TWI771524B - Infrared absorbing fine particle dispersion liquid, infrared absorbing fine particle dispersion body, and method for producing the same - Google Patents

Abstract

The present invention provides an infrared absorbing fine particle dispersion liquid and an infrared absorbing fine particle dispersion which are excellent in moist heat resistance and heat resistance and have excellent infrared absorbing properties.

The present invention provides an infrared absorbing fine particle dispersion liquid, which contains a liquid medium, surface-treated infrared absorbing fine particles dispersed in the medium, and a phosphite compound, wherein the surface of the surface-treated infrared absorbing fine particles is composed of The coating film containing the hydrolyzate of a metal chelate compound etc. is covered, and the addition amount of the said phosphite type compound exceeds 500 mass parts and is 50000 mass parts or less with respect to 100 mass parts of said infrared absorbing fine particles.

Description

Infrared absorbing fine particle dispersion, infrared absorbing fine particle dispersion and method for producing the same

The present invention relates to an infrared-absorbing fine particle dispersion liquid, an infrared-absorbing fine particle dispersion, and a method for producing the same, which transmit light in the visible light region and absorb light in the infrared region.

In recent years, the demand for infrared absorbers has increased rapidly, and many patents related to infrared absorbers have been proposed. Considering these proposals from the viewpoint of functionality, for example, in the fields of various buildings, windows of vehicles, etc., it is possible to sufficiently absorb visible light while shielding the light of the near-infrared region, and to suppress the brightness while maintaining the brightness. Those whose purpose is to increase the indoor temperature; those whose purpose is to prevent the infrared rays emitted forward from the PDP (plasma display panel) from causing malfunction of the remote control devices of wireless phones or home appliances, or adverse effects on optical transmission and communication, etc.

In addition, from the viewpoint of a light-shielding member, for example, a light-shielding member used as a window material, etc., a light-shielding film containing a black-based pigment, a semi-mirror-type light-shielding member in which a metal such as aluminum is vapor-deposited, and the black-based pigment have been proposed. It includes inorganic pigments such as carbon black and titanium black, which have absorption properties from the visible light region to the near-infrared region, and organic pigments such as aniline black, which have strong absorption properties only in the visible light region.

For example, Patent Document 1 proposes an infrared blocking glass, which is provided on a transparent glass substrate, and which is formed from the periodic table group IIIa, IVa, Vb, VIb, and VIIb group from the substrate side. A composite tungsten oxide film of at least one metal ion selected from the group is used as the first layer, a transparent dielectric film is arranged on the first layer as the second layer, and a group IIIa containing from the periodic table is arranged on the second layer. , a composite tungsten oxide film of at least one metal ion selected from the group consisting of Group IVa, Group Vb, Group VIb and Group VIIb as the third layer, and by making the refractive index of the transparent dielectric film of the second layer The refractive index of the composite tungsten oxide film is lower than that of the first layer and the third layer above; it can be suitably used for parts that require high visible light transmittance and good infrared blocking performance.

In addition, Patent Document 2 proposes an infrared cut glass in which a first dielectric film is provided as a first layer on a transparent glass substrate from the substrate side by the same method as in Patent Document 1, and the first dielectric film is formed on the first layer. A tungsten oxide film is provided on the first layer as a second layer, and a second dielectric film is provided on the second layer as a third layer.

In addition, Patent Document 3 proposes a heat ray blocking glass in which a composite tungsten oxide film containing the same metal element as in Patent Document 1 is provided on a transparent substrate from the substrate side by the same method as in Patent Document 1. As the first layer, a transparent dielectric film is provided on the first layer as the second layer.

In addition, in Patent Document 4, a solar light control glass sheet having solar light shielding properties is proposed, wherein tungsten trioxide (WO) containing an additive element such as hydrogen, lithium, sodium, or potassium is coated by a CVD method or a spray method. ₃ ), molybdenum trioxide (MoO ₃ ), niobium pentoxide (Nb ₂ O ₅ ), tantalum pentoxide (Ta ₂ O ₅ ), vanadium pentoxide (V ₂ O ₃ ) and vanadium dioxide (VO ₂ ) 1 A metal oxide film selected above is formed by thermal decomposition at about 250°C.

In addition, in Patent Document 5, a solar tunable light-insulating material is proposed, which uses tungsten oxide obtained by hydrolyzing tungstic acid, and adds an organic compound having a specific structure such as polyvinylpyrrolidone to the tungsten oxide. made of polymer. If the sun-tunable light-tunable thermal insulation material is irradiated with sunlight, the tungsten oxide absorbs ultraviolet rays in the light to generate excited electrons and holes, and the appearance of 5-valent tungsten increases significantly due to a small amount of ultraviolet rays, and the coloring reaction changes. fast, and the coloring density becomes high. On the other hand, by blocking light, the tungsten electrode with a valence of five is rapidly oxidized to a valence of 6, and the decolorization reaction is accelerated. It has been proposed to use this coloring/decolorizing property to obtain a faster coloring and decolorizing reaction to sunlight, and an absorption peak appears at a wavelength of 1250 nm in the near-infrared region during coloring, which can block the near-infrared sunlight of sunlight. Adjustable dimming insulation.

On the other hand, the inventor of the present invention disclosed in Patent Document 6 that tungsten hexachloride is dissolved in alcohol, the medium is directly evaporated, or the medium is evaporated after heating under reflux, and then the medium is heated at 100° C. to 500° C. This obtains a tungsten oxide fine particle powder containing tungsten trioxide or its hydrate or a mixture of the two. In addition, it is disclosed that an electrochromic element can be obtained by using the tungsten oxide fine particles, and that the optical properties of the film can be changed when a multilayer laminate is formed and protons are introduced into the film.

In addition, in Patent Document 7, it is disclosed that meta-type ammonium tungstate and various water-soluble metal salts are used as raw materials, and the dried product of the mixed aqueous solution is heated at a heating temperature of about 300 to 700°C. MxWO ₃ (M; alkali, alkaline earth, rare earth and other metal elements, 0 Various methods of tungsten bronze represented by x<1). In addition, a method for producing various tungsten bronze-coated composites by performing the same operation on a support is disclosed, and use as an electrode catalyst material for fuel cells and the like is disclosed.

In addition, in Patent Document 8, the present inventors disclose an infrared shielding material fine particle dispersion in which the infrared shielding material fine particles are dispersed in a medium, and the optical properties, conductivity, and production method of the infrared shielding material fine particle dispersion. The infrared shielding material microparticles are microparticles of tungsten oxide represented by the general formula WyOz (wherein, W is tungsten, O is oxygen, and 2.2≦z/y≦2.999), or/and the general formula MxWyOz (wherein, M is from 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, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I One or more elements selected from the group, W is tungsten, O is oxygen, and the fine particles of composite tungsten oxide represented by 0.001≦x/y≦1, 2.2≦z/y≦3.0), and the infrared shielding material particles The particle diameter is 1 nm or more and 800 nm or less.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 8-59300

[Patent Document 2] Japanese Patent Laid-Open No. 8-12378

[Patent Document 3] Japanese Patent Laid-Open No. 8-283044

[Patent Document 4] Japanese Patent Laid-Open No. 2000-119045

[Patent Document 5] Japanese Patent Laid-Open No. 9-127559

[Patent Document 6] Japanese Patent Laid-Open No. 2003-121884

[Patent Document 7] Japanese Patent Laid-Open No. 8-73223

[Patent Document 8] International Publication No. 2005/37932

[Patent Document 9] International Publication No. 2010/55570

According to the research of the inventors of the present application, it was found that in the optical member (film, resin sheet, etc.) containing the above-mentioned tungsten oxide fine particles or/and composite tungsten oxide fine particles, the water vapor or water in the air, depending on the usage conditions or methods, may The system slowly penetrates into the solid resin. In addition, it was found that if water vapor or water gradually penetrates into the solid resin, the surface of the oxide fine particles containing tungsten is decomposed, and the transmittance of light with a wavelength of 200 to 2600 nm increases with time, and the above The infrared absorption performance of the optical member gradually decreases.

In addition, according to the research of the inventors of the present application, it was found that in the tungsten oxide fine particles or composite tungsten oxide fine particles disclosed in Patent Document 8, harmful radicals that are active in polymer media such as solid resins due to heat exposure are generated. , due to the harmful free radicals, the surface of the microparticles is also decomposed and deteriorated, and even the infrared absorption effect is lost.

Under the above circumstances, the inventors of the present application disclosed in Patent Document 9, as infrared shielding fine particles having excellent water resistance and excellent infrared shielding properties, the following infrared shielding fine particles and a method for producing the same. Represented tungsten oxide or/and composite tungsten oxide microparticles represented by the general formula MxWyOz, the average primary particle size of the microparticles is 1 nm or more and 800 nm or less, and the surface of the microparticles is a 4-functional silane compound or its partial hydrolysis product , or/and coated with organometallic compounds.

However, infrared absorbing materials are basically used outdoors due to their characteristics, and most of them require higher weather resistance. In addition, with the increasing demand in the market year by year, the infrared shielding fine particles disclosed in Patent Document 9 have also been demanded for further improvement in water resistance and moist heat resistance. In addition, the infrared shielding fine particles disclosed in Patent Document 9 have a low resistance to heat exposure, that is, the improvement effect of heat resistance, and have a certain problem.

The present invention has been accomplished under the circumstances described above, and an object of the present invention is to provide an infrared absorbing fine particle dispersion liquid, an infrared absorbing fine particle dispersion, and a method for producing the same, which are excellent in moist heat resistance and heat resistance, and have excellent infrared absorbing properties.

In order to solve the above-mentioned problems, the inventors of the present invention have aimed to use the above-mentioned tungsten oxide fine particles or/and composite tungsten oxide fine particles having excellent optical properties as infrared absorbing fine particles, and to enable the heat and humidity resistance and chemical stability of the infrared absorbing fine particles. The composition of improvement was studied. As a result, the key idea is to coat the surface of each infrared absorbing fine particle with a compound that has excellent affinity with the surface of the infrared absorbing fine particle, and which is uniformly adsorbed on the surface of each infrared absorbing fine particle to form a strong coating film.

The inventors of the present invention have further studied and considered metal chelate compounds or metal cyclic oligomer compounds as compounds having excellent affinity for the above-mentioned infrared absorbing fine particles and forming a coating film. Then, further research was carried out, and the result was considered that the hydrolyzed products of these compounds generated when the metal chelate compound or the metal cyclic oligomer compound was hydrolyzed, or the polymers of the hydrolyzed products, were uniformly adsorbed on each infrared ray A compound that absorbs the surface of fine particles and forms a firm coating.

That is, it is considered that the surface of the tungsten oxide microparticles or/and the composite tungsten oxide microparticles is hydrolyzed by the hydrolysis of the hydrolyzed product of the metal chelate compound, the polymer of the hydrolyzed product of the metal chelate compound, and the metal cyclic oligomer compound. Infrared absorbing fine particles (in the present invention, may be described as "surface-treated infrared absorbing fine particles") coated with a coating film of one or more polymers selected from the product and the polymer of the hydrolyzate of the metal cyclic oligomer compound. In addition, it was found that the surface-treated infrared absorbing fine particles have excellent heat and humidity resistance.

Furthermore, it has been found that an infrared absorbing fine particle dispersion or the like produced using an infrared absorbing fine particle dispersion liquid obtained by dispersing the surface-treated infrared absorbing fine particles in a suitable medium has excellent heat and humidity resistance and has excellent infrared absorbing properties.

The inventors of the present invention have further studied and found an infrared absorbing dispersion obtained by adding a phosphite compound having a specific structure in an amount that is not considered in general resin moldings and the like, and an infrared absorbing dispersion using the same. The produced infrared absorbing dispersion exhibits long-term stable heat-and-moisture resistance and is excellent in heat resistance, thereby solving the above-mentioned problems.

That is, the first invention for solving the above-mentioned problems is an infrared-absorbing fine particle dispersion liquid comprising a liquid medium, surface-treated infrared-absorbing fine particles dispersed in the medium, and a phosphite-based compound, characterized by: The surface of the above-mentioned surface-treated infrared absorbing fine particles is composed of hydrolyzates of metal chelate compounds, polymers of hydrolyzates of metal chelate compounds, hydrolyzates of metal cyclic oligomer compounds, and polymers of metal cyclic oligomer compounds. The hydrolyzate polymer is covered with one or more coating films; the above-mentioned phosphite-based compound is a phosphite-based compound represented by the structural formula (1), and the addition amount of the above-mentioned phosphite-based compound is relative to 100 parts by mass of the infrared absorbing fine particles is more than 500 parts by mass and not more than 50,000 parts by mass.

Wherein, in the above structural formula (1), R1, R2, R4 and R5 are independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 1 to 12 carbon atoms, and an alkyl group having 7 to 12 carbon atoms. Any one of an aralkyl group and an aromatic group, R3 is any one of a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X is a single bond, or a bivalent represented by the following structural formula (1-1) any of the residues,

A is an alkylene group having 2 to 8 carbon atoms or any of the divalent residues represented by the following structural formula (1-2),

Either Y or Z is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aralkoxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or any one of the alkyl groups with 1 to 8 carbon atoms, in the above structural formula (1-1), R6 is any one of a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, in the above structural formula (1- In 2), R7 is either a single bond or an alkylene group having 1 to 8 carbon atoms, and * indicates that the terminal is bonded to the oxygen atom side of the phosphite-based compound represented by structural formula (1).

A second invention is the infrared-absorbing fine particle dispersion liquid according to the first invention, wherein the film thickness of the coating film is 0.5 nm or more.

The third invention is the infrared-absorbing fine particle dispersion liquid according to the first or second invention, wherein the metal chelate compound or/and the metal cyclic oligomer compound contain a compound selected from Al, Zr, Ti, Si, and Zn. One or more metal elements.

A fourth invention is the infrared-absorbing fine particle dispersion liquid according to any one of the first to third inventions, wherein the metal chelate compound or the metal cyclic oligomer compound has an ether bond, an ester bond, an alkoxyl One or more selected from group and acetyl group.

A fifth invention is the infrared-absorbing fine particle dispersion liquid according to any one of the first to fourth inventions, wherein the infrared-absorbing fine particles are of the general formula WyOz (wherein W is tungsten, O is oxygen, and 2.2≦z/y ≦2.999), or/and the general formula MxWyOz (wherein, M element is selected from 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, One or more elements selected from V, Mo, Ta, Re, Be, Hf, Os, Bi, I, and Yb, W is tungsten, O is oxygen, and 0.001≦x/y≦1, 2.0≦z/y ≦3.0) Infrared absorbing fine particles.

A sixth invention is the infrared absorbing fine particle dispersion liquid 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, and Sn .

A seventh invention is the infrared absorbing fine particle dispersion liquid according to any one of the first to sixth inventions, wherein the infrared absorbing fine particles are fine particles having a hexagonal crystal structure.

An eighth invention is the infrared absorbing fine particle dispersion liquid according to any one of the first to seventh inventions, wherein the crystallite diameter of the infrared absorbing fine particle is 1 nm or more and 200 nm or less.

A ninth invention is the infrared-absorbing fine particle dispersion liquid according to any one of the first to eighth inventions, wherein in the surface-treated infrared-absorbing fine-particle powder containing the surface-treated infrared-absorbing fine particles, the carbon concentration is 0.2 mass % or more and 5.0 mass % or less.

A tenth invention is the infrared-absorbing fine particle dispersion liquid according to any one of the first to ninth inventions, wherein the liquid medium is a compound selected from organic solvents, oils and fats, liquid plasticizers, and polymerized by curing , One or more liquid medium selected by water.

The eleventh invention is the infrared-absorbing fine particle dispersion liquid according to any one of the first to tenth inventions, further comprising a phosphoric acid-based stabilizer, a hindered phenol-based stabilizer, and a thioether-based stabilizer other than the above-mentioned phosphite-based compound One or more stabilizers selected from the agent and metal deactivator.

A twelfth invention is an infrared absorbing fine particle dispersion comprising surface-treated infrared absorbing fine particles dispersed in a medium and a phosphite compound, wherein the surface of the surface-treated infrared absorbing fine particles is made of a metal containing a metal Coating of one or more selected from hydrolyzate of chelate compound, polymer of hydrolyzate of metal chelate compound, hydrolyzate of metal cyclic oligomer compound, and polymer of hydrolyzate of metal cyclic oligomer compound Film coating, the phosphite-based compound is a phosphite-based compound represented by structural formula (1), and the addition amount of the phosphite-based compound is more than 500 parts by mass relative to 100 parts by mass of the infrared absorbing fine particles and 50,000 parts by mass or less.

