WO2014162619A1 - Heat-ray-shielding film, heat-ray-shielding transparent substrate, vehicle, and building - Google Patents

Abstract

Provided are: a heat-ray-shielding film which exhibits excellent heat-shielding properties while having a polyvinyl acetal resin as a main component thereof; a heat-ray-shielding transparent substrate using said heat-ray-shielding film; a vehicle in which the heat-ray-shielding transparent substrate is provided as a window material; and a building in which the heat-ray-shielding transparent substrate is used as a window material. Provided is a heat-ray-shielding film which includes: composite tungsten oxide fine particles which are represented by the general formula M_yWO_z, and which have a hexagonal crystal structure; a selective-wavelength absorbing material; a polyvinyl acetal resin; and a plasticizing agent. The selective-wavelength absorbing material is provided with a transmission profile in which the transmittance of light having a wavelength of 550 nm is at least 90%, and the transmittance of light having a wavelength of 420 nm, when the transmittance of light having a wavelength of 460 nm is at least 90%, is not more than 40%. The weight ratio (the composite tungsten oxide fine particles/the selective-wavelength absorbing material) of the composite tungsten oxide fine particles to the selective-wavelength absorbing material is in the range 100/2 to 100/800. Also provided is a heat-ray-shielding transparent substrate using said heat-ray-shielding film.

Description

Heat ray shielding film, heat ray shielding laminated transparent base material, automobile and building

The present invention relates to a heat ray shielding film having good visible light transmittance and an excellent heat ray shielding function, a heat ray shielding laminated transparent base material, an automobile on which the heat ray shielding laminated transparent base material is mounted as a window material, and the heat ray. The present invention relates to a building in which a shielding laminated transparent base material is used as a window material.

As safety glass used in window materials for automobiles or buildings, a transparent base material is used in which a laminated glass is formed by sandwiching an intermediate layer containing polyvinyl acetal resin or the like between a plurality of (for example, two) opposing glass plates. ing. Furthermore, a transparent base material has been proposed for the purpose of reducing the cooling load and the heat of human heat by blocking incident solar energy by providing the intermediate layer with a heat ray shielding function.

For example, Patent Document 1 discloses a laminated glass in which a soft resin layer containing a heat ray shielding metal oxide made of tin oxide or indium oxide having a fine particle diameter of 0.1 μm or less is sandwiched between two opposing plate glasses. Is disclosed.

Patent Document 2 discloses that Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, at least between two opposing glass plates. Metals such as Ta, W, V, and Mo, oxides of the metals, nitrides of the metals, sulfides of the metals, Sb and F dopants to the metals, and intermediate layers in which these composites are dispersed A laminated glass sandwiching a glass is disclosed.

In Patent Document 3, fine particles composed of TiO ₂ , ZrO ₂ , SnO ₂ , and In ₂ O ₃ and a glass component composed of organosilicon or an organosilicon compound are sandwiched between opposing transparent plate-like members. An automotive window glass is disclosed.

Furthermore, in Patent Document 4, an intermediate layer composed of three layers is provided between at least two opposing transparent glass plates, and Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, Mo metal, metal oxide, metal nitride, metal sulfide, metal A laminated glass is disclosed in which a dope of Sb or F or a composite of these is dispersed and an intermediate layer of the first layer and the third layer is used as a resin layer.

However, each of the conventional laminated glasses disclosed in Patent Documents 1 to 4 has a problem that the heat ray shielding function is not sufficient when high visible light transmittance is required.

Furthermore, as a method for improving the heat ray shielding function of laminated glass, Patent Document 5 discloses that a metal oxide semiconductor, a near infrared absorber, and an ultraviolet absorber are mixed with a transparent synthetic resin and molded on a film. An ultraviolet and infrared shield is disclosed.

On the other hand, the applicant forms an intermediate layer having a heat ray shielding function between two sheet glasses, and this intermediate layer is composed of hexaboride fine particles alone, or hexaboride fine particles and ITO fine particles and / or ATO fine particles. And a heat ray-shielding laminated glass comprising a heat ray shielding film containing vinyl resin, or a heat ray containing the fine particles formed on the surface of the intermediate layer facing the inside of at least one plate glass Patent Document 6 discloses a heat ray shielding laminated glass composed of a shielding film and a heat ray shielding film containing a vinyl resin interposed between the two plate glasses.

