and the amount of the element M that generates free electrons in combination with _{respect to the WO 3, more efficient infrared absorbing fine particles can be obtained.} The general formula of the composite tungsten oxide in which the control of the amount of oxygen and the addition of the element M for generating free electrons are used in combination is described as MxWyOz (where M is the M element, W is tungsten, and O is oxygen). When, a composite tungsten oxide satisfying the relationship of 0.01 ≦ x / y ≦ 1 and 2.0 ≦ z / y ≦ 3 is preferable.

First, the value of x / y indicating the amount of the element M added will be described.
When the value of x / y is larger than 0.001, a sufficient amount of free electrons are generated in the composite tungsten oxide, and the desired infrared absorption effect can be obtained. Then, as the amount of the element M added increases, the amount of free electrons supplied increases and the infrared absorption efficiency also increases, but the effect is saturated when the value of x / y is about 1. Further, when the value of x / y is smaller than 1, it is preferable because it is possible to avoid the formation of an impurity phase in the infrared absorbing fine particles.

The element M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au. , Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be , Hf, Os, Bi, I, Yb, preferably one or more.

Here, from the viewpoint of stability in the MxWyOz to which the element M is added, the element M is an alkali metal, an alkaline earth metal, a rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir. , Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti , Nb, V, Mo, Ta, Re, more preferably one or more elements selected from. From the viewpoint of improving the optical properties and weather resistance of the infrared absorbing fine particles, it is more preferable that the element M belongs to an alkaline earth metal element, a transition metal element, a group 4B element, and a group 5B element.

Next, the value of z / y indicating the control of the amount of oxygen will be described. Regarding the value of z / y, in addition to the same mechanism as the tungsten oxide represented by WyOz described above, the composite tungsten oxide represented by MxWyOz also has z / y = 3.0 and 2. Even in 0 ≦ z / y ≦ 2.2, there is a supply of free electrons depending on the amount of the element M added as described above. Therefore, 2.0 ≦ z / y ≦ 3.0 is preferable, 2.2 ≦ z / y ≦ 3.0 is more preferable, and 2.45 ≦ z / y ≦ 3.0 is more preferable.

Further, when the composite tungsten oxide has a hexagonal crystal structure, the transmission in the visible light region is improved and the absorption in the infrared region is improved. This will be described with reference to FIG. 1, which is a schematic plan view of the crystal structure of the hexagonal crystal.

In FIG. 1, _six octahedrons formed by WO 6 units indicated by reference numeral 11 are assembled to form a hexagonal void, and an element M indicated by reference numeral 12 is arranged in the void to form one. Units are formed, and a large number of these one units are assembled to form a hexagonal crystal structure.

Then, in order to obtain the effect of improving the transmission of light in the visible light region and improving the absorption of light in the infrared region, the composite tungsten oxide contains the unit structure described with reference to FIG. The composite tungsten oxide may be crystalline or amorphous.

When the cation of the element M is added to the hexagonal voids and exists, the transmission of light in the visible light region is improved and the absorption of light in the infrared region is improved. Here, in general, the hexagonal crystal is likely to be formed when the element M having a large ionic radius is added. Specifically, hexagonal crystals are likely to be formed when Cs, K, Rb, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn are added. Of course, elements other than these are not limited to the above-mentioned elements as long as the above-mentioned element M exists in the hexagonal voids formed by _{WO 6 units.}

When the composite tungsten oxide having a hexagonal crystal structure has a uniform crystal structure, the amount of the additive element M added is preferably 0.001 ≦ x / y ≦ 1 in terms of x / y, and 0.2 ≦. x / y ≦ 0.5 is more preferable, and 0.33 is more preferable. When the value of x / y is 0.33, it is considered that the above-mentioned element M is arranged in all the hexagonal voids.

In addition to hexagonal crystals, tetragonal and cubic composite tungsten oxides are also effective as infrared absorbing fine particles. The absorption position in the infrared region tends to change depending on the crystal structure, and the absorption position tends to move to the longer wavelength side in the order of cubic <tetragonal <hexagonal. Hexagonal, tetragonal, and cubic crystals absorb less in the visible light region. Therefore, it is preferable to use a hexagonal composite tungsten oxide for applications in which light in a more visible light region is transmitted and light in a more infrared region is absorbed. However, the tendency of the optical characteristics described here is only a rough tendency and changes depending on the type of added element, the amount of added element, and the amount of oxygen, and the present invention is not limited to this.

(5) Optical Characteristics of Tungsten Oxide Fine Particles and Composite Tungsten Oxide Fine Particles The infrared absorbing fine particles containing the tungsten oxide fine particles and the composite tungsten oxide fine particles according to the present invention emit light in the near infrared region, particularly in the vicinity of a wavelength of 1000 nm. Since it absorbs a large amount of light, the transmitted color tone often changes from bluish to greenish.

Further, the dispersed particle diameters of the tungsten oxide fine particles and the composite tungsten oxide fine particles in the infrared absorbing fine particles can be selected according to the purpose of use.
First, when used in an application in which transparency is desired to be maintained, it is preferable to have a particle size of 800 nm or less. This is because particles having a particle size smaller than 800 nm do not completely block light due to scattering, and can maintain visibility in the visible light region and at the same time efficiently maintain transparency. In particular, when the transparency in the visible light region is emphasized, it is preferable to further consider scattering by particles.

When the reduction of scattering by the particles is emphasized, the dispersed particle size is preferably 200 nm or less, preferably 100 nm or less. The reason for this is that if the dispersed particle size of the particles is small, the scattering of light in the visible light region having a wavelength of 400 nm to 780 nm due to geometric scattering or Mie scattering is reduced, and as a result, the infrared absorbing film becomes like frosted glass. It is possible to avoid the loss of clear transparency. That is, when the dispersed particle size is 200 nm or less, the geometrical scattering or Mie scattering is reduced, and a Rayleigh scattering region is formed. This is because in the Rayleigh scattering region, the scattered light is reduced in proportion to the sixth power of the particle size, so that the scattering is reduced and the transparency is improved as the dispersed particle size is reduced.

Further, when the dispersed particle size is 100 nm or less, the scattered light becomes very small, which is preferable. From the viewpoint of avoiding light scattering, it is preferable that the dispersed particle size is small, and if the dispersed particle size is 1 nm or more, industrial production is easy.