Wherein, in the above structural formula (1), R1, R2, R4 and R5 are independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 1 to 12 carbon atoms, and an alkyl group having 7 to 12 carbon atoms. Either an aralkyl group or an aromatic group, R3 is any one of a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X is a single bond, or a divalent residue represented by the following structural formula (1-1) either of the bases,

A is an alkylene group having 2 to 8 carbon atoms or any of the divalent residues represented by the following structural formula (1-2),

One of Y and Z is any one of hydroxyl, alkyl group with 1 to 8 carbon atoms, alkoxy group with 1 to 8 carbon atoms, or aralkoxy group with 7 to 12 carbon atoms, and the other is hydrogen atom or any one of alkyl groups having 1 to 8 carbon atoms, in the above structural formula (1-1), R6 is any one of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and in the above structural formula (1) In -2), R7 is either a single bond or an alkylene group having 1 to 8 carbon atoms, and * indicates that the terminal is bonded to the oxygen atom side of the phosphite compound represented by the structural formula (1).

A thirteenth invention is the infrared-absorbing fine particle dispersion according to the twelfth invention, wherein the metal chelate compound or/and the metal cyclic oligomer compound contain one selected from Al, Zr, Ti, Si, and Zn the above metal elements.

A fourteenth invention is the infrared-absorbing fine particle dispersion according to the twelfth or thirteenth invention, wherein the metal chelate compound or the metal cyclic oligomer compound has an ether bond, an ester bond, an alkoxy group, or an acetyl group. One or more types of base selection.

A fifteenth invention is the infrared-absorbing fine particle dispersion according to any one of the twelfth to fourteenth inventions, wherein the infrared-absorbing fine particles are of the general formula WyO _Z (wherein W is tungsten, O is oxygen, and 2.2≦z/ y≦2.999), or/and the general formula MxWyOz (wherein, M element is selected from H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni , Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb , V, Mo, Ta, Re, Be, Hf, Os, Bi, I, Yb, one or more elements selected, W is tungsten, O is oxygen, and 0.001≦x/y≦1, 2.0≦z/ Infrared absorbing fine particles represented by y≦3).

A sixteenth invention is the infrared-absorbing fine particle dispersion 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, and Sn .

A seventeenth invention is the infrared absorbing fine particle dispersion according to any one of the twelfth to sixteenth inventions, wherein the infrared absorbing fine particle is a fine particle having a hexagonal crystal structure.

An eighteenth invention is the infrared absorbing fine particle dispersion according to any one of the twelfth to seventeenth inventions, wherein the crystallite diameter of the infrared absorbing fine particle is 1 nm or more and 200 nm or less.

A nineteenth invention is the infrared-absorbing fine particle dispersion according to any one of the twelfth to eighteenth inventions, wherein in the surface-treated infrared-absorbing fine-particle powder containing the surface-treated infrared-absorbing fine particles, the carbon concentration is 0.2 mass % or more and 5.0 mass % or less.

A twentieth invention is the infrared-absorbing fine particle dispersion according to any one of the twelfth to nineteenth inventions, wherein the medium is a polymer.

A twenty-first invention is the infrared-absorbing fine particle dispersion according to any one of the twelfth to twentieth inventions, wherein the medium is a solid resin.

A twenty-second invention is the infrared-absorbing fine particle dispersion according to any one of the twenty-first invention, wherein the solid resin is a self-fluorine resin, a PET resin, an acrylic resin, a polyamide resin, a vinyl chloride resin, or a polycarbonate. One or more resins selected from resin, olefin resin, epoxy resin and polyimide resin.

A 23rd invention is the infrared absorbing fine particle dispersion according to any one of the 12th to 22nd inventions, further comprising a phosphoric acid-based stabilizer, a hindered phenol-based stabilizer, and a thioether-based stabilizer other than the above-mentioned phosphite-based compound One or more stabilizers selected from the agent and metal deactivator.

The twenty-fourth invention is a method for producing a dispersion of infrared-absorbing fine particles, comprising the steps of: mixing the infrared-absorbing fine particles, water, an organic solvent, a liquid resin, grease, a liquid plasticizer for the resin, a polymer A step of mixing a monomer or a mixture of two or more selected from these groups, and performing a dispersion treatment to obtain the above-mentioned dispersion liquid for forming a film of infrared absorbing fine particles; adding a metal chelate compound to the above-mentioned dispersion liquid for forming a film Or/and metal cyclic oligomer compounds, using from the hydrolysis products of metal chelate compounds, polymers of the hydrolysis products of metal chelate compounds, hydrolysis products of metal cyclic oligomer compounds, metal cyclic oligomer compounds The step of coating the surface of the above-mentioned infrared absorbing fine particles by selecting one or more kinds of polymers of the hydrolyzate of The step of surface-treating the surface-treated infrared-absorbing fine particle powder; the step of adding the above-mentioned surface-treated infrared-absorbing fine-particle powder to a specific medium and dispersing it to obtain a dispersion liquid of the surface-treated infrared-absorbing fine particle; and adding the above-mentioned surface-treated infrared-absorbing fine particle powder A step of adding a phosphite compound in an amount exceeding 500 parts by mass and not more than 50,000 parts by mass relative to 100 parts by mass of the infrared absorbing fine particles to obtain a dispersion liquid of surface-treated infrared absorbing fine particles containing a phosphite compound.

The twenty-fifth invention is a method for producing a dispersion liquid of infrared absorbing fine particles, comprising the steps of: mixing the infrared absorbing fine particles, water, an organic solvent, a liquid resin, grease, a liquid plasticizer for the resin, a polymer A step of mixing a monomer or a mixture of two or more selected from these groups, and performing a dispersion treatment to obtain the above-mentioned dispersion liquid for forming a film of infrared absorbing fine particles; adding a metal chelate compound to the above-mentioned dispersion liquid for forming a film Or/and metal cyclic oligomer compounds, using from the hydrolysis products of metal chelate compounds, polymers of the hydrolysis products of metal chelate compounds, hydrolysis products of metal cyclic oligomer compounds, metal cyclic oligomer compounds The step of coating the surface of the infrared absorbing fine particles with one or more selected polymers of the hydrolyzate; after the coating step, the liquid medium constituting the dispersion liquid for coating film formation is solvent-replaced and replaced with a specific medium , and the steps of obtaining a dispersion liquid of surface-treated infrared absorbing fine particles; and adding a phosphite system of more than 500 parts by mass and less than 50,000 parts by mass relative to 100 parts by mass of the above-mentioned infrared absorbing fine particles to the dispersion liquid of said surface-treated infrared absorbing fine particles The step of obtaining a dispersion liquid of surface-treated infrared absorbing fine particles containing a phosphite-based compound.

A twenty-sixth invention is a method for producing an infrared-absorbing fine particle dispersion, comprising the steps of: subjecting the surface-treated infrared-absorbing fine particle dispersion containing a phosphite compound according to the twenty-fourth or twenty-fifth invention, or The step of drying the dispersion liquid of the surface-treated infrared-absorbing fine particles containing the phosphite-based compound obtained by drying the dispersion powder of the surface-treated infrared-absorbing fine particles containing the phosphite-based compound, mixing with a suitable medium to obtain the infrared-absorbing fine particle dispersion .

A twenty-seventh invention is a method for producing a dispersion of infrared-absorbing fine particles, comprising the steps of: the surface-treated infrared-absorbing fine particles obtained by drying the dispersion of the surface-treated infrared-absorbing fine particles described in the twenty-fourth or twenty-fifth invention The step of mixing the loose powder, the phosphite-based compound, and an appropriate medium to obtain a dispersion of infrared-absorbing fine particles; wherein the mixing amount of the phosphite-based compound is more than 500 parts by mass relative to 100 parts by mass of the infrared-absorbing fine particles parts and 50,000 parts by mass or less.

The infrared absorbing fine particle dispersion prepared by using the infrared absorbing fine particle dispersion liquid of the present invention has high humidity and heat resistance and heat resistance, and has excellent infrared absorbing properties.

11‧‧‧Octahedron formed by WO ₆ units

12‧‧‧Element M

FIG. 1 is a schematic plan view of a crystal structure in a composite tungsten oxide having a hexagonal crystal structure.

FIG. 2 is a transmission electron microscope photograph of 300,000 times the surface-treated infrared absorbing microparticles of Example 1. FIG.

The surface-treated infrared absorbing microparticles of the present invention are made of tungsten oxide microparticles or/and composite tungsten oxide microparticles belonging to the infrared absorbing microparticles from a polymer containing hydrolyzed products of metal chelate compounds and hydrolyzed products of metal chelate compounds. , Surface-treated infrared absorbing fine particles covered with a coating film of one or more selected from the hydrolyzate of the metal cyclic oligomer compound and the polymer of the hydrolyzate of the metal cyclic oligomer compound. Moreover, the infrared absorbing fine particle dispersion liquid of this invention, or the infrared absorbing fine particle dispersion system produced using this dispersion liquid contains the phosphite compound which has a specific structure.

Hereinafter, [1] Infrared absorbing fine particles, [2] Surface treatment agent used for surface coating of infrared absorbing fine particles, [3] Surface coating method of infrared absorbing fine particles, [4] Phosphite compound, [5] Infrared The present invention will be described in detail in the order of the absorbing fine particle dispersion, [6] Infrared absorbing fine particle dispersion, infrared absorbing substrate, and articles.

Furthermore, in the present invention, "in order to impart moisture and heat resistance to the infrared absorbing fine particles, a metal chelate compound hydrolyzate, a polymer of a metal chelate compound hydrolyzate, and a metal cyclic oligomer compound may be used. The coating film formed on the surface of the fine particles by selecting one or more polymers of the hydrolyzate and the hydrolyzate of the metal cyclic oligomer compound" is abbreviated as "coating film".

[1] Infrared absorbing fine particles

It is known that materials generally containing free electrons exhibit a reflection-absorption response to electromagnetic waves around the region of solar rays with a wavelength of 200 nm to 2600 nm by plasma vibration. If the powder of this substance is made into particles with a smaller wavelength than light, the geometrical scattering in the visible light region (wavelength 380nm to 780nm) can be reduced to obtain transparency in the visible light region.

Furthermore, the term "transparency" in the present invention is used in the sense of "less scattering of light in the visible light region and high transmittance".

Generally, tungsten oxide (WO ₃ ) does not have effective free electrons, so the absorption and reflection characteristics in the infrared region are low, and it cannot be effectively used as infrared absorbing fine particles.

On the other hand, it is known that WO ₃ having an oxygen defect, or a composite tungsten oxide obtained by adding a positive element such as Na to WO ₃ is a conductive material and a material having free electrons. Furthermore, by analyzing the single crystals and the like of these materials having free electrons, the response of free electrons to light in the infrared region is taught.

The inventors of the present application have found that in a specific part of the composition range of tungsten and oxygen, there is a range that is particularly effective as infrared absorbing fine particles, so that tungsten oxide fine particles that are transparent in the visible light region and have absorption in the infrared region, Composite tungsten oxide fine particles.

Here, with respect to the tungsten oxide fine particles or/and composite tungsten oxide fine particles belonging to the infrared absorbing fine particles of the present invention, (1) tungsten oxide fine particles, (2) composite tungsten oxide fine particles, and (3) tungsten oxide fine particles and the order of the composite tungsten oxide fine particles will be described.

(1) Tungsten oxide fine particles

The tungsten oxide fine particles of the present invention are fine particles of tungsten oxide represented by the general formula WyOz (wherein W is tungsten, O is oxygen, and 2.2≦z/y≦2.999).

In the tungsten oxide represented by the general formula WyOz, the composition range of the tungsten and oxygen is preferably that the composition ratio of oxygen to tungsten is less than 3, and when the infrared absorbing fine particles are described as WyOz, 2.2≦z/y≦ 2.999.

If the value of z/y is 2.2 or more, undesired crystal phase of WO ₂ can be avoided in the tungsten oxide, and chemical stability as a material can be obtained, so it becomes effective infrared absorbing fine particles. On the other hand, when the value of this z/y is 2.999 or less, a required amount of free electrons are generated, and the infrared absorbing fine particles with high efficiency are obtained.

(2) Composite tungsten oxide fine particles

A composite tungsten oxide is prepared by adding the following element M to the above-mentioned WO ₃ , and free electrons are generated in the WO ₃ , especially in the near-infrared region, showing strong absorption characteristics derived from free electrons, which can be effectively used as a wavelength of 1000nm. Nearby near-infrared absorbing fine particles.

That is, by controlling the amount of oxygen to this WO ₃ and adding the element M that generates free electrons, more efficient infrared absorbing fine particles can be obtained. When the general formula of the infrared absorbing fine particles obtained by controlling the amount of oxygen and adding the element M that generates free electrons is described as MxWyOz (wherein M is the above-mentioned M element, W is tungsten, and O is oxygen), it is preferable to satisfy 0.001 Infrared absorbing fine particles with the relationship of ≦x/y≦1, 2.0≦z/y≦3.

First, the value of x/y representing the addition amount of the element M will be described.

If the value of x/y is greater than 0.001, a sufficient amount of free electrons is generated in the composite tungsten oxide to obtain the target infrared absorption effect. In addition, as the addition amount of element M increases, the supply amount of free electrons increases, and the infrared absorption efficiency also increases. However, when the value of x/y is about 1, the effect is saturated. Moreover, it is preferable that the value of x/y is less than 1, since the generation of the impurity phase in the infrared absorbing fine particles can be avoided.

Further, the element M is preferably selected from 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, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be , Hf, Os, Bi, I, Yb at least one selected.

Here, from the viewpoint of the stability of the MxWyOz to which the element M is added, the element M is more preferably selected from 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, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, One or more elements selected from Ti, Nb, V, Mo, Ta, and Re. In addition, from the viewpoint of improving the optical properties and weather resistance of the infrared absorbing fine particles, the element M is more preferably one belonging to an alkaline earth metal element, a transition metal element, a 4B group element, or a 5B group element.

Next, the value of z/y representing the control of the oxygen amount will be described. Regarding the value of z/y, in the composite tungsten oxide represented by MxWyOz, it functions according to the same mechanism as the tungsten oxide represented by WyO _Z above, and in addition, when z/y=3.0 or 2.0≦z/y When ≦2.2, free electron supply is also caused by the addition amount of the above-mentioned element M. Therefore, 2.0≦z/y≦3.0 is preferable, 2.2≦z/y≦3.0 is more preferable, and 2.45≦z/y≦3.0 is still more preferable.

Furthermore, when the composite tungsten oxide fine particles have a hexagonal crystal structure, the transmission of the visible light region and the absorption of the infrared region of the fine particles are improved. The description will be made with reference to FIG. 1 which is a schematic plan view of the crystal structure of the hexagonal crystal.

In FIG. 1 , the hexagonal space is formed by the collection of 6 octahedrons formed by the WO ₆ units indicated by the symbol 11, and the element M indicated by the symbol 12 is arranged in the space to form one unit, and the 1 A plurality of units are assembled to form a hexagonal crystal structure.

In addition, in order to obtain the effect of improving the transmission of light in the visible light region and the absorption of light in the infrared region, it is only necessary to include the unit structure described in FIG. 1 in the composite tungsten oxide fine particles. It may be crystalline or amorphous.

When the cation of the element M is added to the hexagonal space, the transmission of light in the visible light region is improved, and the absorption of light in the infrared region is improved. Here, in general, the hexagonal crystal is easily formed when the element M having a large ionic radius is added. Specifically, when Cs, K, Rb, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn are added, hexagonal crystals are easily formed. Of course, even if it is an element other than these, as long as the said element M exists in the space|gap of the hexagonal shape formed by _WO6 unit, it is not limited to the said element.

When the composite tungsten oxide fine particles having a hexagonal crystal structure have a uniform crystal structure, the addition amount of the additive element M is preferably 0.2 or more and 0.5 or less, and more preferably 0.33 in terms of x/y. It is considered that the above-mentioned element M is arranged in all the voids of the hexagon by making the value of x/y 0.33.

Furthermore, in addition to hexagonal crystals, tetragonal and cubic composite tungsten oxides 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 may shift to the longer wavelength side in the order of cubic < tetragonal < hexagonal. In addition, along with this, the order of less absorption in the visible light region is hexagonal, tetragonal, and cubic. Therefore, it is preferable to use a hexagonal composite tungsten oxide for the purpose of making the light in the visible region more transparent and absorbing the light in the infrared region more. However, the tendency of the optical properties described here is only an approximate tendency, and the present invention is not limited to those that vary depending on the type of added element, the amount of addition, and the amount of oxygen.

(3) Tungsten oxide fine particles and composite tungsten oxide fine particles

The infrared absorbing microparticles containing tungsten oxide microparticles or composite tungsten oxide microparticles of the present invention absorb a large amount of light in the near-infrared region, especially in the vicinity of a wavelength of 1000 nm, and therefore most of the transmitted hues are blue to green.

In addition, the dispersed particle size of the tungsten oxide fine particles or the composite tungsten oxide fine particles in the infrared absorbing fine particles can be selected according to the purpose of use.

First of all, when it is used for an application in which transparency is to be maintained, it is preferable to have a particle size of 800 nm or less. The reason is that the particles smaller than 800 nm do not completely absorb light due to scattering, and the visibility in the visible light region can be maintained, and the transparency can be maintained efficiently at the same time. In particular, when transparency in the visible light region is important, it is preferable to consider scattering by particles.

