JP6171733B2 - Heat ray shielding dispersion forming coating solution and heat ray shielding body - Google Patents

Description

  The present invention relates to a heat ray shielding dispersion, a coating solution for forming a heat ray shielding dispersion, and a heat ray shielding body using a near infrared shielding material that transmits light in the visible light region and absorbs light in the near infrared region.

Sun rays are broadly divided into three types: heat rays (near infrared light), visible light, and ultraviolet light. The heat ray is a wavelength region that is perceived by the human body as heat energy, and causes a rise in indoor temperature in summer. In addition, it has been pointed out that the ultraviolet light region adversely affects the human body, such as sunburn and skin cancer.
In recent years, it may be required to impart heat retention and heat insulation performance to a transparent substrate by shielding near infrared rays as heat rays. For this reason, it may be requested | required to provide near-infrared absorptivity to transparent base materials, such as glass, a polycarbonate resin, and an acrylic resin.

  For example, in Patent Document 1, on a transparent glass substrate, at least one selected from the group consisting of IIIa group, IVa group, Vb group, VIb group and VIIb group of the periodic table as the first layer from the substrate side. A composite tungsten oxide film containing metal ions is provided, a transparent dielectric film is provided as a second layer on the first layer, and a group IIIa of the periodic table is provided as a third layer on the second transparent dielectric film, A composite tungsten oxide film containing at least one metal ion selected from the group consisting of IVa group, Vb group, VIb group and VIIb group is provided, and the refractive index of the transparent dielectric film constituting the second layer Is made lower than the refractive index of the composite tungsten oxide film of the first layer and the third layer, and a heat ray-shielding glass that can be suitably used for a portion requiring high visible light transmittance and good heat ray shielding performance is proposed. ing.

  Further, 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 the second layer is oxidized on the first layer. There has been proposed a heat ray shielding glass in which a tungsten film is provided and the same dielectric film as the first layer is provided as a third layer on the second layer.

  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 the transparent substrate by the same method as Patent Document 1, and the first layer is formed on the first layer. Heat ray blocking glass having a transparent dielectric film as two layers has been proposed.

Further, in Patent Document 4, tungsten trioxide (WO ₃ ), molybdenum trioxide (MoO ₃ ), niobium pentoxide (Nb ₂ O ₅ ), and tantalum pentoxide containing additional elements such as hydrogen, lithium, sodium, and potassium. Coating a glass sheet with 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 ) by CVD or spraying; and A solar control glass sheet having solar light shielding properties formed by thermal decomposition at about 250 ° C. has been proposed.

  Patent Document 5 proposes a sunlight-modulable light heat insulating material using tungsten oxide obtained by hydrolyzing tungstic acid and adding an organic polymer having a specific structure called polyvinylpyrrolidone to the tungsten oxide. .

  In Patent Document 6, tungsten trichloride or its solvent is obtained by dissolving tungsten hexachloride in alcohol and evaporating the solvent as it is, or evaporating the solvent after heating to reflux, and then heating at 100 ° C. to 500 ° C. It is noted that a powder consisting of a hydrate or a mixture of both is obtained. It has been proposed that an electrochromic element is obtained using the tungsten oxide fine particles, and that the optical characteristics of the film are changed when protons are introduced into the film by forming a multilayer stack.

Further, in Patent Document 7, meta-type ammonium tungstate and various water-soluble metal salts are used as raw materials, and heated to about 300 to 700 ° C., the inert gas (addition amount; about By supplying hydrogen gas to which 50 vol% or more or water vapor (added amount; about 15 vol% or less) is added, M _x WO ₃ (M: metal element such as alkali, group Ia, group IIa, rare earth, 0 < Methods for preparing various tungsten bronzes denoted by x <1) have been proposed.

  Further, Patent Document 8 discloses a near-infrared shielding material fine particle dispersion in which near-infrared shielding material fine particles composed of tungsten oxide fine particles and / or composite tungsten oxide fine particles are dispersed in a medium such as a resin or glass. A near-infrared shielding body produced from a dispersion, a method for producing the above-mentioned near-infrared shielding material fine particles, and near-infrared shielding material fine particles have been proposed.

  Patent Document 9 discloses an infrared shielding material fine particle dispersant in which composite tungsten oxide fine particles are dispersed in a resin component such as an ultraviolet curable resin or a medium such as a metal alkoxide, an infrared shielding film using the same, and a plasma display. Describes infrared absorption filters. For the purpose of preventing deterioration of optical characteristics of the infrared shielding film over time, it has been proposed to add a metal salt.

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 Japanese Patent No. 4096205 JP 2009-197146 A

However, according to the study by the present inventors, the near-infrared shielding bodies (heat ray shielding glass) described in Patent Documents 1 to 3 are mainly sputtering, vapor deposition, ion plating, and chemical vapor deposition (CVD). ) And the like using a dry method by a vacuum film formation method. For this reason, there is a problem that a large manufacturing apparatus is required for film formation, and the manufacturing cost increases.
Moreover, since it manufactures with the said vacuum film-forming method, the base material of a near-infrared shield is exposed to a high temperature plasma, or a heating is needed after film-forming. For this reason, in the case of using a resin such as a film as a base material instead of glass, it is necessary to separately examine the film forming conditions on equipment.