By setting the dispersed particle size to 800 nm or less, the haze value of the infrared absorbing fine particle dispersion in which the infrared absorbing fine particles according to the present invention are dispersed in a solvent is such that the visible light transmittance is 85% or less and the haze is 30% or less. be able to. If the haze is a value larger than 30%, it becomes like frosted glass and clear transparency cannot be obtained.
The dispersed particle size of the infrared absorbing fine particles can be measured by using ELS-8000 or the like manufactured by Otsuka Electronics Co., Ltd. based on the dynamic light scattering method.

Further, in the tungsten oxide fine particles, the so-called "magneti phase" having a composition ratio represented by 2.45 ≦ z / y ≦ 2.999 is chemically stable and has good absorption characteristics in the infrared region. Preferable as infrared absorbing fine particles.

Further, from the viewpoint of exhibiting excellent infrared absorption characteristics, the crystallite diameter of the infrared absorbing fine particles is preferably 1 nm or more and 200 nm or less, more preferably 1 nm or more and 100 nm or less, and further preferably 10 nm or more and 70 nm or less. For the measurement of the crystallite diameter, the measurement of the X-ray diffraction pattern by the powder X-ray diffraction method (θ-2θ method) and the analysis by the Rietveld method are used.
The crystallite diameter can be determined by Rietveld analysis based on the analysis result of XRD (X-ray diffraction method). Specifically, using a powder X-ray diffractometer "X'Pert-PRO / MPD" manufactured by Spectris Co., Ltd. PANalytical Co., Ltd., diffraction of infrared absorption appearing at a diffraction angle of 2θ = 10 ° to 120 ° at a Cu radiation source. The crystallite diameter can be obtained by performing Rietveld analysis based on the peak position.

[2] Raw material for core-shell fine particle forming agent In the present invention, a metal chelate compound is used as a raw material for a core-shell fine particle forming agent. That is, the total amount of the alkoxy group, the ether bond, and the ester bond in the metal chelate compound is hydrolyzed to become a hydroxyl group or a carboxyl group, a partially hydrolyzed partial hydrolysis product, or / and. The polymer self-condensed through the hydrolysis reaction is used as a core-shell fine particle forming agent, and the conductive fine particles which are the cores of the core-shell fine particles according to the present invention are coated as a shell.
That is, the hydrolysis product in the present invention is a concept including a partial hydrolysis product.

Further, in the present invention, a hydrate of a metal oxide can also be used as a raw material for a core-shell fine particle forming agent. The metal oxide preferably contains one or more metal elements selected from Al, Zr, Ti, Si and Zn. Specifically, for example, Al ₂ O ₃ · nH ₂ O (0 <n ≦ 3), ZrO ₂ · nH ₂ O (0 <n ≦ 2), TiO ₂ · nH ₂ O (0 <n ≦ 2). , SiO ₂ · nH ₂ O (0 <n ≦ 2), ZnO · nH ₂ O (0 <n ≦ 1). The hydrates of these metal oxides are also hydrolysis products of the above-mentioned metal chelate compounds.

The raw materials for the core-shell fine particle forming agent according to the present invention include (1) metal chelate compounds, (2) metal cyclic oligomers, (3) hydrolysis products and polymers of metal chelate compounds and metal cyclic oligomer compounds, and (4) metal oxidation. The items will be explained in this order.

(1) Metal Chelate Compound The metal chelate compound used as a raw material for the core-shell fine particle forming agent according to the present invention is one selected from Al-based, Zr-based, Ti-based, Si-based, and Zn-based chelate compounds containing an alkoxy group. It is preferable that there are two or more types.
From the viewpoint that the metal chelate compound is preferably a metal alkoxide, a metal acetylacetonate, or a metal carboxylate, it is preferable to have one or more selected from an ether bond, an ester bond, an alkoxy group, and an acetyl group.

Examples of the aluminum-based chelate compound include aluminum alcoholates such as aluminum ethylate, aluminum isopropyrate, aluminum sec-butyrate, and mono-sec-butoxyaluminum diisopropyrate, or polymers thereof, ethylacetacetate aluminum diisopropyrate, and aluminum tris. (Ethyl acetoacetate), octyl acetoacetate aluminum diisoproplate, stearyl aceto aluminum diisopropylate, aluminum monoacetyl acetonate bis (ethyl acetoacetate), aluminum tris (acetyl acetonate) and the like can be exemplified.
In these compounds, aluminum alcoholate is dissolved in an aproton solvent, a petroleum solvent, a hydrocarbon solvent, an ester solvent, a ketone solvent, an ether solvent, an amide solvent, etc., and β- It is an alkoxy group-containing aluminum chelate compound obtained by adding a diketone, β-ketoester, monovalent or polyhydric alcohol, fatty acid, etc., heating and refluxing, and performing a ligand substitution reaction.

Examples of zirconia-based chelating compounds include zirconium alkylates such as zirconium ethylate and zirconium butyrate or polymers thereof, zirconium tributoxystearate, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, and zirconium dibutoxybis (acetyl). Acetonate), zirconium tributoxyethyl acetoacetate, zirconium butoxyacetyl acetonate bis (ethyl acetoacetate) and the like can be exemplified.

Examples of titanium-based chelate compounds include titanium alcoholates such as methyl titanate, ethyl titanate, isopropyl titanate, butyl titanate, and 2-ethylhexyl titanate, and polymers thereof, titanium acetylacetonate, titanium tetraacetylacetonate, and titanium octylene glycolate. , Titanium Ethylacetacetate, Titanium Lactate, Titanium Triethanol Aminate, etc. can be exemplified.

As the silicon-based chelate compound, a tetrafunctional silane compound represented by the general formula: Si (OR) ₄ (where R is a monovalent hydrocarbon group having the same or different carbon atoms 1 to 6) or hydrolysis thereof. The product can be used. Specific examples of the tetrafunctional silane compound include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like.

Examples of zinc-based chelating compounds include organic carboxylic acid zinc salts such as zinc octylate, zinc laurate, and zinc stearate, acetylacetone zinc chelate, benzoylacetone zinc chelate, dibenzoylmethane zinc chelate, and acetoacetate ethylzinc chelate. It can be preferably exemplified.

