TW201922951A - Infrared absorbing fine particle dispersion liquid, infrared absorbing fine particle dispersion body, and method for producing the same - Google Patents

Abstract

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

Description

   Infrared absorbing fine particle dispersion, infrared absorbing fine particle dispersion, and manufacturing method thereof   

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

In recent years, the demand for infrared absorbers has increased rapidly, and many patents related to infrared absorbers have been proposed. If these proposals are reviewed from a functional point of view, for example, in various fields such as window materials of buildings and vehicles, they can fully absorb visible light while shielding light in the near-infrared region while maintaining brightness while suppressing it. For the purpose of increasing the temperature in the room; for the purpose of preventing infrared rays emitted from the PDP (plasma display panel) to cause the remote control device of the radiotelephone or home appliances to malfunction or to adversely affect the optical transmission and communication.

From the viewpoint of a light-shielding member, for example, a light-shielding member for a window material or the like has been proposed as a light-shielding film containing a black pigment, a semi-mirror type light-shielding member on which a metal such as aluminum is vapor-deposited, and the black pigment Including inorganic pigments such as carbon black and titanium black that have absorption characteristics from the visible light region to the near-infrared region, and organic pigments such as aniline black that have strong absorption characteristics only in the visible light region.

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

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

In addition, Patent Document 3 proposes a hot-wire-cut glass, which uses a method similar to that of Patent Document 1 to provide a composite tungsten oxide film containing the same metal element as that of Patent Document 1 on a transparent substrate from the substrate side. As the first layer, a transparent dielectric film was provided as the second layer on the first layer.

In addition, Patent Document 4 proposes a solar control glass sheet having a solar shielding property, which is coated with tungsten trioxide (WO) containing additional elements such as hydrogen, lithium, sodium, or potassium 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 ) A metal oxide film selected from the above and formed by thermal decomposition at about 250 ° C.

In addition, Patent Document 5 proposes a solar tunable light-transmitting heat-insulating material, which uses tungsten oxide obtained by hydrolyzing tungstic acid, and an organic compound having a specific structure such as polyvinylpyrrolidone is added to the tungsten oxide. Made of polymers. If the sunlight is irradiated with the sunlight-adjustable light-varying heat-insulating material, tungsten oxide absorbs ultraviolet rays in the light and generates excited electrons and holes. Due to a small amount of ultraviolet rays, the occurrence of pentavalent tungsten significantly increases and the color reaction changes. Faster, with this, the color density becomes higher. On the other hand, by blocking light, pentavalent tungsten is extremely rapidly oxidized to hexavalent, and the decolorization reaction becomes faster. It has been proposed to use this coloring / decoloring property to obtain fast reaction and decolorization to sunlight. When coloring, an absorption peak appears at a wavelength of 1250 nm in the near-infrared region, and the near-infrared sunlight of the sunlight can be blocked. Adjustable dimmable thermal insulation material.

On the other hand, the inventor of this case is equivalent to that disclosed in Patent Document 6 to dissolve tungsten hexachloride in alcohol and directly evaporate the medium, or evaporate the medium after heating and refluxing, and then heat it at 100 ° C to 500 ° C. This obtains tungsten oxide fine particle powder containing tungsten trioxide or its hydrate or a mixture of both. In addition, it is disclosed that an electrochromic element is obtained using the tungsten oxide fine particles; when a multilayer laminate is formed and a proton is introduced into the film, the optical characteristics of the film can be changed.

In Patent Document 7, it is disclosed that meta-type ammonium tungstate and various metal salts that are water-soluble 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. In this heating, Supply MxWO ₃ (M; alkali, alkaline earth, rare earth and other metal elements by supplying hydrogen gas with inert gas (addition amount; about 50vol% or more) or water vapor (addition amount: about 15vol% or less), 0 < x <1) Various tungsten bronze methods. Further, a method for manufacturing various tungsten bronze-coated composites by performing the same operation on a support is disclosed, and a use as an electrode catalyst material for a fuel cell or the like is disclosed.

In addition, the present inventors have disclosed in Patent Document 8 an infrared shielding material microparticle dispersion in which infrared shielding material microparticles are dispersed in a medium, optical characteristics, conductivity, and manufacturing method of the infrared shielding material microparticle dispersion. The particles of the infrared shielding material are particles of tungsten oxide represented by the general formula WyOz (where W is tungsten, O is oxygen, and 2.2 ≦ z / y ≦ 2.999), or / and the general formula MxWyOz (where 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 1 or more of the elements selected, W is tungsten, O is oxygen, and 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 technical 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 research by the inventors of the present case, it was found that in the optical member (thin film, resin sheet, etc.) containing the above-mentioned tungsten oxide fine particles or / and composite tungsten oxide fine particles, water vapor or water in the air depends on the use conditions or methods. It slowly penetrates into the solid resin. Furthermore, it was found that if water vapor or water slowly penetrates into the solid resin, the surface of the tungsten-containing oxide fine particles is decomposed, and the transmittance of light with a wavelength of 200 to 2600 nm increases over time, and the above The infrared absorption performance of the optical member is gradually reduced.

In addition, according to research by the inventors of the present case, it was found that the tungsten oxide fine particles or composite tungsten oxide fine particles disclosed in Patent Document 8 generate harmful harmful free radicals in a polymer medium such as a solid resin due to heat exposure. Due to the harmful free radicals, the surface decomposition of the fine particles is also deteriorated, and even the infrared absorption effect is lost.

Under the above circumstances, the inventor of the present invention is equivalent to Patent Document 9, as infrared shielding particles having excellent water resistance and excellent infrared shielding properties, the following infrared shielding particles and a manufacturing method thereof are disclosed. The infrared shielding particles are of the general formula WyOz. The represented tungsten oxide or / and the composite tungsten oxide fine particles represented by the general formula MxWyOz, the average primary particle diameter of the fine particles is 1 nm to 800 nm, and the surface of the fine particles is composed of a 4-functional silane compound or a partial hydrolysis product thereof. , Or / and an organometallic compound.

However, due to their characteristics, infrared absorbing materials are basically used outdoors, and most require high weather resistance. In addition, as the requirements in the market have increased year by year, the infrared shielding fine particles disclosed in Patent Document 9 have also started to require further improvement in water resistance or humidity and heat resistance. In addition, the infrared shielding fine particles disclosed in Patent Document 9 have low resistance to heat exposure, that is, the effect of improving heat resistance is low, and there is still a certain problem.

The present invention was completed under the above circumstances, and its object is to provide an infrared absorbing fine particle dispersion, 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 aimed at using the above-mentioned tungsten oxide fine particles or composite tungsten oxide fine particles having excellent optical characteristics as infrared absorbing fine particles, and enabling the infrared absorbing fine particles to have moist heat resistance and chemical stability. The composition of improvement was studied. As a result, it is considered that the key is to coat the surface of each infrared absorbing particle with a compound having excellent affinity with the surface of the infrared absorbing particles and uniformly adsorbing to the surface of each infrared absorbing particle to form a strong coating film.

The inventors of the present case have continued their research, and as a compound having excellent affinity for the infrared absorbing fine particles and forming a coating film, a metal chelate compound or a metal cyclic oligomer compound has been considered. Then, further research was carried out, and the results considered that the hydrolysates of the compounds or the polymers of the hydrolysates generated when the metal chelate compound or metal cyclic oligomer compound was hydrolyzed were uniformly adsorbed to each infrared ray. Compound that absorbs the surface of fine particles and forms a strong coating.

That is, it is considered that the surface of the tungsten oxide fine particles or / and the composite tungsten oxide fine particles is hydrolyzed by a polymer containing a hydrolyzate of a metal chelate compound, a polymer of a hydrolyzate of a metal chelate compound, or a metal cyclic oligomer compound. A product or a polymer of a hydrolysate of a metal cyclic oligomer compound is selected from one or more kinds of coating films coated with infrared-absorbing fine particles (in the present invention, it may be described as "surface-treated infrared-absorbing fine particles"). In addition, the surface-treated infrared-absorbing fine particles were found to have excellent wet heat resistance.

Furthermore, it has been found that an infrared absorbing microparticle dispersion produced by using an infrared absorbing microparticle dispersion obtained by dispersing the surface-treated infrared absorbing microparticles in an appropriate medium is excellent in moist heat resistance and has excellent infrared absorption characteristics.

The inventors of the present case have continued their research and found that an infrared absorbing dispersion liquid obtained by adding a phosphite compound having a specific structure to an unexpected amount such as a general resin molded body, and using the infrared absorbing dispersion liquid The produced infrared absorbing dispersion exhibits long-term stable humidity and heat resistance. In addition, the infrared absorption dispersion is also 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 which contains a liquid medium, surface-treated infrared absorbing fine particles dispersed in the medium, and a phosphite compound, and is characterized by: The surface of the above-mentioned surface-treated infrared-absorbing fine particles is composed of a hydrolyzate of a metal chelate compound, a polymer of a hydrolyzate of a metal chelate compound, a hydrolyzate of a metal cyclic oligomer compound, and a metal cyclic oligomer compound. One or more coating films selected from the polymer of the hydrolysis product; the above-mentioned phosphite compound is a phosphite compound represented by the structural formula (1), and the addition amount of the above-mentioned phosphite compound is relative to 100 parts by mass of the infrared absorbing fine particles is more than 500 parts by mass and less than 50,000 parts by mass.

Among them, in the above structural formula (1), R1, R2, R4, and R5 are each 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 a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X is a single bond or a divalent compound represented by the following structural formula (1-1) Any of the residues,

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

Y and Z are either 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 an alkyl group having 1 to 8 carbons, in the structural formula (1-1), R6 is a hydrogen atom and an alkyl group having 1 to 5 carbons, in the structural formula (1- In 2), R7 is any one of 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 second invention is the infrared absorbing fine particle dispersion 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 contains one selected from Al, Zr, Ti, Si, and Zn. More than one metal element.

The fourth invention is the infrared absorbing fine particle dispersion according to any one of the first to third inventions, wherein the metal chelate compound or the metal cyclic oligomer compound has a self-ether bond, an ester bond, and an alkoxy group. More than one kind of base and acetoyl are selected.

The fifth invention is the infrared absorbing fine particle dispersion according to any one of the first to fourth inventions, wherein the infrared absorbing fine particles are of the general formula WyOz (where W is tungsten, O is oxygen, and 2.2 ≦ z / y ≦ 2.999), or / and the general formula MxWyOz (wherein the M element is 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 / y ≦ 3.0).

The sixth invention is the infrared absorbing fine particle dispersion according to the fifth invention, wherein the M element is one or more selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. .

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

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

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

The 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 self-solvent, a fat, a liquid plasticizer, or a compound that is polymerized by curing. 1, more than one liquid medium selected by water.

The eleventh invention is the infrared absorbing fine particle dispersion 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 phosphite-based compound. Agent, metal deactivator, more than one kind of stabilizer.

The twelfth invention is an infrared absorbing fine particle dispersion containing surface-treated infrared absorbing fine particles and a phosphite-based compound dispersed in a medium, characterized in that the surface of the surface-treated infrared absorbing fine particles is composed of self-metal Hydrolysate of chelate compound, polymer of metal chelate compound, polymer of metal cyclic oligomer compound, polymer of metal cyclic oligomer compound The film is coated, the phosphite compound is a phosphite compound represented by the structural formula (1), and the added amount of the phosphite compound is more than 500 parts by mass with respect to 100 parts by mass of the infrared absorbing fine particles and 50,000 parts by mass or less.

Among them, in the above structural formula (1), R1, R2, R4, and R5 are each 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 a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X is a single bond or a divalent residue represented by the following structural formula (1-1) Either

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

Any one of Y and 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 aralkyloxy group having 7 to 12 carbon atoms, and the other is hydrogen Any one of an atom or an alkyl group having 1 to 8 carbons, in the above structural formula (1-1), R6 is any one of a hydrogen atom and an alkyl group having 1 to 5 carbons, in the above structural formula (1) In -2), R7 is any one of 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 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 contains one selected from Al, Zr, Ti, Si, and Zn The above metal elements.

The 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 a self-ether bond, an ester bond, an alkoxy group, and acetamidine More than one type of base selection.

The 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 (where W is tungsten, O is oxygen, and 2.2 ≦ z / y ≦ 2.999), or / and the general formula MxWyOz (wherein the M element is 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 and more than one element selected, W is tungsten, O is oxygen, and 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ 3) is an infrared absorbing fine particle.

A sixteenth invention is the infrared absorbing fine particle dispersion according to the fifteenth invention, wherein the M element is one or more selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. .

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

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

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

The 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.

