WO2019093526A1

WO2019093526A1 - Infrared-absorbing fine particle dispersion, infrared-absorbing fine particle dispersoid, and methods for producing these

Info

Publication number: WO2019093526A1
Application number: PCT/JP2018/042029
Authority: WO
Inventors: 裕史常松; 長南　武; 英昭福山; 貢尚川野
Original assignee: 住友金属鉱山株式会社
Priority date: 2017-11-13
Filing date: 2018-11-13
Publication date: 2019-05-16
Also published as: JPWO2019093526A1; TW201922951A; JP6769563B2; TWI771524B

Abstract

Provided are an infrared-absorbing fine particle dispersion and an infrared-absorbing fine particle dispersoid having exceptional moist heat resistance and heat resistance as well as exceptional infrared absorption characteristics. Provided is an infrared-absorbing fine particle dispersion containing a liquid medium, surface-treated infrared-absorbing fine particles dispersed in the medium, and a phosphite ester compound, wherein the infrared-absorbing fine particle dispersion is characterized in that: the surface of the surface-treated infrared-absorbing fine particles is coated by a coating film containing a hydrolysis product, etc., of a metal chelate compound; and the amount of phosphite ester compound added is more than 500 parts by mass and no more than 50,000 parts by mass per 100 parts by mass of the infrared-absorbing fine particles.

Description

Infrared absorbing fine particle dispersion, infrared absorbing fine particle dispersion, and method for producing them

The present invention relates to an infrared-absorbing fine particle dispersion, an infrared-absorbing fine particle dispersion, which transmits light in the visible light region and absorbs light in the infrared light region, and a method for producing them.

In recent years, the demand for infrared absorbers has been rapidly increasing, and many patents related to infrared absorbers have been proposed. If these proposals are examined from a functional point of view, for example, in the field of window materials of various buildings and vehicles, light in the near infrared region is shielded while sufficiently incorporating visible light, and the room is maintained while maintaining the brightness. For the purpose of suppressing the temperature rise of the infrared rays emitted forward from the PDP (Plasma Display Panel), the remote control of the cordless phone or the home appliance may cause a malfunction or adversely affect the transmission optical communication. There are things etc. which aimed at preventing doing.

Further, from the viewpoint of the light shielding member, for example, as a light shielding member used for a window material etc., inorganic pigments such as carbon black and titanium black having absorption characteristics from visible light region to near infrared region, and only visible light region Further, a light shielding film containing a black pigment containing an organic pigment such as aniline black having strong absorption characteristics, and a half mirror type light shielding member on which a metal such as aluminum is vapor-deposited are proposed.

For example, in Patent Document 1, at least one selected from the group consisting of a group IIIa, a group IVa, a group Vb, a group VIb and a group VIIb of the periodic table as a first layer on the transparent glass substrate from the substrate side. A composite tungsten oxide film containing metal ions is provided, a transparent dielectric film is provided as a second layer on the first layer, and a group IIIa, IVa, Vb of the periodic table is provided on the second layer as a third layer. A composite tungsten oxide film containing at least one metal ion selected from the group consisting of group VIb and group VIIb, and the refractive index of the transparent dielectric film of the second layer being the first layer and the first layer By lowering the refractive index of the composite tungsten oxide film of the third layer, it is possible to preferably use an infrared ray shielding material which can be suitably used in a portion where high visible light transmittance and good infrared ray shielding performance are required. Vinegar has been proposed.

Further, in Patent Document 2, a first dielectric film is provided as a first layer on a transparent glass substrate from the substrate side by the same method as Patent Document 1, and tungsten oxide is provided as a second layer on the first layer. An infrared blocking glass has been proposed in which a film is provided and a second dielectric film is provided as a third layer on the second layer.

In Patent Document 3, a composite tungsten oxide film containing the same metal element as in Patent Document 1 is provided as a first layer from the substrate side on a transparent substrate by the same method as in Patent Document 1, and the first layer A heat ray blocking glass having a transparent dielectric film provided thereon as a second layer has been proposed.

Further, in Patent Document 4, tungsten trioxide (WO ₃ ), molybdenum trioxide (MoO ₃ ), niobium pentoxide (Nb ₂ O ₅ ), tantalum pentoxide containing an additive element such as hydrogen, lithium, sodium or potassium, etc. A metal oxide film selected from one or more of (Ta ₂ O ₅ ), vanadium pentoxide (V ₂ O ₅ ) and vanadium dioxide (VO ₂ ) is coated by a CVD method or a spray method and is thermally heated at about 250 ° C. A solar control glass sheet having a solar light shielding property formed by being decomposed has been proposed.

Further, Patent Document 5 proposes a solar light-modulating light insulation material using tungsten oxide obtained by hydrolyzing tungstic acid, and adding an organic polymer having a specific structure of polyvinyl pyrrolidone to the tungsten oxide. ing. When the solar light is irradiated with sunlight, the ultraviolet light in the light is absorbed by tungsten oxide to generate excited electrons and holes, and the amount of appearance of pentavalent tungsten is remarkable with a small amount of ultraviolet light. The color reaction is accelerated to increase, and the color density increases accordingly. On the other hand, by blocking the light, pentavalent tungsten is extremely rapidly oxidized to hexavalent to accelerate the decoloring reaction. Using the coloration / decoloring property, the coloration and decoloring reaction to sunlight is fast, an absorption peak appears at a wavelength of 1250 nm in the near-infrared region at the time of coloring, and it is possible to block the near-infrared light of sunlight It has been proposed that a thermal insulation material be obtained.

On the other hand, in Patent Document 6, the present inventors dissolve tungsten hexachloride in alcohol and evaporate the medium as it is or heat it to reflux, then evaporate the medium and then heat it at 100 ° C to 500 ° C. It has been disclosed to obtain a tungsten oxide fine particle powder comprising tungsten trioxide or its hydrate or a mixture of both. The present inventors have also disclosed that an electrochromic device can be obtained by using the tungsten oxide fine particles, that the optical characteristics of the film can be changed when a multilayer laminate is formed and protons are introduced into the film.

Further, Patent Document 7 uses ammonium meta-tungstate and various water-soluble metal salts as raw materials, heats the dried product of the mixed aqueous solution at a heating temperature of about 300 to 700 ° C., and is inactive to this heating MxWO ₃ (M; metal element such as alkali, alkaline earth, rare earth, etc.) by supplying hydrogen gas added with gas (additional amount: about 50 vol% or more) or steam (additional amount: about 15 vol% or less) A method has been proposed for producing various tungsten bronzes represented by <x <1). Also, methods for producing various tungsten bronze-coated composites by performing the same operation on a support are proposed, and use as an electrode catalyst material for fuel cells and the like is proposed.

The inventors of the present invention disclosed in Patent Document 8 an infrared shielding material particle dispersion in which infrared shielding material particles are dispersed in a medium, and optical properties, conductivity, and a manufacturing method of the infrared shielding material particle dispersion. . The infrared shielding material fine particle is a fine particle of tungsten oxide represented by a general formula WyOz (wherein W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), and / or a general formula MxWyOz (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, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0) Particles of the complex tungsten oxide represented by Particle diameter of the infrared shielding material microparticle is 1nm or more 800nm or less.

JP-A-8-59300 Unexamined-Japanese-Patent No. 8-12378 Japanese Patent Application Laid-Open No. 8-283044 Japanese Patent Laid-Open No. 2000-119045 JP-A-9-127559 JP 2003-121884 JP-A-8-73223 WO 2005/37932 International Publication No. 2010/55570

According to the study of the present inventors, in the optical member (film, resin sheet, etc.) containing the tungsten oxide fine particles and / or the composite tungsten oxide fine particles, water vapor or water in the air is used depending on the use situation and method. It was found to gradually penetrate into the solid resin. Then, when water vapor or water gradually penetrates into the solid resin, the surface of the tungsten-containing oxide fine particles is decomposed, and the transmittance of light with a wavelength of 200 to 2600 nm increases with time, and the optical member We found the problem that the infrared absorption performance gradually decreased.

Also, according to the study of the present inventors, in the tungsten oxide fine particles and the composite tungsten oxide fine particles disclosed in Patent Document 8, active harmful radicals are generated in a polymer medium such as a solid resin by heat exposure. It has been found that the harmful radicals also cause the surface of the fine particles to be degraded and degraded, resulting in the loss of the infrared absorption effect.

Under the above-mentioned circumstances, the inventors of the present invention have as disclosed in Patent Document 9 a tungsten oxide represented by the general formula WyOz or / and a general formula as infrared shielding fine particles having excellent water resistance and excellent infrared shielding properties. A composite tungsten oxide fine particle represented by MxWyOz, wherein the average primary particle diameter of the fine particle is 1 nm or more and 800 nm or less, and the fine particle surface is a tetrafunctional silane compound or a partial hydrolysis product thereof, or / and Disclosed an infrared shielding fine particle coated with an organometallic compound and a method for producing the same.

However, the infrared absorbing material is basically used outdoors because of its nature, and high weatherability is often required. And, as market demand increases year by year, further improvement of water resistance and moisture and heat resistance is required for the infrared shielding fine particles disclosed in Patent Document 9. In addition, the infrared shielding fine particles disclosed in Patent Document 9 have a low resistance to heat exposure, that is, an improvement in the heat resistance, and have left a certain problem.

The present invention has been made under the above-mentioned circumstances, and the object of the present invention is an infrared-absorbing fine particle dispersion having excellent moisture-heat resistance and heat resistance and excellent infrared-absorbing properties, an infrared-absorbing fine particle dispersion , And a method of manufacturing them.

In order to solve the above-mentioned problems, the present inventors set the tungsten oxide microparticles and / or composite tungsten oxide microparticles having excellent optical properties as infrared absorbing microparticles, and the heat and humidity resistance and chemical stability of the infrared absorbing microparticles. We researched about the composition which makes it possible to improve the sex. As a result, by using a compound which is excellent in affinity with the surface of the infrared absorbing fine particle and which uniformly adsorbs on the surface of the individual infrared absorbing fine particle to form a strong covering film, the individual infrared ray absorbing of the individual It was considered important to coat the surface of the particles.

The present inventors have further studied, and have conceived metal chelate compounds and metal cyclic oligomer compounds as compounds forming the coating film, which are excellent in affinity in the above-mentioned infrared absorbing fine particles. And, as a result of further research, hydrolysis products of these compounds or polymers of the hydrolysis products, which are formed when the metal chelate compound and the metal cyclic oligomer compound are hydrolyzed, are individual infrared absorptions. It was conceived to be a compound that adsorbs uniformly on the surface of fine particles and forms a strong coating film.

That is, the surface of tungsten oxide fine particles and / or composite tungsten oxide fine particles 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, a metal Infrared absorbing fine particles coated with a coating film containing one or more selected from a hydrolysis product of a cyclic oligomer compound (in the present invention, it may be described as “surface-treated infrared absorbing fine particles”). The idea is to And, it has been found that the surface-treated infrared-absorbing fine particles have excellent moisture and heat resistance.
Furthermore, an infrared-absorbing fine particle dispersion or the like produced using an infrared-absorbing fine particle dispersion prepared by dispersing the surface-treated infrared-absorbing fine particles in an appropriate medium is excellent in heat and humidity resistance and has excellent infrared absorbing properties. I found out.

The inventors of the present invention have continued their research, and have added an infrared absorbing dispersion liquid and an infrared absorbing dispersion liquid, to which a phosphite ester compound having a predetermined structure is added in an amount not anticipated in general resin molded products and the like. It has been found that the infrared absorption dispersion produced by using the resin exhibits long-term stable moist-heat resistance and, in addition, is excellent in heat resistance, and the above problems are solved.

That is, the first invention for solving the above-mentioned problems is:
An infrared-absorbing fine particle dispersion comprising a liquid medium, surface-treated infrared-absorbing fine particles dispersed in the medium, and a phosphite ester compound,
The surface of the surface-treated infrared absorbing fine particle 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, a hydrolysis product of a metal cyclic oligomer compound Is coated with a coating film containing one or more selected from
The phosphite ester compound is a phosphite ester compound represented by the structural formula (1), and the amount of the phosphite ester compound added is 100 parts by mass of the infrared absorbing fine particles. And 50000 parts by mass or less in an amount of 500 parts by mass or less.

However, in the above structural formula (1), R 1, R 2, R 4 and R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 1 to 12 carbon atoms, 7 to carbon atoms Either an aralkyl group of 12 or an aromatic group,
R3 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
X is a single bond or any of divalent residues represented by the following structural formula (1-1),

A represents an alkylene group having 2 to 8 carbon atoms or a divalent residue represented by the following structural formula (1-2),

One of Y and Z is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms, and the other one is hydrogen Either an atom or an alkyl group having 1 to 8 carbon atoms,
In the above structural formula (1-1), R 6 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
In the above structural formula (1-2), R 7 is either a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a phosphite based on which the terminal is represented by the structural formula (1) It shows that it is bound to the oxygen atom side of the compound.
The second invention is
The infrared absorbing particle dispersion liquid according to the first invention, wherein the coating film has a thickness of 0.5 nm or more.
The third invention is
The metal chelate compound or / and the metal cyclic oligomer compound according to the first or second invention characterized in that it contains one or more metal elements selected from Al, Zr, Ti, Si and Zn. Infrared absorbing fine particle dispersion.
The fourth invention is
The metal chelate compound or the metal cyclic oligomer compound according to any one of the first to third inventions characterized in having at least one selected from an ether bond, an ester bond, an alkoxy group and an acetyl group. Infrared absorbing fine particle dispersion.
The fifth invention is
The infrared absorbing fine particles have a general formula WyOz (where W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), or / and a general formula MxWyOz (where M is H, He Alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, T1, Si, Ge, Sn, Pb, Sb, B, F, P, Se, Br, Te, Ti, Nb, Mo, Ta, Re, Be, Hf, Os, Bi, I, One or more elements selected from Yb, W is tungsten, O is oxygen, infrared absorbing fine particles represented by 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ 3.0) Described in any of the first to fourth inventions characterized in that It is an infrared absorption fine particle dispersion.
The sixth invention is
The infrared ray according to the fifth invention, wherein the M element is at least one selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn. It is an absorbing particle dispersion.
The seventh invention is
The infrared-absorbing fine particle dispersion according to any one of the first to sixth inventions, wherein the infrared-absorbing fine particles are fine particles having a hexagonal crystal structure.
The eighth invention is
The infrared absorbing particle dispersion liquid according to any one of the first to seventh inventions, wherein a crystallite diameter of the infrared absorbing particle is 1 nm or more and 200 nm or less.
The ninth invention is
In the surface-treated infrared-absorbing fine particle powder comprising the surface-treated infrared-absorbing fine particle, the carbon concentration is 0.2% by mass or more and 5.0% by mass or less, according to any one of the first to eighth inventions. The infrared absorbing fine particle dispersion of
The tenth invention is
The liquid medium is at least one liquid medium selected from organic solvents, fats and oils, liquid plasticizers, compounds polymerized by curing, and water. It is an infrared rays absorption particulate dispersion given in either of.
The eleventh invention is
Furthermore, it is characterized in that it contains one or more types of stabilizers selected from phosphoric acid stabilizers other than the phosphite ester compounds, hindered phenol stabilizers, sulfide stabilizers, and metal deactivators. The infrared-absorbing fine particle dispersion according to any one of the first to tenth inventions.
The twelfth invention is
An infrared-absorbing fine particle dispersion comprising surface-treated infrared-absorbing fine particles dispersed in a medium and a phosphite ester compound,
The surface of the surface-treated infrared absorbing fine particle 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, a hydrolysis product of a metal cyclic oligomer compound Is coated with a coating film containing one or more selected from
The phosphite ester compound is a phosphite ester compound represented by the structural formula (1), and the amount of the phosphite ester compound added is 100 parts by mass of the infrared absorbing fine particles. And 50000 parts by mass or less, which is an infrared-absorbing fine particle dispersion characterized in that