(2) Metallic Cyclic Oligomer Compound The metal cyclic oligomer compound according to the present invention is preferably one or more selected from Al-based, Zr-based, Ti-based, Si-based, and Zn-based cyclic oligomer compounds. Among them, cyclic aluminum oligomer compounds such as cyclic aluminum oxide octylate can be preferably exemplified.

(3) Hydrolysis products and polymers of metal chelate compounds and metal cyclic oligomer compounds In the present invention, all of the alkoxy groups, ether bonds and ester bonds in the above-mentioned metal chelate compounds and metal cyclic oligomer compounds are hydrolyzed. Hydrolyzed products that have become hydroxyl groups or carboxyl groups, partially hydrolyzed partially hydrolyzed products, or / and self-condensed polymers that have undergone the hydrolysis reaction are used in the infrared absorbing fine particles according to the present invention. The surface is coated to form a coating film, and the surface-treated infrared absorbing fine particles according to the present invention are obtained.
That is, the hydrolysis product in the present invention is a concept including a partial hydrolysis product.

However, for example, in a reaction system in which an organic solvent such as alcohol is interposed, even if necessary and sufficient water is generally present in the system due to the chemical composition, the type and concentration of the organic solvent are generally present. As a result, not all of the alkoxy groups, ether bonds, and ester bonds of the starting metal chelate compound and metal cyclic oligomer compound are hydrolyzed. Therefore, depending on the conditions of the surface coating method described later, the amorphous state in which carbon C is incorporated into the molecule may be obtained even after hydrolysis.
As a result, the coating film may contain an undecomposed metal chelate compound and / and a metal cyclic oligomer compound, but there is no particular problem as long as the amount is small.

(4) Metal Oxide The metal oxide used as the raw material for the core-shell fine particle forming agent according to the present invention preferably contains one or more metal elements selected from Al, Zr, Ti, Si, and Zn. Specifically, for example, aluminum oxide, zirconium oxide, titanium oxide, silicon oxide, and zinc oxide are preferable.

[3] Method for Producing Core-Shell Fine Particles A method for producing core-shell fine particles according to the present invention will be described.
First, a hydrolysis product of a metal chelate compound or a metal cyclic oligomer compound is produced by adding a core-shell fine particle-forming agent raw material to a solvent containing water as a main component and proceeding with a hydrolysis reaction of the core-shell fine particle-forming agent raw material. , A core-shell fine particle-forming agent diluent containing at least one selected from a polymer of the hydrolysis product and a hydrate of a metal oxide is obtained. Further, the metal oxide obtained by heat-treating the hydrate of the metal oxide may be used as a raw material for the core-shell fine particle forming agent. In addition, a hydrate of a metal oxide or a metal oxide synthesized by a known method may be used as it is as a raw material for a core-shell fine particle forming agent.

On the other hand, the fine particle dispersion liquid is produced by dispersing the conductive fine particles described in "[1] Conductive fine particles" in a water-soluble solvent.

Then, the core-shell fine particle dispersion according to the present invention is produced by adding the core-shell fine particle-forming agent diluent to the produced fine particle dispersion and mixing and stirring the mixture.

The production of the core-shell fine particle dispersion liquid according to the present invention will be described in the order of (1) a method for producing a core-shell fine particle forming agent diluent, (2) a method for producing a fine particle dispersion, and (3) a method for producing a core-shell fine particle dispersion. ..

(1) Method for producing diluted solution of core-shell fine particle forming agent By adding a metal chelate compound or a metal cyclic oligomer compound as a raw material for a core-shell fine particle forming agent to a liquid solvent containing water as a main component, the hydrolysis reaction is promoted. Obtain a diluted solution of core-shell fine particle forming agent.
Here, the present inventors added the core-shell fine particle-forming agent raw material to the core-shell fine particle-forming agent while stirring and mixing the solvent containing water as a main component in the production of the core-shell fine particle-forming agent diluent. It was found that it is preferable to immediately complete the hydrolysis reaction of the fine particle forming agent raw material.

It is considered that this is due to the reaction sequence of the core-shell fine particle forming agent raw material added to the solvent containing water as a main component. That is, it is considered that this is because the hydrolysis reaction of the core-shell fine particle forming agent raw material always precedes in the solvent containing water as a main component, and then the polymerization reaction of the produced hydrolysis product occurs.
Based on the reaction sequence, the residual amount of carbon C derived from the core-shell fine particle-forming agent raw material, which is present in the core-shell fine particle-forming agent diluent, is reduced as compared with the case where a solvent containing no water as a main component is used. This is because it is thought that it can be done.

Then, it is considered that the conductive fine particles could be coated with a large amount of the core-shell fine particle forming agent by reducing the residual amount of carbon C derived from the core-shell fine particle forming agent raw material present in the core-shell fine particle forming agent diluent.

When the core-shell fine particle forming agent raw material is added dropwise to a liquid solvent containing water as a main component, the core-shell fine particle forming agent raw material itself is appropriately added in advance in order to adjust the amount of the core-shell fine particle forming agent raw material added per hour. It is also preferable to dilute with a solvent to prepare a diluted raw material, and then add the diluted raw material in a dropping form. As the solvent used for dilution, a solvent that does not react with the core-shell fine particle forming agent raw material or the solvent and has high compatibility with water is preferable. Specifically, alcohol-based, ketone-based, glycol-based solvents and the like can be preferably used.
The dilution ratio of the core-shell fine particle forming agent raw material is not particularly limited. However, from the viewpoint of ensuring productivity, the dilution ratio is preferably 100 times or less.

The optimum content of water in the core-shell fine particle forming agent diluent depends on the hydrolysis reaction rate of the core-shell fine particle forming agent raw material. In general, the higher the water content in the core-shell fine particle forming agent diluent is, the more preferable it is, and it is preferably 50 to 100 parts by weight with respect to 100 parts by weight of the entire solvent. Further, it is also preferable that the amount is 100 parts by weight or more with respect to 100 parts by weight of the core-shell fine particle forming agent raw material.

Further, it is preferable that the core-shell fine particle forming agent is dispersed in a fine particle state in the diluted solution of the core-shell fine particle forming agent. This is because when the core-shell fine particle forming agent is dispersed in the fine particle state, it is easy to coat the conductive fine particles as the core as a shell.