The 21st invention is the infrared-absorbing fine particle dispersion according to any one of the 12th to 20th inventions, wherein the medium is a solid resin.

The twenty-second invention is the infrared absorbing fine particle dispersion according to any one of the twenty-first inventions, wherein the solid resin is a self-fluorine resin, a PET resin, an acrylic resin, a polyamide resin, a vinyl chloride resin, and a polycarbonate. Resin, olefin resin, epoxy resin, and polyimide resin.

The 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. Agent, metal deactivator, more than one kind of stabilizer.

The twenty-fourth invention is a method for producing an infrared absorbing fine particle dispersion, which comprises the steps of: absorbing infrared absorbing fine particles, water, and an organic solvent, a liquid resin, grease, a liquid plasticizer for the resin, and a polymer A step of mixing a monomer or a mixture of two or more kinds selected from these groups and performing a dispersion treatment to obtain the above-mentioned infrared-absorbing fine particle-forming dispersion liquid; and adding a metal chelate compound to the above-mentioned dispersion liquid for film formation Or / and metal cyclic oligomer compounds, using hydrolysates from metal chelate compounds, polymers of metal chelate compounds, hydrolysates of metal cyclic oligomer compounds, metal cyclic oligomer compounds The polymer of the hydrolysate is selected from one or more steps of coating the surface of the infrared absorbing fine particles. After the coating step, the liquid medium constituting the coating liquid forming dispersion liquid is removed to obtain a surface-treated infrared absorption. Surface treatment of micro particles: step of infrared absorbing fine particle powder; surface treatment The step of adding externally absorbing fine particle powder to a specific medium and dispersing it to obtain a surface-treated infrared absorbing fine particle dispersion; and adding more than 500 parts by mass of the infrared absorbing fine particles to 100 parts by mass of the infrared absorbing fine particles described above And a step of obtaining a dispersion of a surface-treated infrared-absorbing fine particle containing a phosphite-based compound with a phosphite-based compound of 50,000 parts by mass or less.

The twenty-fifth invention is a method for producing an infrared absorbing fine particle dispersion, which comprises the steps of: absorbing infrared absorbing fine particles, water, and an organic solvent, a liquid resin, a fat, a liquid plasticizer for the resin, and a polymer A step of mixing a monomer or a mixture of two or more kinds selected from these groups and performing a dispersion treatment to obtain the above-mentioned infrared-absorbing fine particle-forming dispersion liquid; and adding a metal chelate compound to the above-mentioned dispersion liquid for film formation Or / and metal cyclic oligomer compounds, using hydrolysates from metal chelate compounds, polymers of metal chelate compounds, hydrolysates of metal cyclic oligomer compounds, metal cyclic oligomer compounds The polymer of the hydrolysate is selected from one or more steps of coating the surface of the infrared absorbing fine particles; after the coating step, the liquid medium constituting the coating film forming dispersion liquid is replaced with a solvent and replaced with a specific medium. To obtain a surface-treated dispersion of infrared-absorbing particles; and The dispersion liquid of the infrared absorbing fine particles is added with a phosphorous acid ester-based compound in an amount of more than 500 parts by mass and less than 50,000 parts by mass based on 100 parts by mass of the infrared absorbing fine particles to obtain a surface-treated infrared absorbing fine particle dispersion containing a phosphite compound. The steps.

The twenty-sixth invention is a method for producing an infrared-absorbing fine particle dispersion, which comprises the steps of: dispersing a surface-treated infrared-absorbing fine particle dispersion containing a phosphite compound according to the twenty-fourth or twenty-fifth invention; or Step of obtaining a dispersion of a surface-treated infrared-absorbing fine particle containing a phosphite compound by drying the dispersion of a surface-treated infrared-absorbing fine particle containing a phosphite compound and mixing it with an appropriate medium to obtain an infrared-absorbing fine particle dispersion .

The twenty-seventh invention is a method for producing an infrared-absorbing fine particle dispersion, which comprises the steps of: dividing 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; A step of obtaining a dispersion of the infrared absorbing fine particles by mixing loose powder, a phosphite compound, and an appropriate medium; wherein the mixing amount of the phosphite compound is more than 500 masses relative to 100 parts by mass of the infrared absorbing fine particles; 50,000 parts by mass or less.

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

11‧‧‧ Octahedron formed from 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 fine particles of Example 1. FIG.

The surface-treated infrared absorbing fine particles of the present invention are polymers containing tungsten oxide fine particles or composite tungsten oxide fine particles belonging to the infrared absorbing fine particles, which are composed of hydrolysates of metal chelate compounds and hydrolysates of metal chelate compounds. 1. One or more types of surface-treated infrared-absorbing fine particles coated with a coating film of a metal cyclic oligomer compound hydrolysate and a polymer of the metal cyclic oligomer compound hydrolysate. The infrared-absorbing fine particle dispersion liquid of the present invention or the infrared-absorbing fine particle dispersion system produced using the dispersion liquid contains a phosphite compound having a specific structure.

In the following, [1] Infrared absorbing fine particles, [2] Infrared absorbing fine particles for surface coating, [3] Infrared absorbing fine particles, Surface coating method, [4] Phosphite compounds, [5] Infrared The order of the absorbing fine particle dispersion liquid, [6] infrared absorbing fine particle dispersion, infrared absorbing base material, and article will explain the present invention in detail.

Furthermore, in the present invention, "in order to impart moisture and heat resistance to infrared absorbing fine particles, a polymer of a hydrolysate of a metal chelate compound, a polymer of a hydrolyzate of a metal chelate compound, 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 hydrolysate and the hydrolysate of the metal cyclic oligomer compound is simply referred to as the "coating film".

    [1] Infrared absorbing particles    

It is known that materials generally containing free electrons show a reflective absorption response to electromagnetic waves around a region of solar light having a wavelength of 200 to 2600 nm by plasma vibration. If the powder of this substance is made smaller than the wavelength of light, the geometrical scattering in the visible light region (wavelength 380nm to 780nm) can be reduced and the transparency of the visible light region can be obtained.

The "transparency" in the present invention is used in the meaning of "less scattering of light in the visible light region and high transmittance".

Generally, there is no effective free electron in tungsten oxide (WO ₃ ), so the absorption and reflection characteristics in the infrared region are small, and it cannot be effectively used as infrared absorbing fine particles.

On the other hand, it is known that WO ₃ having an oxygen deficiency 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 such single crystals of materials having free electrons, the response of free electrons to light in the infrared region is taught.

The inventors of the present case 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 the tungsten oxide fine particles that are transparent in the visible light region and have absorption in the infrared region are considered, Composite tungsten oxide particles.

Here, the tungsten oxide fine particles or composite tungsten oxide fine particles belonging to the infrared absorbing fine particles of the present invention are (1) tungsten oxide fine particles, (2) composite tungsten oxide fine particles, and (3) tungsten oxide fine particles. The procedure 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 (where 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, a crystalline phase of WO ₂ other than the purpose can be avoided in the tungsten oxide, and chemical stability as a material can be obtained, so it becomes an effective infrared absorbing fine particle. On the other hand, if the value of z / y is 2.999 or less, free electrons in a required amount are generated, and the infrared absorbing fine particles having high efficiency are formed.

    (2) Composite tungsten oxide fine particles    

By adding the following element M to the above WO _{3 to} make a composite tungsten oxide, 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 1000 nm Nearby near-infrared rays absorb fine particles.

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

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

If the value of x / y is greater than 0.001, a sufficient amount of free electrons can be generated in the composite tungsten oxide to obtain the target infrared absorption effect. In addition, the more the element M is added, the more free electrons are supplied, and the infrared absorption efficiency is also increased, but the effect is saturated when the value of x / y is about 1. In addition, if the value of x / y is less than 1, the generation of an impurity phase in the infrared absorbing fine particles can be avoided, which is preferable.

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.

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

Next, a value of z / y indicating the control of the amount of oxygen will be described. The value of z / y is in the composite tungsten oxide represented by MxWyOz, and functions according to the same mechanism as the tungsten oxide represented by the aforementioned WyO _Z. In addition, the 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, it is preferably 2.0 ≦ z / y ≦ 3.0, more preferably 2.2 ≦ z / y ≦ 3.0, and even more preferably 2.45 ≦ z / y ≦ 3.0.

Furthermore, in the case where the composite tungsten oxide fine particles have a hexagonal crystal structure, the visible light region of the fine particles is improved in transmission, and the infrared region is improved in absorption. A description will be given with reference to FIG. 1 of a schematic top view of the crystal structure of the hexagonal crystal.

In FIG. 1, a set of 6 octahedrons formed by WO ₆ units as shown by symbol 11 constitutes a hexagonal void, and an element M shown as symbol 12 is disposed in the void to constitute a unit. The 1 A plurality of units are assembled to form a hexagonal crystal structure.

In addition, in order to obtain the effect of increasing the transmission of light in the visible region and the absorption of light in the infrared region, the composite tungsten oxide fine particles only need to contain the unit structure described in FIG. 1. The composite tungsten oxide fine particles It may be crystalline or amorphous.

When the cation of the element M is added to the hexagonal gap, the transmission of light in the visible region is enhanced, and the absorption of light in the infrared region is increased. Here, generally, the hexagonal crystal is easily formed when an element M having a large ionic radius is added. Specifically, hexagonal crystals are easily formed when Cs, K, Rb, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn are added. Of course, even if it is an element other than these, as long as the above-mentioned element M is present in the hexagonal void formed by the WO ₆ unit, it is not limited to the above-mentioned 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, more preferably 0.33 in terms of the value of x / y. It is considered that by setting the value of x / y to 0.33, the above-mentioned element M is arranged in all the voids of the hexagon.

In addition to hexagonal crystals, the compound tungsten oxides of tetragonal crystals and cubic crystals are also effective as infrared absorbing fine particles. Depending on the crystal structure, the absorption position in the infrared region tends to change, and the absorption position may shift to the long-wavelength side in the order of cubic crystal <cubic crystal <hexagonal crystal. In addition, in this case, the order of less absorption in the visible light region is hexagonal, cubic, and cubic. Therefore, for applications in which light in the visible region is more transmitted and light in the infrared region is more absorbed, it is preferable to use a hexagonal composite tungsten oxide. However, the tendency of the optical characteristics described here is only approximate, and the present invention is not limited to those that change depending on the type of the additive element, or the amount of addition, and the amount of oxygen.

    (3) Tungsten oxide particles and composite tungsten oxide particles    

Since the infrared absorbing fine particles containing the tungsten oxide fine particles or the composite tungsten oxide fine particles of the present invention absorb a large amount of light in the near-infrared region, especially around a wavelength of 1000 nm, the transmission color tone is mostly blue to green.

The dispersed particle diameter of the tungsten oxide fine particles or the composite tungsten oxide fine particles in the infrared absorbing fine particles can be selected depending on the purpose of use.

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

When it is important to reduce the scattering caused by the particles, the dispersed particle diameter may be 200 nm or less, and preferably 100 nm or less. The reason is that if the dispersed particle size of the particles is small, the light scattering in the visible light region with a wavelength of 400 nm to 780 nm caused by geometric scattering or Mie scattering is reduced, and as a result, the infrared absorbing film can be prevented from becoming as instable as frosted glass. Obtaining clear transparency. That is, when the dispersed particle diameter is 200 nm or less, the above-mentioned geometrical scattering or Mie scattering is reduced to become a Rayleigh scattering region. The reason for this is that in the Rayleigh scattering region, the scattered light is reduced proportionally to the 6th power of the particle size, so with the decrease in the dispersed particle size, the scattering is reduced and the transparency is improved.

When the dispersed particle diameter is 100 nm or less, scattered light is very small, which is preferable. From the standpoint of avoiding light scattering, the smaller the dispersed particle diameter is preferred, and if the dispersed particle diameter is 1 nm or more, industrial production is easy.

The haze value of the infrared absorbing fine particle dispersion obtained by dispersing the infrared absorbing fine particles of the present invention in a medium by setting the above-mentioned dispersed particle diameter to 800 nm or less can be set to 30% when the visible light transmittance is 85% or less. the following. If the haze is more than 30%, it becomes impossible to obtain clear transparency like ground glass.

The dispersed particle diameter of the infrared absorbing fine particles can be measured using ELS-8000, etc. manufactured by Otsuka Electronics Co., Ltd. based on the principle of dynamic light scattering.

The tungsten oxide fine particles or composite tungsten oxide fine particles have a composition ratio represented by 2.45 ≦ 2 / y ≦ 2.999, which is chemically stable and has good absorption characteristics in the infrared region. Therefore, it is suitable as infrared absorbing fine particles.

