JP2017155105A - Infrared shielding material fine particle dispersion liquid, coating liquid for forming infrared shielding film, infrared shielding film, and infrared shielding optical member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an infrared shielding material fine particle dispersion liquid and a coating liquid capable of preventing decrease in infrared shielding characteristics with time due to reduction in a particle size and capable of preventing degradation in haze when a UV curable resin is used, and an infrared shielding film and an infrared shielding optical member.SOLUTION: The infrared shielding material fine particle dispersion liquid comprises infrared shielding material fine particles selected from tungsten oxide fine particles and composite tungsten oxide fine particles, dispersed in an organic solvent; the infrared shielding material fine particle dispersion liquid with addition of an ultraviolet curable resin that is not included in the dispersion liquid constitutes a coating liquid for forming an infrared shielding film. The infrared shielding material fine particle dispersion liquid contains a first additive composed of a metal salt comprising an element such as Cs, Sr, Ba, Ti, Zr, and Cr and a second additive composed of ammonia or an amine compound, in which a weight ratio of the content of the second additive to the first additive is 5% or more and 300% or less.SELECTED DRAWING: Figure 1

Description

  The present invention provides an infrared shielding material in which one or more infrared shielding material fine particles selected from tungsten oxide fine particles and composite tungsten oxide fine particles which are transparent in the visible light region and have absorption in the near infrared region are dispersed in a solvent. The present invention relates to a material fine particle dispersion and a coating liquid for forming an infrared shielding film, and in particular, it is possible to prevent deterioration of infrared shielding characteristics with time due to the miniaturization of infrared shielding material fine particles, and deterioration of haze when an ultraviolet curable resin is applied. Improvement of infrared shielding material fine particle dispersion and infrared shielding film forming coating solution, and improvement of infrared shielding film and infrared shielding optical member obtained by using the infrared shielding material fine particle dispersion and infrared shielding film forming coating liquid It is about.

  In recent years, the demand for infrared shielding bodies has increased rapidly, and many patents relating to infrared shielding bodies have been proposed. From a functional standpoint, for example, in the fields of various buildings and vehicle window materials, it is possible to block near-infrared light while sufficiently incorporating visible light, and to suppress the rise in indoor temperature while maintaining brightness. It is intended to prevent the near infrared rays radiated forward from the plasma display panel from causing malfunctions in the cordless phone and the remote control of home appliances, and adversely affecting the transmission optical communication. There is a purpose.

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

  In Patent Document 1, on a transparent glass substrate, at least one metal ion selected from the group consisting of Group IIIa, Group IVa, Group Vb, Group VIb and Group VIIb of the periodic table as a first layer from the substrate side. A composite tungsten oxide film containing, a transparent dielectric film as a second layer on the first layer, a group IIIa, IVa group, Vb group of the periodic table as a third layer on the second layer, A composite tungsten oxide film containing at least one metal ion selected from the group consisting of group VIb and group VIIb is provided, and the refractive index of the transparent dielectric film of the second layer is set to the first layer and the third layer. There has been proposed an infrared shielding glass that can be suitably used for a portion requiring high visible light transmittance and good infrared shielding performance by lowering the refractive index of the composite tungsten oxide film.

  In Patent Document 2, a first dielectric film is provided as a first layer from the substrate side on a transparent glass substrate in the same manner as Patent Document 1, and a tungsten oxide film is formed as a second layer on the first layer. Infrared shielding glass in which a second dielectric film is provided as a third layer on the second layer has been proposed.

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

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

  In Patent Document 5, sunlight is irradiated by using tungsten oxide (tungsten oxide) obtained by hydrolyzing tungstic acid and adding an organic polymer having a specific structure called polyvinylpyrrolidone to the tungsten oxide. Then, the ultraviolet rays in the light are absorbed by tungsten oxide, and excited electrons and holes are generated. The appearance amount of pentavalent tungsten is remarkably increased by a small amount of ultraviolet rays, and the coloring reaction is accelerated. As the concentration increases, the property that the pentavalent tungsten is oxidized to hexavalent very quickly by blocking the light and the decoloring reaction is accelerated, the coloring and decoloring reaction to sunlight is fast, and the near red at the time of coloring Proposal of a solar-modulable light insulating material capable of blocking near-infrared rays of sunlight with an absorption peak appearing at an outer wavelength of 1250 nm It has been.

  Patent Document 6 discloses that tungsten trichloride or tungsten trioxide is dissolved in alcohol by evaporating the solvent as it is or by heating and refluxing, evaporating the solvent, and then heating at 100 ° C. to 500 ° C. Obtaining a powder composed of the hydrate or a mixture of the two, obtaining an electrochromic device using the tungsten oxide fine particles, and forming an optical layer of the film when protons are introduced into the film by forming a multilayer laminate. It has been proposed that the characteristics can be changed.

Further, in Patent Document 7, a meta-type ammonium tungstate and various water-soluble metal salts are used as raw materials, and a dried solid solution of the mixed aqueous solution is heated at a heating temperature of about 300 to 700 ° C., and inactive during the heating. By supplying hydrogen gas to which gas (addition amount: about 50 vol% or more) or water vapor (addition amount: about 15 vol% or less) is added, M _x WO ₃ (M: metal such as alkali, alkaline earth, rare earth, etc.) Various methods for producing tungsten bronzes represented by the element 0 <x <1) have been proposed. In addition, a method for producing various tungsten bronze-coated composites by performing the same operation on the support has been proposed, and it has been proposed to be used as an electrode catalyst material for fuel cells and the like.

  Further, Patent Document 8 discloses an infrared shielding material fine particle dispersion in which infrared shielding material fine particles are dispersed in a medium such as a resin or glass, and the infrared shielding material fine particles have a general formula WyOz (W is tungsten). , O is oxygen, tungsten oxide fine particles represented by 2.2 ≦ z / y ≦ 2.999, or / and general formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal) , Rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, One or more types selected from Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I Elements, W is tungsten, O is Element, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0), and the particle diameter of the infrared shielding material fine particles is 1 nm or more. Infrared shielding material fine particle dispersion characterized by being 800 nm or less, and optical properties, conductivity, manufacturing method and the like of this infrared shielding material fine particle dispersion are disclosed.

  Incidentally, the tungsten oxide fine particles represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999) disclosed in Patent Document 8, or / and the general formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, One or more elements selected from Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0 ) Composite tungsten oxide fine particles represented by The infrared shielding material fine particle dispersion dispersed in the medium exhibits an excellent function of reducing the infrared transmittance while keeping the visible light transmittance high. It has been studied for use in various buildings and vehicle window materials.

  In these applications, since the infrared shielding property and high transparency (low haze value) are required, the tungsten oxide fine particles and the composite tungsten oxide fine particles are used for the purpose of reducing the haze value. Attempts have been made to further reduce the diameter.

  However, when the particle diameters of the tungsten oxide fine particles and the composite tungsten oxide fine particles are further refined, the infrared shielding material fine particle dispersion in which the refined tungsten oxide fine particles and the composite tungsten oxide fine particles are dispersed in a solvent. In addition, in the infrared shielding film (infrared shielding material fine particle dispersion) and the infrared shielding optical member obtained by using this dispersion liquid, the infrared shielding characteristics are gradually deteriorated as the tungsten oxide fine particles and the composite tungsten oxide fine particles are miniaturized. However, in Patent Document 9, the infrared shielding material fine particle dispersion is mixed with Cs, Sr, Ba, Ti, Zr, Cr, Mo, W, Mn, Re, Fe, Ru, Os. , Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, In, Sn We propose a method to solve the problem by adding a metal salt consisting of or more elements.

JP-A-8-59300 JP-A-8-12378 JP-A-8-283044 JP 2000-1119045 A JP-A-9-127559 JP 2003-121884 A JP-A-8-73223 International Publication WO2005 / 37932 JP 2009-197146 A

  According to the method of Patent Document 9 in which a metal salt is added to an infrared shielding material fine particle dispersion, a component that degrades the infrared shielding properties of the infrared shielding material fine particles over time (irradiation of moisture or ultraviolet rays entering from the air) It is said that since the metal salt has the action of capturing radicals generated by the above and the like, the infrared shielding property due to these components can be prevented from decreasing over time.

  By the way, when manufacturing an infrared shielding film using the coating liquid for forming an infrared shielding film of Patent Document 9, when an ultraviolet curable resin is applied as a binder resin, the resulting infrared shielding film becomes more turbid (that is, , The haze gets worse).