As described in Patent Document 6, the optical properties of laminated glass for heat ray shielding in which hexaboride fine particles alone, or hexaboride fine particles and ITO fine particles and / or ATO fine particles are applied, has a transmittance in the visible light region. In addition, it exhibits strong absorption in the near infrared region and has minimum transmittance. As a result, compared with the conventional laminated glass described in Patent Documents 1 to 4, the heat-shielding laminated glass is improved until the solar radiation transmittance when the visible light transmittance is 70% or more is in the 50% range. It was done.

Further, the present inventors disclosed, as Patent Document 7, as a heat ray shielding laminated glass in which a polyvinyl acetal resin is replaced with an ultraviolet curable resin and a heat ray shielding film in which a composite tungsten compound is contained in the ultraviolet curable resin is used as an intermediate layer. is doing.

As described in Patent Document 7, the heat-shielding laminated glass has a solar radiation transmittance when the visible light transmittance is 70% or more as compared with the conventional laminated glass described in Patent Documents 1 to 4 and Patent Document 6. It was improved until the rate was around 35%.

JP-A-8-217500 JP-A-8-259279 Japanese Patent Laid-Open No. 4-160041 Japanese Patent Laid-Open No. 10-297945 JP 2004-37768 A JP 2001-89202 A JP 2010-202495 A

However, as a result of further studies by the present inventors, the following problems have been found.
The first problem is that the laminated glass according to the prior art described in Patent Documents 1 to 5 is not sufficient in heat ray shielding function when high visible light transmittance is required as described above. is there.
Furthermore, in the market, the heat shield function will be further improved in terms of improving comfort in automobiles and buildings, improving fuel efficiency by reducing automobile air-conditioner loads, and saving energy by reducing air-conditioner loads in buildings. The demand is high. From this viewpoint, the laminated glass for heat ray shielding described in Patent Documents 6 and 7 still had room for improvement.

In order to solve the above-mentioned problems, there is also a concept of improving the heat shielding function by containing ATO fine particles, ITO fine particles, hexaboride fine particles and / or composite tungsten oxide fine particles in combination with other selective wavelength absorbing materials in the heat ray shielding film. However, there has been a problem that the absorption of visible light of the selective wavelength absorbing material changes the color of the heat ray shielding film and gives a color tone that is not suitable for being mounted on a car as a laminated glass.

The present invention has been made paying attention to the above problems. The problem to be solved is a heat ray shielding film having an excellent color tone and having an appropriate color tone with a polyvinyl acetal resin as a main component, and a heat ray shielding combined transparent using the heat ray shielding film. It is providing the base material, the motor vehicle in which the said heat ray shielding matching transparent base material is mounted as a window material, and the building in which the said heat ray shielding matching transparent base material is used as a window material.

In order to solve the above-mentioned problems, the present inventors first conducted intensive research on a method for improving the heat ray shielding characteristics while maintaining high visible light transmittance.

The present inventors paid attention to the wavelength distribution of the weight coefficient used in the visible light transmittance calculation described in JIS R 3106. Specifically, the wavelength distribution of the weight coefficient used for calculating the visible light transmittance and the solar radiation energy in the short wavelength region were studied in detail. And the knowledge that it was possible to reduce only the solar radiation transmittance | permeability was maintained, keeping visible light transmittance | permeability high by shielding the short wavelength area | region of visible light suitably.

Specifically, in order to prevent a decrease in visible light transmittance as much as possible, ultraviolet light with a wavelength of 300 nm to 380 nm is used in spite of the common sense of using a conventional ultraviolet shielding agent that cuts the visible light region as much as possible. In addition, while absorbing visible light from 380 nm to 480 nm strongly, a selective wavelength absorbing material having no absorption in the vicinity of wavelength 550 nm, which is a region that greatly contributes to the calculation of visible light transmittance, coexists with the composite tungsten oxide fine particles. I came up with a composition.

However, the coexistence of the selective wavelength absorbing material that absorbs visible light was expected to change the color of the combined transparent substrate. Therefore, the present inventors next applied the tint value calculated based on JIS Z 8701 from the spectral transmittance measurement of the laminated transparent base material, and the yellowness of the plastic calculated based on JIS K 7373 from the tint value (this Various investigations were made using “YI” in the invention as an index. As a result, as a new concept, there is no absorption in the vicinity of the wavelength 550 nm, which is a region that greatly contributes to the calculation of the visible light transmittance, and no absorption in the vicinity of the wavelength 460 nm, which has a great influence on the YI of the laminated transparent substrate, The present invention has been completed by conceiving a configuration in which a selective wavelength absorbing material having a large absorption in the vicinity of a wavelength of 420 nm coexists with the composite tungsten oxide fine particles.