  The near-infrared shielding body (solar control glass sheet) described in Patent Document 4 forms a metal oxide film as a raw material on glass by a CVD method or a combination of a spray method and a thermal decomposition method. However, since the raw material to be a precursor of the metal oxide is expensive, the metal oxide is decomposed at a high temperature, etc., when using a resin such as a film instead of a glass sheet, separately, It was necessary to examine the film formation conditions.

  Further, the sunlight-modulable light insulating material described in Patent Document 5 and the electrochromic element described in Patent Document 6 are materials that change their color tone by ultraviolet rays or a potential difference, and have a complicated film structure. For this reason, there is a problem that it is difficult to apply to application fields where a change in color tone is not desired.

  Patent Document 7 describes a method for preparing tungsten bronze. However, there is no description of the particle diameter and optical characteristics of the obtained powder. This is because in Patent Document 7, electrode materials for electrolytic devices and fuel cells and catalyst materials for organic synthesis are considered as applications of tungsten bronze. That is, it is not considered to apply tungsten bronze to the above-mentioned near-infrared shield.

On the other hand, since the tungsten oxide fine particles and / or the composite tungsten oxide fine particles described in Patent Document 8 have excellent visible light transmittance and a good near-infrared shielding effect, they are used as a medium such as a resin or glass. A near-infrared shielding material fine particle dispersion dispersed in a near-infrared shielding body produced from this dispersion is promising as a near-infrared shielding body suitably used in the fields of various buildings and vehicle window materials. It is.
However, according to the study by the present inventors, there is room for improvement in the near-infrared shielding material fine particle dispersion, the film strength and the wet heat resistance of the near-infrared shielding body produced from this dispersion.

Patent Document 9 describes that by adding a metal salt to an infrared shielding material fine particle dispersant, it is possible to prevent deterioration of optical characteristics of the infrared shielding film over time.
However, in Patent Document 9, since a resin component such as an ultraviolet curable resin or a metal alkoxide is used as a medium, the film strength of the infrared shielding film is low, and it is difficult to apply to applications other than applications such as an infrared absorption filter for plasma displays. Met.

  The present invention has been made paying attention to such problems, and the problem is that it has the ability to absorb near infrared rays from sunlight, has high film strength, and high heat and humidity resistance. The object of the present invention is to provide a heat ray shielding dispersion, a coating liquid for forming the heat ray shielding dispersion, and a heat ray shielding body using the heat ray shielding dispersion.

  As a result of studies conducted by the present inventors in order to achieve the above object, composite tungsten oxide fine particles as a near infrared absorbing material, silane compound, silicate, polyphosphate, silica alumina, titania, cerium oxide , Zirconia, and the like containing any one or more binders, and further containing one or more salts selected from 2-ethylhexanoate and naphthenate to the heat ray shielding dispersion containing, It was found that a heat ray shielding dispersion having a maximum transmittance in the visible light region and strong absorption in the near infrared region and having high film strength and heat-and-moisture resistance can be obtained. The present invention has been completed based on the technical knowledge.

That is, the first invention according to the present invention is:
It is represented by the general formula M _Y WO _Z (0.1 ≦ Y ≦ 0.5, 2.2 ≦ Z ≦ 3.0), and the M element is one or more selected from Cs, Rb, and K. And composite tungsten oxide fine particles having a hexagonal crystal structure;
One or more salts selected from tin 2-ethylhexanoate, barium 2-ethylhexanoate, magnesium naphthenate, and
The weight of the metal contained in one or more kinds of salts selected from tin 2-ethylhexanoate, barium 2-ethylhexanoate, and magnesium naphthenate is 1% by mass with respect to the weight of the composite tungsten oxide fine particles. This is a coating solution for forming a heat ray shielding dispersion, which is 6% by mass or less.
The second invention is
The composite tungsten oxide fine particles are fine particles having an average particle diameter of 40 nm or less. The coating liquid for forming a heat ray shielding dispersion according to the first invention .
The third invention is
The heat ray shielding dispersion forming coating solution according to the first or second invention, further comprising any one or more of a silane compound, a silicate, a polyphosphate, silica alumina, titania, cerium oxide, and zirconia A heat ray shielding dispersion-forming coating solution, comprising a binder containing
The fourth invention is:
The coating solution for forming a heat ray shielding dispersion according to the third invention, wherein the silane compound is a silica binder containing one or more of organosilane, alkoxysilane, organoalkoxysilane, and tetraalkoxysilane. It is.
The fifth invention is:
A heat ray shielding body in which a heat ray shielding dispersion which is a coating film of the coating solution for forming a heat ray shielding dispersion according to the third or fourth invention is formed on one side or both sides of a transparent substrate. is there.
The sixth invention is:
A heat ray shielding dispersion which is a coating film of the coating solution for forming a heat ray shielding dispersion according to the first or second invention is formed on one side or both sides of the transparent substrate,
A heat ray shielding, wherein a binder film containing at least one of silane compound, silicate, polyphosphate, silica alumina, titania, cerium oxide, and zirconia is formed on the heat ray shielding dispersion. Is the body.
The seventh invention
The heat-ray shielding body according to the sixth aspect, wherein the silane compound is a silica binder containing one or more of organosilane, alkoxysilane, organoalkoxysilane, and tetraalkoxysilane.
The eighth invention
The change in visible light transmittance when exposed to an environment of 85 ° C. and 90% RH for 7 days is 3.5% or less, according to any one of the fifth to seventh inventions It is a shield.