  That is, an infrared shielding film is formed by forming a coating film on the surface of a substrate using a coating liquid for forming an infrared shielding film to which an ultraviolet curable resin is applied, evaporating the solvent from the coating film and irradiating ultraviolet rays. In this case, it was confirmed that the fine particles of the infrared shielding material aggregated during drying of the coating film to deteriorate the haze of the infrared shielding film.

  The present invention has been made paying attention to such a problem, and the problem is that an ultraviolet curable resin was applied as well as preventing the deterioration of infrared shielding characteristics with the lapse of time with the miniaturization of the fine particles of the infrared shielding material. Infrared shielding material fine particle dispersion and infrared shielding film forming coating liquid capable of preventing deterioration of haze in some cases, and infrared rays obtained using the infrared shielding material fine particle dispersion and infrared shielding film forming coating liquid The object is to provide a shielding film and an infrared shielding optical member.

  Then, when manufacturing an infrared shielding film using the coating liquid for infrared shielding film formation of Patent Document 9 to which a metal salt is added, the haze of the infrared shielding film is deteriorated when an ultraviolet curable resin is applied as a binder resin. As a result of diligent investigations by the present inventors, there is a difficulty in compatibility between the infrared shielding material fine particles composed of the tungsten oxide fine particles and the composite tungsten oxide fine particles and the ultraviolet curable resin, and the infrared ray shielding is difficult when the coating film is dried. It was confirmed that the aggregation of the material fine particles occurred and the infrared shielding material fine particles were not uniformly dispersed in the ultraviolet curable resin. And, when at least one selected from ammonia and amine compounds is added to the infrared shielding film forming coating solution of Patent Document 9 to which the metal salt is added, the compatibility between the infrared shielding material fine particles and the ultraviolet curable resin is improved, It came to discover that the deterioration of haze is improved. The present invention has been completed by such technical discovery.

That is, the first invention according to the present invention is:
Tungsten oxide fine particles represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), general formula MxWyOz (where M is H, He, alkali metal) , 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 elements selected, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3) Infrared shielding material fine particles composed of more than one kind of fine particles Infrared shielding material fine particle dispersion dispersed in a medium, wherein an ultraviolet curable resin not contained in the dispersion is added to the dispersion to form an infrared shielding film forming coating liquid In
Cs, Sr, Ba, Ti, Zr, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, In, Containing a first additive composed of a metal salt composed of one or more elements selected from Sn, and a second additive composed of one or more selected from ammonia and an amine compound, and The content of the second additive with respect to the first additive is 5% to 300% by weight.

Further, the second invention according to the present invention is:
In the infrared shielding material fine particle dispersion described in the first invention,
The amine compound is one or more selected from diethanolamine, monoethanolamine, and triethanolamine,
The third invention is
In the infrared shielding material fine particle dispersion according to the first invention or the second invention,
The content of the first additive is 0.01 to 20 parts by weight with respect to 100 parts by weight of the infrared shielding material fine particles,
The fourth invention is:
In the infrared shielding material fine particle dispersion according to any one of the first to third inventions,
One or more kinds selected from the tungsten oxide fine particles and the composite tungsten oxide fine particles are a composition represented by the general formula WyOz (W is tungsten, O is oxygen, 2.45 ≦ z / y ≦ 2.999). Characterized by containing a Magneli phase of the ratio,
The fifth invention is:
In the infrared shielding material fine particle dispersion according to any one of the first to fourth inventions,
The composite tungsten oxide fine particles represented by the general formula MxWyOz include one or more of hexagonal, tetragonal or cubic crystal structures,
The sixth invention is:
In the infrared shielding material fine particle dispersion according to the fifth invention,
The M element includes one or more of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn and has a hexagonal crystal structure.

Next, a seventh invention according to the present invention is as follows.
In the coating liquid for forming the infrared shielding film,
An ultraviolet curable resin is added to the infrared shielding material fine particle dispersion according to any one of the first to sixth inventions,
The eighth invention
In infrared shielding film,
It is obtained by applying the infrared shielding film forming coating liquid described in the seventh invention to the substrate surface to form a coating film, evaporating the solvent from the coating film and irradiating with ultraviolet rays,
In addition, the ninth invention,
In the infrared shielding optical member,
It is comprised by the base material and the infrared shielding film as described in 8th invention formed in this base-material surface, It is characterized by the above-mentioned.

  The infrared shielding material fine particle dispersion according to the present invention is an infrared shielding material composed of one or more kinds of fine particles selected from tungsten oxide fine particles represented by the general formula WyOz and composite tungsten oxide fine particles represented by the general formula MxWyOz. Material fine particles, Cs, Sr, Ba, Ti, Zr, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Contains a first additive composed of a metal salt composed of one or more elements selected from Cd, In, and Sn, and a second additive composed of one or more selected from ammonia and an amine compound It is characterized by doing.

  And, it becomes possible to prevent the time-dependent deterioration of the infrared shielding property due to the refinement of the fine particles of the infrared shielding material by the action of the first additive, and the haze when the ultraviolet curable resin is applied by the action of the second additive. It is also possible to prevent the deterioration.

  Therefore, the infrared shielding film and the infrared shielding optical member manufactured using the coating liquid for forming the infrared shielding film according to the present invention to which the ultraviolet curable resin is added are excellent in the temporal stability of the infrared shielding properties and are conventionally known. Therefore, it has an effect that can be applied to a light-shielding film, a light-shielding member, and the like used for various buildings and vehicle window materials.

The schematic diagram of the crystal structure of the composite tungsten oxide fine particle which has a hexagonal crystal applied in this invention. Explanatory drawing which shows the measurement principle of blank transmitted light intensity | strength of the infrared shielding film etc. which concern on this invention. Explanatory drawing which shows the measurement principle of diffuse transmitted light intensity | strength of the infrared shielding film etc. which concern on this invention.

  Hereinafter, embodiments of the present invention will be described in detail.

  First, the infrared shielding material fine particle dispersion according to the present invention is a tungsten oxide fine particle represented by a general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), Formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag , Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re , Be, Hf, Os, Bi, I, one or more elements selected from W, tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3) One or more selected from composite tungsten oxide fine particles represented by An infrared shielding material fine particle dispersion in which infrared shielding material fine particles composed of fine particles are dispersed in an organic solvent, and an ultraviolet curable resin not contained in the dispersion is added to the dispersion to form an infrared shielding film In the infrared shielding material fine particle dispersion constituting the coating liquid for coating, Cs, Sr, Ba, Ti, Zr, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, A first additive composed of a metal salt composed of one or more elements selected from Pt, Cu, Ag, Au, Zn, Cd, In, and Sn, and one or more selected from ammonia and an amine compound And the content of the second additive with respect to the first additive is 5% to 300% by weight.

1. Tungsten oxide fine particles and composite tungsten oxide fine particles In general, it is known that a material containing free electrons exhibits a reflection absorption response to electromagnetic waves such as solar rays having a wavelength of 200 nm to 2600 nm by plasma vibration. It is known that when the powder of such a material is a fine particle smaller than the wavelength of light, the geometric scattering in the visible light region (wavelength 380 nm to 780 nm) is reduced, and transparency in the visible light region can be obtained. In the present specification, “transparency” is used in the sense that the light is less scattered and has high transparency.

Then, since there is no effective free electrons in WO _3, WO ₃ is less absorption reflection characteristics in the near infrared region, it is not effective as an infrared-shielding material. On the other hand, tungsten trioxide having oxygen vacancies and so-called tungsten bronzes obtained by adding a positive element such as Na to tungsten trioxide are known to be conductive materials having free electrons. Analysis of single crystals suggests the response of free electrons to light in the infrared region. And in a specific part of the composition range in the compound of tungsten and oxygen, there is a particularly effective range as an infrared shielding material, a tungsten oxide fine particle, a composite tungsten which is transparent in the visible light region and has absorption in the near infrared region. Infrared shielding material fine particle dispersion in which oxide fine particles are found and at least one selected from the tungsten oxide fine particles and composite tungsten oxide fine particles are dispersed in a medium such as resin or glass, and the infrared shielding material fine particle dispersion The manufactured infrared shielding body etc. are obtained (refer patent document 8).

  First, in the infrared shielding material fine particle dispersion according to the present invention, the infrared shielding material fine particles contained in the solvent have a general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999). ), Tungsten oxide fine particles represented by the general formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, One or more elements selected from Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1 2.2 ≦ z / y ≦ 3) It is comprised by 1 or more types chosen from ngsten oxide fine particles.