However, in the above structural formula (1), R 1, R 2, R 4 and R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 1 to 12 carbon atoms, 7 to carbon atoms Either an aralkyl group of 12 or aromatic,
R3 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
X is a single bond or any of divalent residues represented by the following structural formula (1-1),

One of Y and Z is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms, and the other one is hydrogen Either an atom or an alkyl group having 1 to 8 carbon atoms,
In the above structural formula (1-1), R 6 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
In the above structural formula (1-2), R 7 is either a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a phosphite based on which the terminal is represented by the structural formula (1) It shows that it is bound to the oxygen atom side of the compound.
The thirteenth invention is
The infrared-absorbing fine particles according to the twelfth invention, wherein the metal chelate compound or / and the metal cyclic oligomer compound contain one or more metal elements selected from Al, Zr, Ti, Si and Zn. It is a dispersion.
The fourteenth invention is
The infrared-absorbing fine particles according to the twelfth or thirteenth invention, 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. It is a dispersion.
The fifteenth invention is
The infrared absorbing fine particles have a general formula WyOz (wherein W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), or / and a general formula MxWyOz (where M is H, He Alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, T1, Si, Ge, Sn, Pb, Sb, B, F, P, Se, Br, Te, Ti, Nb, Mo, Ta, Re, Be, Hf, Os, Bi, I, One or more elements selected from Yb, W is tungsten, O is oxygen, and is an infrared-absorbing fine particle represented by 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ 3) Red according to any of the twelfth to fourteenth inventions characterized in that It is a linear absorption fine particle dispersion.
The sixteenth invention is
The infrared ray according to the fifteenth invention, wherein the M element is at least one selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn. It is an absorbing particle dispersion.
The seventeenth invention is
The infrared-absorbing fine particle dispersion according to any of the twelfth to sixteenth inventions, wherein the infrared-absorbing fine particles are fine particles having a hexagonal crystal structure.
The eighteenth invention is
The infrared-absorbing fine particle dispersion according to any of the twelfth to seventeenth inventions, wherein a crystallite diameter of the infrared-absorbing fine particles is 1 nm or more and 200 nm or less.
The nineteenth invention is
In the surface-treated infrared-absorbing fine particle powder comprising the surface-treated infrared-absorbing fine particles, the carbon concentration is 0.2% by mass or more and 5.0% by mass or less, according to any of the twelfth to eighteenth inventions. Infrared-absorbing fine particle dispersion of
The twentieth invention is
The infrared absorbing particle dispersion according to any one of the twelfth to nineteenth inventions, wherein the medium is a polymer.
The twenty-first invention is
The infrared-absorbing fine particle dispersion according to any of the twelfth to twentieth inventions, wherein the medium is a solid resin.
The twenty-second invention is
The solid resin is at least one resin selected from fluorocarbon resin, PET resin, acrylic resin, polyamide resin, vinyl chloride resin, polycarbonate resin, olefin resin, epoxy resin, and polyimide resin. It is an infrared rays absorption particulate dispersion given in the 21st invention.
The twenty-third invention is
Furthermore, it is characterized in that it contains one or more types of stabilizers selected from phosphoric acid stabilizers other than the phosphite ester compounds, hindered phenol stabilizers, sulfide stabilizers, and metal deactivators. The infrared-absorbing fine particle dispersion according to any of the twelfth to twenty-second inventions.
The twenty-fourth invention is
Infrared absorbing particles, water,
An organic solvent, a liquid resin, a fat and oil, a liquid plasticizer for the resin, a polymer monomer, or a mixture of two or more selected from these groups are mixed, subjected to a dispersion treatment, and the infrared ray is absorbed. Obtaining a dispersion for forming a film of fine particles;
A metal chelate compound and / or a metal cyclic oligomer compound is added to the film-forming dispersion, and the surface of the infrared absorbing fine particle is a product of a hydrolysis product of a metal chelate compound and a polymer of a hydrolysis product of a metal chelate compound A coating of at least one selected from a hydrolysis product of a metal cyclic oligomer compound and a polymer of a hydrolysis product of a metal cyclic oligomer compound;
After the covering step, the liquid medium constituting the dispersion liquid for forming a film is removed to obtain surface-treated infrared-absorbing fine particle powder containing surface-treated infrared-absorbing fine particles;
The step of adding the surface-treated infrared-absorbing fine particle powder to a predetermined medium and dispersing it to obtain a dispersion of the surface-treated infrared-absorbing fine particles
The phosphite compound is added to the dispersion of the surface-treated infrared-absorbing fine particles in an amount of more than 500 parts by mass and not more than 50000 parts by mass with respect to 100 parts by mass of the infrared-absorbing fine particles. And obtaining a dispersion of the surface-treated infrared-absorbing fine particles, which is a method of producing an infrared-absorbing fine particle dispersion.
The twenty-fifth invention is
Infrared absorbing particles, water,
An organic solvent, a liquid resin, a fat and oil, a liquid plasticizer for the resin, a polymer monomer, or a mixture of two or more selected from these groups are mixed, subjected to a dispersion treatment, and the infrared ray is absorbed. Obtaining a dispersion for forming a film of fine particles;
A metal chelate compound and / or a metal cyclic oligomer compound is added to the film-forming dispersion, and the surface of the infrared absorbing fine particle is a product of a hydrolysis product of a metal chelate compound and a polymer of a hydrolysis product of a metal chelate compound A coating of at least one selected from a hydrolysis product of a metal cyclic oligomer compound and a polymer of a hydrolysis product of a metal cyclic oligomer compound;
After the covering step, the liquid medium constituting the dispersion for forming a film is solvent-replaced with a predetermined medium to obtain a dispersion of surface-treated infrared-absorbing fine particles;
The phosphite compound is added to the dispersion of the surface-treated infrared-absorbing fine particles in an amount of more than 500 parts by mass and not more than 50000 parts by mass with respect to 100 parts by mass of the infrared-absorbing fine particles. And obtaining a dispersion of the surface-treated infrared-absorbing fine particles, which is a method of producing an infrared-absorbing fine particle dispersion.
The 26th invention is
A dispersion of surface-treated infrared-absorbing fine particles containing the phosphite-based compound according to the twenty-fourth or twenty-fifth invention, or a dispersion of surface-treated infrared-absorbing microparticles containing the phosphite-based compound is dried The obtained dispersed powder of surface-treated infrared-absorbing fine particles containing a phosphite ester compound,
Mixing an appropriate medium to obtain an infrared-absorbing fine particle dispersion, which is a method of producing an infrared-absorbing fine particle dispersion.
The twenty-seventh invention is
A dispersion powder of surface-treated infrared-absorbing fine particles obtained by drying the dispersion of the surface-treated infrared-absorbing fine particles according to the twenty-fourth or twenty-fifth invention, a phosphite compound and an appropriate medium are mixed. And a step of obtaining an infrared-absorbing fine particle dispersion, which is a method of producing an infrared-absorbing fine particle dispersion.
However, the mixing amount of the phosphite ester compound is more than 500 parts by mass and not more than 50000 parts by mass with respect to 100 parts by mass of the infrared absorbing fine particles.

The infrared absorbing particle dispersion produced using the infrared absorbing particle dispersion according to the present invention has high moisture and heat resistance and heat resistance, and has excellent infrared absorption characteristics.

It is a schematic plan view of the crystal structure in complex tungsten oxide which has a crystal structure of a hexagonal crystal. FIG. 7 is a 300,000 times transmission electron micrograph of the surface-treated infrared-absorbing fine particles according to Example 1. FIG.

In the surface-treated infrared-absorbing fine particles according to the present invention, the surface of the tungsten oxide fine particles and / or the composite tungsten oxide fine particles, which are infrared-absorbing fine particles, is a hydrolysis product of a metal chelate compound or a hydrolysis product of a metal chelate compound A surface-treated infrared-absorbing fine particle coated with a coating film containing one or more selected from a polymer, a hydrolysis product of a metal cyclic oligomer compound, and a polymer of a hydrolysis product of a metal cyclic oligomer compound . In addition, the infrared-absorbing fine particle dispersion liquid according to the present invention or the infrared-absorbing fine particle dispersion produced by using the dispersion liquid contains a phosphite ester compound having a specific structure.

Hereinafter, the present invention, the surface treatment agent used for the surface coating of [1] infrared absorbing fine particles, [2] infrared absorbing fine particles, [3] surface coating method of infrared absorbing fine particles, [4] phosphorous acid ester compound, [[ 5) Infrared-Absorbing Fine Particle Dispersion, [6] Infrared-Absorbing Fine Particle Dispersion, Infrared-Absorbing Base Material, and Articles will be described in detail in this order.
In the present invention, “to impart moisture and heat resistance to infrared absorbing fine particles, hydrolysis product of metal chelate compound, polymer of hydrolysis product of metal chelate compound, metal cyclic oligomer compound to the surface of the fine particle” The coating film formed using at least one selected from the hydrolysis products of and the polymers of the hydrolysis products of metal cyclic oligomer compounds may be simply referred to as "coating films".

[1] Infrared absorbing fine particles Generally, it is known that a material containing free electrons shows a reflection and absorption response to electromagnetic waves around a region of sunlight with a wavelength of 200 nm to 2600 nm by plasma vibration. It is known that when the powder of such a substance is made into particles smaller than the wavelength of light, geometric scattering in the visible light region (wavelength 380 nm to 780 nm) is reduced and transparency in the visible light region is obtained.
In the present invention, "transparency" is used in the meaning of "little scattering and high transparency to light in the visible light region".

Generally, tungsten oxide (WO ₃ ) does not have effective free electrons, so it has low absorption and reflection characteristics in the infrared region, and is not effective as infrared absorbing fine particles.
On the other hand, WO ₃ having oxygen deficiency and a composite tungsten oxide obtained by adding a positive element such as Na to WO ₃ are conductive materials and known to have free electrons. Then, analysis of single crystals or the like of materials having these free electrons suggests that free electrons respond to light in the infrared region.
The present inventors have found that in a specific part of the composition range of tungsten and oxygen, there is a particularly effective range as infrared absorbing fine particles, and it is transparent in the visible light region and tungsten oxide having absorption in the infrared region. It was thought to be fine particles and composite tungsten oxide fine particles.
Here, regarding the tungsten oxide particles and / or the composite tungsten oxide particles which are infrared absorbing particles according to the present invention, (1) tungsten oxide particles, (2) composite tungsten oxide particles, (3) tungsten oxide particles And composite tungsten oxide fine particles will be described in this order.

(1) Tungsten oxide fine particles Tungsten oxide fine particles according to the present invention have a tungsten oxide represented by the general formula WyOz (where W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999) Fine particles of

In the tungsten oxide represented by the general formula WyOz, the composition range of tungsten and oxygen is such that the composition ratio of oxygen to tungsten is less than 3 and the infrared absorbing fine particles are described as WyOz. It is preferable that 2 ≦ z / y ≦ 2.999.
If the value of the z / y is 2.2 or more, it is possible to avoid the appearance of the crystal phase of WO ₂ other than the purpose in the tungsten oxide, and the chemical stability as a material. As it is possible to obtain effective infrared absorbing fine particles. On the other hand, if the value of z / y is 2.999 or less, the required amount of free electrons is generated, resulting in efficient infrared-absorbing fine particles.

(2) Composite Tungsten Oxide Fine Particles 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 in particular, derived from free electrons in the near infrared region It exhibits strong absorption characteristics, and is effective as near-infrared absorbing fine particles having a wavelength of about 1000 nm.
That is, by combining the control of the amount of oxygen and the addition of the element M for generating free electrons to the WO ₃ , it is possible to obtain infrared absorbing fine particles with higher efficiency. When the general formula of infrared absorbing fine particles combining this control of the amount of oxygen and the addition of the element M for generating free electrons is described as MxWyOz (where M is the element M, W is tungsten, O is oxygen) It is desirable that the infrared absorbing fine particles satisfy the relationship of 0.001 ≦ x / y ≦ 1 and 2.0 ≦ z / y ≦ 3.

First, the value of x / y indicating the amount of addition of the element M will be described.
If the value of x / y is greater 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 addition amount of the element M is larger, the supply amount of free electrons increases and the infrared absorption efficiency also increases, but the effect is also saturated when the value of x / y is about 1. In addition, it is preferable that the value of x / y is smaller than 1 because generation of an impurity phase in the infrared absorbing fine particles can be avoided.

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

Here, from the viewpoint of the stability of 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 It is more preferable that it is one or more types of elements selected from among Nb, V, Mo, Ta, and Re. And, from the viewpoint of improving the optical characteristics as infrared absorbing fine particles and weatherability, the element M is more preferably an alkaline earth metal element, a transition metal element, a 4B group element and a 5B group 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 the case of the composite tungsten oxide represented by MxWyOz, in addition to the same mechanism as the tungsten oxide represented by WyOz described above works, z / y = 3.0 or 2. Also in the case of 0 ≦ z / y ≦ 2.2, there is supply of free electrons by the addition amount of the element M described above. Therefore, 2.0 ≦ z / y ≦ 3.0 is preferable, more preferably 2.2 ≦ z / y ≦ 3.0, and still more preferably 2.45 ≦ z / y ≦ 3.0.

Furthermore, when the composite tungsten oxide particles have a hexagonal crystal structure, the transmission of the particles 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 this hexagonal crystal structure.
In FIG. 1, a hexagonal air gap is formed by collecting six octahedrons formed of WO ₆ units indicated by reference numeral 11, and the element M indicated by reference numeral 12 is disposed in the space to form one piece. A unit is formed, and a large number of units of one unit are assembled to form a hexagonal crystal structure.
Then, to obtain the effect of improving the light transmission in the visible light region and improving the light absorption in the infrared region, the composite tungsten oxide fine particles include the unit structure described with reference to FIG. The composite tungsten oxide fine particles may be crystalline or amorphous.

When a cation of the element M is added to the void of the hexagonal form, the transmission of light in the visible light region is improved and the absorption of light in the infrared region is improved. Here, generally, when the element M having a large ion radius is added, the hexagonal crystal is easily formed. Specifically, hexagonal crystals are easily formed when Cs, K, Rb, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn are added. Of course, elements other than these may be present as long as the element M described above is present in the hexagonal gap formed of the WO ₆ unit, and the present invention is not limited to the above-described elements.

When the composite tungsten oxide fine particles having a hexagonal crystal structure have a uniform crystal structure, the addition amount of the additional element M is preferably 0.2 or more and 0.5 or less, more preferably 0 in the value of x / y. .33. When the value of x / y is 0.33, it is considered that the above-described element M is disposed in all of the hexagonal voids.

In addition, tetragonal and cubic complex tungsten oxides other than hexagonal crystals are also effective as infrared absorbing fine particles. Depending on the crystal structure, the absorption position in the infrared region tends to change, and the absorption position tends to move to the long wavelength side in the order of cubic crystal <tetragonal crystal <hexagonal crystal. Also, incidentally, it is hexagonal, tetragonal and cubic in order of less absorption in the visible light region. Therefore, it is preferable to use a hexagonal composite tungsten oxide for applications that transmit light in the more visible light region and absorb light in the more infrared region. However, the tendency of the optical characteristics described here is a rough tendency, and changes with the type of the additive element, the addition amount, and the oxygen amount, and the present invention is not limited to this.

(3) Tungsten Oxide Fine Particles and Composite Tungsten Oxide Fine Particles The infrared absorbing fine particles containing tungsten oxide fine particles or composite tungsten oxide fine particles according to the present invention largely absorb light in the near infrared region, particularly around a wavelength of 1000 nm. Therefore, there are many things that the transmission color tone becomes from blue to green.

In addition, the dispersed particle diameter of the tungsten oxide fine particles or the composite tungsten oxide fine particles in the infrared absorbing fine particles can be respectively selected depending on the purpose of use.
First, in the case of using for applications where transparency is desired to be maintained, it is preferable to have a particle diameter of 800 nm or less. This is because particles smaller than 800 nm do not absorb light completely by scattering, and can maintain visibility in the visible light region and at the same time, can efficiently maintain transparency. In particular, when importance is given to transparency in the visible light region, it is preferable to further consider scattering by particles.