From the viewpoint of exhibiting excellent infrared absorption characteristics, the crystallite diameter of the infrared absorbing fine particles is preferably 1 nm or more and 200 nm or less, more preferably 1 nm or more and 100 nm or less, and even more preferably 10 nm or more and 70 nm or less. In the measurement of the crystallite diameter, the X-ray diffraction pattern using the powder X-ray diffraction method (θ-2θ method) was used for the measurement, and the analysis was performed using the Rietwald method. For the measurement of the X-ray diffraction pattern, for example, a powder X-ray diffraction device "X'Pert-PRO / MPD" manufactured by Spectris Corporation PANalytical can be used.

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

The surface treatment agent used for the surface coating of the infrared absorbing fine particles of the present invention is a hydrolyzate of a metal chelate compound, a polymer of a hydrolyzate of a metal chelate compound, a hydrolyzate of a metal cyclic oligomer compound, and a metal ring One or more polymers are selected as the polymer of the hydrolyzate of the oligomer compound.

In addition, the metal chelate compound and the metal cyclic oligomer compound preferably have a self-ether bond and an ester from the viewpoint of metal alkoxide, metal acetamidine pyruvate, and metal carboxylate. Bonding, alkoxy, and ethenyl are selected from one or more.

Here, the surface treating agent of the present invention sequentially hydrolyzes (1) a metal chelate compound, (2) a metal cyclic oligomer compound, (3) a metal chelate compound, or a metal cyclic oligomer compound. The added amount of the product, the polymer, and (4) the surface treatment agent will be described.

    (1) metal chelate compound    

The metal chelate compound used in the present invention is preferably one or two or more kinds selected from alkoxy-containing chelate compounds of Al, Zr, Ti, Si, and Zn.

Examples of the aluminum-based chelate compound include aluminum alkoxides such as aluminum ethoxide, aluminum isopropoxide, aluminum second butyrate, and mono-second butoxy aluminum diisopropyl ester, or these polymers, and acetic acid acetate Ethyl aluminum diisopropyl, ginsyl (ethyl acetoacetic acid) aluminum, octyl aluminum diisopropyl acetic acid acetate, stearyl ethyl aluminum diisopropyl ester, monoethyl ethyl pyruvate bis (ethyl ethyl醯 acetic acid) aluminum, ginseng (acetamidinepyruvate) aluminum, and the like.

These compounds dissolve the aluminum alkoxide in an aprotic solvent, or a petroleum-based solvent, a hydrocarbon-based solvent, an ester-based solvent, a ketone-based solvent, an ether-based solvent, and an amidine-based solvent, and β- is added to the solution. Diketones, β-ketoesters, monohydric and polyhydric alcohols, fatty acids, etc. are heated and refluxed, and the alkoxy-containing aluminum chelate compound obtained by the substitution reaction of the ligand is obtained.

Examples of the zirconium oxide-based chelate compound include zirconium alkoxides such as zirconium ethanol and zirconium butoxide, or these polymers, zirconium tributoxystearate, zirconium tetraacetonate pyruvate, and tributoxyacetamidine Zirconium pyruvate, zirconium dibutoxybis (acetamidinepyruvate), zirconium tributoxyethylacetonate acetate, zirconium bis (ethylacetamidineacetate) butoxyacetamidine pyruvate, and the like.

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 such polymers; Titanium acetoacetate, titanium tetraacetonate, titanium octanediol, titanium acetoacetate, titanium lactate, titanium triethanolamine, and the like.

As the silicon-based chelating compound, a 4-functional silane compound or a hydrolyzed product thereof represented by the general formula: Si (OR) ₄ (where R is the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms) can be used. . Specific examples of the tetrafunctional silane compound include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like. Furthermore, one or all of the alkoxy groups of these alkoxysilane monomers can be partially or completely hydrolyzed to form silane monomers (or oligomers) based on silanols (Si-OH), and self-condensed by hydrolysis Into a polymer.

In addition, as a hydrolyzate of a tetrafunctional silane compound (the proper term indicating the entirety of the intermediate of the 4-functional silane compound does not exist), a part or all of an alkoxy group is hydrolyzed to form a silanol (Si-OH) group The resulting silane monomer, oligomer of 4 to 5 polymers, and polymer (polysiloxane resin) having a weight average molecular weight (Mw) of about 800 to 8000. Moreover, the alkoxysilyl group (Si-OR) in the alkoxysilane monomer will not be completely hydrolyzed during the hydrolysis reaction to become silanol (Si-OH).

As the zinc-based chelate compound, zinc octylate, zinc laurate, zinc stearate, and other organic carboxylic acid zinc salts, acetoacetone zinc chelate, benzamidine zinc acetone chelate, and Benzamidine zinc zinc chelate, acetamidine ethyl zinc chelate and the like.

    (2) Metal cyclic oligomer compound    

As the metal cyclic oligomer compound of the present invention, one or more kinds selected from cyclic oligomer compounds of Al, Zr, Ti, Si, and Zn are preferable. Among them, a cyclic aluminum oligomer compound such as cyclic octoate alumina can be preferably exemplified.

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

In the present invention, the alkoxy group, the ether bond, and the ester bond in the metal chelate compound or the metal cyclic oligomer compound are all hydrolyzed to form a hydrolyzate of a hydroxyl group or a carboxyl group, a partially hydrolyzed product obtained by 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 hydrolysate in the present invention is a concept including a partial hydrolysate.

However, for example, in a reaction system in which an organic solvent such as an alcohol is interposed, generally, even in a stoichiometric composition, sufficient water required exists in the system, and depending on the type or concentration of the organic solvent, it becomes a metal of the starting material. Not all of the alkoxy or ether or ester bonds of the chelate compound or the metal cyclic oligomer compound are necessarily hydrolyzed. Therefore, depending on the conditions of the surface coating method described below, there may be an amorphous state in which carbon C is taken up in the molecule after hydrolysis.

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

    (4) Addition amount of surface treatment agent    

The amount of the metal chelate compound or metal cyclic oligomer compound added is preferably 0.1 parts by mass or more and 1,000 parts by mass or less based on 100 parts by mass of the infrared-absorbing fine particles. It is more preferably in a range of 1 part by mass to 500 parts by mass. Still more preferred is a range of 10 parts by mass or more and 150 parts by mass or less.

The reason is that if the metal chelate compound or metal cyclic oligomer compound is 0.1 parts by mass or more, the hydrolysate of the compound or the polymer of the hydrolysate exhibits the effect of covering the surface of the infrared absorbing fine particles, and is obtained Effect of improving heat and humidity resistance.

In addition, if the metal chelate compound or metal cyclic oligomer compound is 1,000 parts by mass or less, it is possible to avoid excessive adsorption of the infrared absorbing fine particles. In addition, it is expected that the coating effect will be improved by improving the humidity and heat resistance caused by the surface coating without being saturated.

Furthermore, by setting the metal chelate compound or metal cyclic oligomer compound to 1,000 parts by mass or less, it is possible to avoid excessive adsorption of infrared absorbing fine particles and to pass through the metal chelate compound or metal cyclic oligomerization when the medium is removed. A hydrolysate of a chemical compound or a polymer of the hydrolysate, and the fine particles tend to form particles. By preventing the undesirable particles from forming particles with each other, good transparency can be ensured.

In addition, it is also possible to avoid an increase in production costs caused by an increase in the addition amount and processing time due to an excess of a metal chelate compound or a metal cyclic oligomer compound. Therefore, from an industrial viewpoint, the amount of the metal chelate compound or metal cyclic oligomer compound added is preferably 1,000 parts by mass or less.

    [3] Surface coating method    

In the surface coating method of the infrared absorbing fine particles of the present invention, first, an infrared absorbing fine particle dispersion liquid for coating film formation is prepared by dispersing the infrared absorbing fine particles in an appropriate medium (it is described in the present invention as "the coating film" "Formation dispersion"). Then, a surface treatment agent is added to the prepared dispersion liquid for forming a coating film, and the mixture is stirred. In this way, the surface of the infrared absorbing fine particles is composed of a hydrolysate of a metal chelate compound, a polymer of a hydrolyzate of a metal chelate compound, a hydrolyzate of a metal cyclic oligomer compound, and a hydrolyzate of a metal cyclic oligomer compound. The polymer is selected from one or more kinds of coating films.

Here, regarding the surface coating method of the present invention, (1) preparation of a dispersion liquid for forming a coating film, (2) preparation of a dispersion liquid for coating film formation using water as a medium, and (3) adjustment were sequentially performed. Preparation of a coating liquid-forming dispersion liquid to which an amount of water is added, and (4) processing after mixing and stirring in the coating film-forming dispersion liquid.

    (1) Preparation of dispersion for coating film formation    

In the dispersion for forming a coating film of the present invention, it is preferable that the tungsten oxide or composite tungsten oxide belonging to the infrared absorbing fine particles is carefully pulverized in advance, and dispersed in an appropriate medium, and prepared into a single unit in advance. Decentralized state. In addition, the key is to ensure a dispersed state in this pulverization and dispersion treatment step and not to agglomerate the fine particles. The reason is that: during the surface treatment of the infrared-absorbing particles, the particles can be agglomerated, and the particles are covered with the surface of the aggregates, and the aggregates remain even in the infrared-absorbing particle dispersions described below. As a result, the transparency of the infrared-absorbing fine particle dispersion or the infrared-absorbing substrate described below may be reduced.

Therefore, by pulverizing and dispersing the dispersion liquid for forming a coating film of the present invention, when the surface treatment agent of the present invention is added, the hydrolysis product of the surface treatment agent and the polymer of the hydrolysis product can be made uniform and Each infrared absorbing fine particle is firmly covered.

As a specific method of the pulverizing and dispersing processing, for example, a pulverizing and dispersing processing method using a device such as a bead mill, a ball mill, a sand mill, a paint shaker, and an ultrasonic homogenizer. Among them, in terms of the short time required to reach the required dispersed particle size, it is preferred to use a bead mill, ball mill, sand mill, paint shaker and other media mixers using media such as beads, steel balls, and Ottawa sand. Crush and disperse.

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

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

It can be considered that it is affected by the reaction order of the surface treatment agent of the present invention added. That is, it is considered that the reason is that in the dispersion for forming a coating film using water as a medium, the hydrolysis reaction of the surface treatment agent necessarily proceeds first, and thereafter, the polymerization reaction of the generated hydrolysate 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 existing in the coating film can be reduced. By reducing the residual amount of carbon C in the molecules of the surface treatment agent present 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, a metal chelate compound, a metal cyclic oligomer compound, a hydrolysate thereof, and a polymer of the hydrolysate are also immediately after addition. That is, a case where the metal ions are dispersed, and in this case, when it becomes a saturated aqueous solution, the decomposition until the metal ions is completed.

On the other hand, in the coating film-forming dispersion liquid using water as a medium, the dispersion concentration of tungsten oxide or / and composite tungsten oxide in the coating film-forming dispersion liquid is preferably 0.01% by mass. Above 80% by mass. When the dispersion concentration is within 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 surface of all the infrared absorbing fine particles is composed of a hydrolyzate of a metal chelate compound, a polymer of a hydrolyzate of a metal chelate compound, a hydrolyzate of a metal cyclic oligomer compound, and a metal cyclic oligomer. The polymer selected from the hydrolysate of the compound is coated with one or more coating films 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 is that if the film thickness of the coating film is 0.5 nm or more, the surface-treated infrared-absorbing fine particles exhibit sufficient wet heat resistance and chemical stability. On the other hand, from the viewpoint of ensuring predetermined optical characteristics from the surface-treated infrared-absorbing fine particles, the film thickness of the coating film is preferably 100 nm or less. 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 grid pattern (arrangement of atoms in the crystal) of the infrared absorbing fine particles is equivalent to the coating film.

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

As a modified example of the above-mentioned method for preparing a dispersion liquid for forming a coating film using water as a medium, there is also a method in which an organic solvent is used as a medium for the dispersion liquid for forming a coating film, and the amount of water added is adjusted to an appropriate value. While implementing the above reaction sequence. In the present invention, it may be described as "a dispersion liquid for forming a coating film using an organic solvent as a medium".

This preparation method is also convenient when it is desired to reduce the amount of water contained in the dispersion for forming a coating film according to the situation of the subsequent steps.

Specifically, the surface treatment agent and pure water of the present invention are simultaneously dropped while agitating and mixing the dispersion liquid for forming a coating film using an organic solvent as a medium. At this time, appropriately control the temperature of the medium that affects the reaction speed, or the dripping speed of the surface treatment agent and pure water. In addition, as the organic solvent, any alcohol-based, ketone-based, or glycol-based solvent that is soluble in water at room temperature may be used, and various solvents can be selected.