In the tungsten oxide fine particles represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), a preferable composition range of tungsten and oxygen is The composition ratio of oxygen is less than 3, and when the infrared shielding material fine particles are described as WyOz, 2.2 ≦ z / y ≦ 2.999. If this z / y value is 2.2 or more, it is possible to avoid the appearance of a WO ₂ crystal phase other than the intended purpose in the infrared shielding material and to obtain chemical stability as the material. Therefore, it can be applied as an effective infrared shielding material. On the other hand, if the value of z / y is 2.999 or less, a required amount of free electrons is generated, and an efficient infrared shielding material is obtained.

  In addition, WyOz includes element M (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Add one or more elements selected from Mo, Ta, Re, Be, Hf, Os, Bi, and I), and freely in the WyOz including the case of z / y = 3.0 Electrons are generated, absorption characteristics derived from free electrons appear in the near-infrared region, and it is effective as a near-infrared absorbing material near 1000 nm. Here, a more efficient infrared shielding material can be obtained by combining the above-described control of the amount of oxygen and addition of an element that generates free electrons with respect to WyOz. When the general formula of the infrared shielding material that combines the control of the amount of oxygen and the addition of an element that generates free electrons is expressed as MxWyOz (where M is the M element, W is tungsten, and O is oxygen), An infrared shielding material that satisfies the relationship of 001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0 is desirable.

  First, the value of x / y indicating the amount of element M added will be described. If the value of x / y is larger than 0.001, a sufficient amount of free electrons is generated and the intended infrared shielding effect can be obtained. As the amount of the element M added increases, the supply amount of free electrons increases and the infrared shielding efficiency also increases. However, when the value of x / y is about 1, the effect is saturated. Moreover, if the value of x / y is smaller than 1, it is preferable because an impurity phase can be prevented from being generated in the infrared shielding material.

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

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

  Next, the value of z / y indicating the control of the oxygen amount will be described. Regarding the value of z / y, the same mechanism as that of the above-described infrared shielding material represented by WyOz works also in the infrared shielding material represented by MxWyOz, and also at z / y = 3.0. Therefore, 2.2 ≦ z / y ≦ 3.0 is preferable, and 2.45 ≦ z / y ≦ 3.0 is more preferable.

Furthermore, when the composite tungsten oxide fine particles have a hexagonal crystal structure, the transparency of the fine particles in the visible light region is improved, and the absorption in the near infrared region is improved. The hexagonal crystal structure will be described with reference to the plan view of FIG. In FIG. 1, _six octahedrons formed of WO ₆ units indicated by reference numeral 1 are assembled to form a hexagonal void, and an element M indicated by reference numeral 2 is arranged in the void to form one unit. The hexagonal crystal structure is composed of a large number of these one units.

In the present invention improves the permeability of the visible light region, formed in order to obtain the effect of improving the absorption of near-infrared region, the composite tungsten oxide fine particles, a unit structure (WO ₆ units described in FIG. 1 The hexagonal voids are formed by assembling six octahedrons and a structure in which the element M is arranged in the voids is included, and the composite tungsten oxide fine particles are crystalline. It may be amorphous. When the cation of the element M is added to the hexagonal void, the transmittance in the visible light region is improved and the absorption in the near infrared region is improved. Here, generally, when the element M having a large ionic radius is added, the hexagonal crystal is formed. Specifically, Cs, K, Rb, Tl, In, Ba, Sn, Li, Ca, Sr, When Fe is added, hexagonal crystals are easily formed. Of course, other elements may be used as long as the additive element M is present in the hexagonal void formed by the WO ₆ unit, and is not limited to the above elements.

  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 in terms of x / y, more preferably 0. .33. When the value of x / y is 0.33, it is considered that the additive element M is arranged in all the hexagonal voids.

  In addition to hexagonal crystals, tetragonal and cubic tungsten bronzes are also effective as infrared shielding materials. These crystal structures tend to change the absorption position in the near-infrared region, and the absorption position tends to move to the longer wavelength side in the order of cubic <tetragonal <hexagonal. Further, the accompanying absorption in the visible light region is small in the order of hexagonal crystal <tetragonal crystal <cubic crystal. Therefore, hexagonal tungsten bronze is preferably used for the purpose of transmitting light in the visible light region and shielding light in the infrared region. However, the tendency of the optical characteristics described here is merely a rough tendency, and changes depending on the kind of additive element, the amount of addition, and the amount of oxygen, and the present invention is not limited to this.

  The tungsten oxide fine particles and the composite tungsten oxide fine particles according to the present invention absorb a large amount of light in the near-infrared region, particularly in the vicinity of a wavelength of 1000 nm, so that the transmitted color tone is often from blue to green.

  The particle diameter of the infrared shielding material fine particles can be selected according to the purpose of use. First, when it is used for an application that maintains transparency, it is preferable that the dispersed particle diameter is 800 nm or less. This is because particles smaller than 800 nm do not completely block light due to scattering, and can maintain visibility in the visible light region and at the same time efficiently maintain transparency. In particular, when importance is attached to transparency in the visible light region, it is preferable to further consider scattering by particles. When importance is attached to the reduction of scattering by the particles, the dispersed particle diameter is 200 nm or less, preferably 100 nm or less. The reason for this is that if the dispersed particle size of the particles is small, the scattering of light in the visible light region having a wavelength of 400 nm to 780 nm due to geometric scattering or Mie scattering is reduced. This is because it is possible to avoid that clear transparency cannot be obtained. That is, when the dispersed particle diameter is 200 nm or less, the geometric scattering or Mie scattering is reduced, and a Rayleigh scattering region is obtained. This is because, in the Rayleigh scattering region, the scattered light decreases in inverse proportion to the sixth power of the dispersed particle diameter, so that the scattering is reduced and the transparency is improved as the dispersed particle diameter is decreased. Furthermore, when the dispersed particle size is 100 nm or less, the scattered light is preferably extremely small. From the viewpoint of avoiding light scattering, it is preferable that the dispersed particle diameter is small. If the particle diameter is 1 nm or more, industrial production is easy.

  In the present invention, the dispersed particle diameter of the fine particles means the diameter of the aggregated particles produced by agglomeration of the fine particles dispersed in the medium, and measured with various commercially available particle size distribution meters. can do. For example, a sample in a state where single particles or aggregates of fine particles are present from a fine particle dispersion, and the sample can be measured and determined using a particle size distribution meter based on the dynamic light scattering method.

  By selecting the dispersed particle diameter to be 800 nm or less, the haze value of the infrared shielding material fine particle dispersion (infrared shielding film) in which the infrared shielding material fine particles are dispersed in a medium such as a resin has a visible light transmittance of 85% or less. The haze can be 30% or less. Here, when the haze is a value larger than 30%, it becomes like frosted glass, and clear transparency cannot be obtained.

  Moreover, it is preferable from the viewpoint of improving the weather resistance of the infrared shielding material that the surface of the infrared shielding material fine particles according to the present invention is coated with an oxide containing one or more of Si, Ti, Zr, and Al. .

  In addition, at least one kind selected from tungsten oxide fine particles and composite tungsten oxide fine particles has a composition ratio represented by 2.45 ≦ z / y ≦ 2.999 when expressed as a general formula WyOz. “Magnel phase” is preferable as an infrared shielding material because it is chemically stable and has good absorption characteristics in the near infrared region.

2. Method for Producing Tungsten Oxide Fine Particles and Composite Tungsten Oxide Fine Particles Tungsten oxide fine particles represented by the general formula WyOz and composite tungsten oxide fine particles represented by MxWyOz are obtained by converting a tungsten compound starting material into an inert gas atmosphere or reduction. It can be obtained by heat treatment in a reactive gas atmosphere.

  Then, tungsten oxide obtained by dissolving tungsten trioxide powder, tungsten oxide hydrate powder, tungsten hexachloride powder, ammonium tungstate powder, tungsten hexachloride in alcohol and then drying as the tungsten compound starting material. Hydrate powder of tungsten oxide, obtained by dissolving tungsten hexachloride in alcohol, adding water and precipitating and drying it, obtained by drying aqueous ammonium tungstate solution It is preferable that it is any one or more selected from tungsten compound powder and metallic tungsten powder.