When importance is attached to the reduction of scattering by the particles, 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, scattering of light in the visible light region with a wavelength of 400 nm to 780 nm due to geometric or Mie scattering is reduced, resulting in an infrared absorbing film like frosted glass, It is possible to avoid losing clear transparency. That is, when the dispersed particle size is 200 nm or less, the geometric scattering or Mie scattering is reduced to be a Rayleigh scattering region. In the Rayleigh scattering region, the scattered light is reduced in proportion to the sixth power of the particle diameter, so that the scattering is reduced as the dispersed particle diameter is reduced, and the transparency is improved.
Further, when the dispersed particle size is 100 nm or less, the scattered light is extremely reduced, which is preferable. From the viewpoint of avoiding light scattering, it is preferable that the dispersed particle size is smaller, and industrial production is easy if the dispersed particle size is 1 nm or more.

By setting the dispersed particle diameter 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 medium has a visible light transmittance of 85% or less and a haze of 30% or less be able to. If the haze is more than 30%, it looks like frosted glass and sharp transparency can not be obtained.
The dispersed particle diameter of the infrared absorbing fine particles can be measured using ELS-8000 or the like manufactured by Otsuka Electronics Co., Ltd. based on the dynamic light scattering method.

Also, in tungsten oxide fine particles and composite tungsten oxide fine particles, the so-called "Magnellie phase" having a composition ratio represented by 2.45 z z / y 2.99 2.999 is chemically stable, and in the infrared region. As the absorption characteristics are also good, they are 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 still more preferably 10 nm or more and 70 nm or less preferable. For measurement of the crystallite diameter, measurement of an X-ray diffraction pattern by powder X-ray diffraction method (θ-2θ method) and analysis by Rietveld method are used. For the measurement of the X-ray diffraction pattern, for example, a powder X-ray diffractometer "X'Pert-PRO / MPD" manufactured by Spectrum S Corporation PANalytical can be used.

[2] Surface treating agent used for surface coating of infrared absorbing fine particles The surface treating agent used for surface coating of infrared absorbing fine particles according to the present invention is a polymerization product of a metal chelate compound and a polymerization product of a metal chelate compound hydrolysis product And at least one selected from the group consisting of hydrolysis products of metal cyclic oligomer compounds and polymers of hydrolysis products of metal cyclic oligomer compounds.
And, the metal chelate compound and the metal cyclic oligomer compound are at least one selected from an ether bond, an ester bond, an alkoxy group and an acetyl group from the viewpoint of being preferably a metal alkoxide, a metal acetylacetonate and a metal carboxylate. It is preferable to have.
Here, with respect to the surface treatment agent according to the present invention, (1) metal chelate compound, (2) metal cyclic oligomer compound, (3) hydrolysis product and polymer of metal chelate compound or metal cyclic oligomer compound, (4) The addition amount of the surface treatment agent will be described in order.

(1) Metal Chelate Compound The metal chelate compound used in the present invention is preferably one or more selected from Al-based, Zr-based, Ti-based, Si-based, and Zn-based chelate compounds containing an alkoxy group. .

As the aluminum-based chelate compound, aluminum alcoholates such as aluminum ethylate, aluminum isopropylate, aluminum sec-butylate, mono-sec-butoxyaluminum diisopropylate or the like, or polymers thereof, ethylacetoacetate aluminum diisopropylate, aluminum tris (Ethyl acetoacetate), octyl acetoacetate aluminum diisopropyl plate, stearyl acetoaluminum diisopropiolate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetonate), etc. can be exemplified.
These compounds dissolve aluminum alcoholate in aprotic solvents, petroleum solvents, hydrocarbon solvents, ester solvents, ketone solvents, ether solvents, amide solvents, etc., and Diketones, β-ketoesters, monohydric or polyhydric alcohols, fatty acids and the like are added, and the mixture is heated under reflux to be an alkoxy group-containing aluminum chelate compound obtained by a substitution reaction of a ligand.

Zirconium-based chelate compounds such as zirconium ethylate, zirconium alcoholate such as zirconium butyrate or polymers thereof, zirconium tributoxystearate, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium dibutoxybis (acetyl) Examples include acetonate), zirconium tributoxyethylacetoacetate, zirconium butoxyacetylacetonate bis (ethylacetoacetate) and the like.

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, titanium octylene glycolate And titanium ethyl acetoacetate, titanium lactate, titanium triethanol aminate, and the like.

As a silicon-based chelate compound, a tetrafunctional silane compound represented by the general formula: Si (OR) ₄ (wherein R is the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms) or a hydrolysis thereof The product can be used. Specific examples of the tetrafunctional silane compound include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like. Furthermore, application of a silane monomer (or an oligomer) in which a part or the whole of the alkoxy group of these alkoxysilane monomers is hydrolyzed to give a silanol (Si-OH) group, and a polymer self-condensed through a hydrolysis reaction Is also possible.
In addition, as a hydrolysis product of a tetrafunctional silane compound (there is no appropriate term indicating the entire intermediate of a tetrafunctional silane compound), a part or the whole of an alkoxy group is hydrolyzed to give a silanol Examples thereof include silane monomers converted to (Si-OH) groups, oligomers of 4- to 5-mers, and polymers (silicone resins) having a weight average molecular weight (Mw) of about 800 to 8000. The alkoxysilyl group (Si-OR) in the alkoxysilane monomer is not all hydrolyzed into silanol (Si-OH) in the course of the hydrolysis reaction.

Examples of zinc-based chelate compounds include zinc salts of organic carboxylic acids such as zinc octylate, zinc laurate and zinc stearate, zinc acetylacetonate chelates, benzoylacetone zinc chelates, dibenzoylmethane zinc chelates, ethyl acetoacetate zinc chelates, etc. It can be preferably exemplified.

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

(3) Hydrolyzate and polymer of metal chelate compound or metal cyclic oligomer compound In the present invention, all the alkoxy groups, ether bonds and ester bonds in the metal chelate compound or metal cyclic oligomer compound mentioned above are hydrolyzed, Hydrolyzate formed into a hydroxyl group or a carboxyl group, a partially hydrolyzed partially hydrolyzed product, and / or a polymer self-condensed through the hydrolysis reaction according to the present invention for infrared absorbing fine particles The surface is coated to form a coating film to obtain surface-treated infrared-absorbing fine particles according to the present invention.
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 present, the type and concentration of the organic solvent are generally present even if water necessary and sufficient for the stoichiometric composition is present in the system. Thus, not all of the alkoxy group, ether bond or ester bond of the metal chelate compound or metal cyclic oligomer compound to be the starting material is hydrolyzed. Therefore, depending on the conditions of the surface coating method described later, even after hydrolysis, it may be in an amorphous state in which carbon C is incorporated in its molecule.
As a result, the coating film may contain an undecomposed metal chelate compound or / and a metal cyclic oligomer compound, but there is no particular problem if it is a trace amount.

(4) Addition amount of surface treatment agent The addition amount of the metal chelate compound and the metal cyclic oligomer compound described above is 0.1 parts by mass or more and 1000 parts by mass or less in terms of metal element with respect to 100 parts by mass of infrared absorbing fine particles. Is preferred. More preferably, it is in the range of 1 part by mass or more and 500 parts by mass or less. More preferably, it is in the range of 10 parts by mass or more and 150 parts by mass or less.

This is because, if the metal chelate compound or the metal cyclic oligomer compound is 0.1 parts by mass or more, the hydrolysis product of those compounds and the polymer of the hydrolysis product cover the surface of the infrared absorbing fine particles The heat and humidity resistance is improved.
In addition, when the amount of the metal chelate compound or the metal cyclic oligomer compound is 1000 parts by mass or less, it can be avoided that the adsorption amount with respect to the infrared absorbing fine particles becomes excessive. Further, the improvement of the heat and moisture resistance by the surface coating is not saturated, and the improvement of the coating effect can be expected.
Furthermore, when the amount of the metal chelate compound or the metal cyclic oligomer compound is 1000 parts by mass or less, the amount of adsorption to the infrared absorbing fine particles becomes excessive, and the hydrolysis product of the metal chelate compound or the metal cyclic oligomer compound at the time of medium removal, It is because it can avoid that microparticles | fine-particles become easy to granulate via the polymer of the said hydrolysis product. Good transparency can be secured by avoiding granulation of the undesirable fine particles.
In addition, an increase in the production cost due to the increase in the addition amount and the processing time due to the excess of the metal chelate compound or the metal cyclic oligomer compound can be avoided. Therefore, the addition amount of the metal chelate compound or the metal cyclic oligomer compound is preferably 1000 parts by mass or less also from the industrial viewpoint.

[3] Surface Coating Method In the surface coating method of infrared absorbing fine particles according to the present invention, first, an infrared absorbing fine particle dispersion for forming a coating film in which the infrared absorbing fine particles are dispersed in a suitable medium (in the present invention (It may be described as "coating liquid formation dispersion liquid.)". Then, a surface treatment agent is added to the prepared dispersion for forming a coating film, and mixed and stirred. Then, the surface of the infrared absorbing fine particle 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, a hydrolysis product of a metal cyclic oligomer compound It is coated with a coating film containing one or more selected from polymers.
Here, regarding the surface coating method according to the present invention, (1) preparation of a dispersion for forming a coating film, (2) preparation of a dispersion for forming a coating film using water as a medium, and (3) adjusting the amount of added water The preparation of the coating film-forming dispersion, and (4) treatment after mixing and stirring in the coating film-forming dispersion will be described in this order.

(1) Preparation of dispersion for forming a coating film In the dispersion for forming a coating film according to the present invention, tungsten oxide or / and composite tungsten oxide which is infrared absorbing fine particles is finely pulverized in advance, It is preferable to disperse in a medium and keep it in a monodispersed state. Then, it is important to secure the dispersed state in the pulverization and dispersion treatment steps and to prevent the fine particles from aggregating each other. This is because in the process of surface treatment of the infrared absorbing fine particles, the fine particles cause aggregation, the fine particles are surface-coated in the form of aggregates, and the aggregates remain even in the infrared absorbing fine particle dispersion described later. It is for avoiding the situation where the transparency of the infrared rays absorption particulate dispersion and infrared rays absorption base material which are mentioned below falls.

Therefore, when the surface treatment agent according to the present invention is added by subjecting the dispersion for forming a coating film according to the present invention to a pulverization / dispersion treatment, the surface treatment agent is applied to each infrared absorbing fine particle. The product of hydrolysis and the polymer of the product of hydrolysis can be uniformly and strongly coated.
As a specific method of the said grinding * dispersion processing, the grinding * dispersion processing method using apparatuses, such as a bead mill, a ball mill, a sand mill, a paint shaker, an ultrasonic homogenizer, is mentioned, for example. Among them, grinding and dispersing with a medium stirring mill such as a bead mill, a ball mill, a sand mill, a paint shaker, etc. using medium media such as beads, balls, and Ottawa sand has a short time to reach the desired dispersed particle size. It is preferable from that.

(2) Preparation of a dispersion for forming a coating film using water as a medium The present inventors stir the dispersion for forming a coating film using water as a medium in the preparation of the dispersion for forming a coating film described above. It has been found that it is preferable to add the surface treatment agent according to the present invention to this while mixing and to immediately complete the hydrolysis reaction of the added metal chelate compound and metal cyclic oligomer compound. In the present invention, it may be described as “a dispersion for forming a coating film using water as a medium”.
This is considered to be affected by the reaction order of the added surface treatment agent according to the present invention. That is, in the dispersion for forming a coating film using water as a medium, the hydrolysis reaction of the surface treatment agent necessarily precedes the polymerization reaction of the generated hydrolysis product. As a result, it is considered that the carbon C remaining amount in the surface treatment agent molecule present in the coating film can be reduced as compared with the case where water is not used as the medium. It is considered that a high-density coating film could be formed by reducing the amount of carbon C remaining in the surface treatment agent molecules present in the coating film.

The metal chelate compound, the metal cyclic oligomer compound, the hydrolysis product thereof, and the polymer of the hydrolysis product in the dispersion for forming a coating film using water as a medium as described above are metal ions immediately after addition. In such a case, the decomposition of the metal ion soot is completed when it becomes a saturated aqueous solution.
On the other hand, the dispersion concentration of the tungsten oxide and / or the composite tungsten oxide in the dispersion for forming a coating film is 0.01% by mass to 80% by mass in the dispersion for forming a coating film using the water as a medium. It is preferable to set it as the following. If the dispersion concentration is in this range, the pH can be 8 or less, and the infrared absorbing fine particles according to the present invention maintain the dispersion by electrostatic repulsion.
As a result, the surface of all infrared absorbing fine particles 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 a hydrolysis of a metal cyclic oligomer compound It is considered that the surface-treated infrared-absorbing fine particles according to the present invention are formed by being coated with a coating film containing one or more selected from polymer of the product.

It is preferable that the film thickness of the coating film of the surface treatment infrared rays absorption microparticle which concerns on this invention is 0.5 nm or more. This is because if the film thickness of the coating film is 0.5 nm or more, it is considered that the surface-treated infrared-absorbing fine particles exhibit sufficient wet heat resistance and chemical stability. On the other hand, it is considered that the film thickness of the coating film is preferably 100 nm or less from the viewpoint that the surface-treated infrared-absorbing fine particles secure predetermined optical properties. The film thickness is preferably 0.5 nm or more and 20 nm or less, more preferably 1 nm or more and 10 nm or less.
The film thickness of the coating film can be measured by a transmission electron microscope, and a portion without the lattice of the infrared absorbing fine particles (arrangement of atoms in the crystal) corresponds to the coating film.

(3) Preparation of a dispersion for forming a coating film by adjusting the amount of added water As a modification of the method of preparing a dispersion for forming a coating film using water as a medium described above, an organic solvent as a medium for a dispersion for forming a coating film There is also a method of realizing the above-described reaction sequence while adjusting the amount of added water to an appropriate value using a solvent. In the present invention, it may be described as "a dispersion for forming a coating film using an organic solvent as a medium".
The preparation method is also convenient when it is desired to reduce the amount of water contained in the dispersion for forming a coating film due to the convenience of the subsequent steps.
Specifically, the surface treatment agent according to the present invention and the pure water are dropped in parallel while stirring and mixing the dispersion for forming a coating film using an organic solvent as a medium. At this time, the medium temperature that affects the reaction rate, and the dropping rate of the surface treatment agent and the pure water are appropriately controlled. In addition, as an organic solvent, what is necessary is just a solvent which melt | dissolves in water at room temperature, such as alcohol type, ketone type, glycol type etc., and it is possible to select various things.

(4) Treatment after mixing and stirring in the dispersion for forming a coating film The surface-treated infrared-absorbing fine particles according to the present invention obtained in the step of preparing the dispersion for forming a coating film described above are an infrared-absorbing fine particle dispersion or As a raw material of an infrared rays absorption base material, it can be used in the state disperse | distributed to a fine particle state, a liquid medium, or a solid medium.
That is, the generated surface-treated infrared-absorbing fine particles do not need to be further subjected to a heat treatment to increase the density and chemical stability of the coating film. This is because the density and adhesion of the coating film are sufficiently increased so that desired heat and humidity resistance can be obtained without the heat treatment.

However, the dispersion for forming a coating film or the surface-treated infrared absorbing fine particle according to the purpose of obtaining the powder of the surface-treated infrared absorbing fine particle from the dispersion for forming a coating film, the purpose of drying the obtained surface-treated infrared absorbing fine particle powder, etc. It is possible to heat treat the powder. However, in this case, it is noted that the heat treatment temperature does not exceed the temperature at which the surface-treated infrared-absorbing fine particles strongly aggregate to form strong aggregates.
This is because the surface-treated infrared-absorbing fine particle according to the present invention is required to have transparency in many cases from the use thereof in the infrared-absorbing fine particle dispersion and the infrared-absorbing base material to be finally used. When an infrared-absorbing fine particle dispersion or an infrared-absorbing substrate is produced by using an aggregate as the infrared-absorbing material, one having a high haze (haze) will be obtained.
If heat treatment is carried out above the temperature at which strong aggregates are formed, the strong aggregates are crushed dry or / and wet in order to ensure the transparency of the infrared absorbing fine particle dispersion or the infrared absorbing substrate. Will be redispersed. However, the coating film on the surface of the surface-treated infrared-absorbing fine particles may be scratched, and in some cases, part of the coating film may be exfoliated, and the surface of the fine particles may be exposed during the disintegration and redispersion. Conceivable.