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

The surface-treated infrared-absorbing fine particles of the present invention obtained in the above-mentioned preparation process of the dispersion for forming a coating film can be used as an infrared-absorbing fine particle dispersion or an infrared-absorbing group depending on the state of the particles, dispersed in a liquid medium or a solid medium. Raw materials.

That is, the generated surface-treated infrared-absorbing fine particles do not need to be further subjected to a heating treatment to increase the density or chemical stability of the coating film. The reason is that even if the heat treatment is not performed, the density or adhesiveness of the coating film has been sufficiently increased to a level where the required humidity and heat resistance can be obtained.

However, depending on the purpose of obtaining a powder of surface-treated infrared-absorbing fine particles from the dispersion for coating film formation, the purpose of drying the obtained surface-treated infrared-absorbing fine particles, etc., the dispersion or surface treatment for coating film formation can be performed. The infrared-absorbing fine particle powder is heat-treated. However, in this case, care must be taken not to cause the heat treatment temperature to exceed a temperature at which the surface-treated infrared-absorbing particles are strongly aggregated to form a strong aggregate.

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

When the heat treatment is performed at a temperature exceeding the temperature at which the aggregates are formed, in order to ensure the transparency of the infrared absorbing particle dispersion or the infrared absorbing substrate, the aggregates are crushed dry or / and wet to re-disperse them. . 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 depending on the situation, and the surface of the fine particles may be exposed.

As described above, since the surface-treated infrared absorbing particles of the present invention do not need to be heat-treated after the treatment after mixing and stirring, they do not undergo strong agglutination, and therefore do not need a dispersing treatment for crushing agglutination, or it can be 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 is in a state of being covered with each infrared-absorbing fine particles. In addition, it is considered that the infrared-absorbing fine particle dispersion or the infrared-absorbing base material produced by using the surface-treated infrared-absorbing fine particles exhibits superior moist heat resistance than those obtained by a conventional method.

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

    [4] Phosphite compounds    

The inventors of the present case have found that the infrared absorption of the present invention can be achieved by adding a phosphorous acid ester-based compound having a specific structure to the above-mentioned infrared-absorbing fine particle dispersion containing the 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 manufactured using the same is improved, and the decrease in infrared absorption characteristics when the dispersion and the infrared-absorbing substrate are used for a long period of 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 infrared absorption characteristics when the dispersion is used for a long period of time, the dispersion is prepared to the infrared absorbing fine particle dispersion or prepared using the dispersion. The dispersion is added with the phosphite compound of the present invention.

Then, in addition to the phosphite compound, a combination of one or more phosphoric acid stabilizers, hindered phenol stabilizers, thioether stabilizers, and metal deactivators selected from the phosphite compounds is used to improve the weather resistance. It is also preferable to add an agent.

Hereinafter, (1) a phosphite compound, (2) a phosphate stabilizer other than the phosphite compound, (3) a hindered phenol stabilizer, (4) a thioether stabilizer, and (5) a metal. The deactivator is explained.

    (1) Phosphite compound    

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

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

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

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

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

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

R2 is preferably an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, and third pentyl, and more preferably methyl , Third butyl, third pentyl and the like. R5 is preferably a carbon atom of 1 to 5 such as a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, and third pentyl. alkyl.

R3 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups having 1 to 8 carbon atoms as described in 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, and 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 the 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. Here, the carbon number is 1 to 8 Examples of the alkyl group and the alicyclic group having 5 to 12 carbon atoms include the same alkyl groups and alicyclic groups as described in the foregoing R1, R2, R4, and R5.

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

A represents an alkylene group having 2 to 8 carbon atoms or a divalent residue represented by the structural formula (1-2), preferably an alkylene group having 2 to 8 carbon atoms. As the alkylene group, for example: Ethyl, propyl, butyl, pentyl, hexamethylene, octamethylene, 2,2-dimethyl-1,3-propyl, etc., more preferably propyl. 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, as the alkylene group having 1 to 8 carbon atoms, for example, methylene, ethylene, propyl, butyl, or butyl Amyl, hexamethylene, octamethylene, 2,2-dimethyl-1,3-propene and the like. The R7 is preferably a single bond, ethylene, or the like.

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

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

Preferred specific examples of the phosphites include: 2,4,8,10-tetra-third-butyl-6- [3- (3-methyl-4-hydroxy-5-third-butyl) Phenyl) propoxy] dibenzo [d, f] [1,3,2] Dioxaphosphacycloheptene [as "Sumilizer (registered trademark) GP" (manufactured by Sumitomo Chemical Co., Ltd.) Sale], 2,10-dimethyl-4,8-di-third-butyl-6- [3- (3,5-di-third-butyl-4-hydroxyphenyl) propoxy]- 12H-dibenzo [d, g] [1,3,2] dioxo-octacyclic, 2,4,8,10-tetra-third-butyl-6- [3- (3,5-di -Third-butyl-4-hydroxyphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphacycloheptene, 2,4,8,10-tetra- Third pentyl-6- [3- (3,5-di-third-butyl-4-hydroxyphenyl) propoxy] -12-methyl-12H-dibenzo [d, g] [1 , 3,2] dioxaphosphatacyclo, 2,10-dimethyl-4,8-di-third-butyl-6- [3- (3,5-di-third-butyl-4- Hydroxyphenyl) propanyloxy] -12H-dibenzo [d, g] [1,3,2] dioxophosphooctacyclo, 2,4,8,10-tetra-tertiarypentyl-6 -[3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propanyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] Dioxaphosphatacyclo, 2,4,8,10-tetra-tertiary-butyl-6- [3- (3,5-di-tertiary-butyl-4-hydroxy Phenyl) propionyloxy] -dibenzo [d, f] [1,3,2] dioxaphosphacycloheptene, 2,10-dimethyl-4,8-di-third Butyl-6- (3,5-di-tert-butyl-4-hydroxybenzyloxy) -12H-dibenzo [d, g] [1,3,2] dioxophosphate octacyclic , 2,4,8,10-tetra-third-butyl-6- (3,5-di-third-butyl-4-hydroxybenzyloxy) -12-methyl-12H-dibenzo [d, g] [1,3,2] Dioxooctacyclic, 2,10-dimethyl-4,8-di-third-butyl-6- [3- (3-methyl-4 -Hydroxy-5-third butylphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxophosphate octacyclic, 2,4,8,10-tetrakis -Third-butyl-6- [3- (3,5-di-third-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2 ] Dioxooctacyclic, 2,10-diethyl-4,8-di-third-butyl-6- [3- (3,5-di-third-butyl-4-hydroxyphenyl) Propoxy] -12H-dibenzo [d, g] [1,3,2] dioxophosphate octacyclic, 2,4,8,10-tetra-third-butyl-6- [2,2 -Dimethyl-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -dibenzo [d, f] [1,3,2] dioxaphos Heterocycloheptene and the like.

Commercially available phosphorous acid esters can also be used. Examples thereof include a trade name Sumilizer (registered trademark) GP (manufactured by Sumitomo Chemical Co., Ltd.).

The addition amount of the phosphite is preferably more than 500 parts by mass and less than 50,000 parts by mass with respect to 100 parts by mass of the infrared absorbing fine particles, and particularly preferred is 700 parts by mass or more and 2000 parts by mass or less.

When the amount of phosphite is more than 500 parts by mass relative to 100 parts by mass of fine particles, the haze is suppressed from rising even after being maintained in a high-temperature atmospheric environment of 120 ° C, and the transmittance, especially insolation, is ensured. Rates are kept at a better level.

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

Here, in order to clarify the characteristics of the present invention, a method for adding a phosphite-based stabilizer to a dispersion / dispersion containing the surface-treated infrared-absorbing microparticles of the present invention, and a conventional technique of dispersing to the absence of infrared-absorbing microparticles A comparison of methods for adding a phosphite-based stabilizer to a dispersion / dispersion will be described.

As described above, the added amount of the phosphite-based stabilizer of the present invention is more than 500 parts by mass and less than 50,000 parts by mass based on 100 parts by mass of the infrared absorbing fine particles. On the other hand, the addition amount of the phosphite stabilizer in the general dispersion which does not contain the conventional technology of 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-based stabilizer in the dispersion of the conventional technology containing infrared absorbing fine particles, it is equivalent to the addition amount of 50 to 200 parts by mass, and the addition amount of the present invention exceeds 500 There are significant differences between parts by mass and less than 50,000 parts by mass.

According to the findings of the present inventors, when the dispersion liquid / dispersion contains the surface-treated infrared-absorbing fine particles of the present invention, the amount of the phosphite-based stabilizer added to the mass of the infrared-absorbing fine particles is more than 500 parts by mass. Part by mass and not more than 50,000 parts by mass exert an effect on the stability of the dispersion / dispersion.

On the other hand, when a phosphite-based stabilizer equivalent to more than 500 parts by mass and less than 50,000 parts by mass is added to the dispersion / dispersion of the conventional technology that does not contain infrared absorbing fine particles, the dispersion / dispersion Visible white mist is generated in the body due to hydrolysis of the stabilizer, and the optical characteristics are significantly deteriorated (see Comparative Example 5). Moreover, the level of deteriorated optical characteristics in the dispersion / dispersion of the conventional technique is lower than that of the dispersion / dispersion without adding surface-treated infrared absorbing fine particles and stabilizers (see Comparative Examples 5 and 13).

    (2) Other phosphorus stabilizers    

Examples of the phosphorus-based stabilizer other than the phosphite compound described in (1) include those having a phosphorus-based functional group containing a 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.

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

The "phosphorus functional group" in this embodiment refers to a portion other than R1 in the general formulae (2) and (3) (that is, the general formula: -Ox-P (OyR2) (OzR3), or Formula: -Ox-P (O) (OyR2) (OzR3)). Specific examples of the phosphorus-based functional group include a phosphonic acid group (-P (O) (OH) ₂ ), a phosphoric acid group (-OP (O) (OH) ₂ ), and a 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, functional groups containing pentavalent phosphorus, such as phosphonic acid groups, phosphate groups, phosphonate groups, and phosphate groups, can be considered to have a chain-initiating hindrance function (that is, adjacent phosphorus-based functional groups The chelate has the function of capturing metal ions).

On the other hand, it is considered that a phosphorus-based functional group containing a trivalent phosphorus such as a phosphine group mainly has a peroxide decomposition function (that is, a function of decomposing a peroxide into a stable compound by oxidation of a P atom itself).

Among these phosphorus-based functional groups, a phosphonic acid-based anti-staining agent having a phosphonic acid group can efficiently capture metal ions and has excellent stability such as hydrolysis resistance. Therefore, it is particularly suitable as a reduction inhibitor of infrared absorption characteristics.

Preferred examples of the low-molecular-weight phosphorus-based anti-colorant include, specifically, phosphoric acid (H ₃ PO ₄ ), triphenyl phosphite ((C ₆ H ₅ O) ₃ P), and tri-desulfurous acid. Octyl 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 the polymer-type phosphorus-based anti-colorant, specifically, polyvinylphosphonic acid, polystyrenephosphonic acid, and ethylene-based phosphoric acid (for example, propylene phosphonium phosphate (CH ₂ = CHCOOPO (OH)) ₂ ), a vinyl alkyl phosphate (a polymer of CH ₂ = CHR-O-PO (OH) ₂ and R is-(CH ₂ ) n-), etc.), a polyether resin having a phosphonic acid group introduced, Polyetheretheretherketone resin, linear phenol-formaldehyde resin, linear polystyrene resin, crosslinked polystyrene resin, linear poly (trifluorostyrene) resin, crosslinked (trifluorobenzene) Ethylene) resin, poly (2,3-diphenyl-1,4-phenyl ether) resin, poly (allyl ether ketone) resin, poly (propyne ether fluorene) resin, poly (phenylquinoline) resin, Poly (benzyl silane) resin, polystyrene-grafted-ethylene tetrafluoroethylene resin, polystyrene-grafted-polyvinylidene fluoride resin, polystyrene-grafted-tetrafluoroethylene resin, and the like.

As the phosphoric acid-based stabilizer, a commercially available product may be used. Examples thereof include Adekastab AS2112 (manufactured by ADEKA Corporation).

    (3) Hindered phenol stabilizer    

An example of a hindered phenol-based stabilizer is a compound obtained by introducing a larger group such as a third butyl group into one of the phenolic OH groups. It is considered that the hindered phenol-based stabilizer mainly has a polymerization inhibitory function (that is, a function in which a phenolic OH group captures a radical and suppresses a chain reaction caused by the radical).