  Here, when producing tungsten oxide fine particles, it is further preferable to use tungsten oxide hydrate powder or tungsten compound powder obtained by drying an ammonium tungstate aqueous solution from the viewpoint of ease of the production process. Preferably, in the case of producing composite tungsten oxide fine particles, an ammonium tungstate aqueous solution or a tungsten hexachloride solution is more preferably used from the viewpoint that each element can be easily and uniformly mixed when the starting material is a solution. These raw materials are used, and these are heat-treated in an inert gas atmosphere or a reducing gas atmosphere to obtain tungsten oxide fine particles and composite tungsten oxide fine particles having the above-mentioned particle diameter.

  The composite tungsten oxide fine particles represented by the general formula MxWyOz containing the element M are the same as the tungsten compound starting material of the tungsten oxide fine particles represented by the general formula WyOz described above. A tungsten compound contained in the form of a simple substance or a compound is used as a starting material. Here, in order to produce a starting material in which each component is uniformly mixed at the molecular level, it is preferable to mix each material with a solution, and the tungsten compound starting material containing the element M is dissolved in a solvent such as water or an organic solvent. Preferably it is possible. Examples thereof include tungstate, chloride, nitrate, sulfate, oxalate, oxide, and the like containing element M, but are not limited to these and are preferably in the form of a solution.

Here, the heat treatment condition in the inert atmosphere is preferably 650 ° C. or higher. Tungsten oxide fine particles and composite tungsten oxide fine particles obtained by heat-treating the starting material at 650 ° C. or higher have sufficient infrared shielding properties and can be practically used in a relatively small amount as infrared shielding material fine particles. Is good. An inert gas such as Ar or N ₂ is preferably used as the inert gas. As the heat treatment conditions in the reducing atmosphere, first, the starting material is heat-treated at 100 ° C. to 650 ° C. in the reducing gas atmosphere, and then heat-treated at a temperature of 650 ° C. to 1200 ° C. in an inert gas atmosphere. Good to do. The reducing gas at this time is not particularly limited, but H ₂ is preferable. When H ₂ is used as the reducing gas, the volume ratio of H ₂ is preferably 0.1% or more, more preferably 2% or more, as the composition of the reducing atmosphere. If it is 0.1% or more, the reduction can proceed efficiently.

Tungsten oxide fine particles and composite tungsten oxide fine particles obtained by reducing raw material powder with hydrogen show a good infrared shielding property including a magnetic phase, and can be used as infrared shielding material fine particles in this state. However, since hydrogen contained in tungsten oxide is unstable, application may be limited in terms of weather resistance. Therefore, by further heat-treating the tungsten oxide compound containing hydrogen at 650 ° C. or higher in an inert atmosphere, more stable infrared shielding material fine particles can be obtained. The atmosphere during the heat treatment at 650 ° C. or higher is not particularly limited, but N ₂ and Ar are preferable from an industrial viewpoint. By the heat treatment at 650 ° C. or higher, a magnetic phase is obtained in the infrared shielding material fine particles, and the weather resistance is improved.

  As described above, it is preferable from the viewpoint of improving the weather resistance that the surface of the obtained infrared shielding material fine particles is coated with an oxide containing one or more kinds of metals of Si, Ti, Zr, and Al. . Although the coating method is not particularly limited, it is possible to coat the surface of the infrared shielding material fine particles by adding the metal alkoxide to the solution in which the infrared shielding material fine particles are dispersed.

3. Metal salt (first additive)
As a reason why the metal salt as the first additive contained in the infrared shielding material fine particle dispersion acts on the infrared shielding material fine particle dispersion to reduce the deterioration of the infrared shielding properties over time, the present inventors, I guess as follows. That is, in the infrared shielding material fine particle dispersion, the metal salt is present in the vicinity or / and on the surface of the infrared shielding material fine particles, and the action of this metal salt sufficiently captures moisture that has entered from the air, etc. As a result of sufficiently capturing radicals generated due to the above and suppressing the generation of harmful radicals in a chain, it is assumed that the deterioration of the infrared shielding property with time is reduced. However, there are many unclear points about the action of the metal salt, and there is a possibility that actions other than those described above are working, so that the action is not limited to the above actions.

  And as a metal salt applied to this invention, Cs, Sr, Ba, Ti, Zr, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt , Cu, Ag, Au, Zn, Cd, In, and Sn, and a salt composed of an inorganic acid or an organic acid, and it is preferable to use one or more of these. In addition, although the effect of the salts with alkali metals other than the above metals, alkaline earth metals, Sc, Y, V, Al, Pb, Bi is slightly reduced, the infrared shielding characteristics of the infrared shielding material fine particle dispersion are changed over time. It is effective to reduce the general decline. In addition, metal salts other than these are not suitable because they are ineffective.

  Further, the metal salt applied to the present invention is a salt of the metal, carboxylate, carbonyl complex, carbonate, phosphate, perchlorate, hypochlorite, chlorite, It is preferably selected from chlorate and hydrochloride.

  Examples of the carboxylic acid constituting the carboxylate include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octylic acid, naphthenic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid. Acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid, oxalic acid, malonic acid, succinic acid, benzoic acid, phthalic acid, Examples include isophthalic acid, terephthalic acid, salicylic acid, gallic acid, mellitic acid, cinnamic acid, pyruvic acid, lactic acid, malic acid, citric acid, maleic acid, aconitic acid, glutaric acid, adipic acid, and amino acids. Examples of the β-diketone constituting the carbonyl complex salt include acetylacetone, benzoylacetone, benzoyltrifluoroacetone, hexafluoroacetylacetone, and 2-thenoyltrifluoroacetone.

  The content of the metal salt in the infrared shielding material fine particle dispersion is one or more fine particles selected from tungsten oxide fine particles represented by the general formula WyOz and composite tungsten oxide fine particles represented by the general formula MxWyOz. The amount is preferably 0.01 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the constituted infrared shielding material fine particles.

  When the content is less than 0.01 parts by weight, it is difficult to sufficiently capture moisture that has entered from the air and the like, and it is difficult to sufficiently capture radicals generated by ultraviolet rays and the like. In some cases, it becomes impossible to suppress the occurrence of radicals in a chain, and the effect of reducing the temporal deterioration of the infrared shielding properties may be insufficient. On the other hand, when the content exceeds 20 parts by weight, the infrared shielding material fine particle dispersion, the infrared shielding film-forming coating liquid, and the infrared shielding material fine particles in the infrared shielding film and the infrared shielding optical member obtained by using these are used. Dispersibility may deteriorate and haze may deteriorate.

  Therefore, the content of the metal salt in the infrared shielding material fine particle dispersion is based on 100 parts by weight of the infrared shielding material fine particles composed of one or more kinds of fine particles selected from the tungsten oxide fine particles and the composite tungsten oxide fine particles. It is preferably 0.01 parts by weight or more and 20 parts by weight or less.

4). Ammonia, amine compound (second additive)
Infrared shielding material fine particle dispersion in which at least one selected from ammonia and an amine compound as a second additive contained in the infrared shielding material fine particle dispersion is added with an ultraviolet curable resin (that is, a coating liquid for forming an infrared shielding film) As a reason for improving the compatibility between the infrared shielding material fine particles and the ultraviolet curable resin by acting on the above, the present inventors infer as follows. That is, in the coating solution for forming an infrared shielding film, ammonia and amine compound as the second additive are oriented to the metal ion of the metal salt as the first additive, and the infrared shielding is performed due to effects such as steric hindrance and surface modification. It is speculated that the compatibility between the material fine particles and the ultraviolet curable resin is improved, and in particular, the result of inhibiting the aggregation of the infrared shielding material fine particles during drying is to enable the haze reduction of the manufactured infrared shielding film. . However, there are many unclear points regarding the actions of ammonia and amine compounds, and there is a possibility that actions other than those described above are involved, and therefore, the action is not limited to the above actions.

  And as a solution of ammonia applied to this invention, it is preferable to use the solution selected from methanol solution, ethanol solution, and 2-propanol solution. Ammonia water is not suitable because the dispersibility of the infrared shielding material fine particle dispersion deteriorates.

  In addition, the amine compound applied to the present invention is diethanolamine, monoethanolamine, triethanolamine, methylamine, ethylamine, laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, behenylamine, dimethylamine, diethylamine, dimethyllauryl. Amine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, trimethylamine, triethylamine, biperidine, pyridine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethyleneexamine, oleylpropylenediamine, N-hydroxyethyllauryl Amine, polyoxyethylene lauryl amine, polyoxyethylene stearyl amine Emissions, it is preferably selected from among polyoxyethylene oleylamine.