As described above, the surface-treated infrared-absorbing fine particles according to the present invention do not require a heat treatment after the treatment after mixing and stirring, and thus do not cause strong aggregation, and therefore, a dispersion treatment for disaggregating aggregation is unnecessary. Or in a short time. As a result, the coating film of the surface-treated infrared-absorbing fine particles according to the present invention remains coated with the individual infrared-absorbing fine particles without being damaged. And it is thought that the infrared rays absorption fine particle dispersion and infrared rays absorption base material which are manufactured using the surface treatment infrared rays absorption microparticles show moisture heat resistance superior to those obtained by the conventional method.

In addition, as described above, a high density coating film can be formed by reducing the amount of carbon C remaining in the surface treatment agent molecules present in the coating film. From this viewpoint, in the surface-treated infrared-absorbing fine particle powder comprising the surface-treated infrared-absorbing fine particle, the carbon concentration to be contained is preferably 0.2% by mass or more and 5.0% by mass or less. More preferably, it is 0.5 mass% or more and 3.0 mass% or less.

[4] Phosphite Ester-Based Compound The inventors of the present invention made an infrared absorbing fine particle dispersion containing the surface-treated infrared absorbing fine particle described above, and a phosphorous having a specific structure to a dispersion prepared using the dispersion. By adding an acid ester compound, the weatherability of the infrared absorbing fine particle dispersion according to the present invention and the infrared absorbing base manufactured using the same is improved, and the dispersion and the infrared absorbing base are used for a long time It has been found that it is possible to suppress the decrease in infrared absorption characteristics at the time of
That is, for the purpose of improving the weatherability of the dispersion containing the surface-treated infrared-absorbing fine particles and suppressing the deterioration of the infrared absorption characteristics when the dispersion is used for a long period of time, the phosphite based on the present invention The compound is added to the infrared absorbing fine particle dispersion or the dispersion prepared using the dispersion.

Then, in addition to the phosphite ester compound, at least one selected from phosphate stabilizers other than the phosphite ester compound, hindered phenol stabilizers, sulfide stabilizers, and metal deactivators It is also preferable to add the weather resistance improver of the present invention in combination.
Hereinafter, (1) phosphite compounds, (2) phosphate stabilizers other than phosphite compounds, (3) hindered phenol stabilizers, (4) sulfide stabilizers, (5) metal Deactivating agents will be described in order.

(1) Phosphite Ester Compound The phosphite ester used in the present invention is a compound represented by the structural formula (1), wherein R 1, R 2, R 4 and R 5 are each independently a hydrogen atom, having 1 to 8 carbon atoms And an alkyl group, an alicyclic group having 5 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aromatic group.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group and t- group. Examples thereof include pentyl group, i-octyl group, t-octyl group and 2-ethylhexyl group.
Examples of the alicyclic group having 5 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a 1-methylcyclopentyl group, a 1-methylcyclohexyl group, and a 1-methyl-4-i-propylcyclohexyl group. Groups and the like.

Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group and the like.
Examples of the aromatic group having 7 to 12 carbon atoms include phenyl group, naphthyl group, 2-methylphenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group and 2,6-dimethylphenyl group. .

R1, R2 and R4 are preferably an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 5 to 12 carbon atoms, or the like. More preferably, R 1 and R 4 are a t-butyl group, a t-alkyl group such as a t-pentyl group or a t-octyl group, a cyclohexyl group, a 1-methylcyclohexyl group or the like.

R2 is preferably an alkyl group having a carbon number of 1 to 5, such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group and t-pentyl group, Methyl, t-butyl, t-pentyl and the like are more preferable. R 5 represents a hydrogen atom, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl or t-pentyl, etc. An alkyl group of -5 is preferred.

R3 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and as the alkyl group having 1 to 8 carbon atoms, the same alkyl group having 1 to 8 carbon atoms as described above for R1, R2, R4 and R5 is exemplified. It can be mentioned. R 5 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms as described above for R 2, more preferably a hydrogen atom, a methyl group or the like.

X represents a single bond, a sulfur atom or a divalent residue represented by Structural Formula (1-1). In the divalent residue represented by the structural formula (1-1), R 6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alicyclic group having 5 to 12 carbon atoms, in which Examples of the alkyl group of 8 and the alicyclic group of 5 to 12 carbon atoms include the same alkyl groups and alicyclic groups as described above for R 1, R 2, R 4 and R 5.

R6 is preferably an alkyl group having 1 to 5 carbon atoms such as hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group and the like. X is preferably a single bond or a divalent residue represented by Structural Formula (1-1), more preferably a single bond.

A represents an alkylene group having 2 to 8 carbon atoms or a divalent residue represented by Structural Formula (1-2), and an alkylene group having 2 to 8 carbon atoms is preferable, and such an alkylene group is, for example, ethylene. Groups, a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a 2,2-dimethyl-1,3-propylene group and the like are mentioned, and a propylene group is more preferable. The divalent residue represented by the structural formula (1-2) is bonded to an oxygen atom and a benzene nucleus, while * indicates that it is bonded to an oxygen atom. R7 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and examples of the alkylene group having 1 to 8 carbon atoms include methylene, ethylene, propylene, butylene, pentamethylene and hexamethylene groups. And octamethylene, 2,2-dimethyl-1,3-propylene and the like. As such R 7, a single bond, an ethylene group and the like are preferable.

Y and Z each represents a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms, and the other one is a hydrogen atom or a carbon number 1 to 8 alkyl groups are shown. Here, examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups as described above as R 1, R 2, R 4 and R 5. The alkoxyl group having 1 to 8 carbon atoms is, for example, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, sec-butoxy, t-butoxy, t- And pentoxy group, i-octoxy group, t-octoxy group, 2-ethylhexoxy group and the like. Examples of the aralkyloxy group having 7 to 12 carbon atoms include benzyloxy group, α-methylbenzyloxy group, α, α-dimethylbenzyloxy group and the like. In Y and Z, Y is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and Z is a hydrogen atom or 1 to 8 carbon atoms And Z is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms, and Y is a hydrogen atom or It may be an alkyl group having 1 to 8 carbon atoms.

Among the phosphites represented by the structural formula (1), R 1 and R 4 are t-alkyl groups, cyclohexyl or 1-methylcyclohexyl group, R 2 is an alkyl group having 1 to 5 carbon atoms, and R 5 is A hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 3 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X is a single bond, and A is an alkylene group having 2 to 8 carbon atoms Is particularly preferred.

Preferred specific examples of phosphite esters include 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo It is marketed as [d, f] [1, 3, 2] dioxaphosphepin ("Sumilizer (registered trademark) GP" (manufactured by Sumitomo Chemical Co., Ltd.)). 2, 10-Dimethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] dibenzo [D, f] [1,3,2] dioxaphosphepin, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4-) Hydroxyphenyl) propoxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3 -(3,5-Di-t-butyl-4-hydroxyphenyl) propionyloxy] -12H Dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4-] Hydroxyphenyl) propionyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-Di-t-butyl-4-hydroxyphenyl) propionyloxy] -dibenzo [d, f] [1,3,2] dioxaphosphepin, 2,10-dimethyl-4,8-di -T-Butyl-6- (3,5-di-t-butyl-4-hydroxybenzoyloxy) -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8 , 10-Tetra-t-butyl-6- (3,5-di-t-butyl-4-hyd) Ryloxybenzoyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3-Methyl-4-hydroxy-5-t-butylphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t -Butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2, 10 -Diethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3, 2] Dioxaphosphocin, 2,4,8,10-Tetra-t-Buchi Le-6- [2,2-Dimethyl-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -dibenzo [d, f] [1,3,2] dioxaphosphepine Etc.
As the phosphite esters, commercially available products can also be used. For example, the trade name Sumilizer (registered trademark) GP (manufactured by Sumitomo Chemical Co., Ltd.) may, for example, be mentioned.

The amount of the phosphite ester added is preferably more than 500 parts by mass and 50000 parts by mass or less, and particularly preferably 700 parts by mass or more and 2000 parts by mass or less with respect to 100 parts by mass of the infrared absorbing fine particles.
When the addition amount of the phosphite esters exceeds 500 parts by mass with respect to 100 parts by mass of the fine particles, the increase in haze is suppressed even after holding in the air atmosphere at a high temperature of 120 ° C., and the transmittance, particularly, The solar radiation transmittance is also secured to a desirable level.
On the other hand, if the addition amount of the phosphite esters is 50000 parts by mass or less with respect to 100 parts by mass of the infrared absorbing fine particles, the increase in haze is suppressed before and after the holding in the air atmosphere at a high temperature of 120 ° C. Both the transmittance and the solar radiation transmittance are secured to desirable levels.

Here, in order to clarify the features of the present invention, a method of adding a phosphite ester stabilizer to a dispersion / dispersion containing surface-treated infrared-absorbing fine particles according to the present invention, and infrared absorption according to the prior art The comparison with the method of adding the phosphite stabilizer to the dispersion / dispersion free of fine particles will be described.
As described above, the addition amount of the phosphite ester stabilizer in the present invention is more than 500 parts by mass and not more than 50000 parts by mass with respect to 100 parts by mass of the infrared absorbing fine particles. On the other hand, the addition amount of the phosphite ester stabilizer in the general dispersion according to the prior art which does not contain the surface-treated infrared-absorbing fine particle according to the present invention is the conventional art not containing the infrared-absorbing fine particle When the addition amount of the phosphite ester stabilizer in the dispersion according to is calculated assuming that it contains 100 parts by mass of the infrared absorbing fine particles, the addition amount corresponds to 50 parts by mass to 200 parts by mass The amount of addition exceeds 500 parts by mass of the present invention and 50000 parts by mass or less.

According to the findings of the present inventors, when the dispersion / dispersion contains the surface-treated infrared-absorbing fine particles according to the present invention, the addition amount of the phosphite ester stabilizer is 100 parts by mass of the infrared-absorbing fine particles. When the amount is more than 500 parts by mass and not more than 50000 parts by mass, the stability of the dispersion / dispersion is exerted.
On the other hand, when a phosphite based stabilizer corresponding to more than 500 parts by mass and not more than 50000 parts by mass is added to the dispersion / dispersion containing no infrared absorbing fine particles according to the prior art, the dispersion / In the dispersion, a white haze which is considered to be caused by the hydrolysis of the stabilizer is generated, and the optical properties are significantly deteriorated (see Comparative Example 5). And the level of the deteriorated optical properties in the dispersion / dispersion according to the prior art is lower than the level of the dispersion / dispersion not containing the surface-treated infrared absorbing fine particles and the stabilizer (comparative example) 5, 13).

(2) Other Phosphorous Stabilizers As phosphorus stabilizers other than the phosphite ester compounds described in (1), provided with a phosphorus functional group containing trivalent phosphorus shown in the general formula (2) And those having a phosphorus-based functional group containing pentavalent phosphorus shown in the general formula (3) can be mentioned.

In the general formula (2) and the general formula (3), x, y and z take values of 0 or 1. R1, R2 and R3 each represent a linear, cyclic or branched hydrocarbon group represented by the general formula CmHn, or a halogen atom such as fluorine, chlorine or bromine, or a hydrogen atom. Furthermore, when y or z is 1, R2 or R3 may be a metal atom.

Further, in the present embodiment, the “phosphorus functional group” refers to a portion excluding R1 in the general formulas (2) and (3) (ie, a general formula: —Ox-P (OyR2) (OzR3), or It refers to the general formula: -Ox-P (O) (OyR2) (OzR3)). Specific examples of the phosphorus functional group include phosphonic acid group (-P (O) (OH) ₂ ), phosphoric acid group (-O-P (O) (OH) ₂ ), phosphonic acid ester group (-P (O) (OR2) (OR3)), phosphate ester group (-O-P (O) (OR2) (OR3)), phosphine group (-P (R2) (R3)), etc. may be mentioned. .

Among these phosphorus functional groups, functional groups containing pentavalent phosphorus, such as phosphonic acid group, phosphoric acid group, phosphonic acid ester group and phosphoric acid ester group, mainly have a chain initiation inhibiting function (ie, adjacent to each other) It is considered to have a function of capturing metal ions in a chelating manner by a phosphorus-based functional group.
On the other hand, a phosphorus-based functional group containing trivalent phosphorus such as a phosphine group mainly functions to decompose peroxide (that is, a function to decompose peroxide into a stable compound by oxidizing P atom by itself). It is believed to have.
Among these phosphorus-based functional groups, the phosphonic acid-based color protection agent provided with a phosphonic acid group can efficiently trap metal ions and is excellent in stability such as hydrolysis resistance, so an infrared absorption property decrease inhibitor Are particularly preferred.

Specifically, phosphoric acid (H ₃ PO ₄ ), triphenyl phosphite ((C ₆ H ₅ O) ₃ P), trioctadecyl phosphite (specifically, low-molecular type phosphorus-based coloring inhibitors) (C ₁₈ H ₂₇ O) ₃ P), tridecyl phosphite ((C ₁₀ H ₂₁ O) ₃ P), trilauryl trithiophosphite ([CH ₃ (CH ₂ ) ₁₁ S] ₃ P), etc. Be

Moreover, specifically, polyvinyl phosphonic acid, polystyrene phosphonic acid, vinyl-based phosphoric acid (for example, acrylic phosphoric acid ester (CH ₂ = CHCOOPO (OH) ₂ ) are specifically mentioned as preferable examples of high molecular weight phosphorus-based coloring inhibitors. ), Vinyl alkyl phosphate (CH ₂ CHCHR—O—PO (OH) ₂ , R is a polymer such as — (CH ₂ ) n —), polyether sulfone resin having a phosphonic acid group introduced, poly Ether ether ether ketone resin, linear phenol-formaldehyde resin, linear polystyrene resin, crosslinked polystyrene resin, linear poly (trifluorostyrene) resin, crosslinked (trifluorostyrene) resin, poly (2,3 -Diphenyl-1,4-phenylene oxide) resin, poly (allyl ether ketone) resin, poly (allylene ether) Tersulphone) resin, poly (phenyl quinosan phosphorus) resin, poly (benzyl silane) resin, polystyrene-graft-ethylene tetrafluoro ethylene resin, polystyrene-graft-polyvinylidene fluoride resin, polystyrene-graft-tetrafluoro ethylene resin, etc. Be
A commercial item can also be used for this phosphoric acid stabilizer. For example, trade name Adekastab AS2112 (manufactured by ADEKA Co., Ltd.) may, for example, be mentioned.

(3) Hindered Phenol-Based Stabilizers Examples of hindered phenol-based stabilizers are compounds in which a large group such as a tertiary butyl group is introduced at the 1-position of a phenolic OH group. Hindered phenolic stabilizers are considered to have mainly a chain inhibiting function (that is, a function in which a phenolic OH group captures a radical and suppresses a chain reaction by the radical).

Preferred examples of low molecular type hindered phenol type stabilizers include 2,6-tert-butyl-p-cresol, 2,6-di-tert-butyl-phenol and 2,4-di-methyl-6- Tert-Butyl-phenol, butylhydroxyanisole, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4 ' -Thiobis (3-methyl-6-tert-butylphenol), tetrakis [methylene-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl) -4-hydroxy-5-tert-butylphenyl) butane and the like.

Further, as preferable examples of the high molecular type hindered phenol-based stabilizer, polymers of monomers such as vinyl, acrylic, methacrylic and styryl having the above-mentioned hindered phenol-based color inhibitors in the side chain, and the above-mentioned hindered The polymer etc. with which the structure of the phenol type color protection agent was integrated in the principal chain are mentioned.