  The heat-ray shielding dispersion and heat-ray shielding body according to the present invention have high film strength and heat-and-moisture resistance, and even after being exposed to a high-temperature and high-humidity environment, a decrease in near-infrared absorption function was suppressed.

The present invention is represented by the general formula M _Y WO _Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0), and the M element is selected from Cs, Rb, K, and Tl. The heat ray shielding material fine particles, which are one or more kinds of composite tungsten oxide fine particles having a hexagonal crystal structure, are silane compound, silicate, polyphosphate, silica alumina, titania, cerium oxide, zirconia, A heat-ray shielding dispersion dispersed in a binder containing any one or more of the above, a coating solution for forming the heat-ray shielding dispersion, and a heat ray provided with the heat-ray shielding dispersion on one side or both sides of a predetermined substrate It is a shield.
The heat ray shielding dispersion according to the present invention, and the heat ray shield provided with the heat ray shielding dispersion on one or both sides of a predetermined substrate, have high film strength and moisture and heat resistance, and are exposed to a high temperature and high humidity environment. Even after this, a decrease in the near-infrared absorption function is suppressed.

  In the present invention, the heat and moisture resistance means that when the heat ray shielding dispersion or heat ray shield is exposed to a high temperature and high humidity environment of, for example, 85 ° C. and 90% RH, the visible light transmittance is lower than before the exposure. In other words, the deterioration of optical properties such as an increase in solar transmittance is suppressed. That is, it means that the heat ray shielding dispersion and heat ray shield according to the present invention have durability in a high temperature and high humidity environment.

  Hereinafter, regarding the present invention, (1) composite tungsten oxide fine particles, (2) binder, (3) 2-ethylhexanoate, naphthenate, (4) method for producing composite tungsten oxide fine particle dispersion, (5 ) Heat ray shielding dispersion forming coating solution and its manufacturing method, (6) Heat ray shielding dispersion and its formation, (7) Heat ray shielding body and its formation, and (8) Summary.

(1) Composite tungsten oxide fine particles In general, it is known that a substance containing free electrons exhibits a reflection / absorption response to electromagnetic waves in the vicinity of a solar ray region having a wavelength of 200 nm to 2600 nm by plasma oscillation. When the powder of such a substance is a fine particle smaller than the wavelength of light, geometric scattering in the visible light region (wavelength 380 nm to 780 nm) is reduced, and transparency in the visible light region is obtained.

Here, generally because there is no effective free electrons in WO _3, WO ₃ is less absorption reflection characteristics in the near infrared region, is not effective as a near-infrared-absorbing material. On the other hand, tungsten trioxide having oxygen vacancies or so-called tungsten bronze obtained by adding a positive element such as Na to tungsten trioxide is a conductive material and a material having free electrons. The results of analyzing single crystals of these substances suggest the response of free electrons to light in the infrared region.
The present inventors have found that the tungsten trioxide or tungsten bronze having oxygen deficiency is particularly effective as a near-infrared absorbing material when the composition range of tungsten and oxygen is in a specific range.

The fine particles having a near-infrared absorbing function applied to the present invention are represented by a general formula M _Y WO _Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0), and are hexagonal crystals. It is a composite tungsten oxide fine particle having a crystal structure. The composite tungsten oxide fine particles function effectively as a heat ray absorbing component when applied to a heat ray shielding dispersion or a heat ray shielding body.
As the composite tungsten oxide fine particles represented by the general formula M _Y WO _Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0) and having a hexagonal crystal structure, for example, M Examples thereof include composite tungsten oxide fine particles in which the element contains one or more of Cs, Rb, K, and Tl. The amount of additive element M added is preferably 0.1 or more and 0.5 or less, and more preferably around 0.33. This is because the value theoretically calculated from the hexagonal crystal structure is 0.33, and preferable optical characteristics can be obtained with the addition amount before and after this. Typical examples include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Tl _0.33 WO _{3 and the} like. If it falls within the range, useful heat ray absorption characteristics can be obtained.

  Furthermore, considering the design properties of the heat ray shielding dispersion and heat ray shield, it is required to efficiently shield the near infrared region while maintaining the transparency of the visible light region. On the other hand, the near-infrared absorbing material containing the composite tungsten oxide fine particles according to the present invention greatly absorbs light in the near-infrared region, particularly in the wavelength range from 900 nm to 2200 nm, so that the transmitted color tone is from blue to green. There are many.