  Further, the content of the second additive composed of one or more selected from ammonia and an amine compound with respect to the first additive composed of the metal salt is required to be 5% or more and 300% or less by weight ratio. . When the content of the second additive is less than 5% with respect to the first additive, the second additive is insufficiently effective to orient the metal ions and improve the compatibility between the infrared shielding material fine particles and the ultraviolet curable resin. As a result, the infrared shielding material fine particles aggregate during drying to deteriorate the haze. On the other hand, when the content of the second additive with respect to the first additive exceeds 300%, the dispersion of the infrared shielding material fine particle dispersion is made basic due to an increase in the basic component, resulting in poor liquid stability of the dispersion. Thus, the viscosity change becomes large. For this reason, the content of the second additive composed of one or more selected from ammonia and an amine compound with respect to the first additive composed of the metal salt is 5% to 300% by weight. Cost.

5. Solvent The organic solvent used in the infrared shielding material fine particle dispersion according to the present invention containing a second additive composed of one or more selected from ammonia and an amine compound is not particularly limited and is a known organic solvent. Can be used. Specifically, alcohol solvents such as methanol (MA), ethanol (EA), 1-propanol (NPA), isopropanol (IPA), butanol, pentanol, benzyl alcohol, diacetone alcohol, acetone, methyl ethyl ketone (MEK) , Ketone solvents such as methyl propyl ketone, methyl isobutyl ketone (MIBK), cyclohexanone, isophorone, ester solvents such as 3-methyl-methoxy-propionate (MMP), ethylene glycol monomethyl ether (MCS), ethylene glycol monoethyl ether (ECS), ethylene glycol isopropyl ether (IPC), propylene glycol methyl ether (PGM), propylene glycol ethyl ether (PE), propylene glycol methyl Glycol derivatives such as ether acetate (PGMEA), propylene glycol ethyl ether acetate (PE-AC), formamide (FA), N-methylformamide, dimethylformamide (DMF), dimethylacetamide, N-methyl-2-pyrrolidone ( Amides such as NMP), aromatic hydrocarbons such as toluene and xylene, and halogenated hydrocarbons such as ethylene chloride and chlorobenzene. Among them, organic solvents with low polarity are preferable, and particularly highly hydrophobic ones such as ketones such as MIBK and MEK, aromatic hydrocarbons such as toluene and xylene, glycol ether acetates such as PGMEA and PE-AC, and the like. preferable. These organic solvents can be used alone or in combination of two or more.

6). Infrared shielding film, infrared shielding optical member and method for producing the same A preferred method of using the infrared shielding material fine particle dispersion according to the present invention is to form an infrared shielding film-forming coating liquid by adding an ultraviolet curable resin to the dispersion. A method for producing an infrared shielding film by applying the infrared shielding film-forming coating solution to the surface of the substrate as appropriate to form a coating film, evaporating the solvent from the coating film, and irradiating a predetermined amount of ultraviolet rays. Is mentioned.

  In this method of use, the infrared shielding film containing the infrared shielding material fine particles is bonded to the substrate surface using an infrared shielding material fine particle dispersion containing the infrared shielding material fine particles obtained by firing at a high temperature in advance. Can be worn. For this reason, application to a base material having a low heat-resistant temperature is possible, and there is an advantage that a large-sized device is not required when forming an infrared shielding film and it is inexpensive.

  In addition, in the infrared shielding material fine particle dispersion (infrared shielding film forming coating liquid) containing the infrared shielding material fine particles, metal salt (first additive) and ultraviolet curable resin, at least one selected from ammonia and amine compounds A second component composed of at least one selected from infrared rays shielding material fine particles, metal salt (first additive), ammonia and an amine compound simply by adding a necessary amount of the second additive component and forming a coating film. Since an infrared shielding film containing an additive can be obtained, it is possible to easily manufacture an infrared shielding optical member having a low haze that prevents the infrared shielding properties from being lowered over time. By using this infrared shielding optical member, the application can be expanded to outdoor applications that receive sunlight, which is extremely useful.

(6-1) Ultraviolet curable resin The ultraviolet curable resin which is added to the infrared shielding material fine particle dispersion and constitutes the coating liquid for forming the infrared shielding film can be selected according to the purpose. For example, acrylic resin, acrylic urethane resin, acrylic epoxy resin, acrylic polyester resin, silicone resin, epoxy resin, imide resin, polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, ethylene Examples thereof include vinyl acetate copolymer, polyester resin, polyethylene terephthalate resin, fluorine resin, polycarbonate resin, and vinyl butyral resin.

(6-2) Substrate for Forming Coating Film and Coating Method The substrate on which the coating solution for forming an infrared shielding film is coated may be a film or a board as desired, and the shape is not limited. As a material for the transparent substrate, PET, acrylic, urethane, polycarbonate, polyethylene, ethylene vinyl acetate copolymer, polyvinyl chloride, fluorine resin, and the like can be used according to various purposes. In addition to glass, glass can be applied.

  Next, the coating method of the coating liquid for forming the infrared shielding film is not particularly limited as long as the coating film can be uniformly formed on the surface of the base material. However, the bar coating method, the gravure coating method, the spray coating method, the dip coating method, etc. Illustrated.

7). Infrared shielding material fine particle dispersion, transmission scattering profile measurement of infrared shielding film forming coating liquid and infrared shielding film Infrared shielding material fine particle dispersion, infrared shielding film forming coating liquid, or haze measurement method in infrared shielding film Infrared shielding material fine particle dispersion (dispersion in which infrared shielding material fine particles are dispersed in an appropriate medium such as resin or glass: see Patent Document 8) as a component of transmitted light when incident on light The present inventor has already proposed a method for directly evaluating haze by paying attention to the scattered light and determining the transmission scattering rate for each wavelength (see JP 2009-150979 A).

  That is, as described in paragraph 0029 of Japanese Patent Application Laid-Open No. 2009-150979, in the measurement using a conventional haze meter (see paragraph 0015 of Japanese Patent Application Laid-Open No. 2000-213063), the transmission scattering rate for each wavelength (scattered transmission). Rate) cannot be obtained, and only the ratio of the scattered transmission to the total light transmitted is required, so the “blue haze” of the infrared shielding material fine particle dispersion is evaluated (scattering transmittance wavelength: 360 nm to 500 nm) It was difficult to evaluate the size of the blue haze from the local maximum between the two. By the way, when the “blue haze” is large, the dispersion of the fine particles of the infrared shielding material causes poor visibility when applied to the windshield of a car, etc., and the harmful effect of deteriorating the beauty when applied to a building window glass or the like. (See paragraph 0007 of JP2009-150979A).

  For this reason, when strictly evaluating the “haze” in the fine particle dispersion of the infrared shielding material, the “haze value (turbidity)” measured using a conventional haze meter and the transmission scattering profile measuring device developed by the present inventor are used. It is desirable to carry out both of the “transmission scattering rate” measured by using.

  Hereinafter, the principle of measuring the transmission / scattering rate (that is, the transmission / scattering profile) for each wavelength will be described with reference to FIGS.

(7-1) Transmission Scattering Profile Measuring Device First, a measuring device for measuring a transmission / scattering profile is shown in FIGS. 2 and 3, in which the inner surface of the spherical body has diffuse reflectivity and a measurement sample (infrared shielding material fine particles). A first opening (not shown) to which a dispersion, an infrared shielding film or an infrared shielding optical member obtained by using this infrared shielding material fine particle dispersion is attached, a standard reflector 7 or a light trap component 8 is attached. And a second opening (not shown), an integrating sphere 6 having a third opening (not shown) to which the light receiver 5 is attached on the outer surface of the spherical body, and the spherical opening through the first opening. A light source 3 that emits linear light, a spectroscope (not shown) that is attached to the light receiver 5 and that splits the received reflected light or scattered light, and a reflected light that is connected to the spectroscope and dispersed. Or, a data storage means (not shown) for storing the spectral data of the scattered light, and each of the stored spectral data of the blank transmitted light intensity and the diffuse transmitted light intensity for each wavelength of the diffuse transmitted light intensity and the blank transmitted light intensity. Calculation means (not shown) is provided for calculating the transmission scattering rate for each wavelength by calculating the ratio.

  Here, the integrating sphere 6 having the first, second and third openings (not shown) on the outer surface of the spherical body is diffused by applying barium sulfate or Spectralon (registered trademark) or the like on the inner surface of the spherical body. It has reflectivity, and the incident angle to the standard reflecting plate 7 may be 10 ° on both the standard side and the reference side. As the light receiver 5, for example, a photomultiplier tube (ultraviolet / visible region) or a cooled lead sulfide (near infrared region) can be used. Further, a spectroscope (not shown) attached to the light receiver 5 needs to have a wavelength measurement range in the ultraviolet / visible region and photometric accuracy (± 0.002 Abs).