When emphasis is placed on reducing the scattering by particles, the dispersed particle diameter may be 200 nm or less, preferably 100 nm or less. The reason is: if the dispersed particle size of the particles is small, the light scattering in the visible light region of wavelength 400nm~780nm caused by geometric scattering or Mie scattering can be reduced, and as a result, the infrared absorbing film can be prevented from becoming as ineffective as ground glass. Obtaining clear transparency. That is, when the dispersed particle size is 200 nm or less, the above-mentioned geometric scattering or Mie scattering is reduced and a Rayleigh scattering region is formed. The reason for this is that in the Rayleigh scattering region, the scattered light is reduced in proportion to the 6 power of the particle size, and thus the scattering is reduced and the transparency is improved along with the reduction of the dispersed particle size.

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

The haze value of the dispersion of infrared absorbing fine particles obtained by dispersing the infrared absorbing fine particles of the present invention into a medium by setting the above-mentioned dispersed particle diameter to be 800 nm or less can be set to 30% when the visible light transmittance is 85% or less. the following. When the haze is a value greater than 30%, clear transparency like frosted glass cannot be obtained.

In addition, the dispersed particle size of the infrared absorbing fine particles can be measured using ELS-8000 manufactured by Otsuka Electronics Co., Ltd. based on the principle of the dynamic light scattering method, or the like.

In addition, in the tungsten oxide fine particles or the composite tungsten oxide fine particles, the so-called "Magnelli phase" having a composition ratio represented by 2.45≦2/y≦2.999 is chemically stable and has good absorption characteristics in the infrared region. , so it is suitable for infrared absorbing particles.

In addition, from the viewpoint of exhibiting excellent infrared absorption properties, 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 even more preferably 10 nm or more and 70 nm or less. For the measurement of the crystallite diameter, the measurement of the X-ray diffraction pattern by the powder X-ray diffraction method (θ-2θ method) and the analysis by the Rittwald method were used. For the measurement of the X-ray diffraction pattern, for example, a powder X-ray diffraction apparatus "X'Pert-PRO/MPD" manufactured by Spectris Co., Ltd. PANalytical can be used.

[2] Surface treatment agent used for surface coating of infrared absorbing fine particles

The surface treatment agents used for the surface coating of the infrared absorbing fine particles of the present invention are selected from the hydrolyzed products of metal chelate compounds, polymers of hydrolyzed products of metal chelate compounds, hydrolyzed products of metal cyclic oligomer compounds, metal cyclic oligomer compounds One or more selected from the polymer of the hydrolyzate of the oligomer compound.

In addition, the metal chelate compound and the metal cyclic oligomer compound are preferably metal alkoxides, metal acetylacetonates, and metal carboxylates, and preferably have an ether bond, an ester One or more selected from a bond, an alkoxy group, and an acetyl group.

Here, regarding the surface treatment agent of the present invention, hydrolysis of (1) metal chelate compound, (2) metal cyclic oligomer compound, (3) metal chelate compound or metal cyclic oligomer compound in order The product, the polymer, and (4) the addition amount of the surface treatment agent will be described.

(1) Metal chelate compounds

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 alkoxy groups.

Examples of the aluminum-based chelate compound include aluminum alkoxides such as aluminum ethoxide, aluminum isopropoxide, second aluminum butyrate, and mono-second butoxide aluminum diisopropyl ester, or these polymers, and acetoxyacetic acid. Ethyl aluminum diisopropyl ester, aluminum ginseng (ethyl acetoacetate), octyl aluminum diisopropyl acetoacetate, stearyl acetyl aluminum diisopropyl ester, bis(ethyl ethyl acetate) Acetate) aluminum, ginseng (acetopyruvate) aluminum, etc.

These compounds are made by dissolving aluminum alkoxides in aprotic solvents, petroleum-based solvents, hydrocarbon-based solvents, ester-based solvents, ketone-based solvents, ether-based solvents, amide-based solvents, etc., and β- Diketones, β-ketoesters, monovalent and polyhydric alcohols, fatty acids, etc., are heated and refluxed to obtain an alkoxy-containing aluminum chelate compound by the substitution reaction of ligands.

Examples of the zirconia-based chelate compound include zirconium alkoxides such as zirconium ethoxide and zirconium butoxide, or polymers thereof, zirconium tributoxy stearate, zirconium tetraacetylacetonate, zirconium tributoxyacetate, and the like. Zirconium pyruvate, zirconium dibutoxybis(acetylacetonate), zirconium tributoxyethylacetate, zirconium bis(ethylacetate)butoxyacetate, etc.

Examples of the titanium-based chelate compound include titanium alkoxides such as methyl titanate, ethyl titanate, isopropyl titanate, butyl titanate, and 2-ethylhexyl titanate, or polymers thereof, Titanium acetylacetonate, titanium tetraacetylacetonate, titanium octanediol, titanium ethylacetate, titanium lactate, titanium triethanolamine, etc.

As a silicon-based chelate compound, a tetrafunctional silane compound represented by the general formula: Si(OR) ₄ (wherein R is a monovalent hydrocarbon group with the same or different carbon atoms of 1 to 6) or a hydrolyzate thereof can be used . Specific examples of the tetrafunctional silane compound include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like. Furthermore, part or all of the alkoxy groups of these alkoxysilane monomers can be hydrolyzed to become silane monomers (or oligomers) of silanol (Si-OH) groups, and self-condensation by hydrolysis reaction formed aggregates.

In addition, as a hydrolysis product of a 4-functional silane compound (there is no appropriate term indicating the entire intermediate of the 4-functional silane compound), a part or all of an alkoxy group is hydrolyzed to become a silanol (Si-OH) group. The resulting silane monomers, oligomers of 4-5 polymers, and polymers (polysiloxane resins) with a weight average molecular weight (Mw) of about 800-8000. Furthermore, the alkoxysilyl group (Si-OR) in the alkoxysilane monomer is not completely hydrolyzed to become silanol (Si-OH) during the hydrolysis reaction.

Preferred examples of the zinc-based chelate compound include organic carboxylic acid zinc salts such as zinc octoate, zinc laurate, and zinc stearate, zinc acetylacetonate chelate, zinc benzylacetonate chelate, and diacetate zinc chelate. Zinc benzyl methane chelate, ethyl zinc acetyl acetate chelate, etc.

(2) Metal cyclic oligomer compound

The metal cyclic oligomer compound of the present invention is preferably at least one selected from Al-based, Zr-based, Ti-based, Si-based, and Zn-based cyclic oligomer compounds. Among them, cyclic aluminum oligomer compounds such as cyclic octoate alumina can be preferably exemplified.

(3) Hydrolysis products and polymers of metal chelate compounds or metal cyclic oligomer compounds

In the present invention, all the alkoxy groups, ether bonds, and ester bonds in the above-mentioned metal chelate compounds or metal cyclic oligomer compounds are hydrolyzed to become hydrolyzed products of hydroxyl or carboxyl groups, partial hydrolyzed products of partial hydrolysis, Or/and, the polymer formed by self-condensation through the hydrolysis reaction is coated on the surface of the infrared absorbing fine particles of the present invention as a coating film to obtain the surface-treated infrared absorbing fine particles of the present invention.

That is, the hydrolyzate in the present invention is a concept including a partial hydrolyzate.

However, for example, in a reaction system with an organic solvent such as alcohol, in general, even in terms of stoichiometric composition, sufficient water is present in the system. Depending on the type or concentration of the organic solvent, it becomes the metal of the starting material. All of the alkoxy or ether bonds or ester bonds of the chelate compound or the metal cyclic oligomer compound are not necessarily hydrolyzed. Therefore, depending on the conditions of the following surface coating method, it may be in an amorphous state in which carbon C is taken up in the molecule even after hydrolysis.

As a result, undecomposed metal chelate compound and/or metal cyclic oligomer compound may be contained in the coating film, but there is no particular problem if it is a trace amount.

(4) The amount of surface treatment agent added

The addition amount of the metal chelate compound or the metal cyclic oligomer compound is preferably 0.1 parts by mass or more and 1000 parts by mass or less in terms of metal elements with respect to 100 parts by mass of the infrared absorbing fine particles. More preferably, it is the range of 1 mass part or more and 500 mass parts or less. More preferably, it is the range of 10 mass parts or more and 150 mass parts or less.

The reason is that if the metal chelate compound or the metal cyclic oligomer compound is 0.1 part by mass or more, the hydrolyzate of these compounds or the polymer of the hydrolyzate exerts the effect of covering the surface of the infrared absorbing fine particles, and the obtained product is obtained. Improves heat and humidity resistance.

In addition, when the metal chelate compound or the metal cyclic oligomer compound is 1000 parts by mass or less, it is possible to avoid excessive adsorption of the infrared absorbing fine particles. Moreover, the improvement of the heat-and-moisture resistance by surface coating is not saturated, and the coating effect can be expected to be improved.

Furthermore, by making the metal chelate compound or the metal cyclic oligomer compound to be 1000 parts by mass or less, it is possible to avoid excessive adsorption of the infrared absorbing fine particles, and the metal chelate compound or the metal cyclic oligomer compound can be used for the removal of the medium through the metal chelate compound or the metal cyclic oligomer compound. A hydrolysis product of a chemical compound, or a polymer of the hydrolysis product, and the microparticles easily form particles with each other. By preventing the undesired microparticles from forming particles with each other, good transparency can be ensured.

In addition, an increase in production cost due to an increase in addition amount and treatment time due to excess metal chelate compound or metal cyclic oligomer compound can also be avoided. Therefore, from an industrial viewpoint, the addition amount of the metal chelate compound or the metal cyclic oligomer compound is preferably 1000 parts by mass or less.

[3] Surface coating method

In the method for coating the surface of infrared absorbing fine particles of the present invention, first, an infrared absorbing fine particle dispersion liquid for forming a coating film prepared by dispersing the infrared absorbing fine particles in a suitable medium (described in the present invention as "coating film") is prepared. Forming a dispersion"). Then, a surface treatment agent is added to the prepared dispersion liquid for forming a coating film, and the mixture is mixed and stirred. In this way, the surface of the infrared absorbing microparticles is composed of hydrolyzates of metal chelate compounds, polymers of hydrolyzates of metal chelate compounds, hydrolyzates of metal cyclic oligomer compounds, and hydrolyzates of metal cyclic oligomer compounds. One or more of the selected polymers are coated with a coating film.

Here, regarding the surface coating method of the present invention, (1) preparation of the dispersion liquid for coating film formation, (2) preparation of the dispersion liquid for coating film formation using water as a medium, (3) adjustment Preparation of the dispersion liquid for coating film formation to which the amount of water was added, and (4) treatment after mixing and stirring in the dispersion liquid for coating film formation.

(1) Preparation of dispersion liquid for coating film formation

In the dispersion liquid for forming a coating film of the present invention, it is preferable to carefully pulverize the tungsten oxide or/and the composite tungsten oxide belonging to the infrared absorbing fine particles in advance, so as to disperse them in an appropriate medium, and prepare a single tungsten oxide in advance. state of dispersion. In addition, the key point is to ensure a dispersed state in the pulverization and dispersion treatment steps, and to prevent the fine particles from aggregating each other. The reason is that in the process of surface treatment of the infrared absorbing fine particles, the fine particles can be prevented from agglomerating, the fine particles are coated on the surface in the state of agglomerates, and even the agglomerates remain in the following infrared absorbing fine particle dispersions, Therefore, the following cases are the case where the transparency of the infrared absorbing fine particle dispersion or the infrared absorbing substrate is lowered.

Therefore, by pulverizing and dispersing the dispersion liquid for forming a coating film of the present invention, when the surface treating agent of the present invention is added, the hydrolyzate of the surface treating agent and the polymer of the hydrolyzate can be made uniform and Firmly coat each infrared absorbing fine particle.

As a specific method of the pulverization and dispersion treatment, for example, a pulverization and dispersion treatment method using devices such as a bead mill, a ball mill, a sand mill, a paint shaker, and an ultrasonic homogenizer can be mentioned. Among them, it is preferable to use media mixers such as bead mills, ball mills, sand mills, paint shakers, etc. using media such as beads, steel balls, Ottawa sand, etc. Pulverize and disperse.

(2) Preparation of dispersion liquid for coating film formation using water as medium

The inventors of the present application found that, in the preparation of the above-mentioned dispersion liquid for coating film formation, it is preferable to add the surface treatment agent of the present invention to the dispersion liquid for coating film formation using water as a medium while stirring and mixing, and further The hydrolysis reaction of the added metal chelate compound and metal cyclic oligomer compound is completed immediately. In the present invention, it may be described as "a dispersion liquid for forming a coating film using water as a medium".

It is considered that it is affected by the reaction order of the surface treating agent of the present invention added. That is, the reason is considered to be that, in the dispersion liquid for forming a coating film using water as a medium, the hydrolysis reaction of the surface treating agent necessarily proceeds first, and then the polymerization reaction of the generated hydrolyzate occurs. As a result, compared with the case where water is not used as a medium, the residual amount of carbon C in the molecules of the surface treatment agent in the coating film can be reduced. By reducing the residual amount of carbon C in the molecule of the surface treatment agent in the coating film, a high-density coating film can be formed.

Furthermore, in the above-mentioned dispersion liquid for forming a coating film using water as a medium, the metal chelate compound, the metal cyclic oligomer compound, the hydrolyzate of these, and the polymer of the hydrolyzate are also added immediately after the addition. That is, when it is dispersed into metal ions, in this case, when it becomes a saturated aqueous solution, that is, the decomposition of the metal ions is completed.

On the other hand, in the dispersion liquid for forming a coating film using water as a medium, it is preferable that the dispersion concentration of the tungsten oxide or/and the composite tungsten oxide in the dispersion liquid for forming a coating film is 0.01 mass % More than 80 mass % or less. When the dispersion concentration is in this range, the pH value can be set to 8 or less, and the infrared absorbing fine particles of the present invention are kept dispersed by electrostatic repulsion.

As a result, it can be considered that the surfaces of all the infrared absorbing fine particles are composed of hydrolyzates of metal chelate compounds, polymers of hydrolyzates of metal chelate compounds, hydrolyzates of metal cyclic oligomer compounds, and metal cyclic oligomers. The polymer of the hydrolyzate of the compound is coated with one or more types of coating films selected to form the surface-treated infrared absorbing fine particles of the present invention.

The film thickness of the coating film of the surface-treated infrared-absorbing fine particles of the present invention is preferably 0.5 nm or more. The reason for this is that when the film thickness of the coating film is 0.5 nm or more, the surface-treated infrared-absorbing fine particles exhibit sufficient heat-and-moisture resistance and chemical stability. On the other hand, the film thickness of the coating film is preferably 100 nm or less from the viewpoint of securing predetermined optical properties by the surface-treated infrared-absorbing fine particles. Moreover, the film thickness is preferably 0.5 nm or more and 20 nm or less, and 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 the lattice (arrangement of atoms in the crystal) of the non-infrared absorption fine particles corresponds to the coating film.

(3) Preparation of dispersion liquid for coating film formation with adjusted amount of added water

As a modified example of the above-mentioned preparation method of the dispersion liquid for coating film formation using water as the medium, there is also a method of using an organic solvent as the medium of the dispersion liquid for coating film formation, while adjusting the amount of water added to an appropriate value, On the one hand, the above-mentioned reaction sequence is realized. In the present invention, it is described as "a dispersion liquid for forming a coating film using an organic solvent as a medium".

This preparation method is also convenient in the case of reducing the amount of water contained in the dispersion liquid for coating film formation according to the situation of the subsequent steps.

Specifically, the surface treatment agent of the present invention and pure water are simultaneously dropped while stirring and mixing the dispersion liquid for forming a coating film using an organic solvent as a medium. At this time, the temperature of the medium that affects the reaction speed, or the dropping speed of the surface treatment agent and pure water is appropriately controlled. In addition, as an organic solvent, what is necessary is just to be an alcohol type, a ketone type, and a glycol type solvent which dissolves in water at room temperature, and various ones can be selected.

(4) Treatment after mixing and stirring of the dispersion liquid for coating film formation

The surface-treated infrared absorbing fine particles of the present invention obtained in the above-mentioned preparation step of the dispersion liquid for coating film formation can be used as an infrared absorbing fine particle dispersion or an infrared absorbing base in a fine particle state, a state dispersed in a liquid medium or a solid medium material raw materials.

That is, the generated surface-treated infrared-absorbing fine particles do not require further heat treatment to improve the density or chemical stability of the coating film. The reason for this is that even if the heat treatment is not performed, the density and the adhesiveness of the coating film are sufficiently improved to the extent that the desired heat and humidity resistance can be obtained.