In the core-shell fine particle forming agent diluent, the added core-shell fine particle forming agent raw material may be decomposed into metal ions immediately after the start of addition. However, even in such a case, there is no particular problem because the decomposition to the metal ion is completed when the saturated aqueous solution of the core-shell fine particle forming agent is obtained.

Further, when the core-shell fine particle forming agent raw material is added to the liquid solvent containing water as a main component, the hydrolysis reaction rate of the core-shell fine particle forming agent raw material can be adjusted by heating the liquid medium. .. Further, the amount of hydrolysis of the obtained core-shell fine particle-forming agent changes depending on the water content in the core-shell fine particle-forming agent diluent and the heating state, but in any case, the partial hydrolysis product is produced by the hydrolysis reaction. A diluted solution of one or more core-shell fine particle forming agents selected from a hydrolysis product, a polymer of the hydrolysis product, and a hydrate of a metal oxide can be obtained.

Further, by heat-treating the hydrate of the metal oxide at a predetermined temperature or higher, an anhydrous metal oxide can be obtained, and the anhydrous metal oxide can be used as a core-shell fine particle forming agent.

(2) Method for Producing Fine Particle Dispersion Liquid In the fine particle dispersion liquid according to the present invention, one or more selected from hexaborates, tungsten oxides and composite tungsten oxides are finely pulverized in advance as conductive fine particles. It is preferable to disperse it in a water-soluble solvent to make it monodisperse. Then, in the pulverization and dispersion treatment steps, it is important to ensure the dispersed state and not to agglomerate the fine particles. This is to avoid a situation in which the fine particles agglomerate, the agglomerates remain even in the core-shell fine particle dispersion liquid described later, and the transparency of the infrared shielding film (core-shell fine particle dispersion) described later decreases. ..

As a result, by performing pulverization / dispersion treatment on the fine particle dispersion liquid according to the present invention, when the core-shell fine particle forming agent diluent according to the present invention is added, the core-shell fine particle forming agent is uniformly applied to the individual conductive fine particles. Can be coated on.

Specific methods for the pulverization / dispersion treatment for producing the conductive fine particles include a pulverization / dispersion treatment method using an apparatus such as a bead mill, a ball mill, a sand mill, a paint shaker, or an ultrasonic homogenizer. Among them, when pulverizing and dispersing with a medium stirring mill such as a bead mill, a ball mill, a sand mill, or a paint shaker using a medium medium such as beads, balls, or Ottawa sand, the conductive fine particles reach a desired dispersed particle size. It is preferable because the time to do is short.

As the water-soluble solvent, water, alcohol-based, ketone-based, glycol-based or the like can be preferably used.

(3) Method for Producing Core-Shell Fine Particle Dispersant The amount of the core-shell fine particle forming agent diluent described above is the value of parts by mass of the metal element contained in the core-shell fine particle forming agent diluent with respect to 100 parts by mass of the conductive fine particles. In the case of notation (in the present invention, it may be described as "(metal element equivalent amount)"), it is preferably 0.1 part by mass or more and 1000 parts by mass or less. More preferably, it is in the range of 1 part by mass or more and 500 parts by mass or less (metal element equivalent amount). More preferably, it is in the range of 10 parts by mass or more and 150 parts by mass or less (metal element equivalent amount).

This means that if the amount of the core-shell fine particle forming agent diluent is 0.1 parts by mass or more (metal element equivalent amount) with respect to 100 parts by mass of the conductive fine particles, the hydrolysis products of those compounds and the hydrolysis products thereof. This is because the polymer of the above exhibits the effect of coating the conductive fine particles, and the effect of improving the moisture and heat resistance can be obtained.

Further, if the diluted solution of the core-shell fine particle forming agent is 1000 parts by mass or less (metal element equivalent amount) with respect to 100 parts by mass of the conductive fine particles, the improvement in moisture and heat resistance due to the coating of the conductive fine particles is not saturated. This is because the addition effect can be expected to be improved.
Further, when the amount of the core-shell fine particle forming agent diluent is 1000 parts by mass or less (metal element equivalent amount) with respect to 100 parts by mass of the conductive fine particles, the amount added to the conductive fine particles becomes excessive, and the core shell is added when the solvent is removed. This is because it is possible to prevent the fine particles from being easily granulated through the fine particle forming agent. Good transparency can be ensured by avoiding granulation of the unwanted fine particles.
In addition, it is possible to avoid an increase in raw material cost due to an excess of the core-shell fine particle forming agent and an increase in production cost due to an increase in processing time. Therefore, from an industrial point of view, the amount of the core-shell fine particle forming agent diluted solution added is preferably 1000 parts by mass or less (metal element equivalent amount) with respect to 100 parts by mass of the conductive fine particles.

While stirring the above-mentioned fine particle dispersion, the core-shell fine particle-forming agent diluent is added, for example, by dropping, and the mixture is mixed and stirred to obtain a core-shell fine particle-forming agent-containing core-shell fine particle dispersion. At this time, a stirring device capable of mixing and stirring so that the core-shell fine particle forming agent is uniformly present in the core-shell fine particle-forming agent containing the core-shell fine particle forming agent is used. For example, a stirrer having a shearing force with blades is preferable, but the present invention is not particularly limited.

[4] Powder Containing Core-Shell Fine Particles The core-shell fine particle-forming agent obtained by the above-mentioned mixing and stirring is dried to remove the liquid solvent, and the core-shell fine particle-forming agent becomes conductive. A powder containing core-shell fine particles according to the present invention, which is coated with fine particles, is obtained.

The mechanism by which the core-shell fine particle forming agent coated with the conductive fine particles improves the water resistance and moist heat resistance of the conductive fine particles has not yet been elucidated. The present inventors presume that the core-shell fine particle forming agent changes the electrostatic potential around the core-shell fine particle forming agent to form a field in which the deterioration reaction of the conductive fine particles does not occur.

Here, during the drying treatment, care should be taken so that the drying treatment temperature does not exceed the temperature at which the powder containing the core-shell fine particles strongly aggregates to form a strong agglomerate. Therefore, it is preferable to dry the core-shell fine particle dispersion by, for example, vacuum flow drying or spray drying at around room temperature to obtain a powder containing the core-shell fine particles according to the present invention.