  Next, as the light source 3 that emits linear light that enters the spherical space, for example, a deuterium lamp is applied in the ultraviolet region, and a 50 W halogen lamp is applied in the visible / near infrared region.

  The standard reflector 7 can be a white plate made of, for example, SPECTRALON (registered trademark), and the light trap component 8 has a function of trapping incident linear light without reflecting it. For example, a dark box that absorbs incident linear light almost completely is used.

(7-2) Method of evaluating the maximum value of the transmission / scattering profile Next, using the transmission / scattering profile measurement device, the maximum value of the transmission / scattering profile of the infrared shielding material fine particle dispersion or infrared shielding film as the measurement sample is measured. For the evaluation, the steps of “blank transmitted light intensity measuring step”, “diffuse transmitted light intensity measuring step”, and “diffuse transmittance calculating step” are required.

(7-2-1) First, in the “blank transmitted light intensity measurement step”, as shown in FIG. 2, the standard reflector 7 is attached to the second opening of the integrating sphere 6 and the measurement sample ( Infrared shielding material fine particle dispersion, coating liquid for forming infrared shielding film, infrared shielding film or infrared shielding optical member obtained using this infrared shielding material fine particle dispersion) is not attached, and linear light from external light source 3 is applied. While making it enter into spherical space through a 1st opening part, the reflected light reflected by the standard reflecting plate 7 is light-received with the light receiver 5, and it spectroscopically analyzes with the spectroscope (not shown) attached to the light receiver 5. FIG. Thus, spectral data of the reflected light is obtained.

(7-2-2) Next, in the “transmitted scattered light intensity measurement step”, a light trap part 8 is attached to the second opening of the integrating sphere 6 as shown in FIG. (Infrared shielding material fine particle dispersion, infrared shielding film or infrared shielding optical member obtained using this infrared shielding material fine particle dispersion) 4 with linear light from the external light source 3 being measured with the sample 4 and the first A spectroscope (not shown) that enters the spherical space through the opening, receives scattered light other than the light trapped by the light trap component 8 by the light receiver 5, and is attached to the light receiver 5. To obtain spectral data of scattered light.

(7-2-3) In the “transmission / scattering rate calculation step”, calculation means (not shown) based on the spectral data of the blank transmitted light intensity and transmitted scattered light intensity stored by the data storage means (not shown). ) To calculate the ratio of the transmitted scattered light intensity and the transmitted light intensity of the blank for each wavelength to determine the transmitted scattering ratio for each wavelength, and from the obtained transmitted scattering ratio for each wavelength, the infrared shielding material fine particles as the measurement sample The maximum value in the wavelength region of 360 nm to 500 nm in the transmission scattering profile of the dispersion, the infrared shielding film or the infrared shielding optical member obtained using the infrared shielding material fine particle dispersion can be obtained.

(7-2-4) The maximum value of the transmission scattering profile in the wavelength region of 360 nm to 500 nm of the infrared shielding material fine particle dispersion with the visible light transmittance set to 40% to 60% is 1.5% or less. It is preferable. When this condition is satisfied, the infrared shielding material fine particle dispersion (infrared shielding film and infrared shielding optical member) produced using this infrared shielding material fine particle dispersion has almost no haze (the “blue haze” described above). It has been confirmed that it is not observed.

(7-3) In the measuring apparatus for measuring the transmission / scattering profile, the light source 3 and the measurement sample (infrared shielding material fine particle dispersion, infrared shielding film obtained using this infrared shielding material fine particle dispersion or An optical system for adjusting the light beam may be provided between the infrared shielding optical member 4). In this optical system, for example, parallel light is adjusted by combining a plurality of lenses, and the amount of light is adjusted by a diaphragm. In some cases, a specific wavelength may be cut by a filter.

8). Infrared shielding optical member The infrared shielding material fine particle dispersion according to the present invention includes an infrared shielding material fine particle composed of one or more fine particles selected from tungsten oxide fine particles and composite tungsten oxide fine particles, Cs, Sr, Ba, Selected from Ti, Zr, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, In, Sn A first additive composed of a metal salt composed of one or more elements and a second additive composed of one or more selected from ammonia and an amine compound.

  And, it becomes possible to prevent the time-dependent deterioration of the infrared shielding property due to the refinement of the fine particles of the infrared shielding material by the action of the first additive, and the haze when the ultraviolet curable resin is applied by the action of the second additive. It is also possible to prevent the deterioration.

  Therefore, an infrared shielding film and a substrate manufactured using the infrared shielding film-forming coating liquid according to the present invention, an infrared shielding material fine particle dispersion added with an ultraviolet curable resin (that is, an infrared shielding film-forming coating liquid), In the infrared shielding optical member composed of an infrared shielding film, since it is excellent in the stability over time of infrared shielding properties and can reduce haze, a light shielding film used for window materials of various buildings and vehicles, It can be applied to a light shielding member or the like.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not necessarily limited to these Examples.

  The visible light transmittance in the examples is the ratio of the daylight beam perpendicularly incident on the sample to the incident beam. Here, daylight means CIE daylight established by the International Lighting Commission. In this CIE daylight, the spectral illuminance distribution of daylight having the same color temperature as the color temperature of blackbody radiation is shown as a relative value with respect to the value of wavelength 560 nm based on the observation data. The luminous flux is obtained by integrating the numerical value of the product of the value of the radiant flux for each wavelength of radiation and the visibility (sensitivity to the light of the human eye) with respect to the wavelength. That is, “visible light transmittance (%)” means the brightness perceived by the human eye by the integrated value of the transmitted light amount obtained by normalizing the light transmission amount in the wavelength region of 380 nm to 780 nm with the human eye visibility. Value.

  The "transmittance (%)" is measured at intervals of 5 nm in the wavelength range of 300 nm to 2600 nm using a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.).

  The “transmission scattering rate (%)” is measured using a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.) at an interval of 1 nm in the wavelength range of 300 nm to 800 nm by the method described above.

  The “haze value (%)” of the film was measured based on JIS K 7105.

[Example 1]
Cs _0.33 WO ₃ powder, 100 parts by weight, 320 parts by weight of methyl isobutyl ketone (hereinafter sometimes abbreviated as MIBK), and 80 parts by weight of a dispersing agent are mixed and subjected to dispersion treatment to obtain a dispersion having an average dispersed particle diameter of 5 nm. (A liquid).

  UV curing resin UV-7600B (Nippon Gosei Chemical Co., Ltd.) 350 parts by weight, photopolymerization initiator “IRGACURE 184” (Ciba Specialty Chemicals Co., Ltd.) 20 parts, and MIBK 130 parts by weight Resin (Liquid B) was used.

  500 parts by weight of the liquid A and 500 parts by weight of the liquid B, 5 parts by weight of nickel acetate, and 0.25 parts by weight of ammonia (5% with respect to the metal salt) were mixed to prepare an infrared shielding material fine particle dispersion.

  This infrared shielding material fine particle dispersion (coating solution) was applied onto a 50 μm thick PET film using a bar coater to form a coating film, and this coating film was dried at 70 ° C. for 60 seconds to evaporate the solvent. Thereafter, it was cured with a high-pressure mercury lamp to obtain an infrared shielding film.

  When the optical characteristics of the infrared shielding film were measured, it was found that the visible light transmittance was 65% and the light in the visible light region was sufficiently transmitted. Further, the haze was 0.8%, and the transparency was extremely high, and the internal situation could be clearly confirmed from the outside.

  When the maximum value (transmission scattering rate) of the transmission / scattering profile in the wavelength region of 360 nm to 500 nm was measured according to the measurement principle of the diffuse transmission profile described above, the low scattering rate was 1.4%. Further, the transmittance T at a wavelength of 820 nm was 6.5%, and it was confirmed that the filter was a good near infrared filter.

  When this infrared shielding film was exposed to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours and the transmission profile was measured in the same manner, the transmittance at 820 nm was 9.3%. It was found that the increase in transmittance (ΔT) at 820 nm due to exposure to high temperature and humidity at 95 RH% at 80 ° C. was as small as 2.8%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Example 2]
An infrared shielding film was produced in the same manner as in Example 1 except that the amount of ammonia added was 5 parts by weight (100% based on the metal salt).

  The obtained infrared shielding film was evaluated in the same manner as in Example 1.