In addition, when the dispersed particle diameter of the composite tungsten oxide fine particles is smaller than 800 nm, visible light is not blocked, so that it is possible to efficiently shield near infrared rays while maintaining transparency in the visible light region. However, when emphasizing transparency in the visible light region, the dispersed particle size is preferably 200 nm or less, and more preferably 100 nm or less.
This is because when the dispersed particle size of the fine particles is small, light in the visible light region having a wavelength of 400 nm to 780 nm is scattered by geometric scattering or diffraction scattering to become like frosted glass, and sufficient transparency cannot be obtained. This is because it can be avoided. Furthermore, when the dispersed particle diameter is 200 nm or less, the above-mentioned scattering is reduced and a Mie scattering or Rayleigh scattering region is obtained. In particular, when the dispersed particle diameter decreases to 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 decreases. Furthermore, when the dispersed particle diameter is 100 nm or less, the scattered light is preferably extremely small. From the viewpoint of avoiding the light scattering, it is preferable that the dispersed particle diameter is small. On the other hand, if the dispersed particle diameter is 1 nm or more, industrial production is easy.

  In addition, the composite tungsten oxide fine particles have a very high heat-absorbing ability per unit weight, which is about 4 to 10 times less than ITO (indium tin oxide) or ATO (antimony tin oxide). To demonstrate its effect.

(2) Binder As the binder according to the present invention, a binder containing any one or more of silane compounds, silicates, polyphosphates, silica alumina, titania, cerium oxide, zirconia, and the like can be used.
Among them, the silane compound includes a compound having a structure in which metal elements or silicon are bonded to each other through oxygen. A structure in which metal elements or silicon are bonded to each other via oxygen is preferable because a heat ray shielding dispersion and a heat ray shielding member having high film strength can be obtained.
Further, the silane compound is a silica binder containing one or more selected from organosilane, alkoxysilane, organoalkoxysilane, tetraalkoxysilane, and the like. As a preferred silica binder, a silica binder containing an organosilane can be mentioned. This is because organosilane has a siloxane bond and excellent strength, and also has an organic group such as a methyl group at the terminal group, and therefore has excellent water resistance.

(3) 2-ethylhexanoate and naphthenate In the present invention, 2-ethylhexanoate and naphthenate used together with the composite tungsten oxide fine particles and the binder are a heat ray shielding dispersion and a heat ray shield. It is added for the purpose of improving the heat-and-moisture resistance. It is because the change in optical characteristics when used for a long period of time can be suppressed by improving the heat and heat resistance of the heat ray shielding dispersion and the heat ray shielding body.

The detailed reason why the addition of 2-ethylhexanoate or naphthenate improves the heat and heat resistance of the heat ray shielding dispersion or heat ray shield according to the present invention is not clear. However, the binder containing any one or more of the aforementioned silane compounds, silicates, polyphosphates, silica aluminas, titania, cerium oxide, zirconia, etc. reacts with 2-ethylhexanoate or naphthenate. It is speculated that the effect of wet heat on the heat shield is reduced by densifying the binder film.
Furthermore, in the kind of 2-ethylhexanoate or naphthenate metal added, for example, naphthenic acid magnesium salt is particularly excellent in wet heat resistance. Further, tin 2-ethylhexanoate and barium 2-ethylhexanoate are particularly preferable because of their excellent heat and moisture resistance.

(4) Manufacturing method of composite tungsten oxide fine particle dispersion (i) Dispersion of composite tungsten oxide fine particles The composite tungsten oxide fine particle dispersion according to the present invention is obtained by the following method.
First, composite tungsten oxide fine particles, a solvent, and a dispersing agent are mixed and a dispersion treatment is performed. The dispersion treatment method is not particularly limited as long as the composite tungsten oxide fine particles have a desired dispersed particle size. The dispersion treatment is performed until the dispersed particle diameter of the composite tungsten oxide fine particles becomes 200 nm or less. More preferably, the dispersed particle diameter of the composite tungsten oxide fine particles is 100 nm or less.
This is because the transparency of the finally obtained heat ray shielding dispersion or heat ray shielding body is improved as the dispersed particle size of the composite tungsten oxide fine particles is smaller.

  The dispersant used for the production of the composite tungsten oxide fine particle dispersion is not particularly limited as long as the effect of improving the dispersibility of the composite tungsten oxide fine particles can be obtained.

  The solvent used in the production of the composite tungsten oxide fine particle dispersion is not particularly limited as long as the composite tungsten oxide fine particles can be dispersed. For example, water, ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol, diacetone alcohol and other alcohols, ethers such as methyl ether, ethyl ether, propyl ether, esters, acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, methyl Various organic solvents such as ketones such as isobutyl ketone can also be used.

(Ii) Addition of 2-ethylhexanoate and naphthenate The composite tungsten oxide fine particles are mixed with 2-ethylhexanoate and / or naphthenate as described above. After the dispersion treatment is performed to obtain a dispersion, 2-ethylhexanoate and / or naphthenate may be added to the composite tungsten oxide fine particle dispersion.
Alternatively, the composite tungsten oxide fine particles and 2-ethylhexanoate and / or naphthenate may be mixed in advance, and the mixture may be subjected to the dispersion treatment described above to obtain a dispersion.