In addition, the compound of a polymer type may be preferable to the compound of a low molecular type, and in the case of using a compound of a polymer type, the crosslinking structure may be further introduced. The same as in the case of
However, the harmful radical-supplementing process of the above-mentioned various color preventing agents has many unexplained points, and there is a possibility that actions other than the above are working, and it is not necessarily limited to the above-mentioned actions.
A commercial item can also be used as a hindered phenol type stabilizer. For example, trade name Irganox 1010 (manufactured by BASF) may be mentioned.

(4) Sulfide-based stabilizer An example of the sulfide-based stabilizer is a compound having divalent sulfur in the molecule (sometimes referred to as "sulfur-based color protection agent" in the present embodiment). It is considered that the sulfur-based color protection agent mainly has a peroxide decomposition function (that is, a function to decompose peroxide into a stable compound by oxidizing S atoms by itself). Preferred examples of low molecular weight sulfur-based color inhibitors include dilauryl thiodipropionate (S (CH ₂ CH ₂ COOC ₁₂ H ₂₅ ) ₂ ), distearyl thiodipropionate (S (CH ₂ CH ₂₎ COOC ₁₈ H ₃₇ ) ₂ ), lauryl stearyl thiodipropionate (S (CH ₂ CH ₂ COOC ₁₈ H ₃₇ ) (CH ₂ CH ₂ COOC ₁₂ H ₂₅ )), dimyristyl thiodipropionate (S (CH ₂ CH) _{_{_{_{2 COOC 14 H 29) 2)}}}} , distearyl beta, beta .'- thio dibutyrate _{_{(S (CH (CH 3)}} CH 2 COOC 18 H 39) 2), 2- mercaptobenzimidazole _(C ₆ H 4 NHNCSH), Examples include dilauryl sulfide (S (C ₁₂ H ₂₅ ) ₂ ) and the like.
A commercial item can also be used as a sulfide type stabilizer. For example, there may be mentioned trade name Sumilizer (registered trademark) TPM (manufactured by Sumitomo Chemical Co., Ltd.).
(5) Metal deactivator As the metal deactivator, hydrazine derivatives, salicylic acid derivatives, oxalic acid derivatives and the like are preferably used, and in particular, 2 ', 3-bis [[3- [3,5-di-tert] -Butyl-4-hydroxyphenyl] propionyl]] propionohydrazide, 2-hydroxy-N- (2H-1,2,4-triazol-3-yl) benzamide, dodecanedioic acid bis [2- (2-hydroxybenzoyl) ) Hydrazide] and the like are preferable.

The addition amount of the metal deactivator to the infrared ray absorbing fine particle dispersed body fluid or infrared ray absorbing fine particle dispersion according to the present invention depends on the required performance and the type and use of other phosphite compounds and other additives used in combination. Although it is also limited depending on the amount, it is not particularly limited, but 1 to 10 parts by mass is preferable, and 3 to 8 parts by mass with respect to 100 parts by mass of the infrared absorbing fine particles in the infrared absorbing fine particle dispersed body fluid or infrared absorbing fine particle dispersion Is more preferred. When the addition amount of the metal deactivator is 1 part by mass or more, the reduction preventing effect of the infrared absorption function is recognized, and the effect is substantially saturated at 10 parts by mass.

[5] Infrared-Absorbing Fine Particle Dispersion The infrared-absorbing fine particle dispersion according to the present invention has a surface-treated infrared-absorbing fine particle according to the present invention in a liquid medium (sometimes referred to as "liquid medium" in the present invention). It is dispersed. As the liquid medium, one or more liquid mediums selected from organic solvents, fats and oils, liquid plasticizers, compounds polymerized by curing, water, and the like can be used.
(1) Production method, (2) Organic solvent used, (3) Oil and fat used, (4) Liquid plasticizer used, (5) Polymerized by curing used The compound to be used, (6) the dispersant to be used, and (7) the method of using the infrared-absorbing fine particle dispersion will be described in this order.

(1) Manufacturing method In order to manufacture the infrared absorbing fine particle dispersion according to the present invention, the above-mentioned dispersion for forming a coating film is heated, dried, or under the condition that strong aggregation of the surface treated infrared absorbing fine particles can be avoided. For example, it is dried by vacuum drying at room temperature, spray drying or the like to obtain a surface-treated infrared-absorbing fine particle powder according to the present invention. Then, the surface-treated infrared-absorbing fine particle powder may be added to the above-mentioned liquid medium, and further, a phosphite ester compound may be added and dispersed. In addition, the dispersion for forming a coating film is separated into the surface-treated infrared absorbing fine particles and the medium, and the medium of the dispersion for forming a coating film is replaced with the medium of the infrared absorbing particles dispersion by the operation of solvent substitution It is also a preferable configuration to produce an infrared absorbing fine particle dispersion by further adding a phosphite ester compound by so-called solvent substitution).
On the other hand, the medium of the coating film-forming dispersion and the medium of the infrared absorbing fine particle dispersion are made to coincide in advance, and the phosphite ester compound is added to the coating film-forming dispersion after the surface treatment. It is also a preferable configuration to use an infrared absorbing fine particle dispersion.

(2) Organic Solvents Used As the organic solvent used for the infrared absorbing fine particle dispersion according to the present invention, alcohol solvents, ketone solvents, hydrocarbon solvents, glycol solvents, water systems, etc. can be used.
Specifically, alcohol solvents such as methanol, ethanol, 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol and diacetone alcohol;
Ketone solvents such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone;
Ester solvents such as 3-methyl-methoxy-propionate;
Glycol derivatives such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate;
Amides such as formamide, N-methylformamide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone and the like;
Aromatic hydrocarbons such as toluene and xylene;
Ethylene chloride, chlorobenzene, etc. can be used.
Among these organic solvents, particularly, dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether acetate, n-butyl acetate and the like can be preferably used.

(3) Fats and oils used As fats and oils used for the infrared rays absorption microparticle dispersion liquid which concerns on this invention, vegetable fats and oils or plant origin fats and oils are preferable.
Examples of vegetable oils include dry oils such as linseed oil, sunflower oil, soy sauce and eno oil, sesame oil, cottonseed oil, rapeseed oil, semi-dry oil such as soybean oil, rice bran oil and poppy seed oil, olive oil, palm oil, palm oil and dehydrated castor oil Non-drying oil, etc. can be used.
As compounds derived from vegetable oil, fatty acid monoesters obtained by direct ester reaction of fatty acid of vegetable oil and monoalcohol, ethers, etc. can be used.
Moreover, commercially available petroleum solvents can also be used as fats and oils.
Examples of commercially available petroleum solvents include Isopar (registered trademark) E, Exol (registered trademark) Hexane, Hexane, E, D30, D40, D60, D80, D95, D110, D130 (all manufactured by Exxon Mobil), etc. it can.

(4) Liquid plasticizer to be used As a liquid plasticizer used for the infrared absorption fine particle dispersion according to the present invention, for example, a plasticizer which is a compound of a monohydric alcohol and an organic acid ester, a polyhydric alcohol organic acid ester compound It is possible to use ester-based plasticizers, phosphoric acid-based plasticizers such as organic phosphoric acid-based plasticizers, and the like. In addition, what is liquid at all at room temperature is preferable.
Among them, plasticizers which are ester compounds synthesized from polyhydric alcohols and fatty acids can be preferably used. The ester compound synthesized from the polyhydric alcohol and the fatty acid is not particularly limited, and examples thereof include glycols such as triethylene glycol, tetraethylene glycol and tripropylene glycol, butyric acid, isobutyric acid, caproic acid and 2-ethyl butyric acid Using glycol-based ester compounds, etc. obtained by reaction with monobasic organic acids such as heptyl acid, n-octyl acid, 2-ethylhexyl acid, pelargonic acid (n-nonyl acid), decyl acid and the like It can.
In addition, ester compounds of tetraethylene glycol and tripropylene glycol with the monobasic organic compounds and the like can also be mentioned.
Among them, fatty acid esters of triethylene glycol such as triethylene glycol dihexanate, triethylene glycol di-2-ethyl butyrate, triethylene glycol di-octanate, triethylene glycol di-2-ethyl hexanonate, etc. It can be used. Furthermore, fatty acid esters of triethylene glycol can also be preferably used.

(5) Compound that is polymerized by curing that is used The compound that is polymerized by curing that is used for the infrared absorbing fine particle dispersion according to the present invention is a monomer or oligomer that forms a polymer by polymerization etc. .
Specifically, a methyl methacrylate monomer, an acrylate monomer, a styrene resin monomer, etc. can be used.

The liquid media described above can be used in combination of two or more. Furthermore, if necessary, an acid or an alkali may be added to these liquid media to adjust the pH.

(6) Dispersant to be used In the dispersion liquid of infrared absorbing fine particles according to the present invention, various dispersions of the surface-treated infrared absorbing fine particles are further improved to prevent the dispersion particle diameter from becoming coarse due to reaggregation. The addition of dispersants, surfactants, coupling agents, etc. is also preferred.
Although the said dispersing agent, a coupling agent, and surfactant can be selected according to a use, it is preferable that it is group which has an amine, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group. These functional groups are adsorbed on the surface of the surface-treated infrared absorbing fine particle to prevent aggregation and have an effect of uniformly dispersing. Polymeric dispersants having any of these functional groups in the molecule are more preferred.

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

Specific preferred examples of commercially available dispersants include SOLSPERSE (registered trademark) (the same as the following) 3000, 5000, 9000, 11200, 12000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000 by Nippon Lubrisol Corporation. , 21000, 24000 SC, 24000 GR, 26000, 27000, 28000, 31845, 32000, 32500, 32600, 33000, 33500, 34500, 35100, 35200, 36600, 37500, 38500, 39000, 41000, 41090, 53095, 55000, 56000 , 71000, 76500, J180, J200, M387, etc .; SOLPLUS (registered trademark) (same hereafter) D5 0, D520, D530, D540, DP310, K500, L300, L400, R700, etc .; Disperbyk (registered trademark) (the same as the following) made by BIC Chemie Japan Ltd.-101, 102, 103, 106, 107, 108, 109, 110, 111, 112, 116, 130, 140, 142, 145, 154, 161, 162, 163, 164, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 191, 192, 2000, 2001, 2009, 2020, 2025, 2070, 2095, 2096, 2150, 2151, 2152, 2155, 2163, 2164, Anti-Terra (registered trademark) (hereinafter the same)-U, 203, 204 and so on; YK (registered trademark) (same below)-P104, P104S, P1050, P9051, P9060, P9065, P9080, 051, 052, 053, 054, 055, 057, 063, 065, 066N, 067A, 087, 088, 141, 220S, 300, 302, 306, 307, 310, 315, 320, 322, 323, 325, 330, 331, 333, 337, 340, 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, Dynwet 800, Siclean 3700, UV 3500, UV 3510, UV 3570, etc .; EFKA (registered trademark) (the same applies hereinafter) 2020, 2025, 3030, 3031, 3236, 4008, 4009, 4010, 4015, 4020 manufactured by Efka Additives. , 4046, 4047, 4050, 4055, 4080, 4300, 4310, 4330, 4340, 4340, 4401, 4402, 4406, 5066, 5220, 6220, 6220, 6230, 6700, 6762, 7462 , 8503 et al .; BASF Japan JONCRYL (registered trademark) (same below) 67, 678, 586, 611, 680, 682, 690, 819,-JDX 50 50 ; Otsuka Chemical TERPLUS (registered trademark) (same as the following) MD1000, D1180, D1130, etc .; Ajinomoto Fine Techno Co., Ltd. Addispur (registered trademark) (same as the following) PB-711, PB-821, PB-822, etc .; Company-made Disparon (registered trademark) 1751N, 1831, 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 .; Alphon (registered trademark) manufactured by Toagosei Co., Ltd. (the same applies hereinafter) UH-2170, UC-3000, UC-3910, UC-3920 , UF-5022, UG-4010, UG-4035, UG-4040, UG- 070, RESEDA (registered trademark) (same below) GS-1015, GP-301, GP-301S, etc .; Dianal (registered trademark) (same below) BR-50, BR-52, BR-60, manufactured by Mitsubishi Chemical Corporation BR-73, BR-77, BR80, BR-83, BR85, BR87, BR88, BR-90, BR-96, BR102, BR-113, BR116 and the like can be used.

(7) Method of using the infrared absorbing fine particle dispersion The infrared absorbing fine particle dispersion according to the present invention manufactured as described above is applied to the surface of a suitable substrate, and a coating film is formed there to form an infrared ray. It can be used as an absorbent substrate. That is, the said coating film is 1 type of the dry solidification thing of an infrared rays absorption microparticle dispersion liquid.

In addition, the infrared ray absorbing fine particle dispersion liquid is dried and pulverized to obtain a powdery infrared ray absorbing fine particle dispersion containing the phosphite compound according to the present invention (also referred to as “dispersed powder” in the present invention) Yes). That is, the said dispersed powder is 1 type of the dry solidified thing of an infrared rays absorption microparticle dispersion liquid. The dispersed powder is a powdery dispersion in which surface-treated infrared-absorbing fine particles are dispersed in a solid medium (such as a dispersant) containing a phosphate compound, and is distinguished from the above-mentioned surface-treated infrared-absorbing fine particle powder. Since the dispersed powder contains a dispersant, it is possible to easily re-disperse the surface-treated infrared-absorbing fine particles in the medium by mixing with a suitable medium.

On the other hand, it is also possible to first prepare an infrared-absorbing fine particle dispersion which does not contain a phosphite-based compound without adding the phosphite-based compound to the infrared-absorbing fine particle dispersion. In this case, when mixing and kneading the infrared absorbing fine particle dispersion not containing the phosphite ester compound or the infrared absorbing fine particle dispersed powder obtained by drying this, with a medium such as a resin, a predetermined amount The phosphite ester compound of the present invention can be added to prepare an infrared-absorbing fine particle dispersion according to the present invention.

On the other hand, the infrared absorbing fine particle dispersion in which the surface treated infrared absorbing fine particles according to the present invention are mixed and dispersed in a liquid medium is used for various applications utilizing photothermal conversion.
For example, surface-treated infrared-absorbing fine particles are added to uncured thermosetting resin, or after surface-treated infrared-absorbing fine particles according to the present invention are dispersed in an appropriate solvent, uncured thermosetting resin is added. Thus, a curable ink composition can be obtained. The curable ink composition is provided on a predetermined base material, and when cured by being irradiated with an infrared ray such as infrared rays, it has excellent adhesion to the base material. Then, in addition to the use as a conventional ink, the curable ink composition is applied in a predetermined amount, irradiated with an electromagnetic wave such as infrared rays to be cured, piled up, and then formed into a three-dimensional object. Curing ink composition most suitable for

[6] Infrared absorbing fine particle dispersion, infrared absorbing base material, and article (1) infrared absorbing fine particle dispersion In the infrared absorbing fine particle dispersion according to the present invention, the surface treated infrared absorbing fine particle according to the present invention is dispersed in a solid medium It is what you are doing. In addition, solid media, such as resin and glass, can be used as the said solid media.
The infrared absorbing fine particle dispersion according to the present invention will be described in the order of (i) production method, (ii) moisture and heat resistance, and (iii) heat resistance.

(I) Manufacturing method As described above, when the surface-treated infrared-absorbing fine particles according to the present invention are kneaded into a medium such as a resin and formed into a film or a board, the surface-treated infrared-absorbing fine particles and the phosphite ester compound Directly into the resin. In addition, it is possible to mix the infrared absorbing fine particle dispersion and the resin, or add a powdery dispersion in which the surface treated infrared absorbing fine particles are dispersed in a solid medium to a liquid medium and mix it with the resin. It is.
When a resin is used as the solid medium, for example, a film or board having a thickness of 0.1 μm to 50 mm may be configured.