This is because, in the conductive fine particle dispersion and the infrared absorbing base material to be finally used, transparency is required in many cases due to their use. If an infrared shielding film (core-shell fine particle dispersion) or an infrared-absorbing base material is produced using a powder containing strongly aggregated core-shell fine particles as an infrared-absorbing material, a material having a high degree of haze can be obtained. It will end up.

Therefore, when the powder containing the core-shell fine particles is heat-treated at a temperature exceeding the temperature at which the strong aggregates are formed, in order to ensure the transparency of the infrared shielding film (core-shell fine particle dispersion) and the infrared absorbing base material, The powder containing the strongly aggregated core-shell fine particles will be crushed and redispersed in a dry or / or wet manner. However, when the powder containing the strongly aggregated core-shell fine particles is crushed and redispersed, it becomes difficult for the core-shell fine particle forming agent to coat the conductive fine particles, so that desired water resistance and moisture heat resistance cannot be obtained. In some cases.

On the other hand, in the treatment by vacuum flow drying, the powder containing the core-shell fine particles is dried and crushed at the same time in a reduced pressure atmosphere. Therefore, the drying speed is high and aggregation can be avoided. Further, since the solvent is dried under a reduced pressure atmosphere, the solvent can be removed even at a relatively low temperature, and the amount of residual solvent can be reduced as much as possible. Further, in the treatment by spray drying, secondary agglutination of powder containing core-shell fine particles due to the surface force of the solvent is unlikely to occur, and the core shell contains core-shell fine particles that are relatively non-secondary agglutinated even without crushing treatment. Fine particle powder is obtained.

2. Core-shell fine particle dispersion and its production method The core-shell fine particle dispersion according to the present invention is for producing an infrared shielding film described later, and the surface of the conductive fine particles which is the core is a hydrolysis product of a metal chelate compound or the like. It contains core-shell fine particles coated as a shell, a phosphonic acid derivative or the like as a sequence control agent, and a solvent.
Then, when an infrared shielding film is formed using the core-shell fine particle dispersion liquid, the core-shell fine particles are arranged two-dimensionally, and the distance between the core-shell fine particles in the two-dimensional arrangement can be controlled to 0.5 nm or more and 10 nm or less. can. However, the distance between the core-shell fine particles is the shortest distance between the surfaces of the core-shell fine particles.

The core-shell fine particle dispersion liquid according to the present invention can be produced by dispersing the core-shell fine particle powder, the sequence control agent, and the solvent using a paint shaker or the like. The core-shell fine particle dispersion liquid will be described in the order of (1) sequence control agent, (2) solvent, (3) dispersant, and (4) method for producing a dispersion liquid for forming an infrared shielding film.

(1) Sequence Control Agent The sequence control agent exerts an effect of controlling the interval between the core-shell fine particles arranged two-dimensionally to a predetermined value at the time of manufacturing the infrared shielding film.
A phosphonic acid derivative can be preferably used as the sequence control agent according to the present invention. By adding a phosphonic acid derivative as a sequence control agent, the distance between the core-shell fine particles in the two-dimensional arrangement can be controlled to 0.5 nm or more and 10 nm or less.

Then, it was found that when the core-shell fine particles were two-dimensionally arranged at intervals of 0.5 nm or more and 10 nm or less, the localized surface plasmon resonance was further enhanced in the gaps between the core-shell fine particles, and an extremely strong light reflection / absorption response was exhibited. Further, since the reflection response of the light is also remarkably strengthened, heat generation due to infrared absorption in the infrared shielding film according to the present invention is suppressed, and as a result, thermal deterioration of conductive fine particles having an infrared shielding function is suppressed. can do.

The concentration of the sequence control agent in the core-shell fine particle dispersion is not particularly limited. The intervals between the two are more than 10 nm, and none of them obtain the desired reflection absorption response, especially the desired reflection response. Therefore, the concentration of the sequence control agent is preferably 10 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the core-shell fine particles.

Examples of the phosphonic acid derivative include 1-alkylphosphonic acid, hexylphosphonic acid, 2-ethylhexylphosphonic acid, octylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, tetradecylphosphonic acid, hexadecylphosphonic acid, and 16-methylhepta. Examples thereof include decylphosphonic acid, octadecylphosphonic acid, eicosylphosphonic acid, docosylphosphonic acid, tetracosylphosphonic acid, hexacosylphosphonic acid, octacosylphosphonic acid and the like. Further, those having the terminal of the above-mentioned phosphonic acid derivative having an amino group, a carboxyl group, a perfluoroalkyl group, a hydroxy group, an alkoxide group, or the like can also be used.

(2) Solvent The solvent in the core-shell fine particle dispersion may be any solvent that dissolves the sequence control agent.
When the sequence control agent is a phosphonic acid derivative, for example, n-hexane, diethyl ether, tetrahydrofuran, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, benzene, toluene, xylene, acetone, methanol, ethanol, ethoxyethanol. 2, 2-propanol, water and the like are preferably mentioned.

(3) Dispersant A dispersant may be added to the dispersion liquid for forming an infrared shielding film in order to further improve the dispersion stability of the core-shell fine particles. The dispersant can be selected according to the intended use, but preferably has an amine-containing group, a hydroxyl group, a carboxyl group, a sulfo group, or an epoxy group as a functional group. A polymer-based dispersant having any of these functional groups in the molecule is more preferable.

Further, an acrylic-styrene copolymer system dispersant having a functional group is also mentioned as a preferable dispersant. Among them, an acrylic-styrene copolymer system dispersant having a carboxyl group as a functional group and an acrylic dispersant having an amine-containing group as a functional group are more preferable examples. The dispersant having a group containing an amine as a functional group preferably has a molecular weight of Mw 2000 to 200,000 and an amine value of 5 to 100 mgKOH / g. The dispersant having a carboxyl group preferably has a molecular weight of Mw 2000 to 200,000 and an acid value of 1 to 50 mgKOH / g.