That is, the first invention for solving the above-described problem is
Formula M _y WO _Z (where, M is, Cs, Rb, K, Tl , In, Ba, Li, Ca, Sr, 1 or more elements selected Fe, Sn, Al, from Cu, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) and a composite tungsten oxide fine particle having a hexagonal crystal structure, a selective wavelength absorbing material, a polyvinyl acetal resin, a plasticizer, A heat ray shielding film containing
The selective wavelength absorbing material in the first period has a transmittance of light having a wavelength of 550 nm of 90% or more, and a transmittance of light having a wavelength of 420 nm when the transmittance of light having a wavelength of 460 nm is 90% or more. Have a profile,
A heat ray shielding film characterized in that a weight ratio of the composite tungsten oxide fine particles to the selective wavelength absorbing material is in the range of (composite tungsten oxide fine particles / selective wavelength absorbing material) = 100/2 to 100/800. .
The second invention is
The composite tungsten oxide fine particle is at least one selected from Cs _0.33 WO ₃ and Rb _0.33 WO _3. The heat ray shielding film according to the first invention,
The third invention is
2. The heat ray shielding film according to the first or second invention, wherein the composite tungsten oxide fine particles are fine particles having a dispersed particle diameter of 40 nm or less.
The fourth invention is:
The selective wavelength absorbing material is at least one selected from a benzotriazole compound, a benzophenone compound, a hydroxyphenyltriazine compound, an indole compound, an azomethine compound, a benzotriazolyl compound, and a benzoyl compound. It is a heat ray shielding film in any one of 3rd invention.
The fifth invention is:
4. The heat ray shielding film according to any one of the first to third inventions, wherein the selective wavelength absorbing material is an indole compound.
The sixth invention is:
The selective wavelength absorbing material is an indole compound represented by (Chemical Formula 1), wherein R is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. A heat ray shielding film according to any one of the first to third inventions.
The seventh invention
4. The heat ray shielding according to any one of the first to third inventions, wherein the selective wavelength absorbing material is a compound in which R in the formula is a methyl group among the indole compounds represented by (Chemical Formula 1) It is a membrane.
The eighth invention
The heat ray shielding film according to any one of the first to seventh inventions, wherein the heat ray shielding film further contains an ultraviolet absorber.
The ninth invention
The heat ray shielding film according to the eighth invention, wherein the ultraviolet absorber is at least one selected from a benzotriazole compound and a benzophenone compound.
The tenth invention is
The heat ray shielding film according to the eighth or ninth invention, wherein the content of the ultraviolet absorber in the heat ray shielding film is 0.1 wt% or more and 5.0 wt% or less.
The eleventh invention is
When the transmittance of the light of wavelength 550 nm is 90% or more and the transmittance of light of wavelength 460 nm is 90% or more, the selective wavelength absorbing material in the previous period has a transmission profile of 15% or less of light of wavelength 420 nm. A heat ray shielding film according to any one of the first to tenth inventions, wherein
The twelfth invention is
The heat ray shielding film according to any one of the first to eleventh aspects, wherein the heat ray shielding film further contains an infrared absorbing organic compound.
The thirteenth invention is
The infrared absorbing organic compound is a phthalocyanine compound, naphthalocyanine compound, imonium compound, diimonium compound, polymethine compound, diphenylmethane compound, triphenylmethane compound, quinone compound, azo compound, pentadiene compound, azomethine compound, squarylium compound, organometallic complex The heat ray shielding film according to the twelfth aspect of the invention, wherein the heat ray shielding film is at least one selected from cyanine compounds.
The fourteenth invention is
The infrared ray absorbing organic compound is at least one selected from a phthalocyanine compound and a diimonium compound. The heat ray shielding film according to the twelfth aspect of the invention.
The fifteenth invention
The weight ratio of the infrared absorbing organic compound and the composite tungsten oxide fine particles is (composite tungsten oxide fine particles / infrared absorbing organic compound) = 100/5 to 100/100. To the 14th invention.
The sixteenth invention is
A heat ray shielding laminated transparent substrate, wherein the heat ray shielding film according to any one of the first to fifteenth inventions is present between a plurality of transparent substrates.
The seventeenth invention
The heat ray-shielding laminated transparent base material according to the sixteenth aspect, wherein the yellowness (YI) calculated by JIS K 7373 is -20.0 or more and 10.0 or less.
The eighteenth invention
The heat ray shielding laminated transparent base material according to the sixteenth aspect, wherein the yellowness (YI) calculated in accordance with JIS K 7373 is from -20.0 to 5.0.
The nineteenth invention
Any of the sixteenth to eighteenth inventions, wherein an infrared reflective film having a visible light transmittance of 88% or more and a solar reflectance of 21% or more is present between the plurality of transparent substrates. It is a heat ray shielding laminated transparent base material as described above.
The twentieth invention is
The heat ray shielding laminated transparent base material according to any one of the sixteenth to nineteenth aspects, wherein at least one of the transparent base materials is glass.
The twenty-first invention
The visible light transmittance calculated by JIS R 3106 is 70% or more, and the solar radiation transmittance when the visible light transmittance is 70% is 32.5% or less. The heat ray shielding laminated transparent substrate according to any one of the inventions.
The twenty-second invention relates to
A heat ray shielding laminated transparent base material according to any one of the sixteenth to twenty-first aspects of the present invention is mounted on a window material.
The twenty-third invention
A heat ray shielding laminated transparent base material according to any of the sixteenth to twenty-first aspects is a building characterized in that it is used as a window material.