However, depending on the purpose of obtaining the powder of the surface-treated infrared absorbing fine particles from the dispersion liquid for coating film formation, the purpose of drying the obtained surface-treated infrared absorbing fine particle powder, etc., the dispersion liquid for forming a coating film or the surface treatment may be used. The infrared absorbing fine particle powder is heat-treated. In this case, however, care should be taken not to increase the heat treatment temperature beyond the temperature at which the surface-treated infrared absorbing fine particles are firmly agglomerated to form strong agglomerates.

The reason for this is that the surface-treated infrared absorbing fine particles of the present invention often require transparency in the infrared absorbing fine particle dispersion or infrared absorbing substrate to be finally used depending on the application. When an infrared absorbing fine particle dispersion or an infrared absorbing substrate is produced using the aggregate as an infrared absorbing material, a higher haze may be obtained.

In the case of heat treatment exceeding the temperature for forming strong aggregates, in order to ensure the transparency of the infrared absorbing fine particle dispersion or the infrared absorbing substrate, the strong aggregates are crushed dry or/and wet to redisperse. . However, during the crushing and redispersion, the coating film existing on the surface of the surface-treated infrared absorbing fine particles may be damaged, and a part of the coating film may be peeled off and the surface of the fine particles may be exposed.

As described above, since the surface-treated infrared absorbing fine particles of the present invention do not require heat treatment after mixing and stirring, strong aggregation does not occur, and therefore, dispersion treatment for crushing aggregation is not required or completed in a short time. As a result, the coating film of the surface-treated infrared-absorbing fine particles of the present invention is not damaged, and the respective infrared-absorbing fine particles are covered. In addition, it is considered that the infrared absorbing fine particle dispersion or infrared absorbing substrate produced by using the surface-treated infrared absorbing fine particles exhibits superior moist heat resistance compared with those obtained by conventional methods.

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

[4] Phosphite-based compounds

The inventors of the present invention have found that the infrared absorption of the present invention can be achieved by adding a phosphite compound having a specific structure to the above-mentioned infrared absorbing fine particle dispersion containing surface-treated infrared absorbing fine particles and a dispersion prepared using the dispersion. The weather resistance of the microparticle dispersion and the infrared absorbing substrate produced by using the same is improved, and the reduction of the infrared absorbing properties when the dispersion and the infrared absorbing substrate are used for a long time is suppressed.

That is, for the purpose of improving the weather resistance of the dispersion containing the surface-treated infrared absorbing fine particles and suppressing the decrease in the infrared absorbing properties of the dispersion when the dispersion is used for a long time, the infrared absorbing fine particle dispersion liquid, or the dispersion liquid prepared by using the dispersion liquid is used. The dispersion adds the phosphite compound of the present invention.

Then, in addition to the phosphite compound, one or more selected from a phosphoric acid-based stabilizer, a hindered phenol-based stabilizer, a thioether-based stabilizer, and a metal deactivator other than the phosphite compound are used to improve the weather resistance It is also a preferred composition to add an agent.

Below, (1) phosphite-based compound, (2) phosphoric acid-based stabilizer other than phosphite compound, (3) hindered phenol-based stabilizer, (4) sulfide-based stabilizer, (5) metal Deactivators are described.

(1) Phosphite compound

The phosphites used in the present invention are in the compound represented by the structural formula (1), wherein R1, R2, R4 and R5 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 5 to 12 carbon atoms. cycloaliphatic group, aralkyl group or aromatic group with 7-12 carbon atoms.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and tert-pentyl , isooctyl, third octyl, 2-ethylhexyl, etc.

Examples of the alicyclic group having 5 to 12 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 1-methylcyclopentyl, 1-methylcyclohexyl, and 1-methyl. -4-Isopropylcyclohexyl, etc.

Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, and the like.

Examples of the aromatic group having 7 to 12 carbon atoms include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 4-methylphenyl group, a 2,4-dimethylphenyl group, and a 2,6-dimethylphenyl group. methylphenyl, etc.

R1, R2 and R4 are preferably alkyl groups having 1 to 8 carbon atoms, alicyclic groups having 5 to 12 carbon atoms, and the like. R1 and R4 are more preferably tertiary alkyl groups such as tertiary butyl group, tertiary pentyl group, and tertiary octyl group, cyclohexyl group, 1-methylcyclohexyl group, and the like.

R2 is preferably an alkyl group with 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-pentyl, more preferably methyl , tertiary butyl, tertiary pentyl, etc. R5 is preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, etc. with 1 to 5 carbon atoms alkyl.

R3 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups having 1 to 8 carbon atoms as described above for R1, R2, R4, and R5. R5 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which is the same as described in R2 above, 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), R6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alicyclic group having 5 to 12 carbon atoms. The alkyl group and the alicyclic group having 5 to 12 carbon atoms are exemplified respectively: the same alkyl group and alicyclic group as described in the aforementioned R1, R2, R4 and R5.

R6 is preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and other alkyl groups having 1 to 5 carbon atoms. 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), preferably an alkylene group having 2 to 8 carbon atoms. Examples of the alkylene group include: Ethylidene, propylidene, butylene, pentylene, hexamethylene, octamethylene, 2,2-dimethyl-1,3-propylidene, etc., more preferably propylidene. The divalent residue represented by the structural formula (1-2) is bonded to an oxygen atom and a benzene nucleus, and * represents a bond to an oxygen atom. R7 represents a single bond or an alkylene group having 1 to 8 carbon atoms. Here, examples of the alkylene group having 1 to 8 carbon atoms include methylene, ethylidene, propylidene, butylene, and Pentyl, hexamethylene, octamethylene, 2,2-dimethyl-1,3-propylidene, etc. As this R7, a single bond, an ethylidene group, etc. are preferable.

Either one of Y and Z represents a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aralkoxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or a carbon number 1 ~8 alkyl groups. Here, as the alkyl group having 1 to 8 carbon atoms, the same alkyl groups as described above as R1, R2, R4 and R5 can be mentioned. Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, th Tributoxy, tert-pentyloxy, isooctyloxy, tert-octyloxy, 2-ethylhexyloxy and the like. Examples of the aralkoxy group having 7 to 12 carbon atoms include benzyloxy group, α-methylbenzyloxy group, α,α-dimethylbenzyloxy group, and the like. Y and Z can be hydroxy, alkyl with 1-8 carbons, alkoxy with 1-8 carbons or aralkoxy with 7-12 carbons, Z is hydrogen atom or alkane with 1-8 carbons base, or Z is hydroxyl, alkyl with 1-8 carbons, alkoxy with 1-8 carbons or aralkoxy with 7-12 carbons, Y is hydrogen atom or alkane with 1-8 carbons base.

Among the phosphites represented by the structural formula (1), R1 and R4 are particularly preferably a third alkyl group, a cyclohexyl group or a 1-methylcyclohexyl group, R2 is an alkyl group with 1 to 5 carbon atoms, and R5 is a A hydrogen atom or an alkyl group with 1-5 carbon atoms, R3 is a hydrogen atom or an alkyl group with 1-5 carbon atoms, X is a single bond, and A is an alkyl group with 2-8 carbon atoms.

Preferable specific examples of phosphites include: 2,4,8,10-tetra-tert-butyl-6-[3-(3-methyl-4-hydroxy-5-tert-butyl Phenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphetene [marketed as "Sumilizer (registered trademark) GP" (manufactured by Sumitomo Chemical Co., Ltd.) sold], 2,10-dimethyl-4,8-di-tert-butyl-6-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propoxy]- 12H-Dibenzo[d,g][1,3,2]dioxacyclo, 2,4,8,10-tetra-tert-butyl-6-[3-(3,5-di - tert-butyl-4-hydroxyphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphine, 2,4,8,10-tetra- tert-pentyl-6-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propoxy]-12-methyl-12H-dibenzo[d,g][1 ,3,2] Dioxaphosphatacyclo, 2,10-dimethyl-4,8-di-tert-butyl-6-[3-(3,5-di-tert-butyl-4- Hydroxyphenyl)propionyloxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphacycle, 2,4,8,10-tetra-tert-pentyl-6 -[3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionyloxy]-12-methyl-12H-dibenzo[d,g][1,3,2] Dioxaphosphacyclo, 2,4,8,10-tetra-tert-butyl-6-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy] -Dibenzo[d,f][1,3,2]dioxaphosphetene, 2,10-dimethyl-4,8-di-tert-butyl-6-(3,5 -Di-tert-butyl-4-hydroxybenzyloxy)-12H-dibenzo[d,g][1,3,2]dioxacyclo, 2,4,8,10- Tetra-tert-butyl-6-(3,5-di-tert-butyl-4-hydroxybenzyloxy]-12-methyl-12H-dibenzo[d,g][1,3 ,2] Dioxaphosphacyclo, 2,10-dimethyl-4,8-di-tert-butyl-6-[3-(3-methyl-4-hydroxy-5-tert-butyl Phenyl)propoxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphacycle, 2,4,8,10-tetra-tert-butyl-6-[ 3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propoxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphacyclo, 2 ,10-Diethyl-4,8-di-tert-butyl-6-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propoxy]-12H-diphenyl And[d,g][1,3,2]dioxaphosphacyclo, 2,4,8,10-tetra-tert-butyl-6-[2,2-dimethyl-3-(3 -tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-dibenzo[d,f] [1,3,2]dioxaphosphetene, etc.

A commercial item can also be used for phosphites. For example, a brand name Sumilizer (registered trademark) GP (manufactured by Sumitomo Chemical Co., Ltd.) etc. is mentioned.

The addition amount of the phosphites is preferably more than 500 parts by mass and 50,000 parts by mass or less with respect to 100 parts by mass of the infrared absorbing fine particles, and particularly preferably 700 parts by mass or more and 2,000 parts by mass or less.

When the amount of phosphites added is more than 500 parts by mass relative to 100 parts by mass of the fine particles, even after being kept in an atmospheric environment with a high temperature of 120°C, the increase in haze is suppressed, and the transmittance, especially sunlight transmission, is ensured rates were maintained at a good level.

On the other hand, if the amount of phosphites added is 50,000 parts by mass or less relative to 100 parts by mass of the infrared absorbing fine particles, the increase in haze is suppressed before and after holding in a high temperature atmosphere of 120°C, and transmittance, The solar transmittance is at a good level.

Here, in order to clarify the characteristics of the present invention, the method of adding a phosphite-based stabilizer to a dispersion/dispersion containing the surface-treated infrared absorbing fine particles of the present invention, and the conventional technique of dispersion without infrared absorbing fine particles A comparison of the method of adding a phosphite-based stabilizer to a dispersion/dispersion will be described.

As mentioned above, the addition amount of the phosphite-type stabilizer of this invention is more than 500 mass parts and 50000 mass parts or less with respect to 100 mass parts of infrared absorbing fine particles. On the other hand, the addition amount of the stabilizer such as phosphite in the conventional dispersion without the surface-treated infrared absorbing fine particles of the present invention is calculated based on the assumption that 100 parts by mass of the infrared absorbing fine particles are contained. In the case of the addition amount of the phosphite stabilizer in the dispersion of the conventional technology containing infrared absorbing fine particles, it is equivalent to the addition amount of 50 parts by mass to 200 parts by mass, and the addition amount in the present invention is more than 500 parts by mass. Parts by mass and 50,000 parts by mass or less are significantly different.

According to the findings of the present inventors, when the dispersion/dispersion contains the surface-treated infrared-absorbing fine particles of the present invention, the amount of the phosphite-based stabilizer to be added is more than 500 parts by mass relative to 100 parts by mass of the infrared-absorbing fine particles Parts by mass and 50,000 parts by mass or less are effective for the stability of the dispersion/dispersion.

On the other hand, when a phosphite-based stabilizer equivalent to more than 500 parts by mass and not more than 50,000 parts by mass is added to the dispersion/dispersion that does not contain infrared absorbing fine particles of the prior art, the dispersion/dispersion Visible white fog was generated in the body due to the hydrolysis of the stabilizer, and the optical properties were significantly deteriorated (refer to Comparative Example 5). Furthermore, the level of degraded optical properties in the conventional dispersion/dispersion is lower than that of the dispersion/dispersion without adding surface-treated infrared absorbing fine particles and stabilizer (refer to Comparative Examples 5 and 13).

(2) Other phosphorus stabilizers

Examples of phosphorus-based stabilizers other than the phosphite compounds described in (1) include those having a phosphorus-based functional group containing trivalent phosphorus represented by the general formula (2), and those represented by the general formula (3). Those with a phosphorus-based functional group containing pentavalent phosphorus.

Furthermore, in the general formula (2) and the general formula (3), x, y, and z take a value of 0 or 1. Further, R1, R2 and R3 are linear, cyclic, or branched hydrocarbon groups represented by the general formula CmHn, or halogen atoms such as fluorine, chlorine, and bromine, or hydrogen atoms. Furthermore, when y or z is 1, R2 or R3 may be a metal atom.

In addition, the "phosphorus functional group" in the present embodiment refers to the part other than R1 in the general formula (2) (3) (that is, the general formula: -Ox-P(OyR2)(OzR3), or the general formula: -Ox-P(OyR2)(OzR3) Formula: -Ox-P(O)(OyR2)(OzR3) Represented). Specific examples of phosphorus-based functional groups include: phosphonic acid group (-P(O)(OH) ₂ ), phosphoric acid group (-OP(O)(OH) ₂ ), phosphonate group (-P(O) )(OR2)(OR3)), phosphate group (-OP(O)(OR2)(OR3)), phosphine group (-P(R2)(R3)) and the like.

Among these phosphorus-based functional groups, the functional groups containing pentavalent phosphorus, such as phosphonic acid group, phosphoric acid group, phosphonate group, and phosphate ester group, can be considered to mainly have the function of inhibiting chain initiation (that is, by the adjacent phosphorus-based functional groups) And chelate to capture the function of metal ions).

On the other hand, phosphorus-based functional groups containing trivalent phosphorus such as a phosphine group can be considered to mainly have a function of decomposing peroxides (ie, a function of decomposing peroxides into stable compounds by oxidation of the P atom itself).

Among these phosphorus-based functional groups, the phosphonic acid-based anti-coloring agent having a phosphonic acid group can efficiently capture metal ions, and is excellent in stability such as hydrolysis resistance, and thus is particularly suitable as a reduction inhibitor of infrared absorption properties.

Preferable examples of the low-molecular-weight phosphorus-based anti-coloring agent include phosphoric acid (H ₃ PO ₄ ), triphenyl phosphite ((C ₆ H ₅ O) ₃ P), and tris-decyl phosphite. Octaalkyl ester ((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) and so on.

In addition, as a preferable example of a polymer type phosphorus-based anti-coloring agent, specifically, polyvinylphosphonic acid, polystyrenephosphonic acid, vinyl-based phosphoric acid (for example, acryloyl phosphate (CH ₂ =CHCOOPO(OH)) can be mentioned. ₂ ), vinyl alkyl phosphate (CH ₂ =CHR-O-PO(OH) ₂ and R is a polymer of -(CH ₂ )n-), etc.), polyether resin with phosphonic acid group introduced, Polyetheretheretherketone resin, linear phenol-formaldehyde resin, linear polystyrene resin, cross-linked polystyrene resin, linear poly(trifluorostyrene) resin, cross-linked (trifluorobenzene) Vinyl) resin, poly(2,3-diphenyl-1,4-phenylene ether) resin, poly(allyl ether ketone) resin, poly(propynyl ether) resin, poly(phenylquinoline) resin, Poly(benzylsilane) resin, polystyrene-graft-ethylene tetrafluoroethylene resin, polystyrene-graft-polyvinylidene fluoride resin, polystyrene-graft-tetrafluoroethylene resin, etc.

A commercial item can also be used for this phosphoric acid-based stabilizer. For example, Adekastab AS2112 (made by ADEKA Co., Ltd.) etc. is mentioned.

(3) Hindered phenol stabilizer

An example of a hindered phenol-based stabilizer is a compound in which a large group such as a tertiary butyl group is introduced into one position of a phenolic OH group. It is considered that the hindered phenol-based stabilizer mainly has a polymerization inhibitory function (that is, a function of trapping free radicals by phenolic OH groups and suppressing a chain reaction caused by free radicals).

Preferred examples of low molecular weight hindered phenol stabilizers include 2,6-tert-butyl-p-cresol, 2,6-di-tert-butyl-phenol, 2,4-di- Methyl-6-tert-butyl-phenol, butylhydroxyanisole, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylene Bis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), tetra[methylene-3(3,5- Di-tert-butyl-4-hydroxyphenyl)propionate]methane, 1,1,3-para(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, etc.

In addition, as a preferable example of the polymer-type hindered phenol-based stabilizer, monomers such as vinyl group, acryl group, methacryloyl group, and styryl group having the above-mentioned hindered phenol-based anti-coloring agent in the branch chain can be mentioned. A polymer of a body, or a polymer formed by incorporating the structure of the hindered phenol-based anti-coloring agent into the main chain, and the like.