Preferable examples of the low-molecular-type hindered phenol stabilizer include 2,6-third-butyl-p-cresol, 2,6-di-third-butyl-phenol, and 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), [Methylene-3 (3,5- Di-third butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-ginseng (2-methyl-4-hydroxy-5-third butylphenyl) butane, and the like.

In addition, as a preferable example of the polymer-type hindered phenol-based stabilizer, vinyl, acryl fluorenyl, methacryl fluorenyl, and styryl groups such as the above-mentioned hindered phenol anti-coloring agent are branched. Polymer, or a polymer obtained by incorporating the structure of the hindered phenol-based colorant into the main chain.

Furthermore, as in the case of the phosphorus-based anti-colorant, there are cases where a polymer compound is superior to a low molecular compound, and when a polymer compound is used, a crosslinked structure may be further introduced.

Among them, there are many points that have not been clearly explained about the harmful free radical capture processes of the above various anti-colorants, and there are possibilities of actions other than the above, which are not limited to the above actions.

As the hindered phenol-based stabilizer, a commercially available product may be used. Examples of the product include Irganox 1010 (manufactured by BASF).

    (4) thioether stabilizer    

As an example of a thioether-based stabilizer, a compound having divalent sulfur in its molecule (this may be referred to as a "sulfur-based anti-colorant" in this embodiment). It is considered that the sulfur-based anti-coloring agent mainly has a peroxide decomposition function (that is, a function of decomposing a peroxide into a stable compound by oxidation of the S atom itself). Preferred examples of the low-molecular sulfur-based anti-colorant include dilauryl thiodipropionate (S (CH ₂ CH ₂ COOC ₁₂ H ₂₅ ) ₂ ), and 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 dipropionate (S (CH ₂ CH ₂ COOC ₁₄ H ₂₉ ) ₂ ), β, β'-Distearylthiobutyrate (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 the thioether-based stabilizer, a commercially available product may be used. Examples thereof include a trade name Sumilizer (registered trademark) TPM (manufactured by Sumitomo Chemical Co., Ltd.).

    (5) Metal deactivator    

As the metal deactivator, a hydrazine derivative, a salicylic acid derivative, an oxalic acid derivative, or the like can be preferably used, and particularly preferred is 2 ', 3-bis [[3- [3,5-di-third-butyl -4-Hydroxyphenyl] propanyl]] propanazine, 2-hydroxy-N- (2H-1,2,4-triazol-3-yl) benzidine, dodecanedioic acid bis [ 2- (2-hydroxybenzyl) hydrazine] and the like.

The amount of the metal deactivator added to the infrared absorbing fine particle dispersion liquid or the infrared absorbing fine particle dispersion of the present invention also depends 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, and is preferably 1 to 10 parts by mass, and more preferably 3 to 8 parts by mass, with respect to 100 parts by mass of the infrared absorbing microparticles in the infrared absorbing microparticle dispersion liquid or the infrared absorbing microparticle dispersion. When the addition amount of the metal deactivator is 1 part by mass or more, the effect of preventing the reduction of the infrared absorption function is exhibited, and the effect is approximately saturated at 10 parts by mass.

    [5] Infrared absorbing particle dispersion    

The infrared-absorbing fine particle dispersion liquid of the present invention is one in which the surface-treated infrared-absorbing fine particles of the present invention are dispersed in a liquid medium (hereinafter sometimes referred to as a "liquid medium"). As the liquid medium, one or more liquid mediums selected from organic solvents, oils and fats, liquid plasticizers, compounds that are polymerized by hardening, and water can be used.

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

    (1) Manufacturing method    

When manufacturing the infrared absorbing fine particle dispersion liquid of the present invention, the dispersion liquid for forming the 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, and the like 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 liquid medium, and a phosphite compound may be further added and dispersed. In addition, the dispersion liquid for forming a coating film is separated into a surface-treated infrared absorbing fine particle and a medium, and a solvent replacement operation is used to replace the medium for the coating film forming dispersion with a medium for an infrared absorbing fine particle dispersion (so-called solvent replacement). ), And further adding a phosphite compound to produce an infrared absorbing fine particle dispersion liquid is also a preferable structure.

On the other hand, the medium of the dispersion for coating film formation and the medium of the infrared absorbing fine particle dispersion liquid are made in advance, and a phosphorous acid ester-based compound is added to the dispersion for coating film formation after the surface treatment to produce infrared absorbing fine particles. A dispersion is also preferable.

    (2) Organic solvents used    

Examples of the organic solvent used in the infrared-absorbing fine particle dispersion liquid of the present invention include alcohol-based, ketone-based, hydrocarbon-based, glycol-based, and water-based solvents.

Specifically, alcohol solvents such as methanol, ethanol, 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol, and diacetone alcohol; acetone, methyl ethyl ketone, methyl propyl ketone, Ketone solvents such as methyl isobutyl ketone, cyclohexanone, isophorone; ester solvents such as 3-methyl-methoxy-propionate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol ether acetate and other diol derivatives; methylformamide, N-methylformamide, dimethylformamide Ammonium amines such as fluorenamine, dimethylacetamide, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene and xylene; dichloroethane and chlorobenzene.

Among these organic solvents, dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether acetate, n-butyl acetate, and the like are particularly preferably used.

    (3) Grease used    

The fats and oils used in the infrared-absorbing fine particle dispersion liquid of the present invention are preferably vegetable fats or oils derived from plants.

As vegetable oils, dry oils such as linseed oil, sunflower oil, tung oil, and perilla oil; semi-dry 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 and dehydrated castor oil.

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 monoester directly can be used.

A commercially available petroleum-based solvent may be used as the 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 (above, manufactured by Exxon Mobil), etc. .

    (4) Liquid plasticizer used    

As the liquid plasticizer used in the infrared absorbing fine particle dispersion liquid of the present invention, for example, a plasticizer belonging to a compound of a monohydric alcohol and an organic acid ester, an ester plasticizer such as a polyhydric alcohol organic acid ester compound, or an organic phosphoric acid-based plasticizer Phosphoric acid-based plasticizers and the like. In addition, any of them is preferably a 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. For example, diols such as triethylene glycol, tetraethylene glycol, and tripropylene glycol, and butyric acid, isobutyric acid, hexanoic acid, 2- Diol-based ester compounds obtained by the reaction of mono-organic acids such as ethyl butyric acid, heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, nonanoic acid (n-nonanoic acid), and capric acid.

In addition, examples thereof include tetraethylene glycol, tripropylene glycol, and ester compounds with the above-mentioned monoorganic acids.

Among them, triethylene glycol dihexanoate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-octanoate, and triethylene glycol di-2-ethylhexanoate can be used. And other fatty acid esters of triethylene glycol. Furthermore, fatty acid esters of triethylene glycol can also be preferably used.

    (5) Compounds that are polymerized by hardening    

The compound that is polymerized by hardening and 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, a methyl methacrylate monomer, an acrylate monomer, a styrene resin monomer, etc. can be used.

The liquid medium described above can be used in combination of two or more kinds. Further, if necessary, an acid or an alkali may be added to the liquid medium to adjust the pH value.

    (6) Dispersant used    

In the infrared absorbing fine particle dispersion liquid of the present invention, in order to further improve the dispersion stability of the surface-treated infrared absorbing fine particles and avoid coarsening of the dispersed particle diameter caused by re-aggregation, it is also preferable to add various dispersants, surfactants, Coupling agent, etc.

The dispersant, coupling agent, and surfactant can be selected according to the application, and it is preferred to have a functional group containing an amine group, a hydroxyl group, a carboxyl group, or an epoxy group. These functional groups have the effect of adsorbing on the surface of the surface-treated infrared absorbing fine particles to prevent aggregation and to disperse them uniformly. It is more preferably a polymer-based dispersant having any of these functional groups in the molecule.

In addition, an acrylic-styrene copolymer dispersant having a functional group may be cited as a preferable dispersant. Among them, acryl-styrene copolymer dispersant having a carboxyl group as a functional group, and an acrylic dispersant having a amine-containing group as a functional group are mentioned as more preferable examples. The dispersant having a functional group having an amine-containing group is preferably one having a molecular weight of Mw 2000 to 200000 and an amine value of 5 to 100 mgKOH / g. The dispersant having a carboxyl group is preferably one having a molecular weight of Mw 2000 to 200000 and an acid value of 1 to 50 mgKOH / g.

As a preferable specific example of a commercially available dispersant, SOLSPERSE (registered trademark) (the same applies hereinafter) 3000, 5000, 9000, 11200, 12000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000SC, 24000GR, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 32600, 3600, 33000, 33500, 34750, 35100, 35200, 36600, 37500, 38500, 39000, 41000, 41090, 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 .; manufactured by BYK-Chemie Japan 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 applies hereinafter) -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, W985, W995, W996, W9010, Dynwet800, Siclean3700, UV3500, UV3510, UV3570, etc .; EFKA (registered trademark) manufactured by Efka Additive (the same below) 2020, 2025, 3030, 3031, 3236, 4008, 4009, 4010, 4015, 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 .; JONCRYL (registered trademark) manufactured by BASF Japan (the same below) 67, 678, 586, 611, 680, 682, 690, 819 -JDX5050, etc .; TERPLUS (registered trademark) manufactured by Otsuka Chemical Company (the same below) MD1000, D1180, D1130, etc .; Ajisper (registered trademark) manufactured by Ajinomoto Fine-Techno (the same below) PB-711, PB-821, PB -822, etc .; Disparlon (registered trademark) (hereinafter the same) manufactured by Nanben Chemical Co., Ltd. 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 .; ARUFON (registered trademark) (hereinafter the same) UH-2170, UC-3000 manufactured by Toa Synthesis Corporation , UC-3910, UC-3920, UF-5022, UG-4010, UG-4035, UG-4040, UG-4070, Reseda (registered trademark) (the same below) GS-1015, GP-301, GP-301S, etc. ; Dianal (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 of the present invention produced as described above can be applied to an appropriate substrate surface, a coating film can be formed thereon, and it can be used as an infrared absorbing substrate. That is, the coating film is one type of the dried and cured product of the infrared absorbing fine particle dispersion liquid.

The infrared absorbing fine particle dispersion is dried and pulverized to obtain a powdery infrared absorbing fine particle dispersion containing the phosphite compound of the present invention (the "dispersion powder" may be described in the present invention) . That is, this dispersion powder is one of the dried and solidified products of the infrared absorbing fine particle dispersion liquid. This dispersion powder is a powdery dispersion in which surface-treated infrared-absorbing fine particles are dispersed in a solid medium (dispersant, etc.) containing a phosphate-based compound, and is different from the surface-treated infrared-absorbing fine particles. Since the dispersing powder contains a dispersant, the surface-treated infrared-absorbing fine particles can be easily redispersed in the medium by being mixed with an appropriate medium.

In addition, a configuration may be adopted in which an infrared-absorbing fine particle dispersion containing no phosphite-based compound is prepared without adding a phosphite-based compound to the infrared-absorbing fine-particle dispersion. In this case, when mixing or kneading the infrared-absorbing fine particle dispersion liquid containing no phosphite compound or drying the infrared-absorbing fine particle dispersion powder obtained by drying the medium, a specific amount of phosphorous acid may be added. An ester-based compound to prepare the infrared absorbing fine particle dispersion of the present invention.

On the other hand, the infrared-absorbing fine particle dispersion obtained by mixing and dispersing the surface-treated infrared-absorbing fine particles of the present invention in a liquid medium can be used for various applications in which light-to-heat conversion is applied.

For example, the surface-treated infrared-absorbing fine particles are added to an unhardened thermosetting resin, or the surface-treated infrared-absorbing fine particles of the present invention are dispersed in an appropriate solvent, and then the non-hardened thermosetting resin is added to obtain hardening. Type ink composition. When the curable ink composition is provided on a specific substrate and cured by irradiating infrared rays such as infrared rays, the adhesiveness to the substrate is excellent. In addition, the hardening ink composition is not only used as a conventional ink, but also a hardening ink composition that is most suitable for photoforming. The photoforming method is a coating of a specific amount of the hardening ink composition. It irradiates electromagnetic waves such as infrared rays to harden and stack them to form a three-dimensional object.

    [6] Infrared absorbing microparticle dispersions, infrared absorbing substrates, and articles         (1) Infrared absorbing microparticle dispersion    

The infrared absorbing fine particle dispersion system of the present invention disperses the surface-treated infrared absorbing fine particles of the present invention in a solid medium. As the solid medium, a solid medium such as resin or glass can be used.