Preferred specific examples of commercially available dispersants include SOLPERSE® (registered trademark) manufactured by Japan Lubrizol Co., Ltd. (the same applies hereinafter) 3000, 5000, 9000, 11200, 12000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000. , 21000, 24000SC, 24000GR, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 32600, 33000, 33500, 34750, 35100, 35200, 36600, 37500, 38500, 39000, 41000, 41090, 53095, 55000, 56000 , 71000, 76500, J180, J200, M387, etc .; SOLPLUS (registered trademark) (same below) D510, D520, D530, D540, DP310, K500, L300, L400, R700, etc .; Disperbyk (registered trademark) manufactured by Big Chemie Japan. (The same applies hereinafter) -101, 102, 103, 106, 107, 108, 109, 110, 111, 112, 116, 130, 140, 142, 145, 154, 161, 162, 163, 164, 165, 166, 167. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 191, 192, 2000, 2001, 2009, 2020, 2025, 2050, 2070, 2095, 2096, 2150, 2151, 2152 , 2155, 2163, 2164, Anti-Terra® (same below) -U, 203, 204, etc .; BYK® (same below) -P104, P104S, P105, P9050, P9051, P9060, P9065, P9080, 051, 052, 053, 054, 055, 057, 063, 065, 066N, 067A, 077, 088, 141, 220S, 300, 302, 306, 307, 310, 315, 320, 322, 323, 325, 330, 331, 333, 337, 340, 345, 346, 347, 348, 350, 354, 355, 358N, 361N, 370, 375, 377, 378, 380N, 381, 392, 410, 425, 430, 1752, 4510, 6919, 9076, 9077, W909, W935, W940, W961, W966, W969, W972, W980, W985, W995, W996, W9010, Dynawet800, Silkean3700, UV3500, UV3510, UV3570, etc .; 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4310, 4320, 4330, 4340, 4400, 4401, 4402, 4403, 4500, 5066, 5220, 6220, 6225, 6230, 6700, 6780, 6782, 7462, 8503 etc.; BASF Japan JONCRYL® (registered trademark) (same below) 67, 678, 586, 611, 680, 682, 690, 819, -JDX5050, etc .; , D1180, D 1130, etc .; Ajinomoto Fine Techno Co., Ltd. Ajispar (registered trademark) (same below) PB-711, PB-821, PB-822, etc .; , 1850, 1860, 1934, DA-400N, DA-703-50, DA-325, DA-375, DA-550, DA-705, DA-725, DA-1401, DA-7301, DN-900, NS -5210, NVI-8514L, etc .; Alfon (registered trademark) manufactured by Toa Synthetic Co., Ltd. (same below) UH-2170, UC-3000, UC-3910, UC-3920, UF-5022, UG-4010, UG-4035, UG -4040, UG-4070, Rezeda (registered trademark) (same below) GS-1015, GP-301, GP-301S, etc .; Mitsubishi Chemical Co., Ltd. Dianal (registered trademark) (same below) BR-50, BR-52 , BR-60, BR-73, BR-80, BR-83, BR-85, BR-87, BR-88, BR-90, BR-96, BR-102, BR-113, BR-116, etc. Can be mentioned.

(4) Manufacturing method of dispersion liquid for forming infrared shielding film,
The dispersion liquid for forming an infrared shielding film is, for example, a medium stirring mill such as a bead mill, a ball mill, a sand mill, a paint shaker or the like using a medium medium as a raw material (conductive fine particles, an arrangement control agent and a solvent) of the dispersion liquid for forming an infrared shielding film. It can be manufactured by dispersion treatment.

Then, in the pulverization / dispersion treatment using the medium stirring mill, at the same time as the dispersion treatment of the conductive fine particles, the particles are made into fine particles due to collisions between the conductive fine particles and collisions of the medium media with the fine particles, so that the conductive fine particles are produced. It can be made into finer particles and dispersed. Further, the dispersion liquid for forming an infrared shielding film preferably has an average dispersed particle size of 1 nm or more and 800 nm or less of the conductive fine particles contained therein, but is desired by a pulverization / dispersion treatment using a medium stirring mill. The time to reach the particle size may be short. Therefore, it is preferable to produce a dispersion liquid for an infrared shielding film using a medium stirring mill.

3. 3. Infrared shielding film and its manufacturing method In the infrared shielding film according to the present invention, core-shell fine particles are arranged two-dimensionally, and in the two-dimensional arrangement of the core-shell fine particles, the distance between them is 0.5 nm or more and 10 nm or less, and light having a wavelength of 1300 nm. The absorption coefficient per unit weight is 5 L / (g · cm) or more.

In order to produce the infrared shielding film according to the present invention, the above-mentioned core-shell fine particle dispersion liquid may be applied to the surface of an appropriate base material, and a dispersion film of core-shell fine particles may be formed therein to form an infrared shielding film. That is, the infrared shielding film is a kind of core-shell fine particle dispersion, and is also a kind of dry solidified liquid of core-shell fine particle dispersion.
The method for forming the infrared shielding film in which the core-shell fine particles are two-dimensionally arranged is not particularly limited, and examples thereof include a wet method such as a spin coating method, a dipping method, and a Langmuir-projet method (LB method).

The material of the base material described above is not particularly limited as long as it is a transparent material, and examples thereof include a glass substrate and a resin substrate.
The form of the resin substrate may be a resin board, a resin sheet, a resin film, or the like, and the resin used is not particularly limited as long as it does not cause any problems in the surface condition or durability of the required board, sheet, or film. .. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, polycarbonate polymers, acrylic polymers such as polymethyl methacrylate, and styrene such as polystyrene and acrylonitrile / styrene copolymers. Polymers, polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, olefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as aromatic polyamides, imide polymers, sulfone polymers, poly Ethersulfone polymers, polyether ether ketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, allylate polymers, polyoxymethylene polymers, epoxy polymers, and more. Examples thereof include boards, sheets and films made of transparent polymers such as binary and ternary various copolymers, graft copolymers and blends. In particular, polyester-based biaxially oriented films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate are preferable in terms of mechanical properties, optical properties, heat resistance, and economic efficiency. The polyester-based biaxially oriented film may be a copolymerized polyester-based film.

The transparent substrate used in the present invention may be subjected to surface treatment or provided with a simple adhesive layer in order to ensure the wettability and adhesiveness of the core-shell fine particle dispersion liquid. Known techniques can be used for the surface treatment and the simple adhesive layer. For example, examples of the surface treatment include surface activation treatments such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.

Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to the following examples.
The crystallite diameter of the fine particles in the dispersion liquid in Examples and Comparative Examples was determined by a powder X-ray diffraction method (θ-2θ method) using a powder X-ray diffractometer (X'Pert-PRO / MPD manufactured by Spectris Co., Ltd. PANalytical). And calculated using the Rietveld method.
The optical characteristics of the fine particle dispersion and the infrared shielding film were measured using a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.). Of these, the dispersion is diluted with a solvent so that the visible light transmittance is 80% in a glass cell for measurement of a spectrophotometer, and then the light transmittance in the wavelength range of 200 nm to 2600 nm is set at intervals of 5 nm. Measured at. The extinction coefficient was first _{calculated by the formula of A = -log 10} (T / 100) (A: absorbance, T: transmittance), and further calculated by Lambert Vale's law. That is, the extinction coefficient includes both the absorption component and the reflection component. The optical characteristic values (transmittance, reflectance) of the infrared shielding film are values including the optical characteristic values of soda lime glass as a base material.

[Example 1]
1 g of tungsten hexachloride was dissolved in 31 mL of ethanol, 5 mL of a 25 wt% aqueous ammonia solution was added, and the mixture was stirred at room temperature for 15 minutes. Then, it was placed in a flask and refluxed at 100 ° C. for 3.5 hours to synthesize _{(NH 4} ) _x WO _3-y. After removing the solvent and drying at 80 ° C. for 24 hours, the obtained (NH ₄ ) _x WO _3-y was added to ethanol together with 0.425 g of cesium chloride, the solvent was removed again, and 24 at 80 ° C. Allowed to dry for hours. The obtained dry solid material was heat-treated at 450 ° C. for 2 hours in an Ar atmosphere to obtain Cs _0.33 WO _3-x fine particles according to Example 1. The crystallite diameter of Cs _0.33 WO _3-x was measured and found to be 30 nm.

The mixed solution obtained by mixing 0.2% by mass of the obtained Cs _0.33 WO _3-x fine particles and 99.8% by mass of pure water was loaded into a paint shaker containing _{0.3 mmφZrO 2 beads.} The dispersion treatment was carried out for 10 minutes to obtain a fine particle dispersion liquid A.

On the other hand, 0.25% by mass of aluminum ethylacetate acetate diisopropylate and 99.75% by mass of isopropyl alcohol (IPA) were mixed as an aluminum-based chelate compound to obtain a core-shell fine particle-forming agent diluent a.

89 g of the obtained fine particle dispersion liquid A was placed in a beaker, and 36 g of the core-shell fine particle forming agent diluent a was added dropwise thereto over 3 hours while vigorously stirring with a stirrer equipped with blades. After the dropwise addition of the core-shell fine particle forming agent diluent a, the core-shell fine particle dispersion liquid according to Example 1 was further stirred at a temperature of 20 ° C. for 24 hours.

Next, using vacuum flow drying, a drying treatment was performed at a temperature of 70 ° C. for 1 hour, and the medium was evaporated from the core-shell fine particle dispersion liquid. Then, it was heat-treated at 200 ° C. for 1 hour in an Ar atmosphere to obtain a powder containing core-shell fine particles of the _{Cs 0.33} WO _{3-x / Al compound according to Example 1.}

0.2 g of the core-shell fine particle powder of the obtained Cs _0.33 WO _3-x / Al compound, 0.02 g of n-octadecylphosphonic acid and 19.78 g of toluene were mixed, and the obtained mixed solution was 0.3 mmφZrO ₂ The mixture was placed in a bottle together with the beads and subjected to dispersion treatment for 10 minutes with a paint shaker to obtain a core-shell fine particle dispersion liquid according to Example 1, which contained core-shell fine particles of _{a Cs 0.33} WO _{3-x / Al compound and an sequence control agent.} .. The dispersed particle size of the core-shell fine particles was 110 nm. The values are shown in Table 1.

When the optical characteristics of the core-shell fine particle dispersion liquid according to Example 1 were measured and the absorption coefficient per unit weight was calculated, the absorption coefficient per unit weight for light having a wavelength of 1300 nm was 6.22 L / (g · cm). rice field. The values are shown in Table 1.

Subsequently, a Langmuir film of core-shell fine particles of _{Cs 0.33} WO _3-x / Al compound was produced on a glass substrate using an LB film producing apparatus. First, soda lime glass having a thickness of 3 mm, which had been hydrophilized with atmospheric pressure plasma, was immersed perpendicular to the liquid surface. Next, 0.2 g of the core-shell fine particle dispersion liquid according to Example 1 was floated on pure water placed in the LB film preparation apparatus, and toluene was evaporated to distribute Cs _0.33 WO _3-x / Al in an island shape. A Langmuir film of the core-shell fine particles of the compound was prepared. Further, an island-shaped Langmuir film was collected using a compression rod to obtain a Langmuir film in which fine particles were two-dimensionally arranged in a range of 20 mm × 40 mm. Then, the soda lime glass soaked was gradually lifted, the Langmuir film was transferred onto the glass, and air-dried to obtain an infrared shielding film according to Example 1. At this time, the liquid temperature and the atmospheric temperature were 25 ° C.

When the light transmittance of the infrared shielding film according to Example 1 was measured, it was 86% at a wavelength of 500 nm, 55% at a wavelength of 900 nm, and 44% at a wavelength of 1300 nm. Moreover, when the reflectance of light was measured, it was 14% at a wavelength of 900 nm and 30% at a wavelength of 1300 nm. The values are shown in Table 2.

[Comparative Example 1]
0.2 g of ITO fine particles (trade name: UFP-HX, manufactured by Sumitomo Metal Mining Co., Ltd.) having a tin content of 4.4% by weight and an average particle size of 0.03 μm, 0.02 g of n-octadecylphosphonic acid, and 19.78 g of toluene. Was mixed, and the obtained mixed solution _{was placed in a bottle together with 0.3 mmφZrO 2} beads and subjected to dispersion treatment for 10 minutes with a paint shaker to obtain an ITO fine particle dispersion according to Comparative Example 1. The dispersed particle size of the ITO fine particles was 90 nm. The values are shown in Table 1.