Furthermore, as in the case of phosphorus-based anti-coloring agents, there are cases where high molecular weight compounds are preferred to low molecular weight compounds, and when high molecular weight compounds are used, a cross-linked structure may be introduced.

Among them, there are many points that have not been clearly explained in the process of capturing harmful radicals of the above-mentioned various anti-colorants, and there may be functions other than those described above, which are not limited to the above-mentioned functions.

As the hindered phenol-based stabilizer, a commercially available product can also be used. For example, brand name Irganox 1010 (manufactured by BASF) etc. are mentioned.

(4) Sulfide-based stabilizer

An example of a sulfide-based stabilizer is a compound having divalent sulfur in the molecule (in this embodiment, it may be referred to as a "sulfur-based anti-coloring agent"). It is considered that the sulfur-based anti-coloring agent mainly has a peroxide decomposition function (ie, a function of decomposing a peroxide into a stable compound by oxidation of the S atom itself). Preferable examples of the low molecular weight sulfur-based anti-coloring agent 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 )), sulfur Dimyristyl substituted dipropionate (S(CH ₂ CH ₂ COOC ₁₄ H ₂₉ ) ₂ ), β,β'-distearyl thiodibutyrate (S(CH(CH ₃ )CH ₂ COOC ₁₈ H ) ₃₉ ) ₂ ), 2-mercaptobenzimidazole (C ₆ H ₄ NHNCSH), dilauryl sulfide (S(C ₁₂ H ₂₅ ) ₂ ) and the like.

As a sulfide-based stabilizer, a commercial item can also be used. For example, trade name Sumilizer (registered trademark) TPM (made by Sumitomo Chemical Co., Ltd.) etc. are mentioned.

(5) Metal deactivator

As the metal deactivator, hydrazine derivatives, salicylic acid derivatives, oxalic acid derivatives, etc. can be preferably used, and 2',3-bis[[3-[3,5-di-tert-butyl -4-Hydroxyphenyl]propionyl]]propanehydrazide, 2-hydroxy-N-(2H-1,2,4-triazol-3-yl)benzamide, dodecanedioic acid bis[ 2-(2-Hydroxybenzyl)hydrazine] and the like.

The addition amount of the metal deactivator to the infrared-absorbing fine particle dispersion liquid or the infrared-absorbing fine particle dispersion of the present invention also varies depending on the required performance or the type and amount of the phosphite compound and other additives used in combination. Therefore, it is not particularly limited, but is preferably 1 to 10 parts by mass, more preferably 3 to 8 parts by mass relative to 100 parts by mass of the infrared absorbing fine particles in the infrared absorbing fine particle dispersion liquid or the infrared absorbing fine particle dispersion. When the addition amount of the metal deactivator is 1 part by mass or more, the effect of preventing the decrease of the infrared absorption function is exhibited, and the effect is almost saturated at 10 parts by mass.

[5] Infrared absorption fine particle dispersion

The infrared-absorbing fine particle dispersion liquid of the present invention is obtained by dispersing the surface-treated infrared-absorbing fine particles of the present invention in a liquid medium (sometimes described as a "liquid medium" in the present invention). As the liquid medium, at least one liquid medium selected from organic solvents, oils and fats, liquid plasticizers, compounds to be polymerized by hardening, and water can be used.

Regarding the infrared-absorbing fine particle dispersion of the present invention, (1) the production method, (2) the organic solvent used, (3) the oil and fat used, (4) the liquid plasticizer used, (5) The compound used to be polymerized by curing, (6) the dispersant used, and (7) the method of using the infrared-absorbing fine particle dispersion will be described.

(1) Manufacturing method

When producing the infrared-absorbing fine particle dispersion of the present invention, the above-mentioned dispersion liquid for forming a coating film is heated and dried under conditions that can avoid strong aggregation of the surface-treated infrared-absorbing fine particles, or, for example, at room temperature. Vacuum drying, spray drying, etc. are performed to obtain the surface-treated infrared-absorbing fine particle powder of the present invention. Then, the surface-treated infrared-absorbing fine particle powder may be added to the above-mentioned liquid medium, and a phosphite-based compound may be added and dispersed. In addition, the dispersion liquid for coating film formation is separated into the surface-treated infrared absorbing fine particles and the medium, and the medium of the dispersion liquid for coating film forming is replaced with the medium of the infrared absorbing fine particle dispersion liquid by the operation of solvent replacement (so-called solvent replacement). ), and further adding a phosphite-based compound to produce a dispersion liquid of infrared absorbing fine particles is also a preferable configuration.

On the other hand, the medium of the dispersion liquid for forming a coating film and the medium of the dispersion liquid for infrared absorbing fine particles are matched in advance, and a phosphite compound is added to the dispersion liquid for forming a coating film after the surface treatment to produce infrared absorbing fine particles. A dispersion liquid is also a preferred composition.

(2) Organic solvent used

As the organic solvent used in the infrared-absorbing fine particle dispersion liquid of the present invention, alcohol-based, ketone-based, hydrocarbon-based, glycol-based, water-based, and the like can be used.

Specifically, alcohol-based solvents such as methanol, ethanol, 1-propanol, isopropanol, butanol, amyl alcohol, benzyl alcohol, and diacetone alcohol can be used; acetone, methyl ethyl ketone, methyl propyl ketone, Ketone solvents such as methyl isobutyl ketone, cyclohexanone and isophorone; ester solvents such as 3-methyl-methoxy-propionate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Glycol derivatives such as ethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate; formamide, N-methylformamide, dimethylformamide amides such as amide, dimethylacetamide, N-methyl-2-pyrrolidone, etc.; aromatic hydrocarbons such as toluene and xylene; dichloroethane, chlorobenzene, etc.

In addition, among these organic solvents, dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether acetate, n-butyl acetate, etc. can be preferably used in particular.

(3) Grease used

As the fat and oil used in the infrared-absorbing fine particle dispersion liquid of the present invention, vegetable fats and oils or vegetable-derived fats and oils are preferred.

As vegetable oils, drying oils such as linseed oil, sunflower oil, tung oil, and perilla oil can be used; semi-drying oils such as sesame oil, cottonseed oil, rapeseed oil, soybean oil, rice bran oil, and poppy seed oil; olive oil, coconut oil, Non-drying oils such as palm oil, dehydrated castor oil, etc.

As the vegetable oil-derived compound, fatty acid monoesters, ethers, and the like obtained by reacting a fatty acid of a vegetable oil with a monoalcohol direct ester can be used.

In addition, a commercially available petroleum-based solvent can also be used as the oil and fat.

Examples of commercially available petroleum-based solvents include Isopar (registered trademark) E, EXXSOL (registered trademark) Hexane, Heptane, E, D30, D40, D60, D80, D95, D110, D130 (the above, manufactured by Exxon Mobil), etc. .

(4) Liquid plasticizer used

As the liquid plasticizer used in the infrared-absorbing fine particle dispersion of the present invention, for example, plasticizers belonging to compounds of monohydric alcohols and organic acid esters, ester-based plasticizers such as polyhydric alcohol organic acid ester compounds, and organic phosphoric acid-based plasticizers can be used. Phosphoric acid-based plasticizers, etc. In addition, any one of them is preferably liquid at room temperature.

Among them, a plasticizer which is an ester compound synthesized from a polyhydric alcohol and a fatty acid can be preferably used. The ester compound synthesized from a polyhydric alcohol and a fatty acid is not particularly limited. Diol-based ester compounds obtained by the reaction of mono-organic acids such as ethylbutyric acid, heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, nonanoic acid (n-nonanoic acid), and capric acid, etc.

Moreover, tetraethylene glycol, tripropylene glycol, the ester compound with the said monoorganic acid, etc. are mentioned.

Among them, triethylene glycol dicaproate, triethylene glycol di-2-ethyl butyrate, triethylene glycol di-octanoate, triethylene glycol di-2-ethylhexanoate can be used Such as fatty acid esters of triethylene glycol, etc. Furthermore, fatty acid ester of triethylene glycol can also be preferably used.

(5) Compounds to be polymerized by hardening to be used

The compound to be polymerized by curing used in the infrared-absorbing fine particle dispersion liquid of the present invention is a monomer or oligomer that forms a polymer by polymerization or the like.

Specifically, methyl methacrylate monomers, acrylate monomers, styrene resin monomers, and the like can be used.

The above-described liquid medium can be used in combination of two or more. Furthermore, as needed, acid or alkali may be added to these liquid media, and pH may be adjusted.

(6) The dispersant used

In the infrared-absorbing microparticle dispersion liquid of the present invention, in order to further improve the dispersion stability of the surface-treated infrared-absorbing microparticles and avoid the coarsening of the dispersed particle size caused by re-agglomeration, it is also preferable to add various dispersants, surfactants, coupling agent, etc.

The dispersing agent, coupling agent, and surfactant can be selected according to the application, and those having an amine-containing group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group are preferred. These functional groups have the effect of being adsorbed on the surface of the surface-treated infrared-absorbing fine particles, preventing aggregation, and dispersing them uniformly. More preferably, it is a polymer system dispersing agent which has any of these functional groups in a molecule|numerator.

Moreover, the acrylic-styrene copolymer system dispersing agent which has a functional group can also be mentioned as a preferable dispersing agent. Among them, an acrylic-styrene copolymer system dispersant having a carboxyl group as a functional group and an acrylic dispersant having an amine-containing group as a functional group can be cited as more preferable examples. The functional group of the dispersant having an amine-containing group is preferably one having a molecular weight of Mw of 2,000 to 200,000 and an amine value of 5 to 100 mgKOH/g. In addition, the dispersant having a carboxyl group is preferably one having a molecular weight of Mw of 2,000 to 200,000 and an acid value of 1 to 50 mgKOH/g.

As a preferred specific example of a commercially available dispersant, SOLSPERSE (registered trademark) (hereinafter the same) 3000, 5000, 9000, 11200, 12000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 2000, 21000, 24000SC, 24000GR, 26000, 27000, 28000, 31845, 32500, 32550, 32600, 33500, 34750, 35200, 36600, 37500, 39000, 41000, 53095, 53095, 55000, 56000, 71000, 76500, J180, J200, M387, etc.; SOLPLUS (registered trademark) (the same below) D510, D520, D530, D540, DP310, K500, L300, L400, R700, etc.; Disperbyk (registered trademark) (the same below) - 101, 102, 103, 106, 107, 108, 109, 110, 111, 112, 116, 130, 140, 142, 145, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 191, 192, 2000, 2001, 2009, 2020, 2025, 2050, 2070, 2095, 2096, 2150, 2151, 2152, 2155, 2163, 2164, Anti-Terra (registered trademark) (the same below)-U, 203, 204, etc.; BYK (registered trademark) (the same below)-P104, P104S, P105, P9050, P9051 , P9060, P9065, P9080, 051, 052, 053, 054, 055, 057, 063, 065, 066N, 067A, 077, 088, 141, 220S, 300, 302, 306, 307, 310, 315, 320, 322 , 323, 325, 330, 331, 333, 337, 340, 345, 346, 347, 348, 350, 354, 355, 358N, 361N, 370, 375, 377, 378, 380N, 381, 392, 410, 425 , 430, 1752, 4510, 6919, 9076, 9077, W909, W935, W940, W961, W966, W969, W972, W980, W 985, W995, W996, W9010, Dynwet800, Siclean3700, UV3500, UV3510, UV3570, etc; ,4020,4046,4047,4050,4055,4060,4080,4300,4310,4320,4330,4340,4400,4401,4402,4403,4500,5066,5220,6220,6225,6230,6700,6780,6782 , 7462, 8503, etc; (the same below) MD1000, D1180, D1130, etc.; Ajisper (registered trademark) manufactured by Ajinomoto Fine-Techno Co., Ltd. (the same below) PB-711, PB-821, PB-822, etc.; (Same below) 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; -4010, UG-4035, UG-4040, UG-4070, Reseda (registered trademark) (the same below) GS-1015, GP-301, GP-301S, etc.; Dial (registered trademark) manufactured by Mitsubishi Chemical Corporation (the same below) ) BR-50, BR-52, BR-60, BR-73, BR-77, BR80, BR-83, BR85, BR87, BR88, BR-90, BR-96, BR102, BR-113, BR116, etc.

(7) How to use the infrared absorbing fine particle dispersion

The infrared-absorbing fine particle dispersion liquid of the present invention produced as described above can be coated on the surface of an appropriate substrate, and a coating film can be formed thereon, which can be used as an infrared-absorbing substrate. That is, the coating film is one type of dried and cured product of the dispersion liquid of infrared absorbing fine particles.

Further, by drying and pulverizing the infrared-absorbing fine particle dispersion liquid, a powdery infrared-absorbing fine particle dispersion containing the phosphite compound of the present invention can be prepared (in the present invention, it may be described as "dispersed powder"). . That is, this dispersion powder is one type of dried solidified product of the infrared-absorbing fine particle dispersion liquid. The dispersing powder is a powdery dispersion obtained by dispersing surface-treated infrared-absorbing fine particles in a solid medium (dispersant, etc.) containing a phosphate-based compound, and is different from the above-mentioned surface-treated infrared-absorbing fine particle powder. Since the dispersing powder contains a dispersant, by mixing with an appropriate medium, the surface-treated infrared absorbing fine particles can be easily redispersed in the medium.

Moreover, it is good also as a structure in which a phosphite type compound is not added to this infrared absorbing fine particle dispersion liquid, and the infrared absorbing fine particle dispersion liquid which does not contain a phosphite type compound is prepared first. In this case, a specific amount of phosphorous acid can be added when mixing and kneading the infrared absorbing fine particle dispersion liquid containing no phosphite compound, or the infrared absorbing fine particle dispersion powder obtained by drying it with a resin or other medium. The ester compound is used to prepare the infrared absorbing fine particle dispersion of the present invention.

On the other hand, the infrared absorbing fine particle dispersion liquid obtained by mixing and dispersing the surface-treated infrared absorbing fine particles of the present invention in a liquid medium can be used in various applications applying photothermal conversion.

For example, the surface-treated infrared absorbing fine particles are added to an uncured thermosetting resin, or the surface-treated infrared absorbing fine particles of the present invention are dispersed in a suitable solvent, and then the uncured thermosetting resin is added, whereby curing can be obtained. type ink composition. The curable ink composition is provided on a specific substrate, and when cured by irradiating infrared rays such as infrared rays, it has excellent adhesion to the substrate. In addition, the curable ink composition is not only used as a conventional ink, but also becomes a curable ink composition most suitable for the photoforming method, which is to apply a specific amount of the curable ink composition. It irradiates electromagnetic waves such as infrared rays to harden and stack them to form three-dimensional objects.

[6] Infrared absorbing fine particle dispersion, infrared absorbing substrate, and articles (1) Infrared absorbing fine particle dispersion

The infrared absorbing fine particle dispersion system of the present invention is one in which the surface-treated infrared absorbing fine particles of the present invention are dispersed in a solid medium. In addition, as this solid medium, a solid medium, such as resin and glass, can be used.

Regarding the infrared-absorbing fine particle dispersion of the present invention, (i) the production method, (ii) moist heat resistance, and (iii) heat resistance will be described in this order.

(i) Manufacturing method

As described above, when the surface-treated infrared-absorbing fine particles of the present invention are kneaded into a medium such as a resin to form a film or sheet, the surface-treated infrared-absorbing fine particles and the phosphite compound can be directly kneaded into the resin. Further, the above-mentioned infrared absorbing fine particle dispersion liquid may be mixed with a resin, or a powdery dispersion obtained by dispersing the surface-treated infrared absorbing fine particles in a solid medium may be added to a liquid medium and mixed with the resin.

In the case of using resin as a solid medium, for example, it may be in the form of a film or a plate having a thickness of 0.1 μm to 50 mm.

Generally speaking, when kneading the surface-treated infrared absorbing fine particles of the present invention into a resin, it is heated and kneaded at a temperature near the melting point of the resin (about 200-300°C).

In this case, the surface-treated infrared-absorbing fine particles may be further mixed with resin and pelletized, and the pellets may be formed into a film or a plate in various ways. For example, it can be formed by extrusion molding, inflation molding, solution casting, or film casting. At this time, the thickness of the film or plate can be appropriately set according to the purpose of use, and the amount of filler relative to the resin (ie, the amount of the surface-treated infrared absorbing fine particles formulated in the present invention) depends on the thickness of the substrate or the required optical properties. and mechanical properties, but generally, it is preferably 50% by weight or less relative to the resin.

When the filler content with respect to the resin is 50% by weight or less, fine particles in the solid resin can be prevented from forming particles, and thus good transparency can be maintained. Moreover, since the usage-amount of the surface-treated infrared-absorbing fine particles of the present invention can also be controlled, it is also advantageous in terms of cost.