  First, it was found that the visible light transmittance was 67% and the light in the visible light region was sufficiently transmitted. Furthermore, it was confirmed that the haze was 0.8% and the transparency was extremely high. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 1.1%. Further, the transmittance T at a wavelength of 820 nm was 7.3%, and it was confirmed that the filter was a good near infrared filter.

  Then, it was found that the increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was as small as 2.7%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Example 3]
An infrared shielding film was produced in the same manner as in Example 1 except that the amount of ammonia added was 15 parts by weight (300% based on the metal salt).

  The obtained infrared shielding film was evaluated in the same manner as in Example 1.

  First, it was found that the visible light transmittance was 68% and the light in the visible light region was sufficiently transmitted. Furthermore, it was confirmed that the haze was 0.8% and the transparency was extremely high. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 1.3%. Further, the transmittance T at a wavelength of 820 nm was 7.9%, and it was confirmed that the filter was a good near infrared filter.

  Then, it was found that the increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was as small as 2.9%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Example 4]
An infrared shielding film was produced in the same manner as in Example 1 except that the amount of ammonia added was 5 parts by weight (100% with respect to the metal salt) and the metal salt was changed to zinc acetate.

  The obtained infrared shielding film was evaluated in the same manner as in Example 1.

  First, it was found that the visible light transmittance was 67% and the light in the visible light region was sufficiently transmitted. Furthermore, it was confirmed that the haze was 0.8% and the transparency was extremely high. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 1.1%. Moreover, the transmittance T at a wavelength of 820 nm was 7.6%, and it was confirmed that the filter was a good near infrared filter.

  It was found that the increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was as small as 2.6%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Example 5]
An infrared shielding film was produced in the same manner as in Example 1 except that ammonia was changed to diethanolamine.

  The obtained infrared shielding film was evaluated in the same manner as in Example 1.

  First, it was found that the visible light transmittance was 64% and the light in the visible light region was sufficiently transmitted. Furthermore, it was confirmed that the haze was 0.8% and the transparency was extremely high. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 1.4%. Further, the transmittance T at a wavelength of 820 nm was 6.3%, and it was confirmed that the filter was a good near infrared filter.

  It was found that the increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was as small as 2.1%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Example 6]
An infrared shielding film was prepared in the same manner as in Example 1 except that ammonia was changed to diethanolamine and the addition amount was 5 parts by weight (100% with respect to the metal salt).

  The obtained infrared shielding film was evaluated in the same manner as in Example 1.

  First, it was found that the visible light transmittance was 66% and the light in the visible light region was sufficiently transmitted. Furthermore, it was confirmed that the haze was 0.8% and the transparency was extremely high. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 1.1%. Further, the transmittance T at a wavelength of 820 nm was 7.1%, and it was confirmed that the filter was a good near infrared filter.

  It was found that the increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was as small as 2.3%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Example 7]
An infrared shielding film was produced in the same manner as in Example 1 except that the amount of addition was changed to 15 parts by weight (300% based on the metal salt) by changing ammonia to diethanolamine.

  The obtained infrared shielding film was evaluated in the same manner as in Example 1.

  First, it was found that the visible light transmittance was 68% and the light in the visible light region was sufficiently transmitted. Furthermore, it was confirmed that the haze was 0.8% and the transparency was extremely high. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 1.3%. Further, the transmittance T at a wavelength of 820 nm was 8.0%, and it was confirmed that the filter was a good near infrared filter.

  It was found that the increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was as small as 2.6%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Example 8]
An infrared shielding film was produced in the same manner as in Example 1 except that ammonia was changed to monoethanolamine.

  The obtained infrared shielding film was evaluated in the same manner as in Example 1.

  First, it was found that the visible light transmittance was 66% and the light in the visible light region was sufficiently transmitted. Furthermore, it was confirmed that the haze was 0.8% and the transparency was extremely high. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 1.0%. Further, the transmittance T at a wavelength of 820 nm was 6.9%, and it was confirmed that the filter was a good near infrared filter.

  It was found that the increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was as small as 2.3%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Example 9]
An infrared shielding film was prepared in the same manner as in Example 1 except that ammonia was changed to monoethanolamine and the addition amount was 5 parts by weight (100% based on the metal salt).

  The obtained infrared shielding film was evaluated in the same manner as in Example 1.

  First, it was found that the visible light transmittance was 67% and the light in the visible light region was sufficiently transmitted. Furthermore, it was confirmed that the haze was 0.8% and the transparency was extremely high. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 1.3%. Further, the transmittance T at a wavelength of 820 nm was 7.7%, and it was confirmed that the filter was a good near infrared filter.

  It was found that the increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was as small as 2.6%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Example 10]
An infrared shielding film was produced in the same manner as in Example 1 except that ammonia was changed to monoethanolamine and the addition amount was 15 parts by weight (300% based on the metal salt).

  The obtained infrared shielding film was evaluated in the same manner as in Example 1.

  First, it was found that the visible light transmittance was 68% and the light in the visible light region was sufficiently transmitted. Furthermore, it was confirmed that the haze was 0.8% and the transparency was extremely high. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 1.0%. Moreover, the transmittance T at a wavelength of 820 nm was 8.2%, and it was confirmed that the filter was a good near infrared filter.

  It was found that the increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was as small as 2.3%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Example 11]
An infrared shielding film was produced in the same manner as in Example 1 except that ammonia was changed to triethanolamine.

  The obtained infrared shielding film was evaluated in the same manner as in Example 1.

  First, it was found that the visible light transmittance was 65% and the light in the visible light region was sufficiently transmitted. Furthermore, it was confirmed that the haze was 0.8% and the transparency was extremely high. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 1.4%. Further, the transmittance T at a wavelength of 820 nm was 6.8%, and it was confirmed that the filter was a good near infrared filter.

  It was found that the increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was as small as 2.1%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Example 12]
An infrared shielding film was prepared in the same manner as in Example 1 except that ammonia was changed to triethanolamine and the addition amount was 5 parts by weight (100% based on the metal salt).

  The obtained infrared shielding film was evaluated in the same manner as in Example 1.

  First, it was found that the visible light transmittance was 67% and the light in the visible light region was sufficiently transmitted. Furthermore, it was confirmed that the haze was 0.8% and the transparency was extremely high. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 1.1%. Moreover, the transmittance T at a wavelength of 820 nm was 7.4%, and it was confirmed that the filter was a good near infrared filter.

  It was also found that the increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was as small as 2.2%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Example 13]
An infrared shielding film was prepared in the same manner as in Example 1 except that ammonia was changed to triethanolamine and the addition amount was 15 parts by weight (300% based on the metal salt).

  The obtained infrared shielding film was evaluated in the same manner as in Example 1.

  First, it was found that the visible light transmittance was 69% and the light in the visible light region was sufficiently transmitted. Furthermore, it was confirmed that the haze was 0.8% and the transparency was extremely high. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 1.3%. Moreover, the transmittance T at a wavelength of 820 nm was 8.3%, and it was confirmed that the filter was a good near infrared filter.

  It was found that the increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was as small as 2.4%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Example 14]
An infrared shielding film was produced in the same manner as in Example 1 except that ammonia was changed to ethylenediamine and the addition amount was 5 parts by weight (100% based on the metal salt).

  The obtained infrared shielding film was evaluated in the same manner as in Example 1.

  First, it was found that the visible light transmittance was 67% and the light in the visible light region was sufficiently transmitted. Furthermore, it was confirmed that the haze was 0.8% and the transparency was extremely high. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 1.1%. Moreover, the transmittance T at a wavelength of 820 nm was 7.4%, and it was confirmed that the filter was a good near infrared filter.

  It was found that the increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was as small as 2.3%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Example 15]
An infrared shielding film was produced in the same manner as in Example 1 except that ammonia was changed to oleylamine and the addition amount was 10 parts by weight (200% based on the metal salt).

  The obtained infrared shielding film was evaluated in the same manner as in Example 1.

  First, it was found that the visible light transmittance was 68% and the light in the visible light region was sufficiently transmitted. Furthermore, it was confirmed that the haze was 0.8% and the transparency was extremely high. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 1.5%. Further, the transmittance T at a wavelength of 820 nm was 7.8%, and it was confirmed that the filter was a good near infrared filter.

  Then, it was found that the increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was as small as 2.5%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Comparative Example 1]
An infrared shielding film was produced in the same manner as in Example 1 except that nickel acetate and ammonia were not added, and the same evaluation as in Example 1 was performed.