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

    (i) Manufacturing method    

As described above, when the surface-treated infrared-absorbing fine particles of the present invention are mixed into a medium such as a resin to form a film or a plate, the surface-treated infrared-absorbing fine particles and a phosphite compound may be directly mixed 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.

When a resin is used 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, when the surface-treated infrared-absorbing fine particles of the present invention are kneaded in a resin, they are kneaded by heating and mixing at a temperature near the melting point of the resin (about 200 to 300 ° C).

In this case, the surface-treated infrared-absorbing fine particles may be further mixed with a resin, granulated, and the particles may be formed into a film or a plate in various ways. For example, it can be formed by an extrusion molding method, an inflation molding method, a solution casting method, a cast film method, or the like. The thickness of the film or plate at this time may be appropriately set depending on the purpose of use, and the thickness of the substrate or the required optical characteristics with respect to the amount of filler in the resin (that is, the amount of the surface-treated infrared-absorbing fine particles of the present invention) can be determined. And mechanical properties change, generally it is preferably 50% by weight or less with respect to the resin.

When the amount of the filler relative to the resin is 50% by weight or less, the particles in the solid resin can be prevented from forming particles with each other, and therefore, good transparency can be maintained. In addition, since the usage amount of the surface-treated infrared-absorbing fine particles of the present invention can also be controlled, the cost is also advantageous.

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 may be used in a state of being pulverized to form a powder. When this configuration is adopted, the surface-treated infrared-absorbing fine particles of the present invention are sufficiently dispersed in a solid medium in the powdery infrared-absorbing fine particle dispersion. Therefore, by using a mixture of the powdery infrared absorbing fine particle dispersion and a phosphite compound as a so-called master batch, dissolving it in an appropriate liquid medium, or kneading it with resin particles, etc., it is possible to easily produce a liquid state. Or a solid dispersion of infrared absorbing particles.

In addition, the so-called solid resin constituting a matrix in the above-mentioned film or plate refers to a polymer medium that is solid at room temperature, and also includes a concept of a polymer medium other than those formed by three-dimensional cross-linking. The solid resin is not particularly limited, and can be selected depending on the application. When weather resistance is considered, a fluororesin is preferred. However, PET resin, acrylic resin, polyamide resin, vinyl chloride resin, polycarbonate resin, olefin resin, Epoxy resin, polyimide resin, etc.

    (ii) Damp heat resistance    

When the infrared absorbing fine particle dispersion system of the present invention is exposed to a dispersion set at about 80% visible light transmittance in a hot and humid environment at 85 ° C and 90% for 9 days, the visible light transmittance change before and after the exposure is 2.0 % Or less, with excellent moisture and heat resistance.

    (iii) Heat resistance    

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

    (2) Infrared absorbing substrate    

The infrared absorbing base material of the present invention is formed on the surface of a specific base material and includes 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 damp heat resistance and chemical stability, and can be suitably used. As an infrared absorbing material.

Regarding the infrared absorbing substrate of the present invention, (i) a manufacturing method, (ii) moist heat resistance, and (iii) heat resistance will be described in order.

    (i) Manufacturing method    

For example, the surface-treated infrared-absorbing fine particles and phosphite compounds of the present invention are mixed with an organic solvent such as alcohol or a liquid medium such as water, a resin binder, and a dispersant as necessary to obtain an infrared-absorbing fine particle dispersion, and the obtained After the infrared absorbing fine particle dispersion is applied to a suitable substrate surface, the liquid medium is removed, thereby obtaining an infrared absorbing substrate in which the infrared absorbing fine particle dispersion is directly laminated on the substrate surface.

The resin binder component is selected depending on the application, and examples thereof include an ultraviolet curing resin, a thermosetting resin, a room temperature curing resin, and a thermoplastic resin. On the other hand, as for the infrared absorbing fine particle dispersion containing no resin binder component, an infrared absorbing fine particle dispersion can also be layered on the surface area of the substrate. After the lamination, a liquid medium containing a binder component is applied to the infrared absorbing agent. Microparticle dispersion layer.

Specifically, one or more liquid mediums containing an organic solvent, an organic solvent in which a resin is dissolved, an organic solvent in which the resin is dispersed, and water may contain a phosphite compound, and surface-treated infrared-absorbing fine particles may be dispersed. The liquid infrared absorbing fine particle dispersion in liquid form is an infrared absorbing substrate formed on the surface of the substrate according to the coating film. In addition, an infrared absorbing substrate in which a liquid infrared absorbing fine particle dispersion containing a resin binder component is formed on the surface of a substrate by a coating film can be cited. Furthermore, a liquid infrared absorbing microparticle dispersion containing a phosphite compound in a powdery solid medium and having surface-treated infrared absorbing microparticles dispersed therein and mixed with a specific medium can also be cited. 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 of these various liquid infrared absorbing fine particle dispersion liquids may be formed on the surface of the substrate according to the coating film.

The material of the substrate 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.

The resin used for a resin plate, a resin sheet, or a resin film is not particularly limited as long as the surface state or durability of the required plate, sheet, or film does not cause any abnormality. Examples include polyester polymers such as polyethylene terephthalate, polyethylene naphthalate, cellulose polymers such as diacetyl cellulose, and triethyl cellulose, and polycarbonates. Polymers, acrylic polymers such as polymethyl methacrylate, styrene polymers such as polystyrene, acrylonitrile-styrene copolymer, polyethylene, polypropylene, cyclic or polymer Polyolefins such as olefins, olefin polymers such as ethylene-propylene copolymers, vinyl chloride polymers, fluorene polymers such as aromatic polyamines, fluorene polymers, fluorene polymers, polyethers Polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, ethylene butyraldehyde polymer, aryl ester polymer, polyoxymethylene polymer Plates, sheets, and films of transparent polymers such as polymers, epoxy polymers, and various binary and ternary copolymers, graft copolymers, and blends. In particular, polyester biaxially oriented films, such as polyethylene terephthalate, polybutylene terephthalate, or polyethylene-2,6-naphthalate, have mechanical properties, optical properties, and heat resistance. And economically. The polyester-based biaxially oriented film may also be a copolymerized polyester-based.

    (ii) Damp heat resistance    

In the above infrared absorbing substrate, when the infrared absorbing substrate set to 80% visible light transmittance was exposed for 9 days in a humid and hot environment at 85 ° C and 90%, the change amount of visible light transmittance before and after the exposure was Below 2.0%, it has excellent humidity and heat resistance.

    (iii) Heat resistance    

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

    (3) Articles using an infrared-absorbing particle dispersion or an infrared-absorbing substrate    

As described above, the infrared absorbing articles such as the infrared absorbing fine particle dispersion or the infrared absorbing substrate of the present invention are excellent in moist heat resistance, heat resistance, and chemical stability.

Therefore, these infrared absorbing articles can be preferably used, for example, as window materials for the purpose of sufficiently absorbing visible light in various buildings or vehicles, shielding light in the infrared region, and suppressing temperature rise in the room while maintaining brightness. Filters used in PDPs (plasma display panels) and shielding infrared radiation emitted from the PDPs.

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

In addition, 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, it absorbs infrared rays having a specific wavelength. Therefore, an anti-counterfeit printed matter obtained by printing an anti-counterfeit ink containing the surface-treated infrared-absorbing fine particles on one or both sides of a substrate to be printed is irradiated with infrared rays having a specific wavelength and reading its reflection or transmission. The amount of reflection or transmission determines the authenticity of the printed matter. This anti-counterfeit printed matter is an example of the infrared absorbing fine particle dispersion of the present invention.

In addition, the infrared-absorbing fine particle dispersion liquid of the present invention is mixed with a binder component to produce an ink, and the ink is coated on a substrate and dried, and then the dried ink is hardened to form a light-to-heat conversion layer. The light-to-heat conversion layer is irradiated with electromagnetic waves such as infrared rays, and can generate heat only at a required portion with high accuracy, and can be applied to a wide range of fields such as electronic equipment, medical treatment, agriculture, machinery, and the like.

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

In addition, the surface-treated infrared-absorbing fine particles of the present invention are dispersed in an appropriate medium and contain a phosphite compound to prepare an infrared-absorbing fine particle dispersion, and the surface and / or the inside of the fiber can contain the dispersion, thereby making it possible to Obtain infrared absorbing fibers. With this structure, the infrared-absorbing fiber contains infrared-absorbing particles to efficiently absorb near-infrared rays from sunlight and the like, and becomes an infrared-absorbing fiber with excellent heat retention and transmits light in the visible region. Excellent infrared absorbing fiber. As a result, it can be used in various applications such as cold-proof clothing, sports clothing, stockings, curtains, and other industrial fiber products that require thermal insulation. 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 or exterior wall materials of greenhouses for agriculture and horticulture. This material transmits visible light to ensure the light synthesis of plants in greenhouses for agriculture and horticulture, and efficiently absorbs light such as near-infrared light included in other sunlight, which can be used as heat insulation. Sexual insulation materials for agricultural and horticultural facilities. The thermal insulation 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 an average value measured by a particle size measuring device (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.) based on a dynamic light scattering method. . The crystallite diameter was measured by a powder X-ray diffraction method (θ-2θ method) using a powder X-ray diffraction device (X'Pert-PRO / MPD manufactured by Spectris Co., Ltd. PANalytical Co., Ltd.). Calculate it.

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

The optical characteristics of the infrared absorbing sheet or plate are measured using a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.), and the visible light transmittance and solar transmittance are 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 was calculated in accordance with JISK7105.

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

The method for evaluating the moisture and heat resistance of an infrared absorbing sheet or board is to expose the infrared absorbing sheet having a visible light transmittance of about 80% in an atmospheric environment at 120 ° C for 30 days. Then, for example, in the case of hexagonal cesium tungsten bronze, it is judged that the change in solar transmittance before and after the exposure is 2.0% or less is good heat resistance, and the change is more than 2.0% is judged as insufficient heat resistance.

In addition, the optical characteristic value (visible light transmittance, haze value) of an infrared absorption sheet or board here means the value which includes the optical characteristic value of the resin sheet or board which is a base material.

    [Example 1]    

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 with Cs / W (molar ratio) = 0.33 % And 75% by mass of pure water, filled to 0.3mm In a paint shaker for ZrO ₂ beads, pulverization and dispersion treatment were performed for 10 hours to obtain a dispersion liquid of Cs _0.33 WOz fine particles of Example 1. The dispersion particle diameter of the Cs _0.33 WOz fine particles in the obtained dispersion was measured, and the result was 100 nm. In addition, as a setting of the particle size measurement, the refractive index of the particles was set to 1.81, and the particle shape was set to be non-spherical. The background was measured using pure water, and the refractive index of the solvent was 1.33. The solvent of the obtained dispersion was removed, and the crystallite diameter was measured. As a result, it was 32 nm. The obtained dispersion liquid of Cs _0.33 WOz fine particles and pure water were mixed to obtain a dispersion liquid A for coating film formation of Example 1 having a concentration of Cs _0.33 WOz fine particles of 2% by mass.

On the other hand, 2.5% by mass of ethyl aluminum acetate diisopropylacetate and 97.5% by mass of isopropyl alcohol (IPA) as an aluminum-based chelate compound were mixed to obtain a surface treatment agent diluted solution a.

890 g of the obtained dispersion liquid A for forming a coating film was put into a beaker, stirred thoroughly with a stirrer with a blade, and 360 g of a surface treatment agent dilution liquid a was added dropwise thereto over 3 hours. After the surface treatment agent dilution liquid a was added dropwise, the mixture was further stirred at a temperature of 20 ° C. for 24 hours to prepare a ripening liquid of Example 1. Then, the medium was evaporated from the aging liquid using vacuum flow drying to obtain the powder containing surface-treated infrared-absorbing fine particles (surface-treated infrared-absorbing fine particles) of Example 1.

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

8% by mass of the surface-treated infrared-absorbing fine particle powder of Example 1, 24% by mass of the polyacrylate dispersant, and 68% by mass of toluene were mixed. Fill the obtained mixed solution to 0.3mm In the paint shaker for ZrO ₂ beads, pulverization and dispersion treatment was 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.

The infrared absorbing fine particle dispersion powder of Example 1, a polycarbonate resin which is a solid resin, and Sumilizer GP, which is 2000 parts by mass based on 100 parts by mass of hexagonal cesium tungsten bronze, were added, and the visible light of the infrared absorbing sheet obtained thereafter was added. Dry blending was performed so that the transmittance became about 80%. The obtained blend was kneaded at 290 ° C using a biaxial extruder, extruded from a T-die, and made into a sheet having a thickness of 0.75 mm by a polishing roller method to obtain the infrared absorption of Example 1. sheet. The infrared absorbing sheet is an example of the infrared absorbing fine particle dispersion of the present invention.