On the other hand, the infrared absorbing fine particle dispersion obtained by dispersing the surface-treated infrared absorbing fine particles of the present invention in a solid medium can also be used in the state of being further pulverized to obtain a powder. In the case of adopting this configuration, in the powdery infrared-absorbing fine particle dispersion, the surface-treated infrared-absorbing fine particles of the present invention are sufficiently dispersed in the solid medium. Therefore, liquid can be easily produced by dissolving a mixture of the powdery infrared-absorbing fine particle dispersion and a phosphite compound as a so-called master batch, dissolving it in a suitable liquid medium, or kneading it with resin particles, etc. Or solid infrared absorbing microparticle dispersion.

In addition, the so-called solid resin constituting the matrix in the above-mentioned film or plate refers to a polymer medium that is solid at room temperature, and also includes the concept of a polymer medium other than three-dimensionally cross-linked. The solid resin is not particularly limited and may be selected depending on the application, but is preferably a fluororesin in consideration of weather resistance. However, as low-cost and high-transparency resins with wider versatility than fluororesins, PET resins, acrylic resins, polyamide resins, vinyl chloride resins, polycarbonate resins, olefin resins, Epoxy resin, polyimide resin, etc.

(ii) Moisture and heat resistance

When the infrared absorbing microparticle dispersion system of the present invention is set to be about 80% visible light transmittance, the dispersion is exposed in a humid and hot environment of 85°C and 90% for 9 days, the amount of change in visible light transmittance before and after the exposure is 2.0 % or less, it has excellent heat and humidity resistance.

(iii) Heat resistance

In the infrared absorbing fine particle dispersion system of the present invention, when the dispersion set to a visible light transmittance of about 80% is exposed to an atmospheric environment of 120° C. for 30 days, the amount of change in the visible light transmittance before and after the exposure is 2.0% or less. , has excellent heat resistance.

(2) Infrared absorbing substrate

The infrared absorbing substrate of the present invention is formed on the surface of a specific substrate with a coating film containing the surface-treated infrared absorbing fine particles of the present invention and a phosphite compound.

Since a coating film containing the surface-treated infrared absorbing fine particles of the present invention and a phosphite compound is formed on the surface of a specific substrate, the infrared absorbing substrate of the present invention is excellent in heat and humidity resistance and chemical stability, and can be suitably used As an infrared absorbing material.

With regard to the infrared absorbing substrate of the present invention, (i) the production method, (ii) moisture and heat resistance, and (iii) heat resistance will be described in this order.

(i) Manufacturing method

For example, the surface-treated infrared-absorbing fine particles and phosphite-based compound of the present invention are mixed with an organic solvent such as alcohol, a liquid medium such as water, a resin binder, and a dispersing agent if necessary to obtain an infrared-absorbing fine particle dispersion, and the obtained After the infrared absorbing microparticle dispersion liquid is coated on the surface of a suitable substrate, the liquid medium is removed, thereby obtaining an infrared absorbing substrate directly laminated with the infrared absorbing microparticle dispersion on the surface of the substrate.

The above-mentioned resin binder components are selected depending on the application, and examples thereof include ultraviolet curing resins, thermosetting resins, room temperature curing resins, thermoplastic resins, and the like. On the other hand, as for the infrared absorbing fine particle dispersion liquid not containing the resin binder component, it is also possible to layer the infrared absorbing fine particle dispersion on the surface of the substrate, and after the lamination, apply a liquid medium containing a binder component on the infrared absorbing fine particle dispersion. layer of the microparticle dispersion.

Specifically, one or more liquid media 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 are selected to contain a phosphite compound, and surface-treated infrared absorbing fine particles are dispersed. The liquid infrared absorbing fine particle dispersion is formed on the surface of the substrate according to the coating film of the infrared absorbing substrate. Moreover, the infrared absorption base material which formed the liquid infrared absorption fine particle dispersion containing a resin binder component on the surface of a base material by a coating film is mentioned. Furthermore, the liquid infrared absorbing fine particle dispersion obtained by mixing a powdery solid medium containing a phosphite-based compound and dispersing an infrared absorbing fine particle dispersion with surface-treated infrared absorbing fine particles and mixing it into a specific medium can also be used. , the infrared absorbing substrate formed on the surface of the substrate according to the coating film. Of course, an infrared absorbing fine particle dispersion liquid obtained by mixing two or more kinds of the various liquid infrared absorbing fine particle dispersion liquids, and an infrared absorbing substrate formed on the surface of a substrate by a coating film can also be mentioned.

The material of the above-mentioned base material is not particularly limited as long as it is a transparent body, and glass, a resin plate, a resin sheet, and a resin film can be preferably used.

烯構造之聚烯烴、乙烯-丙烯共聚合體等烯烴系聚合物、氯乙烯系聚合物、芳香族聚醯胺等醯胺系聚合物、醯亞胺系聚合物、碸系聚合物、聚醚碸系聚合物、聚醚醚酮系聚合物、聚苯硫醚系聚合物、乙烯醇系聚合物、偏二氯乙烯系聚合物、乙烯丁醛系聚合物、芳酯系聚合物、聚甲醛系聚合物、環氧系聚合物、或者進而該等之二元系、三元系各種共聚合體、接枝共聚合體、摻合物等透明聚合物之板、片、薄膜。尤其是聚對苯二甲酸乙二酯、聚對苯 二甲酸丁二酯或者聚乙烯-2,6-萘二甲酸酯等聚酯系雙軸配向薄膜係由機械特性、光學特性、耐熱性及經濟性之方面而言較佳。該聚酯系雙軸配向薄膜亦可為共聚合聚酯系。 The resin used as the resin sheet, resin sheet, and resin film is not particularly limited as long as the surface state or durability of the desired sheet, sheet, or film does not cause abnormality. Examples include polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose, and polycarbonate-based polymers. polymers, acrylic polymers such as polymethyl methacrylate, polystyrene, styrene polymers such as acrylonitrile-styrene copolymers, polyethylene, polypropylene,

Olefin-based polymers such as polyolefins with olefinic structures, ethylene-propylene copolymers and other olefin-based polymers, vinyl chloride-based polymers, amide-based polymers such as aromatic polyamides, amide-based polymers, ethylene-based polymers, and polyether sulfones type polymer, polyether ether ketone type polymer, polyphenylene sulfide type polymer, vinyl alcohol type polymer, vinylidene chloride type polymer, vinyl butyral type polymer, arylate type polymer, polyoxymethylene type polymer Plates, sheets, and films of transparent polymers such as polymers, epoxy-based polymers, or further binary and ternary copolymers, graft copolymers, and blends. In particular, polyester-based biaxially oriented films such as polyethylene terephthalate, polybutylene terephthalate, or polyethylene-2,6-naphthalate are based on mechanical properties, optical properties, and heat resistance. and economical aspects are better. The polyester-based biaxially oriented film may also be a copolymerized polyester-based film.

(ii) Moisture and heat resistance

In the above-mentioned infrared absorbing substrate, when the infrared absorbing substrate set to be 80% visible light transmittance was exposed for 9 days in a humid heat environment of 85°C and 90%, the amount of change in visible light transmittance before and after the exposure was: 2.0% or less, with excellent heat and humidity resistance.

(iii) Heat resistance

In the infrared absorbing fine particle dispersion system of the present invention, when the dispersion set to a visible light transmittance of about 80% is exposed to an atmospheric environment of 120° C. for 30 days, the amount of change in the visible light transmittance before and after the exposure is 2.0% or less. , has excellent heat resistance.

(3) Items using infrared absorbing microparticle dispersion or infrared absorbing substrate

As described above, infrared absorbing articles such as the infrared absorbing fine particle dispersion of the present invention or the film or plate of the infrared absorbing base material are excellent in heat and humidity resistance, heat resistance and chemical stability.

Therefore, these infrared absorbing articles can be preferably used, for example, for windows and the like for the purpose of sufficiently absorbing visible light in various buildings and vehicles, shielding light in the infrared region, and suppressing the temperature rise in the room while maintaining brightness. , A filter used for PDP (Plasma Display Panel) and shielding the infrared rays emitted from the PDP to the front.

In addition, if the dispersion liquid of infrared absorbing fine particles of the present invention is mixed with a solid medium such as resin or a compound that is polymerized by curing to prepare a coating liquid, and a known method is used to apply a transparent substrate selected from a substrate film or a substrate glass to a transparent substrate. By forming a coating on it, an infrared absorbing film or an infrared absorbing glass can be produced by dispersing infrared absorbing fine particles in a solid medium. An infrared absorbing film or an infrared absorbing glass is an example of the fine particle dispersion of the present invention.

Furthermore, since the surface-treated infrared-absorbing fine particles of the present invention have absorption in the infrared region, when the printed surface containing the surface-treated infrared-absorbing fine particles is irradiated with an infrared laser, they absorb infrared rays having a specific wavelength. Therefore, the anti-counterfeiting printed matter obtained by printing the anti-counterfeiting ink containing the surface-treated infrared absorbing microparticles on one or both sides of the substrate to be printed can be obtained by irradiating infrared rays with specific wavelengths and reading the reflection or transmission. The difference in the amount of reflection or transmission determines the authenticity of the printed matter. This anti-counterfeiting printed matter is an example of the infrared-absorbing fine particle dispersion of the present invention.

In addition, a light-to-heat conversion layer can be formed by mixing the infrared-absorbing fine particle dispersion of the present invention with a binder component to produce an ink, coating the ink on a substrate and drying it, and then curing the dried ink. By irradiating electromagnetic wave lasers such as infrared rays, the light-to-heat conversion layer can generate heat only at the required parts with high precision, and can be used in a wide range of fields such as electronic equipment, medical treatment, agriculture, and machinery.

For example, it can be preferably used as a donor sheet used in forming an organic electroluminescent element by a laser transfer method, a thermal paper for a thermal printer, or an ink ribbon for a thermal transfer printer. The light-to-heat conversion layer is an example of the infrared-absorbing fine particle dispersion of the present invention.

In addition, by dispersing the surface-treated infrared absorbing fine particles of the present invention in a suitable medium, and containing a phosphite compound to prepare a dispersion liquid of infrared absorbing fine particles, and containing the dispersion on the surface and/or inside of the fibers, it is possible to Infrared absorbing fibers are obtained. With this structure, the infrared absorbing fiber can efficiently absorb near-infrared rays, etc. from sunlight, etc. by containing the infrared absorbing fine particles, and becomes an infrared absorbing fiber excellent in heat retention, and at the same time transmits light in the visible light region, so it is designed. Excellent infrared absorbing fiber. As a result, it can be used for various applications such as cold-proof clothing, sports clothing, fiber products such as stockings, and curtains, and other industrial fiber products that require heat retention. The infrared absorbing fiber is an example of the infrared absorbing fine particle dispersion of the present invention.

In addition, the film-like or plate-like infrared-absorbing fine particle dispersion of the present invention can be applied to materials used for roofs, outer wall materials, and the like of agricultural and horticultural greenhouses. This material can efficiently absorb light such as near-infrared light contained in sunlight other than it under the light required to ensure photosynthesis of plants in agricultural and horticultural greenhouses through the transmission of visible light. Insulation material for agricultural and horticultural facilities. The heat insulating material for agricultural and horticultural facilities is an example of the infrared absorbing fine particle dispersion of the present invention.

[Example]

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 diameters of the fine particles in the dispersion liquids in the examples and comparative examples are represented by the average value measured by a particle diameter measuring apparatus (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.) based on the dynamic light scattering method. . In addition, the crystallite diameter was measured by powder X-ray diffraction (θ-2θ method) using a powder X-ray diffraction apparatus (X'Pert-PRO/MPD manufactured by Spectris Co., Ltd. PANalytical), using Ritworth Calculated by German law.

The film thickness of the coating film of the surface-treated infrared absorbing fine particles is 300,000 times the photographic data obtained by using a transmission electron microscope (HF-2200 manufactured by Hitachi, Ltd.). The check is read as a coating.

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 transmittance were calculated in accordance with JISR3106. The haze value of the infrared absorbing sheet or plate was measured using a haze meter (HM-150 manufactured by Murakami Color Co., Ltd.), and calculated according to JISK7105.

The method for evaluating the heat and humidity resistance of an infrared absorbing sheet or plate is to expose the infrared absorbing sheet with a visible light transmittance of about 80% to a humid and heat environment of 85°C and 90% for 9 days. Then, for example, in the case of hexagonal cesium tungsten bronze, if the amount of change in solar transmittance before and after the exposure is 2.0% or less, it is judged that the moisture and heat resistance is good, and if the change exceeds 2.0%, it is judged that the moisture and heat resistance is insufficient.

The method for evaluating the heat and humidity resistance of an infrared absorbing sheet or plate is to expose the infrared absorbing sheet with a visible light transmittance of about 80% to an atmospheric environment of 120°C for 30 days. Then, for example, in the case of hexagonal cesium tungsten bronze, if the change in solar transmittance before and after exposure is 2.0% or less, it is judged to be good in heat resistance, and if the change exceeds 2.0%, it is judged to be insufficient in heat resistance.

In addition, the optical characteristic value (visible light transmittance, haze value) of the infrared absorbing sheet or plate referred to here includes the value of the optical characteristic value of the resin sheet or plate belonging to the base material.

[Example 1]

ZrO₂珠粒之塗料振盪機中，進行10小時粉碎、分散處理，而獲得實施例1之Cs_0.33WOz微粒子之分散液。對所獲得之分散液中之Cs_0.33WOz微粒子之分散粒徑進行測定，結果為100nm。再者，作為粒徑測定之設定，粒子折射率設為1.81，粒子形狀設為非球形。又，背景係使用純水進行測定，溶劑折射率設為1.33。又，將所獲得之分散液之溶劑去除後，對微晶直徑進行測定，結果為32nm。混合所獲得之Cs_0.33WOz微粒子之分散液與純水，而獲得Cs_0.33WOz微粒子之濃度為2質量%之實施例1之被覆膜形成用分散液A。 Mixed Cs/W (molar ratio)=0.33 hexagonal cesium tungsten bronze (Cs _0.33 WOz, 2.0≦z≦3.0) powder CWO (registered trademark) (YM-01 manufactured by Sumitomo Metal Mining Co., Ltd.) 25 mass % and pure water 75% by mass of the obtained mixed solution, filled with 0.3mm

In the coating shaker of ZrO ₂ beads, pulverization and dispersion treatment were performed for 10 hours to obtain the dispersion liquid of Cs _0.33 WOz microparticles of Example 1. The dispersed particle diameter of the Cs _0.33 WOz fine particles in the obtained dispersion was measured and found to be 100 nm. In addition, as the setting of particle diameter measurement, the particle refractive index was set to 1.81, and the particle shape was set to be non-spherical. In addition, the background was measured using pure water, and the solvent refractive index was set to 1.33. Moreover, after removing the solvent of the obtained dispersion liquid, the crystallite diameter was measured, and it was 32 nm. The obtained dispersion liquid of Cs _0.33 WOz fine particles and pure water were mixed to obtain the coating film-forming dispersion liquid A of Example 1 in which the concentration of Cs _0.33 WOz fine particles was 2 mass %.

On the other hand, 2.5 mass % of ethyl aluminum diisopropyl acetoacetate, which is an aluminum-based chelate compound, and 97.5 mass % of isopropyl alcohol (IPA) were mixed to obtain a surface treatment agent diluent a.

890 g of the obtained dispersion liquid A for coating film formation was put into a beaker, and it was sufficiently stirred by a mixer with a blade, and 360 g of the surface treatment agent diluent a was added dropwise thereto over 3 hours. After the dropwise addition of the surface treatment agent diluent a, stirring was further performed at a temperature of 20° C. for 24 hours to prepare an aging liquid of Example 1. Then, vacuum flow drying was used to evaporate the medium from the maturing liquid to obtain a powder containing surface-treated infrared-absorbing fine particles of Example 1 (surface-treated infrared-absorbing fine particle powder).

Here, the film of the coating film of the surface-treated infrared absorbing fine particles of Example 1 was read based on the photograph data of 300,000 times obtained by using a transmission electron microscope (HF-2200 manufactured by Hitachi, Ltd.). As a result, the thickness was found to be 2 nm. Furthermore, a transmission electron microscope photograph of 300,000 of the surface-treated infrared-absorbing fine particles of Example 1 is shown in Fig. 2 .

ZrO₂珠粒之塗料振盪機中，進行1小時粉碎、分散處理，而獲得實施例1之紅外線吸收微粒子分散液。繼而，藉由真空流動乾燥使介質自該紅外線吸收微粒子分散液蒸發，而獲得實施例1之紅外線吸收微粒子分散粉。 8 mass % of the surface-treated infrared-absorbing fine particle powder of Example 1, 24 mass % of the polyacrylate-based dispersant, and 68 mass % of toluene were mixed. The obtained mixed solution was filled up to 0.3 mm

In the coating shaker of ZrO ₂ beads, pulverization and dispersion treatment were performed for 1 hour to obtain the infrared-absorbing fine particle dispersion liquid of Example 1. Then, the medium was evaporated from the infrared absorbing fine particle dispersion liquid by vacuum flow drying to obtain the infrared absorbing fine particle dispersion powder of Example 1.