Generally, when the surface-treated infrared-absorbing fine particles according to the present invention are kneaded into a resin, they are mixed by heating and mixing at a temperature (about 200 to 300 ° C.) around the melting point of the resin.
In this case, it is also possible to further mix the surface-treated infrared-absorbing fine particles into a resin and pelletize it, and form the film or the board by each method. For example, it can be formed by an extrusion molding method, an inflation molding method, a solution casting method, a casting method or the like. The thickness of the film or board at this time may be appropriately set according to the purpose of use, and the amount of filler to the resin (that is, the amount of the surface treated infrared absorbing fine particles according to the present invention) Although it is variable depending on the optical properties and mechanical properties, generally it is preferably 50% by weight or less based on the resin.
When the amount of the filler to the resin is 50% by weight or less, fine particles in the solid resin can avoid granulation, so that good transparency can be maintained. In addition, the amount of surface-treated infrared-absorbing fine particles according to the present invention can be controlled, which is advantageous in cost.

On the other hand, the infrared absorbing fine particle dispersion in which the surface treated infrared absorbing fine particles according to the present invention are dispersed in a solid medium can be used even in a state of being further pulverized into powder. In the case of adopting the configuration, in the powdered infrared-absorbing fine particle dispersion, the surface-treated infrared-absorbing fine particles according to the present invention are already sufficiently dispersed in the solid medium. Therefore, the mixture of the powdery infrared-absorbing fine particle dispersion and the phosphite ester compound is dissolved as a so-called master batch in an appropriate liquid medium or kneaded with a resin pellet or the like to facilitate liquid or solid. An infrared absorbing fine particle dispersion having a shape can be produced.

The solid resin constituting the matrix in the film or board mentioned above is a polymer medium which is solid at room temperature, and is a concept including a polymer medium other than those three-dimensionally cross-linked. The solid resin is not particularly limited and can be selected according to the application, but in consideration of the weather resistance, a fluorine resin is preferable. However, PET resin, acrylic resin, polyamide resin, vinyl chloride resin, polycarbonate resin, olefin resin, epoxy resin, polyimide resin, etc. are also used as a low-cost, highly transparent and versatile resin compared to fluorine resin. I can do it.

(Ii) Heat-and-moisture resistance The infrared-absorbing fine particle dispersion according to the present invention is exposed when the dispersion having a visible light transmittance of about 80% is exposed to a moist heat atmosphere at 85 ° C. and 90% for 9 days. The amount of change in visible light transmittance before and after is 2.0% or less, and has excellent heat and humidity resistance.

(Iii) Heat resistance The infrared absorbing fine particle dispersion according to the present invention has the dispersion set at about 80% visible light transmittance when exposed to an atmosphere of 120 ° C. for 30 days, before and after the exposure. The amount of change in visible light transmittance is 2.0% or less, and has excellent heat resistance.

(2) Infrared Absorbing Base Material The infrared absorbing base material according to the present invention has a coating film containing the surface-treated infrared absorbing fine particles according to the present invention and the phosphite compound on the surface of a predetermined base material. It is
The infrared-absorbing substrate according to the present invention is resistant to moisture and heat by forming a coating film containing the surface-treated infrared-absorbing fine particles according to the present invention and the phosphite ester compound on a predetermined substrate surface. And excellent in chemical stability, and can be suitably used as an infrared absorbing material.
The infrared absorbing substrate according to the present invention will be described in the order of (i) production method, (ii) moisture and heat resistance, and (iii) heat resistance.

(I) Manufacturing method For example, the surface-treated infrared-absorbing fine particles according to the present invention and a phosphite ester compound are mixed with an organic solvent such as alcohol or a liquid medium such as water, a resin binder, and optionally a dispersant. After the infrared absorbing fine particle dispersion is applied to a suitable substrate surface, the liquid medium is removed to obtain an infrared absorbing substrate in which the infrared absorbing fine particle dispersion is directly laminated on the substrate surface.

The resin binder component can be selected according to the application, and examples thereof include an ultraviolet curable resin, a thermosetting resin, a room temperature curing resin, a thermoplastic resin, and the like. On the other hand, the infrared absorbing fine particle dispersion containing no resin binder component may be laminated on the surface of the substrate, and after the lamination, the infrared absorbing fine particle dispersion containing a binder medium is contained in the liquid medium. It may be applied on the layer of

Specifically, at least one liquid medium selected from an organic solvent, an organic solvent in which a resin is dissolved, an organic solvent in which a resin is dispersed, and water contains a phosphite compound, and surface-treated infrared-absorbing fine particles An infrared-absorbing base material in which a liquid infrared-absorbing fine particle dispersion in which liquid crystal is dispersed has a coating film formed on the surface of the base material can be mentioned. Moreover, the infrared rays absorption base material in which the liquid infrared rays absorption fine particle dispersion containing the resin binder component forms a coating film in the base-material surface is mentioned. Furthermore, a liquid infrared-absorbing fine particle dispersion obtained by mixing an infrared-absorbing fine particle dispersion containing a phosphite-based compound in a powdery solid medium and having surface-treated infrared-absorbing fine particles dispersed therein is mixed in a predetermined medium. There is also mentioned an infrared absorbing substrate having a coating film formed on the surface of the substrate. Of course, there may also be mentioned an infrared-absorbing substrate in which a coating film is formed on the surface of an infrared-absorbing fine particle dispersion obtained by mixing two or more of the various liquid infrared-absorbing fine particle dispersions.

The material of the substrate described above is not particularly limited as long as it is a transparent body, but glass, a resin board, a resin sheet, and a resin film are preferably used.
The resin used for the resin board, the resin sheet, and the resin film is not particularly limited as long as it does not cause a defect in the surface condition and the durability of the required board, sheet, and film. For example, polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose, polycarbonate-based polymers, acrylic polymers such as polymethyl methacrylate, and polystyrenes such as polystyrene and acrylonitrile-styrene copolymer -Based polymer, polyethylene, polypropylene, polyolefin having cyclic or norbornene structure, olefin-based polymer such as ethylene-propylene copolymer, vinyl chloride-based polymer, amide-based polymer such as aromatic polyamide, imide-based polymer, sulfone-based polymer, poly Ether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol poly -, Vinylidene chloride polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene polymers, epoxy polymers, and further binary and ternary copolymers of these, graft copolymers, blends, etc. Boards, sheets and films made of transparent polymers of In particular, polyester-based biaxially oriented films such as polyethylene terephthalate, polybutylene terephthalate or polyethylene-2,6-naphthalate are preferable in view of mechanical properties, optical properties, heat resistance and economy. The polyester-based biaxially oriented film may be a copolyester-based.

(Ii) Moisture and heat resistance In the infrared ray absorbing base material, when exposed to the infrared ray absorbing base material set to 80% visible light transmittance for 9 days in a moist heat atmosphere at 85 ° C. and 90%, before and after the exposure The amount of change in visible light transmittance is 2.0% or less, and has excellent heat and humidity resistance.

(3) An article using an infrared absorbing fine particle dispersion or an infrared absorbing substrate As described above, the infrared absorbing article such as an infrared absorbing fine particle dispersion according to the present invention or a film or board which is an infrared absorbing base has moisture and heat resistance And excellent in heat resistance and chemical stability.
Therefore, for example, in various buildings and vehicles, these infrared absorbing articles are intended to shield light in the infrared region while sufficiently incorporating visible light, and to suppress the temperature rise in the room while maintaining the brightness. It can be suitably used as a window material, etc., which is used in a PDP (plasma display panel), etc., and which filters infrared rays emitted forward from the PDP.

In addition, the infrared absorbing fine particle dispersion according to the present invention is mixed with a solid medium such as a resin or a compound which is polymerized by curing to prepare a coating solution, which is selected from a substrate film or substrate glass by a known method. By forming a coating layer on a transparent substrate, it is possible to produce an infrared absorbing film or infrared absorbing glass in which infrared absorbing fine particles are dispersed in a solid medium. The infrared absorbing film or the infrared absorbing glass is an example of the fine particle dispersion according to the present invention.

Further, since the surface treated infrared absorbing fine particles according to the present invention have absorption in the infrared region, when the printing surface containing the surface treated infrared absorbing fine particles is irradiated with an infrared laser, it absorbs infrared rays having a specific wavelength. Therefore, the forgery prevention printed matter obtained by printing the forgery prevention ink containing the surface-treated infrared absorbing fine particles on one side or both sides of the printing substrate is irradiated with an infrared ray having a specific wavelength, and its reflection or transmission is read. The authenticity of the printed matter can be determined from the difference in the amount of reflection or the amount of transmission. The said forgery prevention printed matter is an example of the infrared rays absorption particulate dispersion concerning the present invention.

In addition, the infrared absorbing fine particle dispersion according to the present invention and a binder component are mixed to produce an ink, the ink is applied on a substrate and dried, and then the dried ink is cured to perform photothermal conversion. Layers can be formed. The light-to-heat conversion layer can generate heat only at a desired place with high accuracy by irradiation of electromagnetic wave laser such as infrared rays, and can be applied to a wide range of fields such as electronics, medicine, agriculture, machinery, etc. .
For example, it can be suitably used as a donor sheet used when forming an organic electroluminescent element by a laser transfer method, a thermal paper for a thermal printer, and an ink ribbon for a thermal transfer printer. The photothermal conversion layer is an example of the infrared absorbing particle dispersion according to the present invention.

In addition, the surface-treated infrared-absorbing fine particles according to the present invention are dispersed in an appropriate medium to contain a phosphite ester compound to form an infrared-absorbing fine particle dispersion, and the dispersion is contained on the surface and / or inside of the fiber. The infrared absorption fiber is obtained by By having the said structure, an infrared rays absorption fiber absorbs near infrared rays etc. from sunlight etc. efficiently by inclusion of infrared rays absorption microparticles, it becomes an infrared rays absorption fiber excellent in heat retention, and light of a visible light region is transmitted simultaneously. Since it is made to be, it becomes an infrared absorption fiber excellent in designability. As a result, it can be used in various applications such as clothing for cold protection requiring thermal insulation, sports clothing, textile products such as stockings and curtains, and other industrial textile products. The infrared absorbing fiber is an example of the infrared absorbing particle dispersion according to the present invention.

In addition, the film-like or board-like infrared-absorbing fine particle dispersion according to the present invention can be applied to a material used for a roof or an outer wall material of a house for agriculture and horticulture. The material transmits visible light and secures the light necessary for photosynthesis of plants in an agricultural and horticultural house, while efficiently absorbing light such as near-infrared light contained in other sunlight. It can be used as a heat insulation material for agricultural and horticultural facilities with heat insulation. The heat insulating material for agricultural and horticultural facilities is an example of the infrared ray absorbing particle dispersion according to the present invention.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples.
The dispersed particle diameter of the fine particles in the dispersion in Examples and Comparative Examples is indicated by an average value measured by a particle size measurement device (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.) based on the dynamic light scattering method. In addition, the crystallite diameter is measured by powder X-ray diffraction method (θ-2θ method) using a powder X-ray diffractometer (X'Pert-PRO / MPD manufactured by Spectris Co., Ltd. PANalytical), using Rietveld method. Calculated.
The film thickness of the coating film of the surface-treated infrared-absorbing fine particles is a place having no checkered infrared-absorbing fine particles according to the 300,000-fold photographic data obtained using a transmission electron microscope (HF-2200 manufactured by Hitachi, Ltd.) Was read as a covering film.
The optical properties of the infrared absorbing sheet or plate were measured using a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.), and the visible light transmittance and the solar radiation transmittance were calculated according to JIS R3106. The haze value of the infrared ray absorbing sheet or plate was measured using a haze meter (HM-150 manufactured by Murakami Color Co., Ltd.), and calculated according to JIS K7105.
In the method for evaluating the heat and moisture resistance of an infrared ray absorbing sheet or plate, the infrared ray absorbing sheet having a visible light transmittance of about 80% is exposed to a moist heat atmosphere at 85 ° C. and 90% for 9 days. And, for example, in the case of hexagonal cesium tungsten bronze, it is judged that the change in solar radiation transmittance is 2.0% or less before and after the exposure is considered to be good in heat and moisture resistance, and the change is more than 2.0% It was judged that heat and humidity resistance was insufficient.
In the method of evaluating the heat and moisture resistance of the infrared ray absorbing sheet or plate, the infrared ray absorbing sheet having a visible light transmittance of about 80% is exposed to the atmosphere at 120 ° C. for 30 days. And, for example, in the case of hexagonal cesium tungsten bronze, it is judged that heat resistance is good when the amount of change of solar radiation transmittance before and after the exposure is 2.0% or less, and the amount of change exceeds 2.0% It was judged that heat resistance was insufficient.
The optical property values (visible light transmittance and haze value) of the infrared absorbing sheet or plate mentioned here are values including the optical property value of the resin sheet or plate as the base material.

Example 1
Hexagonal cesium tungsten bronze (Cs _0.33 WOz, 2.0 ≦ z ≦ 3.0) powder CWO (registered trademark) (Sumitomo Metal Mining Co., Ltd. YM-01, Cs / W (molar ratio) = 0.33 ) the mixture obtained by mixing 25 mass% of pure water 75 wt%, was charged for 10 hours pulverization and dispersion treatment in a paint shaker containing the 0.3MmfaiZrO ₂ beads according to example 1 Cs _{0 .33} A dispersion of WOz microparticles was obtained. It was 100 nm when the dispersion particle diameter of Cs _0.33 WOz microparticles | fine-particles in the obtained dispersion liquid was measured. In addition, as a setting of particle size measurement, the particle refractive index was set to 1.81, and the particle shape was non-spherical. The background was measured using pure water, and the solvent refractive index was 1.33. In addition, after removing the solvent of the obtained dispersion liquid, the crystallite diameter was measured to be 32 nm. The obtained dispersion of Cs _0.33 WOz fine particles and pure water were mixed to obtain a dispersion A for forming a coating film according to Example 1 in which the concentration of Cs _0.33 WOz fine particles was 2% by mass. .
On the other hand, 2.5 mass% of aluminum ethyl acetoacetate diisopropylate and 97.5 mass% of isopropyl alcohol (IPA) were mixed as an aluminum-based chelate compound to obtain a surface treatment agent diluted solution a.

The obtained coating film-forming dispersion A 890 g was placed in a beaker, and while being vigorously stirred by a bladed stirrer, 360 g of a surface treating agent diluted solution was added dropwise over 3 hours. After dropwise addition of the surface treatment agent dilution liquid a, stirring was further performed at a temperature of 20 ° C. for 24 hours to prepare a ripening liquid according to Example 1. Next, the medium was evaporated from the ripening solution using vacuum flow drying to obtain a powder (surface-treated infrared-absorbing fine particle powder) including the surface-treated infrared-absorbing fine particles according to Example 1.
Here, the film thickness of the coating film of the surface-treated infrared-absorbing fine particles according to Example 1 was read from 300,000-fold photographic data obtained using a transmission electron microscope (HF-2200 manufactured by Hitachi, Ltd.). It turned out that it was 2 nm. A 300,000 transmission electron micrograph of the surface-treated infrared-absorbing fine particles according to Example 1 is shown in FIG.

8% by mass of the surface-treated infrared-absorbing fine particle powder according to Example 1 was mixed with 24% by mass of the polyacrylate dispersant and 68% by mass of toluene. The obtained mixed solution was loaded on a paint shaker containing 0.3 mmφ ZrO ₂ beads, ground and dispersed for 1 hour, and an infrared-absorbing fine particle dispersion liquid according to Example 1 was obtained. Subsequently, the medium was evaporated from the infrared absorbing fine particle dispersion by vacuum flow drying to obtain an infrared absorbing fine particle dispersed powder according to Example 1.

An infrared-absorbing fine particle dispersed powder according to Example 1, a polycarbonate resin which is a solid resin, and 2000 parts by mass of Sumilizer GP with respect to 100 parts by mass of hexagonal cesium tungsten bronze are added. It dry-blended so that light transmittance might be around 80%. The obtained blend was kneaded at 290 ° C. using a twin-screw extruder, extruded from a T-die, and made into a sheet material of 0.75 mm thickness by a calender roll method, to obtain an infrared-absorbing sheet according to Example 1 . The infrared absorbing sheet is an example of the infrared absorbing particle dispersion according to the present invention.