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

After the obtained infrared absorbing sheet of Example 1 was exposed to a hot and humid environment at 85 ° C and 90% for 9 days, the optical characteristics 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 hot and humid environment is 0.6%, and the amount of change in solar transmittance is 0.9%, both of which are small, and there is no change in haze.

In addition, after the obtained infrared absorbing sheet of Example 1 was exposed to an atmospheric environment at 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 hot and humid environment is 0.6%, and the amount of change in solar transmittance is 1.4%, both of which are small, and there is no change in haze.

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

    [Examples 2 and 3]    

Example 2 was obtained in the same manner as in Example 1 except that, based on 100 parts by mass of hexagonal cesium tungsten bronze powder, 4,000 parts by mass of Sumilizer GP (Example 2) or 700 parts by mass (Example 3) were added. , 3 of the infrared absorption sheet.

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

The manufacturing conditions and evaluation results of Examples 2 and 3 are shown 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 stirrer so that the concentration of the infrared absorbing fine particles was 0.05% by weight, and then melt-kneaded with a biaxial extruder to extrude the line. The material was cut into granules to obtain a masterbatch containing infrared absorbing fine particles of Example 4. The master batch containing infrared absorbing fine particles is an example of the infrared absorbing fine particle dispersion of the present invention.

10 parts by mass of the obtained master batch containing infrared absorbing fine particles of Example 4 and 90 parts by mass of polycarbonate resin particles were dry-blended and formed into a sheet having a thickness of 10 mm using an injection molding machine to obtain infrared absorption of Example 4. board. 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 manufacturing conditions and evaluation results of Example 4 are described in Tables 1 to 4.

    [Example 5]    

The 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 hexagonal cesium tungsten bronze powder.

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

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

    [Example 6]    

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

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

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

    [Examples 7 and 8]    

Except changing the amount of the surface treatment agent diluent a and the addition time, the same operations as in Example 1 were performed to obtain the surface-treated infrared-absorbing fine particle powders, infrared-absorbing fine particle dispersions of Examples 7 and 8, The infrared-absorbing fine-particle dispersed powder and the infrared-absorbing sheet were evaluated in the same manner as in Example 1.

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

    [Example 9]    

The maturing 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. Then, only the medium belonging to the supernatant was removed to obtain an infrared-absorbing fine particle slurry. Isopropyl alcohol was added to the obtained infrared-absorbing fine particle slurry, and after stirring for 1 hour, it was left for 1 hour to separate the surface-treated infrared-absorbing fine particles from the solid-liquid medium. Then, only the medium belonging to the supernatant liquid is removed, and an infrared absorbing fine particle slurry is obtained again.

16 mass% of the infrared absorbing fine particle slurry obtained again, 24 mass% of the polyacrylate dispersant, and 60 mass% of toluene were mixed and stirred, and then dispersed using an ultrasonic homogenizer to obtain the infrared absorbing fine particle dispersion of Example 9. liquid.

Except that the infrared absorbing fine particle dispersion liquid of Example 9 was used, the same operation as in Example 1 was performed, thereby obtaining the infrared absorbing fine particle dispersion powder and infrared absorbing sheet of Example 9, and the same evaluation as in Example 1 was performed. .

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

    [Example 10]    

2.4% by mass of zirconium tributoxyacetamidine pyruvate and 97.6% by mass of isopropanol were mixed to obtain a surface treatment agent dilution liquid b of Example 10. The surface treatment agent diluent b was used in place of the surface treatment agent diluent a, except that the same operation as in Example 1 was performed, thereby obtaining the surface-treated infrared-absorbing fine particle powder, infrared-absorbing fine particle dispersion, and infrared absorption of Example 10. The fine particle dispersed powder and the infrared absorbing sheet were evaluated in the same manner as in Example 1.

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

    [Example 11]    

The diisopropoxy titanium bis (ethyl acetate) 2.6% by mass and 97.4% by mass of isopropanol were mixed to obtain the surface treatment agent dilution solution c of Example 11. The surface treatment agent diluent c was used in place of the surface treatment agent diluent a, except that the same operation as in Example 1 was performed, thereby obtaining the surface-treated infrared-absorbing fine particle powder, infrared-absorbing fine particle dispersion, and infrared absorption of Example 11. The fine particle dispersed powder and the infrared absorbing sheet were evaluated in the same manner as in Example 1.

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

    [Example 12]    

A polymethyl methacrylate resin was used in place of the polycarbonate resin as the solid resin, and the same operation as in Example 1 was performed to obtain the surface-treated infrared-absorbing fine particle powder of Example 12 and the infrared-absorbing fine particle dispersion. Liquid, infrared absorbing fine particle dispersion powder, and infrared absorbing sheet, and the same evaluation as in Example 1 was performed.

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

    [Example 13]    

25% by mass of cubic sodium sodium tungsten bronze powder (made by Sumitomo Metal Mining Co., Ltd.) with Na / W (molar ratio) = 0.33 was mixed with 75% by mass of isopropanol, and the obtained mixed solution was charged to a content of 0.3 mm In a paint shaker for ZrO ₂ beads, pulverization and dispersion treatment were performed for 10 hours to obtain a dispersion liquid of Na _0.33 WO _Z fine particles of Example 13. The dispersion particle diameter of the Na _0.33 WOz fine particles in the obtained dispersion was measured, and the result was 100 nm. In addition, as a setting of the particle size measurement, the refractive index of the particles was set to 1.81, and the particle shape was set to be non-spherical. The background was measured using isopropanol, and the refractive index of the solvent was 1.38. After removing the solvent of the obtained dispersion, the diameter of the crystallites of the Na _0.33 WOz fine particles was measured. As a result, it was 32 nm.

The dispersion liquid of Na _0.33 WOz microparticles of Example 13 was mixed with isopropyl alcohol to obtain a dispersion liquid B for coating film formation having a concentration of 2% by mass of infrared absorbing microparticles (cubic sodium tungsten bronze microparticles). 520 g of the obtained dispersion liquid B for coating film formation was added to a beaker, and the mixture was thoroughly stirred by a stirrer 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 over 3 hours. 100g of water. After being added dropwise, the mixture was stirred at a temperature of 20 ° C. for 24 hours to prepare a ripening solution of Example 13. Then, the medium was evaporated from the ripening liquid by vacuum flow drying to obtain the surface-treated infrared-absorbing fine particle powder of Example 13.

The surface-treated infrared-absorbing fine particle powder of Example 13 was used in place of the surface-treated infrared-absorbing fine particle powder of Example 1, except that the same operation as in Example 1 was performed to obtain the infrared-absorbing fine particle dispersion of Example 13 and infrared rays. The fine particle-dispersed powder and the infrared absorbing sheet were subjected to the same evaluation as in Example 1.

The manufacturing 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 hexagonal crystalline potassium tungsten bronze powder with K / W (molar ratio) = 0.33 (Example 14), and use hexagonal osmium tungsten bronze with Rb / W (molar ratio) = 0.33. The powder (Example 15) was measured in the same manner as in Example 1 except that W ₁₈ O ₄₉ (Example 16) of the Magnelli phase was used. The dispersion liquids C to E for coating film formation were obtained.

Except that the dispersion liquids C to E for coating film formation were used instead of the dispersion liquid B for coating film formation, the same operations as in Example 1 were performed, thereby obtaining the surface-treated infrared-absorbing fine particle powders of Examples 14 to 16, 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 manufacturing conditions and evaluation results of Examples 14 to 16 are described in Tables 1 to 4.

    [Example 17]    

As surface treatment agent e, 309 g of tetraethoxysilane was used. The surface treatment agent e was used in place of the surface treatment agent dilution solution a, and isopropyl alcohol was not added. The same operation as in Example 1 was performed to obtain the surface-treated infrared-absorbing fine particles and infrared-absorbing fine particles 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]    

4.4 mass% of zinc acetoacetate and 95.6 mass% of isopropanol were mixed to obtain the surface treatment agent dilution liquid f of Example 15. The surface treatment agent diluent f was used in place of the surface treatment agent diluent a, except that the same operation as in Example 1 was performed to obtain the surface-treated infrared-absorbing fine particle powder, infrared-absorbing fine particle dispersion, and infrared absorption of Example 15. The fine particle dispersed 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]    

The powder containing the surface-treated infrared-absorbing fine particles of Example 19 (surface-treated infrared-absorbing fine particles) was obtained by evaporating the medium from the ripening solution of Example 1 by spray drying instead of vacuum flow drying. The obtained surface-treated infrared-absorbing fine particle powder was mixed with pure water to obtain an infrared-absorbing fine particle dispersion, and the same operation as in Example 1 was performed to obtain the infrared-absorbing fine particle dispersion of Example 19, The infrared-absorbing fine-particle dispersed 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.

    [Comparative Example 1]    

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

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

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

    [Comparative Example 2]    

Except having added 500 parts by mass of Sumilizer GP to 100 parts by mass of hexagonal cesium tungsten bronze, a fine particle dispersion liquid and an infrared absorbing sheet of Comparative Example 2 were obtained in the same manner as in Example 1.

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

The manufacturing conditions and evaluation results of Comparative Example 2 are shown 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 instead of Sumilizer GP (Comparative Example 3), or 300 parts by mass of ADEKA STAB 2112 was added instead of Sumilizer GP (Comparative Example 4). In the same manner as in Example 1, the fine particle dispersion liquids and infrared absorbing sheets of Comparative Examples 3 and 4 were obtained.

The obtained microparticle dispersion liquids and infrared absorbing sheets of Comparative Examples 3 and 4 were evaluated in the same manner as in Example 1.

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

    [Comparative Example 5]    

Instead of dispersing powder and not adding it, the same amount of Sumilizr GP as in Example 1 was added to obtain a resin sheet of Comparative Example 5. That is, the resin sheet of Comparative Example 5 is a resin sheet which does not contain absorbent fine particles and contains only a stabilizer of Sumilizer GP (Structural Formula (2)).

The obtained Comparative Example 5 was a transparent resin sheet before the test, which was exposed to a hot and humid environment at 85 ° C and 90% for 9 days, and then white mist occurred and became opaque.

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

    [Comparative Example 6]    

7 mass% of hexagonal cesium tungsten bronze powder, 24 mass% of a polyacrylate dispersant, and 69 mass% of toluene were mixed, and the obtained mixed solution was filled to 0.3 mm. ZrO ₂ beads were pulverized and dispersed in a paint shaker for 4 hours to obtain an infrared-absorbing fine particle dispersion of Comparative Example 6. The dispersion particle diameter of the infrared-absorbing fine particles in the obtained dispersion was measured and found to be 100 nm. In addition, as a setting of the particle size measurement, the refractive index of the particles was set to 1.81, and the particle shape was set to be non-spherical. The background was measured using toluene, and the refractive index of the solvent was set to 1.50. The solvent of the obtained dispersion was removed, and the crystallite diameter was measured. As a result, it was 32 nm.

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 Comparative Example 6.

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

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

    [Comparative Example 7]    

A polymethyl methacrylate resin was used in place of the polycarbonate resin as a solid resin, and the same operation as in Comparative Example 6 was performed, thereby obtaining an infrared-absorbing fine particle dispersion liquid and an infrared-absorbing fine particle dispersion powder of Comparative Example 7. And infrared absorbing sheet, and the same evaluation as in Example 1 was performed.

The manufacturing 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 cubic sodium tungsten bronze powder with Na / W (molar ratio) = 0.33 (Comparative Example 8), or hexagonal potassium potassium tungsten bronze with K / W (molar ratio) = 0.33 Powder (Comparative Example 9), or hexagonal rhenium tungsten bronze powder with Rb / W (molar ratio) = 0.33 (Comparative Example 10), or W ₁₈ O ₄₉ (Comparative Example 11) with Magnelli phase, Other than that, the same operation as in Comparative Example 6 was performed to obtain the infrared absorbing fine particle dispersion liquid, infrared absorbing fine particle dispersion powder, and infrared absorbing sheet of Comparative Examples 8 to 11, and the same evaluation as in Example 1 was performed.