(Iii) Mixing ratio of 2-ethylhexanoate and naphthenate The mixing ratio of the composite tungsten oxide fine particles and the mixture of 2-ethylhexanoate and / or naphthenate will be described.
When the weight of the metal element contained in 2-ethylhexanoate or naphthenate is W _M , W _M / weight of the composite tungsten oxide fine particles = 1 mass% to the weight of the composite tungsten oxide fine particles The range is preferably 6% by mass, and more preferably 2% by mass to 6% by mass.
If the addition amount of 2-ethylhexanoate and / or naphthenate with respect to the weight of the composite tungsten oxide fine particles is in the above range, the composite tungsten oxide fine particles when combined with the binder according to the present invention described above are used. This is because it has an effect of improving the heat and moisture resistance and does not adversely affect the mechanical properties and optical properties such as film strength in the produced heat ray shielding dispersion and heat ray shield.

  If necessary, the pH value may be adjusted by adding acid or alkali to a mixture of the composite tungsten oxide fine particles and 2-ethylhexanoate and / or naphthenate. Furthermore, in order to further improve the dispersion stability of the composite tungsten oxide fine particles in the composite tungsten oxide fine particle dispersion, various surfactants, coupling agents and the like can be added.

(5) Coating solution for forming a heat ray shielding dispersion and its production method The composite tungsten oxide fine particle dispersion produced by the above-mentioned method is mixed with the above-mentioned binder, and diluted with a solvent as necessary. Is obtained.
Here, the mixing amount of the binder described above in the coating solution for forming a heat ray shielding dispersion is preferably 5% by mass or more. If the amount of the binder is 5% by mass or more, it is easy to form a heat ray shielding dispersion having a high heat ray shielding effect.

  Moreover, it is good also as a coating liquid for heat ray shielding dispersion formation by not adding the said binder to composite tungsten oxide fine particle dispersion, but diluting with a solvent suitably. In this case, after forming the heat ray shielding dispersion using the heat ray shielding dispersion forming coating solution, a coating solution containing the binder may be applied, and the heat ray shielding dispersion may be impregnated with the binder.

About the density | concentration of the coating liquid for heat ray shielding dispersion formation, an optimal density | concentration can be suitably selected according to the coating method.
Solvents used for appropriately diluting the coating solution for forming a heat ray shielding dispersion include, for example, alcohols such as ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol, diacetone alcohol, methyl ether, ethyl ether, propyl Various organic solvents such as ethers such as ether, esters, acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, and methyl isobutyl ketone, and water can be used.

If necessary, the pH value may be adjusted by adding an acid or alkali to the solvent.
Furthermore, in order to further improve the dispersion stability of the composite tungsten oxide fine particles, various surfactants, coupling agents and the like can be added.
Furthermore, various pigments and dyes may be added to adjust the color tone of the composite tungsten oxide fine particle dispersion.

(6) Method for forming heat ray shielding dispersion A method for forming a heat ray shielding dispersion using a coating solution for forming a heat ray shielding dispersion will be described.
The coating solution for forming a heat ray shielding dispersion produced by the above-described method is applied on an appropriate transparent substrate, the dispersion medium is evaporated, and heat-cured. Thereby, a heat ray shielding dispersion containing composite tungsten oxide fine particles, a binder, and 2-ethylhexanoate and / or naphthenate is obtained.

(7) Heat ray shielding body and formation thereof A heat ray shielding body can be produced by forming a heat ray shielding dispersion on an appropriate transparent substrate surface.
There is no particular limitation on the method for applying the coating solution for forming the heat ray shielding dispersion on the surface of the appropriate transparent substrate as long as it can be uniformly applied. For example, the bar coating method, gravure coating method, spray coating method, dip coating method, flow A coating method, a spin coating method, a roll coating method, a screen printing method, a blade coating method, or the like can be used.
The layer of the heat ray shielding dispersion containing the composite tungsten oxide fine particles formed by these coating methods is a dry method such as sputtering method, vapor deposition method, ion plating method and chemical vapor deposition method (CVD method), Compared with a layer (film) manufactured by the spray method, light in the near-infrared region is efficiently absorbed particularly without using the light interference effect. At the same time, the layer can transmit light in the visible light region.

It is preferable to heat at 100 ° C. or more and less than 200 ° C. after applying the heat ray shielding dispersion-forming coating solution onto an appropriate transparent substrate surface. By setting the transparent substrate heating temperature to 100 ° C. or higher, the polymerization reaction of the binder according to the present invention contained in the heat ray shielding dispersion can be almost completed. By almost completing the polymerization reaction, it is possible to avoid the cause of reduction in visible light transmittance due to the remaining water or organic solvent in the heat ray shielding dispersion. From this viewpoint, the more preferable heating temperature is 150 ° C. or higher.
Moreover, the base-material heating temperature shall be less than 200 degreeC, and the oxidation of composite tungsten oxide microparticles | fine-particles can be avoided and the loss of heat ray shielding ability can be avoided.

The heat ray shielding body and heat ray shielding dispersion produced by the above-described method have high film strength and excellent moisture and heat resistance.
Specifically, the surface hardness of the heat ray shielding dispersion according to the present invention was evaluated by 4.4 scratch strength (pencil method) of the JIS K 5600 paint general test method. The surface hardness of the heat ray shield was 2H or higher, and further 4H or higher.
And even if the heat ray shielding body and heat ray shielding dispersion manufactured by the above-mentioned method are exposed to a high-temperature and high-humidity environment (for example, 85 ° C., 90% RH), the near-infrared absorption function is reduced. It was suppressed.
Specifically, when exposed to an environment of 85 ° C. and 90% RH for 7 days, the change in visible light transmittance is 3.5% or less, and further 2.5% or less. Further, the change in solar radiation transmittance was 3.5% or less, and further 3.0% or less.