According to the present invention, a composite tungsten oxide fine particle and a selective wavelength absorbing material are used in combination with a polyvinyl acetal resin as a main component, thereby exhibiting excellent optical characteristics and high weather resistance, and a natural color tone. It was possible to obtain a heat ray shielding film having And the heat ray shielding laminated transparent base material which exhibits the outstanding optical characteristic, high weather resistance, and the outstanding mechanical characteristic was able to be obtained by using the said heat ray shielding film. Furthermore, by mounting the heat ray shielding laminated transparent base material on a car as a window material, it has become possible to suppress a rise in the temperature inside the car in summer. Moreover, the said heat ray shielding matching transparent base material was used for the opening part of a building as a window material, and the building which can suppress the temperature rise in the building in summer was implement | achieved.

Hereinafter, embodiments of the present invention will be described in detail.
The heat ray shielding film according to the present invention is composed of composite tungsten oxide fine particles, a dispersant, a selective wavelength absorbing material, an infrared absorbing organic compound if necessary, a polyvinyl acetal resin, a plasticizer, an adhesive strength adjusting agent if desired, and other additions if desired. It contains things.

The heat ray shielding film according to the present invention was obtained by dispersing the composite tungsten oxide fine particles and the dispersant in a part of the plasticizer added to the polyvinyl acetal resin to obtain a composite tungsten oxide fine particle dispersion. It can be manufactured by kneading the dispersion, the selective wavelength absorbing material, the polyvinyl acetal resin, and the plasticizer, and then molding the film by a known method such as an extrusion molding method or a calendar molding method.
Moreover, the heat ray shielding film according to the present invention obtains a dispersion liquid in which the composite tungsten oxide fine particles and the dispersing agent are dispersed in a general organic solvent, and then removes the organic solvent into the solid dispersing agent. A composite tungsten oxide fine particle dispersion in which composite tungsten oxide fine particles are dispersed is obtained, and the obtained dispersion, a selective wavelength absorbing material, a polyvinyl acetal resin, and a plasticizer are kneaded and then extrusion molded. It can also be produced by molding into a film by a known method such as a method or a calender molding method.

Hereinafter, the components of the heat ray shielding film according to the present invention, the heat ray shielding film, and the heat ray shielding laminated transparent base material using the heat ray shielding film will be described in detail.

[1] Constituent Components of Heat Ray Shielding Film Regarding the heat ray shielding film according to the present invention, first, composite tungsten oxide fine particles, a dispersant, a selective wavelength absorbing material, an ultraviolet absorber, an infrared absorbing organic compound, polyvinyl, which are the constituent components. The acetal resin, plasticizer, adhesive strength modifier, and other additives will be described.