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

    [Comparative Example 12]    

13% by mass of hexagonal cesium tungsten bronze powder with Cs / W (molar ratio) = 0.33 was mixed with 87% by mass of isopropyl alcohol, and the obtained mixed solution was filled to a content of 0.3 mm. In a paint shaker for ZrO ₂ beads, pulverization and dispersion treatment were performed for 5 hours to obtain a dispersion liquid of Cs _0.33 WOz fine particles of Comparative Example 7. The dispersion particle diameter of the Cs _0.33 WOz fine particles in the obtained dispersion was measured, and the result was 100 nm. In addition, as a setting of the particle size measurement, the refractive index of the particles was set to 1.81, and the particle shape was set to be non-spherical. The background was measured using isopropanol, and the refractive index of the solvent was 1.38. The solvent of the obtained dispersion was removed, and the crystallite diameter was measured. As a result, it was 32 nm.

The Cs _0.33 WOz microparticle dispersion of Comparative Example 12 was mixed with isopropyl alcohol to obtain a diluent having a concentration of 3.5% by mass of infrared absorbing microparticles (hexagonal cesium tungsten bronze microparticles). To 733 g of the obtained diluent, 21 g of ethyl aluminum acetate diisopropylacetate was added, and after mixing and stirring, dispersion treatment was performed using an ultrasonic homogenizer.

Then, this dispersion-processed material was put into a beaker, stirred thoroughly with a blade-attached mixer, and 100 g of water was added as a diluent d over 1 hour. Further, 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 liquid was heated and matured at 70 ° C. for 2 hours. Then, the medium was evaporated from the ripening liquid by vacuum flow drying, and then subjected to a heat treatment at a temperature of 200 ° C. for 1 hour in a nitrogen atmosphere to obtain a surface-treated infrared-absorbing fine particle powder of Comparative Example 12.

8% by mass of the surface-treated infrared-absorbing fine particle powder of Comparative Example 12, 24% by mass of the polyacrylate dispersant, and 68% by mass of toluene were mixed. Fill the obtained mixed solution to 0.3mm In a paint shaker for ZrO ₂ beads, pulverization and dispersion treatment were performed for 5 hours to obtain an infrared-absorbing fine particle dispersion liquid of Comparative Example 12.

The infrared absorbing fine particle dispersion liquid of Comparative Example 12 was used in place of the infrared absorbing fine particle dispersion liquid of Example 1, except that the same operation as in Example 1 was performed, thereby obtaining the infrared absorbing fine particle dispersion powder and infrared absorbing sheet of Comparative Example 12. And the same evaluation as in Example 1 was performed.

The manufacturing conditions and evaluation results of Comparative Example 12 are shown 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 instead of adding Sumilizer GP and not dispersing powder without adding. That is, the resin sheet of Comparative Example 13 does 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. In the resin sheet of Comparative Example 13, no change in optical characteristics was observed after being kept in an air environment at 120 ° C for 30 days, or after being exposed to a hot and humid environment at 85 ° C for 9 days.

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

Claims (27)

An infrared absorbing fine particle dispersion containing 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 One or more polymers selected from the hydrolysates of metal chelate compounds, polymers of hydrolysates of metal chelate compounds, hydrolysates of metal cyclic oligomer compounds, and hydrolysates of metal cyclic oligomer compounds Film coating; the phosphite compound is a phosphite compound represented by structural formula (1), and the added amount of the phosphite compound is more than 500 parts by mass relative to 100 parts by mass of the infrared absorbing fine particles. And less than 50,000 parts by mass; Among them, in the above structural formula (1), R1, R2, R4, and R5 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 1 to 12 carbon atoms, or 7 to 12 carbon atoms. Either an aralkyl group or an aromatic group, R3 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X is a single bond or a divalent compound represented by the following structural formula (1-1) Any of the residues, A is any of the divalent residues represented by the structural formula (1-2) having an alkylene group having 2 to 8 carbon atoms or less, Y and Z are either 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 an alkyl group having 1 to 8 carbons, in the structural formula (1-1), R6 is a hydrogen atom and an alkyl group having 1 to 5 carbons, in the structural formula (1- In 2), R7 is any one of 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 liquid according to claim 1, wherein the film thickness of the coating film is 0.5 nm or more.         The infrared absorbing fine particle dispersion liquid of claim 1 or 2, wherein the metal chelate compound or / and the metal cyclic oligomer compound contains one or more metal elements selected from Al, Zr, Ti, Si, and Zn .         The infrared absorbing fine particle dispersion liquid according to any one of claims 1 to 3, wherein the metal chelate compound or the metal cyclic oligomer compound has a choice from an ether bond, an ester bond, an alkoxy group, and an acetamyl group. More than one.         The infrared absorbing fine particle dispersion according to any one of claims 1 to 4, wherein the infrared absorbing fine particles are of the general formula WyOz (where W is tungsten, O is oxygen, and 2.2 ≦ z / y ≦ 2.999), or / And the general formula MxWyOz (where M element is 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 selected from one or more elements, W is tungsten, O is oxygen, and 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ 3.0) Infrared absorbing particles.         The infrared absorbing fine particle dispersion liquid according to claim 5, wherein the M element is one or more selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn.         The infrared-absorbing fine particle dispersion according to any one of claims 1 to 6, wherein the infrared-absorbing fine particles are fine particles having a hexagonal crystal structure.         The infrared-absorbing fine particle dispersion liquid according to any one of claims 1 to 7, wherein a crystallite diameter of the infrared-absorbing fine particles is 1 nm or more and 200 nm or less.         The infrared-absorbing fine particle dispersion according to any one of claims 1 to 8, wherein the carbon concentration of the surface-treated infrared-absorbing fine particle powder including the surface-treated infrared-absorbing fine particles is 0.2% by mass or more and 5.0% by mass or less.         The infrared-absorbing fine particle dispersion liquid according to any one of claims 1 to 9, wherein the liquid medium is one selected from organic solvents, oils and fats, liquid plasticizers, compounds that are polymerized by hardening, and water. The above liquid medium.         The infrared absorbing fine particle dispersion according to any one of claims 1 to 10, 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. Choose one or more stabilizers.     An infrared-absorbing fine particle dispersion containing surface-treated infrared-absorbing fine particles dispersed in a medium and a phosphite compound, characterized in that the surface of the surface-treated infrared-absorbing fine particles is composed of a metal containing a self-chelating compound. Hydrolysate, polymer of metal chelate compound, polymer of metal cyclic oligomer compound, polymer of metal cyclic oligomer compound The phosphite compound is a phosphite compound represented by the structural formula (1), and the added amount of the phosphite compound is more than 500 parts by mass and less than 50,000 parts by mass with respect to 100 parts by mass of the infrared absorbing fine particles. ; Among them, in the above structural formula (1), R1, R2, R4, and R5 are each 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 a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X is a single bond or a divalent residue represented by the following structural formula (1-1) Either A is any of the divalent residues represented by the structural formula (1-2) having an alkylene group having 2 to 8 carbon atoms or less, Any one of Y and 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 aralkyloxy group having 7 to 12 carbon atoms, and the other is hydrogen Any one of an atom or an alkyl group having 1 to 8 carbons, in the above structural formula (1-1), R6 is any one of a hydrogen atom and an alkyl group having 1 to 5 carbons, in the above structural formula (1) In -2), R7 is any one of 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 contains 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 one or more selected from an ether bond, an ester bond, an alkoxy group, and an ethanoyl group. .         The infrared absorbing fine particle dispersion according to any one of claims 12 to 14, wherein the infrared absorbing fine particles are of the general formula WyOz (where W is tungsten, O is oxygen, and 2.2 ≦ z / y ≦ 2.999), or / And the general formula MxWyOz (wherein the M element is 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 selected from one or more elements, W is tungsten, O is oxygen, and 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ 3) Infrared absorbing particles.         The infrared absorbing fine particle dispersion of claim 15, wherein the M element is one or more selected from the group consisting of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn.         The infrared-absorbing fine particle dispersion according to any one of claims 12 to 16, wherein the infrared-absorbing fine particles are fine particles having a hexagonal crystal structure.         The infrared absorbing fine particle dispersion according to any one of claims 12 to 17, wherein the crystallite diameter of the infrared absorbing fine particles is 1 nm or more and 200 nm or less.         The infrared-absorbing fine particle dispersion according to any one of claims 12 to 18, wherein in the surface-treated infrared-absorbing fine particle powder including the surface-treated infrared-absorbing fine particles described above, the carbon concentration is 0.2% by mass or more and 5.0% by mass or less.         The infrared absorbing fine particle dispersion according to any one of claims 12 to 19, wherein the medium is a polymer.         The infrared-absorbing fine particle dispersion according to any one of claims 12 to 20, wherein the medium is a solid resin.         The infrared absorbing fine particle dispersion of claim 21, wherein the solid resin is a self-fluorine resin, a PET resin, an acrylic resin, a polyamide resin, a vinyl chloride resin, a polycarbonate resin, an olefin resin, an epoxy resin, One or more resins selected for polyimide resin.         The infrared-absorbing fine particle dispersion according to any one of claims 12 to 22, which further contains 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. Choose one or more stabilizers.         A method for producing an infrared absorbing fine particle dispersion, which comprises the steps of: absorbing infrared absorbing fine particles, water, and an organic solvent, a liquid resin, a fat, a liquid plasticizer for the resin, a polymer monomer, or A step of mixing two or more mixtures selected from these groups and performing a dispersion treatment to obtain the above-mentioned infrared-absorbing fine particle-forming dispersion liquid; adding a metal chelate compound or / and a metal to the above-mentioned dispersion liquid for film formation Cyclic oligomer compounds, which are derived from hydrolysates of metal chelate compounds, polymers of hydrolysates of metal chelate compounds, hydrolysates of metal cyclic oligomer compounds, and hydrolysates of metal cyclic oligomer compounds A polymer-selected step of coating at least one surface of the infrared absorbing fine particles; after the coating step, removing the liquid medium constituting the coating film-forming dispersion liquid to obtain a surface treatment containing surface-treated infrared absorbing fine particles Step of absorbing infrared particles; absorbing infrared rays from the surface treatment A step of adding fine particle powder to a specific medium to disperse it to obtain a surface-treated infrared-absorbing fine particle dispersion; and adding to the above-mentioned surface-treated infrared-absorbing fine particle dispersion more than 500 parts by mass relative to 100 parts by mass of the infrared-absorbing fine particles In addition, a step of obtaining a dispersion liquid of the surface-treated infrared-absorbing fine particles containing the phosphite-based compound with a phosphite-based compound of 50,000 parts by mass or less.         A method for producing an infrared absorbing fine particle dispersion, which comprises the steps of: absorbing infrared absorbing fine particles, water, and an organic solvent, a liquid resin, a fat, a liquid plasticizer for the resin, a polymer monomer, or A step of mixing two or more mixtures selected from these groups and performing a dispersion treatment to obtain the above-mentioned infrared-absorbing fine particle-forming dispersion liquid; adding a metal chelate compound or / and a metal to the above-mentioned dispersion liquid for film formation Cyclic oligomer compounds, which are derived from hydrolysates of metal chelate compounds, polymers of hydrolysates of metal chelate compounds, hydrolysates of metal cyclic oligomer compounds, and hydrolysates of metal cyclic oligomer compounds A step of coating at least one surface of the infrared absorbing fine particles selected by the polymer; after the coating step, the liquid medium constituting the coating film forming dispersion liquid is solvent-substituted and replaced with a specific medium to obtain a surface A step of processing a dispersion of infrared absorbing fine particles; and processing the infrared absorption onto the surface The dispersion liquid containing the fine particles is added with a phosphorous acid ester-based compound in an amount of more than 500 parts by mass and less than 50,000 parts by mass based on 100 parts by mass of the infrared absorbing fine particles, to obtain a dispersion liquid of surface-treated infrared absorbing particles containing a phosphite compound step.         A method for producing an infrared absorbing fine particle dispersion, comprising the steps of: dispersing a surface-treated infrared absorbing fine particle dispersion containing a phosphite compound according to claim 24 or 25, or making the phosphite-containing dispersion liquid A step of obtaining a dispersion of a surface-treated infrared absorbing fine particle containing a phosphite compound by drying the dispersion of the surface-treated infrared absorbing fine particles of the compound containing a phosphite compound and a suitable medium to obtain a dispersion of the infrared absorbing fine particles.         A method for producing an infrared-absorbing fine particle dispersion, comprising the steps of: drying the surface-treated infrared-absorbing fine particle dispersion powder obtained by drying the surface-treated infrared-absorbing fine particle dispersion described in claim 24 or 25; and phosphorous acid A step of obtaining an infrared-absorbing fine particle dispersion by mixing an ester-based compound and an appropriate medium; wherein the mixing amount of the phosphite-based compound is more than 500 parts by mass and 50000 parts by mass relative to 100 parts by mass of the infrared-absorbing particles; The following.