  Furthermore, in the heat ray shielding dispersion film according to the present invention obtained by the above method, since the composite tungsten oxide fine particles are conductive materials, when the fine particles are connected to form a continuous film, There is a risk of interference by absorbing and reflecting radio waves from mobile phones. However, when the composite tungsten oxide fine particles are dispersed using, for example, a bead mill and dispersed in the matrix as fine particles, each particle is dispersed in an isolated state, so that radio wave transmission is exhibited. And can be versatile.

As a transparent base material used for a heat ray shield, a film, a resin substrate, a glass substrate, etc. are mentioned, for example. However, when using these materials as a base material, it is calculated | required to have mechanical strength according to each use condition.
In the case of a resin substrate or film, generally, a colorless and transparent resin having transparency and low scattering is suitable, and a resin suitable for the application may be selected. Specifically, polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, ethylene vinyl acetate copolymer, polyester resin, polyethylene terephthalate (PET) resin, fluorine resin, polycarbonate resin , Acrylic resin, polyvinyl butyral resin, etc., among which polyethylene terephthalate resin is preferred.

  Moreover, when using these resin substrates or films, the surface thereof may be subjected to a surface treatment for the purpose of improving the binding property with an inorganic binder, and a typical treatment method thereof is corona surface treatment, Examples thereof include discharge treatment such as plasma treatment and sputtering treatment, flame treatment, metal sodium treatment, primer layer coating treatment and the like.

When emphasizing the design properties of the resin substrate or film, a pre-colored base material or a shaped base material can be used.
In order to attach the dispersion formed on the resin substrate or the film to a base material such as glass, an adhesive layer and a release film layer may be laminated on the adhesive surface. A film that is easily softened by heat, such as a dryer, may be used so that it can be easily attached to a curved surface like a back window of an automobile.
If an ultraviolet shielding agent is added to the adhesive, it is possible to prevent ultraviolet degradation of the film or resin. Examples of the ultraviolet absorber include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, CeO ₂ , TiO ₂ , and ZnO.

  When the coating solution for forming the heat ray shielding dispersion does not contain the binder according to the present invention, the film of the heat ray shielding dispersion obtained on the transparent substrate is composed of the composite tungsten oxide fine particles and 2-ethylhexanoate. And / or a film structure in which only naphthenate is deposited. In this case, a coating liquid containing the binder according to the present invention is further applied onto the film to form a multilayer film. By adopting this configuration, the binder component according to the present invention is formed by filling the gap in which the fine particles of tungsten oxide in the first layer are deposited, so that the haze of the film is reduced and the visible light transmittance is improved. In addition, the binding property of the fine particles to the base material is improved.

(8) Summary As described above, according to the present invention, the composite tungsten oxide fine particles and the binder according to the present invention contain 2-ethylhexanoate and / or naphthenate, It has the ability to absorb near infrared rays from sunlight, has high film strength, high heat-and-moisture resistance, and can be manufactured by a simple method and can provide a low-cost heat-ray shielding dispersion and heat-ray shielding body. did.
The heat ray shielding dispersion and the heat ray shield of the present invention are used for indoor displays such as automotive glass, side glass and rear glass, railway vehicle door glass and window glass, indoor door glass, window glass and indoor door glass in buildings, etc. It can be used for various applications such as a showcase and a show window.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
In this example, the visible light transmittance and the solar radiation transmittance were calculated according to JIS R 3106 by measuring the transmittance of light having a wavelength of 200 to 2500 nm using a spectrophotometer manufactured by Hitachi, Ltd. The solar radiation transmittance is an index indicating the heat ray shielding performance of the heat ray shielding dispersion and the heat ray shielding member.
The dispersed particle size of the fine particles was measured using a Nikkiso Microtrac particle size distribution meter. The average particle size of the dust particles was D50.
Evaluation of the heat and heat resistance of the change in optical properties of the heat ray shield is performed by exposing the test sample (heat ray shield) to a constant temperature and humidity chamber set at 85 ° C. and 90% RH for 7 days, before and after the accelerated heat and heat resistance test. This was done by measuring changes in visible light transmittance and solar transmittance.
Evaluation of the surface hardness in a heat ray shield evaluated the test sample (heat ray shield) according to 4.4 scratch strength (pencil method) of a JIS K5600 paint general test method.

Example 1
Cs _0.33 WO ₃ 20% by mass of fine particles, 70% by mass of 4-methyl-2-pentanone as a dispersion medium, and 10% by mass of a dispersing agent for fine particle dispersion are mixed and dispersed with a medium stirring mill, and the average dispersed particle size A dispersion of 80 nm Cs _0.33 WO ₃ fine particles was produced (hereinafter sometimes referred to as “liquid A”).
Similarly, commercially available tin 2-ethylhexanoate (liquid) was prepared (hereinafter may be referred to as “liquid B”).
And the liquids A and B were mixed so that the _{Cs 0.33} WO ₃ wt = 1 mass% of Sn by weight / A solution of B solution. A silica binder having a solid content of 25% was mixed with the mixture so that the solid content of the silica binder was 292.5 parts by weight with respect to 100 parts by weight of the composite tungsten oxide fine particles.