Infrared absorbing fine particle dispersion powder of Example 1, polycarbonate resin which is a solid resin, and Sumilizer GP in an amount of 2000 parts by mass relative to 100 parts by mass of hexagonal cesium tungsten bronze were added, and the visible light of the infrared absorbing sheet obtained after that was added. Dry blending is performed so that the transmittance becomes about 80%. Using a twin-screw extruder, the obtained blend was kneaded at 290° C., extruded from a T-die, and made into a sheet with a thickness of 0.75 mm by a polishing roll method to obtain the infrared absorption of Example 1. piece. In addition, the infrared absorption sheet is an example of the infrared absorption fine particle dispersion of this invention.

The optical properties of the obtained infrared absorbing sheet of Example 1 were measured, and as a result, the visible light transmittance was 79.6%, the solar transmittance was 48.6%, and the haze was 0.9%.

After exposing the obtained infrared absorbing sheet of Example 1 in a humid and hot environment of 85°C and 90% for 9 days, the optical properties were measured. As a result, the visible light transmittance was 80.2%, the solar transmittance was 49.5%, and the haze was 0.9. %. It can be seen that the amount of change in visible light transmittance caused by exposure to a humid and hot environment is 0.6%, and the amount of change in solar transmittance is 0.9%, which are both small, and the haze does not change.

Furthermore, after exposing the obtained infrared absorbing sheet of Example 1 to an atmospheric environment of 120° C. for 30 days, the optical properties were measured. As a result, the visible light transmittance was 80.2%, the solar transmittance was 50.0%, and the haze was 0.9. %. It can be seen that the amount of change in visible light transmittance caused by exposure to a humid and hot environment is 0.6%, and the amount of change in solar transmittance is 1.4%, which are both small, and the haze does not change.

The production conditions and evaluation results of Example 1 are described in Tables 1 to 4.

[Example 2, 3]

Example 2 was obtained in the same manner as in Example 1, except that 4000 parts by mass of Sumilizer GP (Example 2) or 700 parts by mass (Example 3) was added to 100 parts by mass of the hexagonal cesium tungsten bronze powder , 3 of the infrared absorption film.

The infrared absorbing sheets of Examples 2 and 3 obtained were evaluated in the same manner as in Example 1.

The production conditions and evaluation results of Examples 2 and 3 are described in Tables 1 to 4.

[Example 4]

The infrared-absorbing fine particle dispersion powder of Example 1 and the polycarbonate resin were uniformly mixed with a mixer so that the concentration of the infrared-absorbing fine particles was 0.05 wt %, and then melt-kneaded with a twin-screw extruder. The material was cut into granules to obtain the masterbatch containing the infrared absorbing microparticles of Example 4. In addition, the master batch containing infrared absorbing fine particles is an example of the infrared absorbing fine particle dispersion of the present invention.

Dry blend 10 parts by mass of the masterbatch containing the infrared absorbing particles of Example 4 and 90 parts by mass of polycarbonate resin particles, and use an injection molding machine to make a plate with a thickness of 10 mm to obtain the infrared absorption of Example 4. plate. Furthermore, the infrared absorbing plate is an example of the infrared absorbing fine particle dispersion of the present invention.

The obtained infrared absorbing plate of Example 4 was evaluated in the same manner as in Example 1.

The production conditions and evaluation results of Example 4 are described in Tables 1 to 4.

[Example 5]

An infrared absorbing sheet of Example 5 was obtained in the same manner as in Example 1, except that 1500 parts by mass of Sumilizer GP and 150 parts by mass of IRGANOX 1010 were added to 100 parts by mass of the hexagonal cesium tungsten bronze powder.

The obtained fine particle dispersion liquid of Example 5 and the infrared absorbing sheet were evaluated in the same manner as in Example 1.

The production conditions and evaluation results of Example 5 are described in Tables 1 to 4.

[Example 6]

The fine particle dispersion liquid and the infrared absorbing sheet of Example 6 were obtained in the same manner as in Example 5, except that ADEKA STAB 2112 was used instead of IRGANOX 1010.

The obtained fine particle dispersion liquid of Example 6 and the infrared absorbing sheet were evaluated in the same manner as in Example 1.

The production conditions and evaluation results of Example 6 are described in Tables 1 to 4.

[Example 7, 8]

The same operations as in Example 1 were carried out except that the amount of the surface treatment agent diluent a and the time for dropping and adding it were changed to obtain the surface-treated infrared-absorbing fine particle powders, infrared-absorbing fine particle dispersions, The same evaluation as in Example 1 was carried out for the dispersion powder of infrared absorbing fine particles and the infrared absorbing sheet.

The production conditions and evaluation results of Examples 7 and 8 are described in Tables 1 to 4.

[Example 9]

The aged liquid of Example 1 was allowed to stand for 1 hour, and the surface-treated infrared absorbing fine particles and the medium were subjected to solid-liquid separation. Next, only the medium belonging to the supernatant was removed to obtain an infrared-absorbing fine particle slurry. Isopropyl alcohol was added to the obtained slurry of infrared absorbing fine particles, and after stirring for 1 hour, it was left to stand for 1 hour, and the surface-treated infrared absorbing fine particles and the medium were solid-liquid separated again. Then, only the medium belonging to the supernatant was removed, and the infrared-absorbing fine particle slurry was obtained again.

After mixing and stirring 16 mass % of the infrared-absorbing fine particle slurry obtained again, 24 mass % of the polyacrylate-based dispersant, and 60 mass % of toluene, dispersion treatment was performed using an ultrasonic homogenizer to obtain the infrared-absorbing fine particle dispersion of Example 9. liquid.

The same operation as in Example 1 was carried out except that the dispersion liquid of infrared absorbing fine particles of Example 9 was used to obtain the dispersion powder of infrared absorbing fine particles and the infrared absorbing sheet of Example 9, and the same evaluation as that of Example 1 was carried out. .

The production conditions and evaluation results of Example 9 are described in Tables 1 to 4.

[Example 10]

The surface treatment agent diluent b of Example 10 was obtained by mixing 2.4 mass % of zirconium tributoxyacetate pyruvate and 97.6 mass % of isopropanol. The same operations as in Example 1 were carried out, except that the surface treatment agent diluent b was used instead of the surface treatment agent diluent a, to obtain the surface-treated infrared absorbing fine particle powder, infrared absorbing fine particle dispersion, and infrared absorbing fine particles of Example 10. The fine particle dispersion powder and the infrared absorbing sheet were evaluated in the same manner as in Example 1.

The production conditions and evaluation results of Example 10 are described in Tables 1 to 4.

[Example 11]

Diisopropoxide titanium bis(ethyl acetate) 2.6 mass % and isopropanol 97.4 mass % were mixed, and the surface treatment agent dilution liquid c of Example 11 was obtained. The same operations as in Example 1 were carried out, except that the surface treatment agent diluent c was used instead of the surface treatment agent diluent a, to obtain the surface-treated infrared-absorbing fine particle powder, infrared-absorbing fine-particle dispersion liquid, and infrared-absorbing fine particles of Example 11. The fine particle dispersion powder and the infrared absorbing sheet were evaluated in the same manner as in Example 1.

The production conditions and evaluation results of Example 11 are described in Tables 1 to 4.

[Example 12]

Except that polymethyl methacrylate resin was used as solid resin instead of polycarbonate resin, the same operation as in Example 1 was carried out to obtain the surface-treated infrared-absorbing fine particle powder and infrared-absorbing fine particle dispersion of Example 12. Liquid, infrared-absorbing fine particle dispersion powder, and infrared-absorbing sheet were subjected to the same evaluation as in Example 1.

The production conditions and evaluation results of Example 12 are described in Tables 1 to 4.

[Example 13]

ZrO₂珠粒之塗料振盪機中，進行10小時粉碎、分散處理，而獲得實施例13之Na_0.33WO_Z微粒子之分散液。對所獲得之分散液中之Na_0.33WOz微粒子之分散粒徑進行測定，結果為100nm。再者，作為粒徑測定之設定，粒子折射率設為1.81，粒子形狀設為非球形。又，背景係使用異丙醇進行測定，溶劑折射率設為1.38。又，將所獲得之分散液之溶劑去除後，對Na_0.33WOz微粒子之微晶直徑進行測定，結果為32nm。 25 mass % of cubic sodium tungsten bronze powder (manufactured by Sumitomo Metal Mining Co., Ltd.) of Na/W (molar ratio) = 0.33 was mixed with 75 mass % of isopropyl alcohol, and the obtained mixed solution was filled with 0.3 mm

In the coating shaker of ZrO ₂ beads, pulverization and dispersion treatment were performed for 10 hours to obtain the dispersion liquid of Na _0.33 WO _Z fine particles of Example 13. The dispersed particle diameter of the Na _0.33 WOz fine particles in the obtained dispersion was measured and found to be 100 nm. In addition, as the setting of particle diameter measurement, the particle refractive index was set to 1.81, and the particle shape was set to be non-spherical. In addition, the background was measured using isopropanol, and the solvent refractive index was set to 1.38. In addition, after removing the solvent of the obtained dispersion liquid, the crystallite diameter of the Na _0.33 WOz fine particles was measured and found to be 32 nm.

The dispersion liquid of Na _0.33 WOz fine particles of Example 13 was mixed with isopropanol to obtain a dispersion liquid B for forming a coating film having a concentration of infrared absorbing fine particles (cubic sodium tungsten bronze fine particles) of 2 mass %. 520 g of the obtained dispersion liquid B for forming a coating film was added to a beaker, and fully stirred by a mixer with a blade, and at the same time, 360 g of the surface treatment agent diluent a and the pure diluent d were added dropwise for 3 hours. Water 100g. After the dropwise addition, stirring was performed at a temperature of 20° C. for 24 hours to prepare an aging liquid of Example 13. Then, the medium was evaporated from the aging liquid by vacuum flow drying, and the surface-treated infrared absorbing fine particle powder of Example 13 was obtained.

The same operations as in Example 1 were performed except that the surface-treated infrared-absorbing fine particle powder of Example 13 was used instead of the surface-treated infrared-absorbing fine particle powder of Example 1, thereby obtaining the infrared-absorbing fine particle dispersion liquid and infrared ray of Example 13. The same evaluation as in Example 1 was carried out on the absorption fine particle dispersion powder and the infrared absorption sheet.

The production conditions and evaluation results of Example 13 are described in Tables 1 to 4.

[Examples 14 to 16]

Instead of hexagonal cesium tungsten bronze powder, use K/W (molar ratio)=0.33 hexagonal potassium tungsten bronze powder (Example 14), use Rb/W (molar ratio)=0.33 hexagonal rubidium tungsten bronze powder The powder (Example 15) was used in the same manner as in Example 1, except that W ₁₈ O ₄₉ (Example 16) of the Magnelli phase was used, and the dispersion particle diameter and crystallite diameter of the infrared absorbing fine particles were measured, and further Dispersions C to E for coating film formation were obtained.

The surface-treated infrared absorbing fine particle powders of Examples 14 to 16 were obtained by carrying out the same operations as in Example 1, except that the dispersion liquids C to E for coating film formation were used in place of the dispersion liquid B for coating film formation. The infrared absorbing fine particle dispersion liquid, the infrared absorbing fine particle dispersion powder, and the infrared absorbing sheet were subjected to the same evaluation as in Example 1.

The production conditions and evaluation results of Examples 14 to 16 are described in Tables 1 to 4.

[Example 17]

309g of tetraethoxysilane was used as the surface treatment agent e. The same operations as in Example 1 were performed except that the surface treatment agent e was used instead of the surface treatment agent diluent a, and no isopropanol was added, thereby obtaining the surface-treated infrared-absorbing fine particle powder and infrared-absorbing fine particle of Example 14. The dispersion liquid, the infrared-absorbing fine particle dispersion powder, and the infrared-absorbing sheet were subjected to the same evaluation as in Example 1. The manufacturing conditions and evaluation results are shown in Tables 1 to 4.

[Example 18]

The surface treatment agent diluent f of Example 15 was obtained by mixing 4.4 mass % of zinc acetylacetonate and 95.6 mass % of isopropanol. The same operations as in Example 1 were carried out except that the surface treatment agent diluent f was used instead of the surface treatment agent diluent a, thereby obtaining the surface-treated infrared absorbing fine particle powder, infrared absorbing fine particle dispersion, and infrared absorbing fine particles of Example 15. The fine particle dispersion powder and the infrared absorbing sheet were evaluated in the same manner as in Example 1. The manufacturing conditions and evaluation results are shown in Tables 1 to 4.

[Example 19]

By spray drying instead of vacuum flow drying, the medium was evaporated from the ripening solution of Example 1 to obtain the powder containing surface-treated infrared-absorbing fine particles of Example 19 (surface-treated infrared-absorbing fine particle powder). Except that the obtained surface-treated infrared absorbing fine particle powder was mixed with pure water to obtain an infrared absorbing fine particle dispersion liquid, the same operation as in Example 1 was carried out, thereby obtaining the infrared absorbing fine particle dispersion liquid of Example 19, The same evaluation as in Example 1 was carried out for the dispersion powder of infrared absorbing fine particles and the infrared absorbing sheet. The manufacturing conditions and evaluation results are shown in Tables 1 to 4.

[Comparative Example 1]

A fine particle dispersion liquid and an infrared absorbing sheet of Comparative Example 1 were obtained in the same manner as in Example 1, except that Sumilizer GP was not added.

The obtained fine particle dispersion liquid and infrared absorbing sheet of Comparative Example 1 were evaluated in the same manner as in Example 1.

The production conditions and evaluation results of Comparative Example 1 are described in Tables 1 to 3 and 5.

[Comparative Example 2]

Except having added 500 mass parts of Sumilizer GP with respect to 100 mass parts of hexagonal cesium tungsten bronzes, it carried out similarly to Example 1, and obtained the fine particle dispersion liquid and infrared absorption sheet of the comparative example 2.

The obtained fine particle dispersion liquid of Comparative Example 2 and the infrared absorbing sheet were evaluated in the same manner as in Example 1.

The production conditions and evaluation results of Comparative Example 2 are described in Tables 1 to 3 and 5.

[Comparative Examples 3 and 4]

With respect to 100 parts by mass of hexagonal cesium tungsten bronze, 300 parts by mass of IRGANOX 1010 was added in place of Sumilizer GP (Comparative Example 3), or 300 parts by mass of ADEKA STAB 2112 was added in place of Sumilizer GP (Comparative Example 4), and the same procedures were carried out. In the same manner as in Example 1, the fine particle dispersions and infrared absorbing sheets of Comparative Examples 3 and 4 were obtained.

The obtained fine particle dispersions and infrared absorbing sheets of Comparative Examples 3 and 4 were evaluated in the same manner as in Example 1.

The production conditions and evaluation results of Comparative Examples 3 and 4 are described in Tables 1 to 3 and 5.

[Comparative Example 5]

A resin sheet of Comparative Example 5 was obtained by adding Sumilizr GP in the same amount as in Example 1, except that the dispersion powder was not added. That is, the resin sheet of the comparative example 5 is a resin sheet which contains only the stabilizer of Sumilizer GP (structural formula (2)) without absorbing fine particles.

The obtained comparative example 5 was a transparent resin sheet before the test, and after being exposed to a humid heat environment of 85°C and 90% for 9 days, white fog occurred and became opaque.

The production conditions and evaluation results of Comparative Example 5 are described in Tables 1 to 3 and 5.

[Comparative Example 6]

ZrO₂珠粒之塗料振盪機中，進行4小時粉碎、分散處理，而獲得比較例6之紅外線吸收微粒子分散液。對所獲得之分散液中之紅外線吸收微粒子之分散粒徑進行測定，結果為100nm。再者，作為粒徑測定之設定，粒子折射率設為1.81，粒子形狀設為非球形。又，背景係使用甲苯進行測定，溶劑折射率設為1.50。又，將所獲得之分散液之溶劑去除後，對微晶直徑進行測定，結果為32nm。 7 mass % of hexagonal cesium tungsten bronze powder, 24 mass % of polyacrylate-based dispersant, and 69 mass % of toluene were mixed, and the obtained mixed solution was filled to a size of 0.3 mm.

In a paint shaker of ZrO ₂ beads, pulverization and dispersion treatment were performed for 4 hours to obtain the infrared-absorbing fine particle dispersion liquid of Comparative Example 6. The dispersion particle diameter of the infrared absorbing fine particles in the obtained dispersion liquid was measured and found to be 100 nm. In addition, as the setting of particle diameter measurement, the particle refractive index was set to 1.81, and the particle shape was set to be non-spherical. In addition, the background was measured using toluene, and the solvent refractive index was set to 1.50. Moreover, after removing the solvent of the obtained dispersion liquid, the crystallite diameter was measured, and it was 32 nm.

Then, the medium was evaporated from the infrared absorbing fine particle dispersion liquid by vacuum flow drying, and the infrared absorbing fine particle dispersion powder of Comparative Example 6 was obtained.