When the optical characteristics of the ITO fine particle dispersion liquid according to Comparative Example 1 were measured and calculated per unit weight, the extinction coefficient per unit weight for light having a wavelength of 1300 nm was 2.39 L / (g · cm). The values are shown in Table 1.

The infrared shielding film according to Comparative Example 1 in the same manner as in Example 1 except that the ITO fine particle dispersion according to Comparative Example 1 was used instead of the _{Cs 0.33} WO _{3-x fine particle dispersion according to Example 1.} Was produced. The light transmittance was 91% at a wavelength of 500 nm, 84% at a wavelength of 900 nm, and 42% at a wavelength of 1300 nm. Moreover, when the reflectance of light was measured, it was 2% at a wavelength of 900 nm and 9% at a wavelength of 1300 nm. The values are shown in Table 2.

[Comparative Example 2]
9.28 g of an aqueous solution of ammonium metatungstate (0.02 mol / 9.28 g) and an aqueous solution of cesium chloride (CsCl) (an aqueous solution of 1.11 g of cesium chloride dissolved in 80 g of water) have an atomic ratio of W and Cs of Cs /. The mixture was mixed so that W = 0.33, and the surfactant DOWNSIL FZ-2105 (manufactured by Dow Toray Co., Ltd.) was added so as to be 0.002% by mass of the whole solution to prepare a solution for film formation. Then, the film-forming solution was dip-coated on one side of a soda lime glass having a thickness of 3 mm, air-dried, and then heat-treated at 550 ° C. for 10 minutes under a supply of 0.6% by volume H _{2 gas using N 2 gas as a carrier.} Then, the infrared shielding film according to Comparative Example 2 was obtained.

When the transmittance of the infrared shielding film according to Comparative Example 2 was measured, the transmittance of light was 84% at a wavelength of 500 nm, 57% at a wavelength of 900 nm, and 43% at a wavelength of 1300 nm. Moreover, when the reflectance of light was measured, it was 8% at a wavelength of 900 nm and 19% at a wavelength of 1300 nm. The values are shown in Table 2.

Claims (14)

Select from hydrolysis products of metal chelate compounds, polymers of hydrolysis products of metal chelate compounds, hydrolysis products of metal cyclic oligomer compounds, polymers of hydrolysis products of metal cyclic oligomer compounds, metal oxides. Core-shell fine particles, which are conductive fine particles whose surfaces are coated with one or more of the following compounds, are arranged in two dimensions.
An infrared shielding film having an extinction coefficient per unit weight of the core-shell fine particles with respect to light having a wavelength of 1300 nm of 5 L / (g · cm) or more. The infrared shielding film according to claim 1, wherein the distance between the core-shell fine particles in the two-dimensional arrangement is 0.5 nm or more and 10 nm or less.
However, the distance between the core-shell fine particles is the shortest distance between the surfaces of the core-shell fine particles. The infrared shielding according to claim 1 or 2, wherein the metal chelate compound and / and the metal cyclic oligomer compound contain one or more kinds of metal elements selected from Al, Zr, Ti, Si, and Zn. film. The invention according to any one of claims 1 to 3, wherein the metal chelate compound and / and the metal cyclic oligomer compound have one or more selected from an ether bond, an ester bond, an alkoxy group, and an acetyl group. Infrared shielding film. The conductive fine particles are derived from the general formula XB _m (where X is from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr, Ca. One or more kinds of metal elements to be selected, m is a number indicating the amount of boron in the general formula), general formula WyOz (where W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), general formula M _x W _y O _z (However, M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt. , Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo , Ta, Re, Be, Hf, Os, Bi, I, Yb, one or more elements, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.0 ≦ The infrared shielding film according to any one of claims 1 to 4, wherein the infrared shielding film is one or more of the conductive fine particles represented by z / y ≦ 3.0). The infrared shielding film according to claim 5, wherein the X element of the general formula XB _{m is La.} The element M of the general formula _M x _W y _{O z} is, Cs, Rb, K, infrared shielding film according to claim 5, characterized in that at least one selected from Na. Select from hydrolysis products of metal chelate compounds, polymers of hydrolysis products of metal chelate compounds, hydrolysis products of metal cyclic oligomer compounds, polymers of hydrolysis products of metal cyclic oligomer compounds, metal oxides. Core-shell fine particles, which are conductive fine particles whose surfaces are coated with one or more of them,
A core-shell fine particle dispersion containing a sequence control agent.
When the core-shell fine particle dispersion liquid is applied to the surface of an appropriate base material to form a dispersion film, the core-shell fine particles are arranged two-dimensionally to form an infrared shielding film.
A core-shell fine particle dispersion having an extinction coefficient per unit weight of the core-shell fine particles of 5 L / (g · cm) or more with respect to light having a wavelength of 1300 nm in the infrared shielding film. The core-shell fine particle dispersion liquid according to claim 8, wherein the distance between the core-shell fine particles in the two-dimensional arrangement is 0.5 nm or more and 10 nm or less.
However, the distance between the core-shell fine particles is the shortest distance between the surfaces of the core-shell fine particles. The core-shell fine particle dispersion according to claim 8 or 9, wherein the metal chelate compound or the metal cyclic oligomer compound contains one or more metal elements selected from Al, Zr, Ti, Si, and Zn. .. The core-shell fine particle according to any one of claims 8 to 10, wherein the metal chelate compound or the metal cyclic oligomer compound has at least one selected from an ether bond, an ester bond, an alkoxy group, and an acetyl group. Dispersion solution. The conductive fine particles are derived from the general formula XB _m (where X is from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr, Ca. One or more metal elements to be selected, m is a number indicating the amount of boron in the general formula), or / and the general formula WyOz (where W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999). ) Or / and the general formula M _x W _{y Oz} (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh. , Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te , Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, Yb, one or more elements, W is tungsten, O is oxygen, 0.001 ≦ x / The core-shell fine particle dispersion liquid according to any one of claims 8 to 11, wherein the conductive fine particles are represented by y ≦ 1, 2.0 ≦ z / y ≦ 3.0). The core-shell fine particle dispersion liquid according to claim 12, wherein the X element of the general formula XB _{m is La.} Core-shell fine particle dispersion according to claim 12, the element M of the general formula _M x _W y _{O z} is Cs, Rb, K, and characterized in that one or more of Na.

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