  First, it was found that the visible light transmittance was 65% and the light in the visible light region was sufficiently transmitted. Furthermore, it was confirmed that the haze was 0.8% and the transparency was extremely high. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 1.1%. Further, the transmittance T at a wavelength of 820 nm was 6.6%, and it was confirmed that the filter was a good near infrared filter.

  The increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was found to be as large as 4.2%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Comparative Example 2]
An infrared shielding film was prepared in the same manner as in Example 1 except that ammonia was not added, and the same evaluation as in Example 1 was performed.

  First, it was found that the visible light transmittance was 66% and the light in the visible light region was sufficiently transmitted. However, it was confirmed that the haze was 1.4% and the transparency was extremely low. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 4.5%, and the scattering rate was also large. Further, the transmittance T at a wavelength of 820 nm was 7.0%, and it was confirmed that the filter was a good near infrared filter.

  It was found that the increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was as small as 2.3%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Comparative Example 3]
An infrared shielding film was produced in the same manner as in Example 1 except that ammonia was not added and the metal salt was changed to zinc acetate, and the same evaluation as in Example 1 was performed.

  First, it was found that the visible light transmittance was 66% and the light in the visible light region was sufficiently transmitted. However, it was confirmed that the haze was 1.4% and the transparency was extremely low. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 4.8%, and the scattering rate was also large. Further, the transmittance T at a wavelength of 820 nm was 7.3%, and it was confirmed that the filter was a good near infrared filter.

  Then, it was found that the increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was as small as 2.5%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Comparative Example 4]
An infrared shielding film was prepared in the same manner as in Example 1 except that the amount of ammonia added was 0.1 parts by weight (2% based on the metal salt), and the same evaluation as in Example 1 was performed.

  First, it was found that the visible light transmittance was 67% and the light in the visible light region was sufficiently transmitted. However, it was confirmed that the haze was 1.3% and the transparency was extremely low. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 3.8%, and the scattering rate was also large. Moreover, the transmittance T at a wavelength of 820 nm was 7.6%, and it was confirmed that the filter was a good near infrared filter.

  It was found that the increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was as small as 2.1%.

  Also, no increase in viscosity was observed after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month.

[Comparative Example 5]
An infrared shielding film was prepared in the same manner as in Example 1 except that the amount of ammonia added was 17.5 parts by weight (350% with respect to the metal salt), and the same evaluation as in Example 1 was performed.

  First, it was found that the visible light transmittance was 69% and the light in the visible light region was sufficiently transmitted. However, it was confirmed that the haze was 1.2% and the transparency was extremely low. The maximum value of transmission scattering (transmission scattering rate) in the wavelength region of 360 nm to 500 nm was 2.5%, and the scattering rate was also large. Further, the transmittance T at a wavelength of 820 nm was 8.1%, and it was confirmed that the filter was a good near infrared filter.

  It was found that the increase in transmittance (ΔT) at 820 nm after exposure to high temperature and humidity of 95 RH% at 80 ° C. for 48 hours was as large as 3.2%.

  Further, after the infrared shielding material fine particle dispersion was stored at 40 ° C. for 1 month, the dispersion was gelled.

[Evaluation]
(1) In Examples 1 to 3, since nickel acetate (metal salt) and ammonia are added, near-infrared shielding in an accelerated test by high temperature and humidity compared to Comparative Example 1 in which no metal salt is added. It is confirmed from the amount of increase (ΔT) in Tables 1 and 2 that the deterioration of characteristics is suppressed.

  In addition, the maximum values of haze and transmission scattering in Tables 1 and 2 are higher than those of Comparative Example 2 in which metal salt is added but ammonia is not added. It is confirmed from (transmission scattering rate).

  As a result, it can be seen that the infrared shielding film (infrared shielding optical member) according to the present invention has unprecedented infrared shielding properties over time and high transparency.

(2) In Examples 5 to 7, diethanolamine was added instead of ammonia, Examples 8 to 10 were changed to ammonia to monoethanolamine, and Examples 11 to 13 were changed to ammonia and triethanolamine was added. Ethanolamine, Example 14 was changed to ammonia to ethylenediamine, and Example 15 was changed to ammonia to be oleylamine, as confirmed from the amount of increase (ΔT), haze, and transmission scattering rate in Table 1. It can be seen that the effect of improving the heat and humidity resistance and a good haze value can be obtained.

(3) Example 4 relates to an example in which the kind of metal salt added to Example 2 was changed, and instead of nickel acetate of Example 2, Example 4 was obtained by adding zinc acetate.

  And it turns out that the improvement effect of moist heat resistance and a favorable haze value are acquired so that the amount of increase ((DELTA) T) of Table 1, haze, and a transmission scattering rate may be confirmed.

(4) Comparative Example 3 relates to a comparative example in which the metal salt of Comparative Example 2 is changed to zinc acetate.
As can be seen from the haze and transmission scattering rate in Table 1, it can be seen that the haze value is high and the transparency is low.

(5) Compared with Examples 1 to 3, Comparative Example 4 has a small amount of ammonia added of 0.1 part by weight (2% with respect to the metal salt). It can be seen that the haze value is high and the transparency is low.

  Further, in Comparative Example 5, compared to Examples 1 to 3, the amount of ammonia added is as large as 17.5 parts by weight (350% with respect to the metal salt), so the stability of the infrared shielding material fine particle dispersion is deteriorated. As can be seen from the haze and transmission scattering rate of Table 1, it can be seen that the haze value is high and the transparency is low.

  The infrared shielding material fine particle dispersion according to the present invention contains a first additive composed of a metal salt and a second additive composed of ammonia and an amine compound. It is possible to prevent a time-dependent decrease in infrared shielding properties due to finer fine particles, and it is also possible to prevent haze deterioration when an ultraviolet curable resin is applied by the action of the second additive. Therefore, the infrared shielding film and the infrared shielding optical member manufactured using the coating liquid for forming the infrared shielding film according to the present invention to which the ultraviolet curable resin is added are excellent in the temporal stability of the infrared shielding properties, and are low in the past. Since it can be hazed, it has industrial applicability that can be applied to light-shielding films, light-shielding members, etc. used in various buildings and vehicle window materials.

1 WO ₆ units 2 Element M
3 Light source 4 Measurement sample 5 Light receiver 6 Integrating sphere 7 Standard reflector 8 Light trap parts

Claims (9)

Tungsten oxide fine particles represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), general formula MxWyOz (where M is H, He, alkali metal) , 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 elements selected, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3) Infrared shielding material fine particles composed of more than one kind of fine particles Infrared shielding material fine particle dispersion dispersed in a medium, wherein an ultraviolet curable resin not contained in the dispersion is added to the dispersion to form an infrared shielding film forming coating liquid In
Cs, Sr, Ba, Ti, Zr, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, In, Containing a first additive composed of a metal salt composed of one or more elements selected from Sn, and a second additive composed of one or more selected from ammonia and an amine compound, and The infrared shielding material fine particle dispersion, wherein the content of the second additive with respect to the first additive is 5% to 300% by weight.   2. The infrared shielding material fine particle dispersion according to claim 1, wherein the amine compound is at least one selected from diethanolamine, monoethanolamine, and triethanolamine.   3. The infrared shielding material fine particle dispersion according to claim 1, wherein the content of the first additive is 0.01 part by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the infrared shielding material fine particles. liquid.   One or more kinds selected from the tungsten oxide fine particles and the composite tungsten oxide fine particles are a composition represented by the general formula WyOz (W is tungsten, O is oxygen, 2.45 ≦ z / y ≦ 2.999). The infrared shielding material fine particle dispersion according to any one of claims 1 to 3, comprising a ratio of a magnetic phase.   The infrared shielding according to any one of claims 1 to 4, wherein the composite tungsten oxide fine particles represented by the general formula MxWyOz include one or more of hexagonal, tetragonal, or cubic crystal structures. Material fine particle dispersion.   The element M includes one or more of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn, and has a hexagonal crystal structure. Item 6. The infrared shielding material fine particle dispersion according to Item 5.   A coating solution for forming an infrared shielding film, wherein an ultraviolet curable resin is added to the infrared shielding material fine particle dispersion according to any one of claims 1 to 6.   An infrared shielding film obtained by coating the coating liquid for forming an infrared shielding film according to claim 7 on a substrate surface to form a coating film, evaporating a solvent from the coating film and irradiating with ultraviolet rays. film.   An infrared shielding optical member comprising: a base material; and the infrared shielding film according to claim 8 formed on the surface of the base material.

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