When the optical characteristic of the infrared absorption sheet according to Example 1 obtained was measured, the visible light transmittance was 79.6%, the solar radiation transmittance was 48.6%, and the haze was 0.9%.

The obtained infrared absorption sheet according to Example 1 was exposed to a moist heat atmosphere at 85 ° C. and 90% for 9 days, and the optical characteristics were measured. The visible light transmittance was 80.2%, and the solar radiation transmittance was 49.5 %, The haze was 0.9%. It was found that the change in visible light transmittance due to exposure to a moist heat atmosphere was 0.6%, the change in solar radiation transmittance was as small as 0.9%, and the haze did not change.

Moreover, when the infrared rays absorption sheet which concerns on obtained Example 1 is exposed in 120 degreeC atmospheric atmosphere for 30 days, when an optical characteristic is measured, visible light transmittance | permeability is 80.2%, solar radiation transmittance is 50.0. %, The haze was 0.9%. It was found that the change in visible light transmittance due to exposure to a moist heat atmosphere was 0.6%, the change in solar radiation transmittance was as small as 1.4%, and the haze did not change.
The manufacturing conditions and the evaluation results of Example 1 are described in Tables 1 to 4.

[Examples 2 and 3]
Example 2 in the same manner as Example 1, except that 4000 parts by mass (Example 2) or 700 parts by mass (Example 3) of Sumilizer GP was added to 100 parts by mass of hexagonal cesium tungsten bronze powder. An infrared absorbing sheet according to No. 3 was obtained.
The infrared ray absorbing sheets according to Examples 2 and 3 obtained were evaluated in the same manner as Example 1.
The production conditions and the evaluation results of Examples 2 and 3 are described in Tables 1 to 4.

Example 4
The infrared ray absorbing fine particle dispersed powder according to Example 1 and the polycarbonate resin were uniformly mixed by a blender so that the concentration of the infrared ray absorbing fine particles was 0.05 wt%, and then melt-kneaded by a twin-screw extruder and extruded The strand was cut into pellets to obtain an infrared-absorbing fine particle-containing master batch according to Example 4. The infrared absorbing fine particle-containing masterbatch is an example of the infrared absorbing fine particle dispersion according to the present invention.

10 parts by mass of the infrared absorbing fine particle-containing masterbatch according to Example 4 and 90 parts by mass of polycarbonate resin pellets are dry-blended to obtain a plate material of 10 mm thickness using an injection molding machine, and the infrared ray according to Example 4 An absorption plate was obtained. The infrared absorbing plate is an example of the infrared absorbing particle dispersion according to the present invention.
The infrared absorption plate according to Example 4 obtained was evaluated in the same manner as Example 1.
The manufacturing conditions and the evaluation results of Example 4 are described in Tables 1 to 4.

[Example 5]
An infrared-absorbing sheet according to Example 5 was obtained in the same manner as Example 1, except that 1500 parts by mass of Sumilizer GP and 150 parts by mass of IRGANOX 1010 were added with respect to 100 parts by mass of hexagonal cesium tungsten bronze powder.
The fine particle dispersion and infrared ray absorbing sheet according to Example 5 obtained were evaluated in the same manner as Example 1.
The production conditions and the evaluation results of Example 5 are described in Tables 1 to 4.

[Example 6]
A fine particle dispersion and an infrared ray absorbing sheet according to Example 6 were obtained in the same manner as in Example 5 except that ADEKA STAB 2112 was used instead of IRGANOX 1010.
The fine particle dispersion and infrared ray absorbing sheet according to Example 6 obtained were evaluated in the same manner as Example 1.
The production conditions and the evaluation results of Example 6 are described in Tables 1 to 4.

[Examples 7 and 8]
Surface-treated infrared-absorbing fine particle powder and infrared-absorbing fine particles according to Examples 7 and 8 by performing the same operation as in Example 1 except that the amount of surface treatment agent dilution liquid a and the dropping addition time thereof are changed. The dispersion, the infrared ray absorbing fine particle dispersed powder, and the infrared ray absorbing sheet were obtained, and the same evaluation as in Example 1 was performed.
The production conditions and the evaluation results of Examples 7 and 8 are described in Tables 1 to 4.

[Example 9]
The ripening solution according to Example 1 was allowed to stand for 1 hour to separate the surface-treated infrared-absorbing fine particles from the medium by solid-liquid separation. Then, only the medium which is the supernatant was removed to obtain an infrared absorbing fine particle slurry. Isopropyl alcohol was added to the obtained infrared-absorbing fine particle slurry and stirred for 1 hour, and then allowed to stand for 1 hour, and solid-liquid separation of the surface-treated infrared-absorbing fine particles and the medium was performed again. Next, only the supernatant medium was removed to obtain an infrared absorbing fine particle slurry again.

After mixing and stirring 16% by mass of the infrared absorbing fine particle slurry again obtained, 24% by mass of the polyacrylate dispersant and 60% by mass of toluene, dispersion treatment is performed using an ultrasonic homogenizer, and infrared absorption according to Example 9 A fine particle dispersion was obtained.

An infrared-absorbing fine particle dispersed powder and an infrared-absorbing sheet according to Example 9 are obtained by performing the same operation as in Example 1 except that the infrared-absorbing fine particle dispersion according to Example 9 is used, Example 1 The same evaluation was performed.
The production conditions and the evaluation results of Example 9 are described in Tables 1 to 4.

[Example 10]
Surface treating agent dilution liquid b concerning Example 10 was obtained by mixing 2.4 mass% of zirconium tributoxy acetylacetonate, and 97.6 mass% of isopropyl alcohol. Surface-treated infrared-absorbing fine particle powder and infrared-absorbing fine particle dispersion according to Example 10 by performing the same operation as in Example 1 except that surface treatment agent dilution liquid b was used instead of surface treatment agent dilution liquid a. A liquid, infrared ray absorbing fine particle dispersed powder, and an infrared ray absorbing sheet were obtained, and the same evaluation as in Example 1 was carried out.
The production conditions and the evaluation results of Example 10 are described in Tables 1 to 4.

[Example 11]
2.6 mass% of diisopropoxy titanium bis ethyl acetoacetate and 97.4 mass% of isopropyl alcohol were mixed to obtain a surface treatment agent diluted solution c according to Example 11. Surface-treated infrared-absorbing fine particle powder and infrared-absorbing fine particle dispersion according to Example 11 by performing the same operation as Example 1 except that surface treatment agent dilution liquid c was used instead of surface treatment agent dilution liquid a A liquid, infrared ray absorbing fine particle dispersed powder, and an infrared ray absorbing sheet were obtained, and the same evaluation as in Example 1 was carried out.
The production conditions and the evaluation results of Example 11 are described in Tables 1 to 4.

[Example 12]
Surface-treated infrared-absorbing fine particle powder and infrared-absorbing fine particle dispersion according to Example 12 by performing the same operation as in Example 1 except that polymethyl methacrylate resin is used instead of polycarbonate resin as the solid resin The infrared ray absorbing fine particle dispersed powder and the infrared ray absorbing sheet were obtained, and the same evaluation as in Example 1 was carried out.
The production conditions and the evaluation results of Example 12 are described in Tables 1 to 4.

[Example 13]
A mixed solution obtained by mixing 25% by mass of cubic sodium tungsten bronze powder (manufactured by Sumitomo Metal Mining Co., Ltd.) with Na / W (molar ratio) = 0.33 and 75% by mass of isopropyl alcohol was 0.3 mm φ ZrO. ₂ Loaded in a paint shaker containing beads and ground and dispersed for 10 hours to obtain a dispersion of Na _0.33 WOz fine particles according to Example 13. The dispersed particle size of the _Na 0.33 WOZ particles in the obtained dispersion was measured, was 100 nm. In addition, as a setting of particle size measurement, the particle refractive index was set to 1.81, and the particle shape was non-spherical. The background was measured using isopropyl alcohol, and the solvent refractive index was 1.38. In addition, after removing the solvent of the obtained dispersion liquid, the crystallite diameter of Na _0.33 WOz fine particles was measured, which was 32 nm.

A dispersion B for forming a coating film was prepared by mixing a dispersion of Na _0.33 WOz fine particles according to Example 13 with isopropyl alcohol and having a concentration of infrared absorbing fine particles (cubic sodium tungsten bronze fine particles) of 2% by mass. Obtained. In a beaker, the obtained dispersion B for forming a coating film B is placed in a beaker, and while the solution is vigorously stirred by a bladed stirrer, 360 g of a surface treatment agent diluent a and 100 g of pure water as a diluent d are paralleled over 3 hours It was added dropwise. After the dropwise addition, the mixture was stirred at a temperature of 20 ° C. for 24 hours to prepare a ripening solution according to Example 13. Next, the medium was evaporated from the ripening solution by vacuum flow drying to obtain a surface-treated infrared-absorbing fine particle powder according to Example 13.

The infrared ray according to Example 13 is carried out in the same manner as in Example 1, except that the surface-treated infrared absorption fine particle powder according to Example 13 is used instead of the surface-treated infrared absorption fine particle powder according to Example 1. An absorbing particle dispersion, an infrared absorbing particle dispersion powder, and an infrared absorbing sheet were obtained, and the same evaluation as in Example 1 was performed.
The production conditions and the evaluation results of Example 13 are described in Tables 1 to 4.

[Examples 14 to 16]
Using a hexagonal potassium tungsten bronze powder (Example 14) with K / W (molar ratio) = 0.33 instead of hexagonal cesium tungsten bronze powder, a hexagonal of Rb / W (molar ratio) = 0.33 The dispersed particle size and the crystallite size of infrared absorbing fine particles in the same manner as in Example 1 except that W ₁₈ O ₄₉ (Example 16) of the magneli phase using crystalline rubidium tungsten bronze powder (Example 15) was used The dispersions C to E for forming a coating film were further obtained.
The surface-treated infrared rays according to Examples 14 to 16 are carried out in the same manner as in Example 1 except that the dispersions C to E for forming a coating film are used instead of the dispersion B for forming a coating film. Absorbent fine particle powder, infrared ray absorbing fine particle dispersion, infrared ray absorbing fine particle dispersed powder, and an infrared ray absorbing sheet were obtained, and the same evaluation as in Example 1 was carried out.
The production conditions and the evaluation results of Examples 14 to 16 are described in Tables 1 to 4.

[Example 17]
309 g of tetraethoxysilane was used as the surface treatment agent e. The surface-treated infrared-absorbing fine particle powder of Example 14 is operated in the same manner as in Example 1 except that the surface treatment agent e is used instead of the surface treatment agent dilution liquid a and isopropyl alcohol is not added. The infrared ray absorbing fine particle dispersion, the infrared ray absorbing fine particle dispersed powder, and the infrared ray absorbing sheet were obtained, and the same evaluation as in Example 1 was carried out. The production conditions and the evaluation results are shown in Tables 1 to 4.

[Example 18]
A surface treatment agent diluted solution f according to Example 15 was obtained by mixing 4.4% by mass of zinc acetylacetonate and 95.6% by mass of isopropyl alcohol. The surface-treated infrared-absorbing fine particle powder and the infrared-absorbing fine particle dispersion according to Example 15 are carried out in the same manner as in Example 1 except that the surface treatment agent dilution liquid f is used instead of the surface treatment agent dilution liquid a. A liquid, infrared ray absorbing fine particle dispersed powder, and an infrared ray absorbing sheet were obtained, and the same evaluation as in Example 1 was carried out. The production conditions and the evaluation results are shown in Tables 1 to 4.

[Example 19]
The medium was evaporated from the ripening liquid according to Example 1 by spray drying instead of vacuum flow drying to obtain a powder (surface treated infrared absorption fine particle powder) containing surface-treated infrared-absorbing fine particles according to Example 19. The infrared-absorbing fine particle dispersion liquid according to Example 19 is carried out by the same operation as in Example 1 except that the obtained surface-treated infrared-absorbing fine particle powder and pure water are mixed to obtain an infrared-absorbing fine particle dispersion liquid. The infrared ray absorbing fine particle dispersed powder and the infrared ray absorbing sheet were obtained, and the same evaluation as in Example 1 was carried out. The production conditions and the evaluation results are shown in Tables 1 to 4.

Comparative Example 1
A fine particle dispersion and an infrared ray absorbing sheet according to Comparative Example 1 were obtained in the same manner as in Example 1 except that nothing was added instead of Sumilizer GP.
The fine particle dispersion and the infrared ray absorbing sheet according to Comparative Example 1 thus obtained were evaluated in the same manner as Example 1.
The production conditions and the evaluation results of Comparative Example 1 are described in Tables 1 to 3 and 5.

Comparative Example 2
A fine particle dispersion and an infrared ray absorbing sheet according to Comparative Example 2 were obtained in the same manner as in Example 1 except that 500 parts by mass of Sumilizer GP was added to 100 parts by mass of hexagonal cesium tungsten bronze.
The fine particle dispersion and infrared ray absorbing sheet according to Comparative Example 2 thus obtained were evaluated in the same manner as Example 1.
The production conditions and the evaluation results of Comparative Example 2 are described in Tables 1 to 3 and 5.

[Comparative Examples 3 and 4]
300 parts by mass of IRGANOX 1010 was added instead of Sumilizer GP with respect to 100 parts by mass of hexagonal cesium tungsten bronze (Comparative Example 3), or 300 parts by mass of ADEKA STAB 2112 was added instead of Sumilizer GP (Comparative Example 4) In the same manner as in Example 1, a fine particle dispersion and infrared absorption sheets according to Comparative Examples 3 and 4 were obtained.
The fine particle dispersion and infrared ray absorbing sheets according to Comparative Examples 3 and 4 thus obtained were evaluated in the same manner as Example 1.
The production conditions and the evaluation results of Comparative Examples 3 and 4 are described in Tables 1 to 3 and 5, respectively.

Comparative Example 5
A resin sheet according to Comparative Example 5 was obtained by adding Sumilizer GP in the same amount as Example 1 except that nothing was added in place of the dispersed powder. That is, the resin sheet which concerns on the comparative example 5 is a resin sheet which does not contain absorption microparticles | fine-particles and contains only the stabilizer of SumilizerGP (structural formula (2)).
The resin sheet that was transparent before the test according to Comparative Example 5 obtained turned white cloudy and opaque after exposure for 9 days in a moist heat atmosphere at 85 ° C. and 90%.
The production conditions and the evaluation results of Comparative Example 5 are described in Tables 1 to 3 and 5.

Comparative Example 6
7% by mass of hexagonal cesium tungsten bronze powder, 24% by mass of polyacrylate dispersant and 69% by mass of toluene were mixed, and the obtained mixture was loaded on a paint shaker containing 0.3 mmφ ZrO ₂ beads for 4 hours. The particles were pulverized and dispersed to obtain an infrared-absorbing fine particle dispersion according to Comparative Example 6. It was 100 nm when the dispersion particle diameter of the infrared rays absorption microparticle in the obtained dispersion liquid was measured. In addition, as a setting of particle size measurement, the particle refractive index was set to 1.81, and the particle shape was non-spherical. In addition, the background was measured using toluene, and the solvent refractive index was 1.50. In addition, after removing the solvent of the obtained dispersion liquid, the crystallite diameter was measured to be 32 nm.
Next, the medium was evaporated from the infrared absorbing fine particle dispersion by vacuum flow drying to obtain an infrared absorbing fine particle dispersed powder according to Comparative Example 6.

An infrared-absorbing sheet according to Comparative Example 6 is obtained in the same manner as in Example 1, except that the infrared-absorbing fine particle dispersed powder according to Comparative Example 6 is used instead of the infrared-absorbing fine particle dispersed powder according to Example 1, Example 1 The same evaluation was performed.
The production conditions and the evaluation results of Comparative Example 6 are described in Tables 1 to 3 and 5.