This coating solution was applied and formed on a substrate (inorganic glass) using a bar coater (No. 20). This film was dried at 180 ° C. for 30 minutes, and the dispersion medium was evaporated and cured to produce a heat ray shield. Table 1 shows the optical characteristics and scratch strength (pencil method) of the manufactured heat ray shield.
The manufactured heat ray shield was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and heat resistance test were measured. And the change of the visible light transmittance before and behind the said accelerated test of the heat-and-moisture resistance was computed. The results are shown in Table 1.

(Example 2)
Example 2 was the same as Example 1 except that A liquid and B liquid were mixed such that Sn weight in B liquid / Cs _0.33 WO ₃ weight in A liquid = 2 wt%. The heat ray shielding body which concerns on was manufactured. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield according to Example 2 was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and moisture resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.

(Example 3)
Example 3 was carried out in the same manner as Example 1 except that A liquid and B liquid were mixed so that Sn weight in B liquid / Cs _0.33 WO ₃ weight in A liquid = 6% by mass. The heat ray shielding body which concerns on was manufactured. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield according to Example 3 was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar radiation transmittance after the accelerated heat and heat resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.

Example 4
Using commercially available barium 2-ethylhexanoate (liquid) (hereinafter sometimes referred to as “C liquid”), this A liquid and C liquid are expressed as Ba weight in C liquid / Cs _{0 in} A liquid. _.33 WO ₃ weight = 1 Heat ray shielding resistance according to Example 4 was produced in the same manner as in Example 1 except that mixing was performed so that 1% by mass. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield according to Example 4 was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and humidity resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.

(Example 5)
In the same manner as in Example 3, except that A liquid and C liquid were mixed so that Ba weight in C liquid / Cs _0.33 WO ₃ weight in A liquid = 2 wt%. Such heat ray shielding resistance was manufactured. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield according to Example 5 was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and moisture resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.

(Example 6)
In the same manner as in Example 3, except that A liquid and C liquid were mixed so that Ba weight in C liquid / Cs _0.33 WO in A liquid was ₃ wt% = 6% by mass. Such heat ray shielding resistance was manufactured. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield according to Example 6 was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and moisture resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.

(Example 7)
Using commercially available magnesium naphthenate (liquid) (hereinafter sometimes referred to as “liquid D”), liquid A and liquid D are divided into Mg weight in liquid D / Cs _{0.33 in} liquid A WO ₃ The heat ray shielding resistance according to Example 7 was manufactured in the same manner as in Example 1 except that mixing was performed so that the weight = 1% by mass. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield according to Example 7 was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar radiation transmittance after the accelerated heat and heat resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.

(Example 8)
In the same manner as in Example 3, except that the A liquid and the D liquid were mixed so that the Mg weight in the D liquid / Cs _0.33 WO in the A liquid was ₃ wt% = 2 mass%. Such heat ray shielding resistance was manufactured. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield according to Example 8 was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar radiation transmittance after the accelerated heat and heat resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.

Example 9
In the same manner as in Example 3, except that A liquid and D liquid were mixed so that Mg weight in D liquid / Cs _0.33 WO ₃ weight in A liquid was 6 mass%. Such heat ray shielding resistance was manufactured. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield according to Example 9 was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and moisture resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.

(Comparative Example 1)
A heat ray shield according to Comparative Example 1 was produced in the same manner as in Example 1 except that the liquid B was not mixed. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield according to Comparative Example 1 was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar radiation transmittance after the accelerated heat and heat resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.

(Comparative Example 2)
Commercially available manganese 2-ethylhexanoate (liquid) (hereinafter sometimes referred to as “E liquid”) is prepared, and A liquid and E liquid are combined with Mn weight in E liquid / Cs _{0 in} A liquid. _.33 WO ₃ weight = 2 A heat ray shielding body was produced in the same manner as in Example 1 except that mixing was performed so that 2% by mass. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and heat resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.

(Comparative Example 3)
Commercially available indium 2-ethylhexanoate (liquid) (hereinafter sometimes referred to as “F liquid”) is prepared, and A liquid and F liquid are combined with In weight in F liquid / Cs _{0 in} A liquid. _.33 WO ₃ weight = 2 A heat ray shielding body was produced in the same manner as in Example 1 except that mixing was performed so that 2% by mass. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and heat resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.

(Comparative Example 4)
Except that A liquid and B liquid were mixed and mixed so that Sn weight in B liquid / Cs _0.33 WO ₃ weight in A liquid = 0.5% by mass = 0.5% by mass. A heat shield was produced. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and heat resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.

(Comparative Example 5)
When A liquid and B liquid were mixed such that Sn weight in B liquid / Cs _0.33 WO ₃ weight in A liquid = 10% by mass, the coating liquid gelled and a coating film could not be prepared. .