The infrared absorbing sheet of Comparative Example 6 was obtained in the same manner as in Example 1, except that the infrared absorbing fine particle dispersion powder of Comparative Example 6 was used in place of the infrared absorbing fine particle dispersing powder of Example 1, and the same procedure as Example 1 was carried out. Evaluation.

The production conditions and evaluation results of Comparative Example 6 are described in Tables 1 to 3 and 5.

[Comparative Example 7]

The same operations as in Comparative Example 6 were carried out, except that polymethyl methacrylate resin was used instead of polycarbonate resin as the solid resin, thereby obtaining the infrared absorbing fine particle dispersion liquid and infrared absorbing fine particle dispersion powder of Comparative Example 7. , an infrared absorbing sheet, and the same evaluation as in Example 1 was carried out.

The production conditions and 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, use cubic sodium tungsten bronze powder with Na/W (molar ratio)=0.33 (Comparative Example 8), or use hexagonal potassium tungsten bronze powder with K/W (molar ratio)=0.33 Powder (Comparative Example 9), or use Rb/W (molar ratio)=0.33 hexagonal rubidium tungsten bronze powder (Comparative Example 10), or use Magnelli phase W ₁₈ O ₄₉ (Comparative Example 11), Except for this, the same operation as in Comparative Example 6 was carried out to obtain infrared-absorbing fine particle dispersion liquid, infrared-absorbing fine particle-dispersed powder, and infrared-absorbing sheet of Comparative Examples 8 to 11, and the same evaluations as in Example 1 were performed.

The production conditions and evaluation results of Comparative Examples 8 to 11 are described in Tables 1 to 3 and 5.

[Comparative Example 12]

ZrO₂珠粒之塗料振盪機中，進行5小時粉碎、分散處理，而獲得比較例7之Cs_0.33WOz微粒子之分散液。對所獲得之分散液中之Cs_0.33WOz微粒子之分散粒徑進行測定，結果為100nm。再者，作為粒徑測定之設定，粒子折射率設為1.81，粒子形狀設為非球形。又，背景係使用異丙醇進行測定，溶劑折射率設為1.38。又，將所獲得之分散液之溶劑去除後，對微晶直徑進行測定，結果為32nm。 13 mass % of hexagonal cesium tungsten bronze powder with Cs/W (molar ratio)=0.33 and 87 mass % of isopropanol were mixed, and the obtained mixed solution was filled to a size of 0.3 mm.

In the coating shaker of ZrO ₂ beads, pulverization and dispersion treatment were performed for 5 hours to obtain the dispersion liquid of Cs _0.33 WOz fine particles of Comparative Example 7. The dispersed particle diameter of the Cs _0.33 WOz fine particles in the obtained dispersion was measured and found to be 100 nm. In addition, as the setting of particle diameter measurement, the particle refractive index was set to 1.81, and the particle shape was set to be non-spherical. In addition, the background was measured using isopropanol, and the solvent refractive index was set to 1.38. Moreover, after removing the solvent of the obtained dispersion liquid, the crystallite diameter was measured, and it was 32 nm.

The dispersion liquid of the Cs _0.33 WOz fine particles of Comparative Example 12 was mixed with isopropanol to obtain a dilution liquid having a concentration of 3.5 mass % of the infrared absorbing fine particles (hexagonal cesium tungsten bronze fine particles). 21 g of ethyl aluminum diisopropyl acetate was added to 733 g of the obtained diluent, and after mixing and stirring, dispersion treatment was performed using an ultrasonic homogenizer.

Next, this dispersion-processed material was put into a beaker, and it stirred sufficiently with the stirrer with a blade, and 100 g of water was added dropwise as a diluent d over 1 hour. Furthermore, 140 g of tetraethoxysilane was added dropwise as a diluent e over 2 hours while stirring, and then stirred at 20°C for 15 hours, and the solution was heated and aged at 70°C for 2 hours. Then, the medium was evaporated from the aging liquid by vacuum flow drying, and further heat treatment was performed at a temperature of 200° C. for 1 hour in a nitrogen atmosphere to obtain the surface-treated infrared-absorbing fine particle powder of Comparative Example 12.

ZrO₂珠粒之塗料振盪機中，進行5小時粉碎、分散處理，而獲得比較例12之紅外線吸收微粒子分散液。 8 mass % of the surface-treated infrared-absorbing fine particle powder of Comparative Example 12, 24 mass % of the polyacrylate-based dispersant, and 68 mass % of toluene were mixed. The obtained mixed solution was filled up to 0.3 mm

In the paint shaker of ZrO ₂ beads, pulverization and dispersion treatment were performed for 5 hours to obtain the infrared-absorbing fine particle dispersion liquid of Comparative Example 12.

The infrared absorbing fine particle dispersion liquid of Comparative Example 12 was used instead of the infrared absorbing fine particle dispersion liquid of Example 1, and the same operation as in Example 1 was carried out, thereby obtaining the infrared absorbing fine particle dispersion powder and the infrared absorbing sheet of Comparative Example 12. , and the same evaluation as in Example 1 was carried out.

The production conditions and evaluation results of Comparative Example 12 are described in Tables 1 to 3 and 5.

[Comparative Example 13]

A resin sheet of Comparative Example 13 was obtained in the same manner as in Example 1, except that the Sumilizer GP was replaced and not added, and the dispersing powder was replaced and not added. That is, the resin sheet of Comparative Example 13 did not contain additives such as surface-treated infrared absorbing fine particles and Sumilizer GP.

The obtained resin sheet of Comparative Example 13 was evaluated in the same manner as in Example 1. The results are described in Table 5. The resin sheet of Comparative Example 13 showed no change in optical properties after being kept in an atmospheric environment of 120°C for 30 days or after being exposed to a humid heat environment of 85°C and 90% for 9 days.

The production conditions and evaluation results of Comparative Example 13 are described in Tables 1 to 3 and 5.

Claims (27)

An infrared absorbing fine particle dispersion liquid, which contains a liquid medium, surface-treated infrared absorbing fine particles dispersed in the medium, and a phosphite compound, characterized in that the surface of the surface-treated infrared absorbing fine particles is composed of a self- Hydrolyzate of metal chelate compound, polymer of hydrolyzate of metal chelate compound, hydrolyzate of metal cyclic oligomer compound, and polymer of hydrolyzate of metal cyclic oligomer compound Film coating; the phosphite-based compound is a phosphite-based compound represented by the structural formula (1), and the addition amount of the phosphite-based compound is more than 500 parts by mass relative to 100 parts by mass of the infrared absorbing fine particles and below 50,000 parts by mass;

Wherein, in the above structural formula (1), R1, R2, R4 and R5 are independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 1 to 12 carbon atoms, and an alkyl group having 7 to 12 carbon atoms. Any one of an aralkyl group and an aromatic group, R3 is any one of a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X is a single bond, or a bivalent represented by the following structural formula (1-1) any of the residues,

A is an alkylene group having 2 to 8 carbon atoms or any of the divalent residues represented by the following structural formula (1-2),

Either Y or Z is a hydroxyl group, an alkyl group with 1 to 8 carbon atoms, an alkoxy group with a carbon number of 1 to 8, or an aralkoxy group with a carbon number of 7 to 12, and the other is a hydrogen atom or any one of the alkyl groups with 1 to 8 carbon atoms, in the above structural formula (1-1), R6 is any one of a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, in the above structural formula (1- In 2), R7 is either a single bond or an alkylene group having 1 to 8 carbon atoms, and * indicates that the terminal is bonded to the oxygen atom side of the phosphite compound represented by the structural formula (1). The infrared-absorbing fine particle dispersion according to claim 1, wherein the film thickness of the coating film is 0.5 nm or more. The infrared-absorbing fine particle dispersion 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, and Zn . The infrared-absorbing fine particle dispersion according to claim 1 or 2, wherein the metal chelate compound or the metal cyclic oligomer compound has at least one selected from ether bonds, ester bonds, alkoxy groups, and acetyl groups . The infrared-absorbing fine particle dispersion according to claim 1 or 2, wherein the above-mentioned infrared The line-absorbing fine particles are of the general formula WyOz (wherein, W is tungsten, O is oxygen, and 2.2≦z/y≦2.999), or/and the general formula MxWyOz (wherein, M element is from H, He, alkali metal, alkaline earth metal , rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, One or more selected from Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, Yb Elements, W is tungsten, O is oxygen, and infrared absorbing fine particles represented by 0.001≦x/y≦1, 2.0≦z/y≦3.0). The infrared-absorbing fine particle dispersion 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. The infrared absorbing fine particle dispersion according to claim 1 or 2, wherein the infrared absorbing fine particle is a fine particle having a hexagonal crystal structure. The infrared absorbing fine particle dispersion liquid according to claim 1 or 2, wherein the crystallite diameter of the infrared absorbing fine particle is 1 nm or more and 200 nm or less. The infrared absorbing fine particle dispersion liquid according to claim 1 or 2, wherein in the surface-treated infrared absorbing fine particle powder containing the surface-treated infrared absorbing fine particles, the carbon concentration is 0.2 mass % or more and 5.0 mass % or less. The infrared-absorbing fine particle dispersion according to claim 1 or 2, wherein the liquid medium is one or more liquids selected from organic solvents, oils and fats, liquid plasticizers, compounds to be polymerized by hardening, and water medium. The infrared absorbing fine particle dispersion according to claim 1 or 2, further comprising a phosphoric acid-based stabilizer, a hindered phenol-based stabilizer, a thioether-based stabilizer, and a metal deactivator other than the above-mentioned phosphite-based compound the above stabilizers. An infrared absorbing fine particle dispersion, which contains surface-treated infrared absorbing fine particles dispersed in a medium, and a phosphite-based compound, wherein the surface of the surface-treated infrared absorbing fine particles is composed of a self-metal chelating compound. Coated with a coating film of one or more selected from hydrolyzates, polymers of hydrolyzates of metal chelate compounds, hydrolyzates of metal cyclic oligomer compounds, and polymers of hydrolyzates of metal cyclic oligomer compounds The phosphite-based compound is a phosphite-based compound represented by the structural formula (1), and the addition amount of the phosphite-based compound is more than 500 parts by mass and not more than 50,000 parts by mass relative to 100 parts by mass of the infrared absorbing fine particles ;

Wherein, in the above structural formula (1), R1, R2, R4 and R5 are independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 1 to 12 carbon atoms, and an alkyl group having 7 to 12 carbon atoms. Either an aralkyl group or an aromatic group, R3 is any one of a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X is a single bond, or a divalent residue represented by the following structural formula (1-1) either of the bases,

A is an alkylene group having 2 to 8 carbon atoms or any of the divalent residues represented by the following structural formula (1-2),

One of Y and Z is any one of hydroxyl, alkyl group with 1 to 8 carbon atoms, alkoxy group with 1 to 8 carbon atoms, or aralkoxy group with 7 to 12 carbon atoms, and the other is hydrogen atom or any one of alkyl groups having 1 to 8 carbon atoms, in the above structural formula (1-1), R6 is any one of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and in the above structural formula (1) In -2), R7 is either a single bond or an alkylene group having 1 to 8 carbon atoms, and * indicates that the terminal is bonded to the oxygen atom side of the phosphite compound represented by the structural formula (1). 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. The infrared-absorbing fine particle dispersion according to claim 12 or 13, wherein the metal chelate compound or the metal cyclic oligomer compound has at least one selected from ether bonds, ester bonds, alkoxy groups, and acetyl groups . The infrared-absorbing fine particle dispersion of claim 12 or 13, wherein the infrared-absorbing fine particles are of the general formula WyOz (wherein W is tungsten, O is oxygen, and 2.2≦z/y≦2.999), or/and the general formula MxWyOz (wherein, M element is selected from 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, One or more elements selected from Hf, Os, Bi, I, and Yb, W is tungsten, O is oxygen, and infrared absorption represented by 0.001≦x/y≦1, 2.0≦z/y≦3) microparticles. The infrared-absorbing fine particle dispersion 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. The infrared absorbing fine particle dispersion according to claim 12 or 13, wherein the infrared absorbing fine particle is a fine particle having a hexagonal crystal structure. The infrared absorbing fine particle dispersion according to claim 12 or 13, wherein the crystallite diameter of the infrared absorbing fine particle is 1 nm or more and 200 nm or less. The infrared-absorbing fine particle dispersion according to claim 12 or 13, wherein in the surface-treated infrared-absorbing fine-particle powder containing the surface-treated infrared-absorbing fine particles, the carbon concentration is 0.2 mass % or more and 5.0 mass % or less. The infrared-absorbing fine particle dispersion according to claim 12 or 13, wherein the medium is a polymer. The infrared-absorbing fine particle dispersion according to claim 12 or 13, wherein the medium is a solid resin. The infrared-absorbing fine particle dispersion of claim 21, wherein the solid resin is a self-fluorine resin, PET resin, acrylic resin, polyamide resin, vinyl chloride resin, polycarbonate resin, olefin resin, epoxy resin, One or more resins selected from polyimide resins. The infrared absorbing fine particle dispersion according to claim 12 or 13, which further contains a phosphoric acid-based stabilizer other than the above-mentioned phosphite-based compound, a hindered phenol-based stabilizer, a thioether-based stabilizer, and a metal deactivator. the above stabilizers. A kind of manufacture method of infrared absorption microparticle dispersion liquid, it is characterized in that, has the following steps: Infrared absorbing fine particles, water, organic solvents, liquid resins, oils and fats, liquid plasticizers for the above resins, polymer monomers, or a mixture of two or more selected from these groups are mixed and dispersed. The step of obtaining the above-mentioned dispersion liquid for forming a film of infrared absorbing fine particles; adding a metal chelate compound or/and a metal cyclic oligomer compound to the above-mentioned dispersion liquid for forming a film, using the hydrolyzate of the metal chelate compound, the metal chelate compound The step of coating the surface of the above-mentioned infrared absorbing fine particles with one or more selected from polymers of hydrolyzed products of chelate compounds, hydrolyzed products of metal cyclic oligomer compounds, and polymers of hydrolyzed products of metal cyclic oligomer compounds; After the coating step, the liquid medium constituting the coating film-forming dispersion liquid is removed to obtain a surface-treated infrared-absorbing fine particle powder containing surface-treated infrared-absorbing fine particles; the surface-treated infrared-absorbing fine particle powder is added to a specific A step of dispersing in a medium to obtain a dispersion of surface-treated infrared-absorbing fine particles; and adding to the dispersion of the surface-treated infrared-absorbing fine particles in an amount exceeding 500 parts by mass and not more than 50,000 parts by mass relative to 100 parts by mass of the infrared-absorbing fine particles The step of obtaining the dispersion liquid of the surface-treated infrared-absorbing fine particles containing the phosphite-based compound. A method for producing an infrared-absorbing fine particle dispersion, comprising the steps of: mixing infrared-absorbing fine particles, water, an organic solvent, a liquid resin, grease, a liquid plasticizer for the resin, a polymer monomer, or A step of mixing two or more mixtures selected from these groups, and performing dispersion treatment to obtain the above-mentioned dispersion liquid for forming a coating of infrared absorbing fine particles; Adding a metal chelate compound or/and a metal cyclic oligomer compound to the above-mentioned dispersion liquid for forming a coating film, using a hydrolyzate of the metal chelate compound, a polymer of the hydrolyzate of the metal chelate compound, and a metal cyclic oligomer A step of coating the surface of the above infrared absorbing fine particles with one or more polymers selected from a hydrolyzate of a compound compound and a hydrolyzate of a metal cyclic oligomer compound; after the step of coating, the dispersion liquid for forming the coating film is formed The liquid medium is replaced with a specific medium by solvent replacement to obtain a dispersion of surface-treated infrared absorbing fine particles; A step of obtaining a dispersion liquid of surface-treated infrared-absorbing fine particles containing a phosphite-based compound in an amount of 500 parts by mass to 50,000 parts by mass or less of a phosphite-based compound. A method for producing an infrared-absorbing fine particle dispersion, comprising the steps of: subjecting the surface-treated infrared-absorbing fine particle dispersion containing a phosphite-based compound as described in claim 24 or 25, or making the phosphite-containing dispersion liquid The step of drying the dispersion of surface-treated infrared-absorbing microparticles of phosphite compounds obtained by drying the dispersion powder of surface-treated infrared-absorbing microparticles containing phosphite compounds, and mixing with a suitable medium to obtain a dispersion of infrared-absorbing microparticles. A method for producing an infrared absorbing fine particle dispersion, comprising the steps of: dispersing powder of surface-treated infrared absorbing fine particles obtained by drying the dispersion liquid of the surface-treated infrared absorbing fine particles described in claim 24 or 25, phosphorous acid The ester compound and the appropriate medium are mixed to obtain the infrared absorbing fine particle dispersion. step; wherein the mixing amount of the phosphite-based compound is more than 500 parts by mass and not more than 50,000 parts by mass relative to 100 parts by mass of the infrared absorbing fine particles.

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