Comparative Example 7
An infrared-absorbing fine particle dispersion, infrared-absorbing fine particle dispersed powder according to Comparative Example 7 by performing the same operation as Comparative Example 6 except that polymethyl methacrylate resin is used instead of polycarbonate resin as the solid resin. An infrared absorption sheet was obtained, and the same evaluation as in Example 1 was performed.
The production conditions and the evaluation results of Comparative Example 7 are described in Tables 1 to 3 and 5.

[Comparative Examples 8 to 11]
Instead of hexagonal cesium tungsten bronze powder, cubic sodium tungsten bronze powder (comparative example 8) with Na / W (molar ratio) = 0.33 and hexagonal potassium with K / W (molar ratio) = 0.33 A tungsten bronze powder (comparative example 9), a hexagonal rubidium tungsten bronze powder (comparative example 10) with Rb / W (molar ratio) = 0.33, and W ₁₈ O ₄₉ (comparative example 11) of a magneli phase were used. Except that the infrared-absorbing fine particle dispersion according to Comparative Examples 8 to 11, the infrared-absorbing fine particle dispersed powder, and the infrared-absorbing sheet are obtained by the same operation as Comparative Example 6, and evaluation similar to Example 1 is carried out. Carried out.
The production conditions and the evaluation results of Comparative Examples 8 to 11 are described in Tables 1 to 3 and 5, respectively.

Comparative Example 12
13 mass% of hexagonal cesium tungsten bronze powder with Cs / W (molar ratio) = 0.33 and 87 mass% of isopropyl alcohol were mixed, and the obtained mixture was added to a paint shaker containing 0.3 mm φ ZrO ₂ beads. It was loaded, and was pulverized and dispersed for 5 hours to obtain a dispersion of Cs _0.33 WOz fine particles according to Comparative Example 7. It was 100 nm when the dispersion particle diameter of Cs _0.33 WOz microparticles | fine-particles in the obtained dispersion liquid was measured. In addition, as a setting of particle size measurement, the particle refractive index was set to 1.81, and the particle shape was non-spherical. The background was measured using isopropyl alcohol, and the solvent refractive index was 1.38. In addition, after removing the solvent of the obtained dispersion liquid, the crystallite diameter was measured to be 32 nm.

A dispersion of Cs _0.33 WOz fine particles according to Comparative Example 12 and isopropyl alcohol were mixed to obtain a diluted solution in which the concentration of the infrared light absorbing fine particles (hexagonal cesium tungsten bronze fine particles) was 3.5% by mass. 21 g of aluminum ethyl acetoacetate diisopropylate was added to 733 g of the diluted solution obtained, mixed and stirred, and then dispersed using an ultrasonic homogenizer.

Then, the dispersion was placed in a beaker, and 100 g of water was added dropwise as a diluent d over 1 hour while vigorously stirring with a bladed stirrer. Further, while stirring, 140 g of tetraethoxysilane was added dropwise as a diluent e over 2 hours, stirring was carried out at 20 ° C. for 15 hours, and this solution was heated and aged at 70 ° C. for 2 hours. Next, the medium was evaporated from the ripening solution by vacuum flow drying, and heat treated at a temperature of 200 ° C. for 1 hour in a nitrogen atmosphere to obtain surface-treated infrared-absorbing fine particle powder of Comparative Example 12.

8% by mass of the surface-treated infrared-absorbing fine particle powder according to Comparative Example 12 was mixed with 24% by mass of the polyacrylate dispersant and 68% by mass of toluene. The obtained mixed solution was loaded on a paint shaker containing 0.3 mmφ ZrO ₂ beads, and was pulverized and dispersed for 5 hours to obtain an infrared absorbing fine particle dispersion according to Comparative Example 12.

The infrared absorption according to Comparative Example 12 is carried out by the same operation as in Example 1 except that the infrared absorption fine particle dispersion according to Comparative Example 12 is used instead of the infrared absorption fine particle dispersion according to Example 1. The fine particle dispersed powder and the infrared absorbing sheet were obtained, and the same evaluation as in Example 1 was carried out.
The production conditions and the evaluation results of Comparative Example 12 are described in Tables 1 to 3 and 5.

Comparative Example 13
A resin sheet according to Comparative Example 13 was obtained in the same manner as Example 1, except that nothing was added in place of Sumilizer GP and nothing was added in place of dispersed powder. That is, the resin sheet according to Comparative Example 13 contains neither the surface-treated infrared-absorbing fine particles nor the additive such as Sumilizer GP.
The obtained resin sheet according to Comparative Example 13 was evaluated in the same manner as Example 1. The results are set forth in Table 5. Almost no change was observed in the optical characteristics of the resin sheet according to Comparative Example 13 after being kept in an air atmosphere at 120 ° C. for 30 days and after being exposed to a moist heat atmosphere at 85 ° C. 90% for 9 days.
The production conditions and the evaluation results of Comparative Example 13 are described in Tables 1 to 3 and 5.

* 1: d is pure water * 2: d is pure water * 3: 360 g of surface treatment agent dilution liquid a dropped, 100 g of pure water d dropped * 4: 100 g of pure water d dropped, 140 g of tetraethoxysilane e dropped * 5: Surface treatment agent dilution liquid a and pure water d are dropped in parallel for 3 hours * 6: Pure water d is dropped for 1 hour, and tetraethoxysilane e is dropped for 2 hours

Addition amount * 1: Addition amount of additive with respect to 100 parts by mass of composite tungsten oxide fine particles [part by mass]

Claims

An infrared-absorbing fine particle dispersion comprising a liquid medium, surface-treated infrared-absorbing fine particles dispersed in the medium, and a phosphite ester compound,
The surface of the surface-treated infrared absorbing fine particle 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, a hydrolysis product of a metal cyclic oligomer compound Is coated with a coating film containing one or more selected from
The phosphite ester compound is a phosphite ester compound represented by the structural formula (1), and the amount of the phosphite ester compound added is 100 parts by mass of the infrared absorbing fine particles. An infrared-absorbing fine particle dispersion, which is more than 500 parts by mass and not more than 50000 parts by mass.

However, in the above structural formula (1), R 1, R 2, R 4 and R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 1 to 12 carbon atoms, 7 to carbon atoms Either an aralkyl group of 12 or an aromatic group,
R3 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
X is a single bond or any of divalent residues represented by the following structural formula (1-1),

A represents an alkylene group having 2 to 8 carbon atoms or a divalent residue represented by the following structural formula (1-2),

One of Y and Z is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms, and the other one is hydrogen Either an atom or an alkyl group having 1 to 8 carbon atoms,
In the above structural formula (1-1), R 6 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
In the above structural formula (1-2), R 7 is either a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a phosphite based on which the terminal is represented by the structural formula (1) It shows that it is bound to the oxygen atom side of the compound.
The film thickness of the said coating film is 0.5 nm or more, The infrared rays absorption particle dispersion liquid of Claim 1 characterized by the above-mentioned.
The infrared absorption according to claim 1 or 2, wherein the metal chelate compound or / and the metal cyclic oligomer compound contain one or more metal elements selected from Al, Zr, Ti, Si, Zn. Fine particle dispersion.
The infrared absorption according to any one of claims 1 to 3, 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. Fine particle dispersion.
The infrared absorbing fine particles have a general formula WyOz (where W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), or / and a general formula MxWyOz (where M is H, He Alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, T1, Si, Ge, Sn, Pb, Sb, B, F, P, Se, Br, Te, Ti, Nb, Mo, Ta, Re, Be, Hf, Os, Bi, I, One or more elements selected from Yb, W is tungsten, O is oxygen, infrared absorbing fine particles represented by 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ 3.0) The method according to any one of claims 1 to 4, characterized in that External absorption fine particle dispersion.
The infrared absorption according to claim 5, wherein the M element is at least one selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. Fine particle dispersion.
The infrared absorbing particle dispersion liquid according to any one of claims 1 to 6, wherein the infrared absorbing particle is a particle having a hexagonal crystal structure.
The infrared absorbing particle dispersion liquid according to any one of claims 1 to 7, wherein a crystallite diameter of the infrared absorbing particle is 1 nm or more and 200 nm or less.
9. The infrared ray according to any one of claims 1 to 8, wherein the carbon concentration of the surface-treated infrared-absorbing fine particle powder comprising the surface-treated infrared-absorbing fine particle is 0.2% by mass or more and 5.0% by mass or less. Absorbing fine particle dispersion.
10. The liquid medium according to any one of claims 1 to 9, wherein the liquid medium is at least one liquid medium selected from organic solvents, fats and oils, liquid plasticizers, compounds polymerized by curing, and water. Infrared absorbing fine particle dispersion described in.
Furthermore, it is characterized in that it contains one or more types of stabilizers selected from phosphoric acid stabilizers other than the phosphite ester compounds, hindered phenol stabilizers, sulfide stabilizers, and metal deactivators. The infrared absorption fine particle dispersion according to any one of claims 1 to 10.
An infrared-absorbing fine particle dispersion comprising surface-treated infrared-absorbing fine particles dispersed in a medium and a phosphite ester compound,
The surface of the surface-treated infrared absorbing fine particle 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, a hydrolysis product of a metal cyclic oligomer compound Is coated with a coating film containing one or more selected from
The phosphite ester compound is a phosphite ester compound represented by the structural formula (1), and the amount of the phosphite ester compound added is 100 parts by mass of the infrared absorbing fine particles. An infrared absorbing fine particle dispersion characterized by having more than 500 parts by mass and not more than 50000 parts by mass.

However, in the above structural formula (1), R 1, R 2, R 4 and R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 1 to 12 carbon atoms, 7 to carbon atoms Either an aralkyl group of 12 or aromatic,
R3 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
X is a single bond or any of divalent residues represented by the following structural formula (1-1),

A represents an alkylene group having 2 to 8 carbon atoms or a divalent residue represented by the following structural formula (1-2),

One of Y and Z is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms, and the other one is hydrogen Either an atom or an alkyl group having 1 to 8 carbon atoms,
In the above structural formula (1-1), R 6 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
In the above structural formula (1-2), R 7 is either a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a phosphite based on which the terminal is represented by the structural formula (1) It shows that it is bound to the oxygen atom side of the compound.
The infrared absorbing fine particle dispersion according to claim 12, wherein the metal chelate compound or / and the metal cyclic oligomer compound contain one or more metal elements selected from Al, Zr, Ti, Si and Zn. body.
The infrared absorbing fine particle dispersion according to claim 12 or 13, wherein the metal chelate compound or the metal cyclic oligomer compound has one or more selected from an ether bond, an ester bond, an alkoxy group, and an acetyl group. .
The infrared absorbing fine particles have a general formula WyOz (wherein W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), or / and a general formula MxWyOz (where M is H, He Alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, T1, Si, Ge, Sn, Pb, Sb, B, F, P, Se, Br, Te, Ti, Nb, Mo, Ta, Re, Be, Hf, Os, Bi, I, One or more elements selected from Yb, W is tungsten, O is oxygen, and is an infrared-absorbing fine particle represented by 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ 3) The infrared according to any one of claims 12 to 14, characterized in that Absorption fine particle dispersion.
The infrared absorption according to claim 15, wherein the M element is at least one selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. Fine particle dispersion.
The infrared absorbing particle dispersion according to any one of claims 12 to 16, wherein the infrared absorbing particle is a particle having a hexagonal crystal structure.
The infrared absorbing fine particle dispersion according to any one of claims 12 to 17, wherein a crystallite diameter of the infrared absorbing fine particles is 1 nm or more and 200 nm or less.
The infrared ray according to any one of claims 12 to 18, wherein in the surface-treated infrared-absorbing fine particle powder comprising the surface-treated infrared-absorbing fine particle, the carbon concentration is 0.2% by mass or more and 5.0% by mass or less. Absorbing fine particle dispersion.
The infrared-absorbing fine particle dispersion according to any one of claims 12 to 19, wherein the medium is a polymer.
The infrared absorbing fine particle dispersion according to any one of claims 12 to 20, wherein the medium is a solid resin.
The solid resin is at least one resin selected from fluorocarbon resin, PET resin, acrylic resin, polyamide resin, vinyl chloride resin, polycarbonate resin, olefin resin, epoxy resin, and polyimide resin. 22. The infrared absorbing particle dispersion according to claim 21.
Furthermore, it is characterized in that it contains one or more types of stabilizers selected from phosphoric acid stabilizers other than the phosphite ester compounds, hindered phenol stabilizers, sulfide stabilizers, and metal deactivators. The infrared-absorbing fine particle dispersion according to any one of claims 12 to 22.
Infrared absorbing particles, water,
An organic solvent, a liquid resin, a fat and oil, a liquid plasticizer for the resin, a polymer monomer, or a mixture of two or more selected from these groups are mixed, subjected to a dispersion treatment, and the infrared ray is absorbed. Obtaining a dispersion for forming a film of fine particles;
A metal chelate compound and / or a metal cyclic oligomer compound is added to the film-forming dispersion, and the surface of the infrared absorbing fine particle is a product of a hydrolysis product of a metal chelate compound and a polymer of a hydrolysis product of a metal chelate compound A coating of at least one selected from a hydrolysis product of a metal cyclic oligomer compound and a polymer of a hydrolysis product of a metal cyclic oligomer compound;
After the covering step, the liquid medium constituting the dispersion liquid for forming a film is removed to obtain surface-treated infrared-absorbing fine particle powder containing surface-treated infrared-absorbing fine particles;
The step of adding the surface-treated infrared-absorbing fine particle powder to a predetermined medium and dispersing it to obtain a dispersion of the surface-treated infrared-absorbing fine particles
The phosphite compound is added to the dispersion of the surface-treated infrared-absorbing fine particles in an amount of more than 500 parts by mass and not more than 50000 parts by mass with respect to 100 parts by mass of the infrared-absorbing fine particles. Obtaining the dispersion of the surface-treated infrared-absorbing fine particles, the method comprising: producing a dispersion of the infrared-absorbing fine particles.
Infrared absorbing particles, water,
An organic solvent, a liquid resin, a fat and oil, a liquid plasticizer for the resin, a polymer monomer, or a mixture of two or more selected from these groups are mixed, subjected to a dispersion treatment, and the infrared ray is absorbed. Obtaining a dispersion for forming a film of fine particles;
A metal chelate compound and / or a metal cyclic oligomer compound is added to the film-forming dispersion, and the surface of the infrared absorbing fine particle is a product of a hydrolysis product of a metal chelate compound and a polymer of a hydrolysis product of a metal chelate compound A coating of at least one selected from a hydrolysis product of a metal cyclic oligomer compound and a polymer of a hydrolysis product of a metal cyclic oligomer compound;
After the covering step, the liquid medium constituting the dispersion for forming a film is solvent-replaced with a predetermined medium to obtain a dispersion of surface-treated infrared-absorbing fine particles;
The phosphite compound is added to the dispersion of the surface-treated infrared-absorbing fine particles in an amount of more than 500 parts by mass and not more than 50000 parts by mass with respect to 100 parts by mass of the infrared-absorbing fine particles. Obtaining the dispersion of the surface-treated infrared-absorbing fine particles, the method comprising: producing a dispersion of the infrared-absorbing fine particles.
A dispersion of surface-treated infrared-absorbing fine particles containing the phosphite ester compound according to claim 24 or 25 or a dispersion of surface-treated infrared-absorbing microparticles containing the phosphite ester compound is dried. A dispersed powder of surface-treated infrared-absorbing fine particles containing a phosphite ester compound,
Mixing an appropriate medium to obtain an infrared-absorbing fine particle dispersion, a method of producing an infrared-absorbing fine particle dispersion.
A dispersion powder of surface-treated infrared-absorbing fine particles obtained by drying the dispersion of surface-treated infrared-absorbing fine particles according to claim 24 or 25, a phosphite ester compound, and an appropriate medium are mixed to obtain infrared rays. And a step of obtaining an absorbing particle dispersion.
However, the mixing amount of the phosphite ester compound is more than 500 parts by mass and not more than 50000 parts by mass with respect to 100 parts by mass of the infrared absorbing fine particles.