(Comparative Example 6)
Except that A liquid and C liquid were mixed and mixed so that Ba weight in C liquid / Cs _0.33 WO ₃ weight in A liquid = 0.5 mass%, and the same as in Example 1. A heat shield was produced. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and heat resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.

(Comparative Example 7)
Production of heat ray shield as in Example 1 except that A liquid and C liquid were mixed such that Ba weight in C liquid / Cs _0.33 WO in A liquid was ₃ wt% = 10 mass%. Tried. However, the coating solution gelled and a coating film could not be produced.

(Comparative Example 8)
Except that A liquid and D liquid were mixed and mixed so that Mg weight in D liquid / Cs _0.33 WO ₃ weight in A liquid = 0.5 mass%, and the same as in Example 1. A heat shield was produced. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and heat resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.

(Comparative Example 9)
When the A liquid and the D liquid were mixed so that the Mg weight in the D liquid / Cs _0.33 WO in the A liquid was ₃ weight = 10% by mass, the coating liquid gelled and a coating film could not be prepared. .

(Comparative Example 10)
A heat ray shielding body was produced in the same manner as in Example 1 except that neither A liquid nor B liquid was mixed and an organic resin binder containing 100% acrylic resin as a solid content was used instead of the silica binder. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and heat resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.

[Evaluation]
In Examples 1-9, the heat ray shielding body which has high visible light transmittance | permeability and the outstanding heat ray shielding characteristic was obtained. Moreover, the heat ray shielding body whose surface hardness is 6H was obtained by using the binder which concerns on this invention. In addition, the addition of octylate and / or naphthenate suppresses the deterioration of composite tungsten oxide fine particles exposed to high temperature and high humidity conditions with time, and provides high heat and heat resistance with little change in optical properties. The heat ray shield which has was obtained. The said heat ray shielding body is a heat ray shielding body which can be used conveniently, for example in severe use conditions like the outdoors.

In Comparative Example 1, the change in visible light transmittance was large in the wet heat resistance test. This is probably because 2-ethylhexanoate was not added.
Next, in Comparative Examples 2 and 3, in the wet heat resistance test, changes in visible light transmittance and solar light transmittance could not be sufficiently suppressed. Although 2-ethylhexanoic acid salt was added, it is considered that manganese salt and indium salt were used.
In Comparative Examples 4, 6, and 8, changes in visible light transmittance and solar light transmittance could not be sufficiently suppressed. This is probably because the amount of 2-ethylhexanoate or naphthenate added was too small.
In Comparative Examples 5, 7, and 9, the coating solution gelled and could not be evaluated. This is probably because the amount of 2-ethylhexanoate or naphthenate added was excessive.
Moreover, in the comparative example 10, the change of visible light transmittance and solar radiation transmittance was large, and the surface hardness was as low as H. This is probably because 2-ethylhexanoate was not added and a resin binder was used as the binder.

Claims (8)

It is represented by the general formula M _Y WO _Z (0.1 ≦ Y ≦ 0.5, 2.2 ≦ Z ≦ 3.0), and the M element is one or more selected from Cs, Rb, and K. And composite tungsten oxide fine particles having a hexagonal crystal structure;
One or more salts selected from tin 2-ethylhexanoate, barium 2-ethylhexanoate, magnesium naphthenate, and
The weight of the metal contained in one or more kinds of salts selected from tin 2-ethylhexanoate, barium 2-ethylhexanoate, and magnesium naphthenate is 1% by mass with respect to the weight of the composite tungsten oxide fine particles. The coating liquid for forming a heat ray shielding dispersion, which is 6% by mass or less . The coating liquid for forming a heat ray shielding dispersion according to claim 1, wherein the composite tungsten oxide fine particles are fine particles having an average particle size of 40 nm or less . The coating solution for forming a heat ray shielding dispersion according to claim 1 or 2, further comprising any one or more of a silane compound, a silicate, a polyphosphate, silica alumina, titania, cerium oxide, and zirconia. The coating liquid for heat ray shielding dispersion formation characterized by including a binder. The coating solution for forming a heat ray shielding dispersion according to claim 3, wherein the silane compound is a silica binder containing at least one of organosilane, alkoxysilane, organoalkoxysilane, and tetraalkoxysilane . A heat ray shielding body, wherein a heat ray shielding dispersion which is a coating film of the coating solution for forming a heat ray shielding dispersion according to claim 3 or 4 is formed on one side or both sides of a transparent substrate. A heat ray shielding dispersion which is a coating film of the coating solution for forming a heat ray shielding dispersion according to claim 1 or 2 is formed on one side or both sides of the transparent substrate,
A heat ray shielding, wherein a binder film containing at least one of silane compound, silicate, polyphosphate, silica alumina, titania, cerium oxide, and zirconia is formed on the heat ray shielding dispersion. body. 7. The heat ray shielding body according to claim 6, wherein the silane compound is a silica binder containing at least one of organosilane, alkoxysilane, organoalkoxysilane, and tetraalkoxysilane. The heat ray shield according to any one of claims 5 to 7, wherein a change in visible light transmittance when exposed to an environment of 85 ° C and 90% RH for 7 days is 3.5% or less. .