(1) Composite tungsten oxide The composite tungsten oxide fine particles have the general formula MyWO _Z (where M is Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn, Al, Cu). One or more selected elements, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0), and preferably have a hexagonal crystal structure .

In the composite tungsten oxide fine particles, examples of preferable composite tungsten oxide fine particles include Cs _0.33 WO ₃ and Rb _0.33 WO ₃ . However, if the values of y and z are within the above ranges, useful heat ray shielding characteristics can be obtained. The addition amount of the additive element M 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. Moreover, about the range of Z, 2.2 <= z <= 3.0 is preferable. Element which, in the composite tungsten oxide material expressed by MyWO _Z, in addition to a mechanism similar tungsten oxide material expressed by the above-mentioned WO _x works, even in z ≦ 3.0, as described above This is because free electrons are supplied by adding M. However, from the viewpoint of optical characteristics, 2.45 ≦ z ≦ 3.00 is more preferable.

The particle diameter of the composite tungsten oxide fine particles can be appropriately selected depending on the purpose of use of the heat ray shielding film. For example, when the heat ray shielding film is used for an application where transparency is required, the volume average diameter measured by dynamic light scattering light of the composite tungsten oxide fine particles (hereinafter referred to as a dispersed particle diameter or a dispersed average particle diameter). ) Is preferably 40 nm or less. If the composite tungsten oxide fine particles have a dispersed particle size smaller than 40 nm, light is not completely blocked by scattering, and visibility in the visible light region is maintained, and at the same time, transparency is efficiently maintained. Because you can.

When the heat ray shielding film or the heat ray shielding laminated transparent base material according to the present invention is applied to an application in which the transparency in the visible light region is particularly important, such as an automobile windshield, the scattering by the composite tungsten oxide fine particles is further performed. It is preferable to consider the reduction. In consideration of the further reduction in scattering, the dispersed particle diameter of the composite tungsten oxide fine particles is 30 nm or less, preferably 25 nm or less.

This is because if the dispersed particle diameter of the composite tungsten oxide fine particles is small, light scattering in the visible light region having a wavelength of 400 nm to 780 nm due to geometric scattering or Mie scattering is reduced. By reducing the scattering of the light having the wavelength, it is possible to avoid a situation in which the heat ray shielding film has an appearance like a frosted glass when strong light is irradiated and the clear transparency is lost.

This is because when the composite tungsten oxide fine particles have a dispersed particle diameter of 40 nm or less, the above-described geometrical scattering or Mie scattering is reduced and a Rayleigh scattering region is obtained. In the Rayleigh scattering region, the scattered light is reduced in inverse proportion to the sixth power of the particle diameter, so that the scattering is reduced and the transparency is improved as the dispersed particle diameter is reduced. Furthermore, it is preferable that the dispersed tungsten oxide fine particles have a dispersed particle diameter of 25 nm or less because the scattered light is extremely reduced.

As described above, from the viewpoint of avoiding light scattering, it is preferable that the dispersed tungsten oxide fine particles have a small dispersed particle diameter. On the other hand, if the dispersed particle diameter of the composite tungsten oxide fine particles is 1 nm or more, industrial production is possible.
The amount of the composite tungsten particles contained in the heat-ray shielding film, per unit area ^{0.2g / m 2 ~ 2.5g / m} 2 is desirable.

(2) Dispersant The dispersant according to the present invention is used for uniformly dispersing the above-described composite tungsten oxide fine particles according to the present invention in a polyvinyl acetal resin described later.
The dispersant according to the present invention has a thermal decomposition temperature of 200 ° C. or higher measured with a differential thermothermal gravimetric simultaneous measurement apparatus (hereinafter sometimes referred to as TG-DTA), and has urethane, acrylic and styrene main chains. It is preferable that it is a dispersing agent which has. Here, the thermal decomposition temperature is a temperature at which weight loss due to thermal decomposition of the dispersant begins in the TG-DTA measurement.
This is because when the thermal decomposition temperature is 200 ° C. or higher, the dispersant does not decompose during kneading with the polyvinyl acetal resin. As a result, it is possible to avoid the browning of the heat ray shielding film for heat ray shielding laminated glass due to the decomposition of the dispersant, the reduction in visible light transmittance, and the inability to obtain the original optical characteristics.

In addition, the dispersant is preferably a dispersant having an amine-containing group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group. These functional groups are adsorbed on the surface of the composite tungsten oxide fine particles, prevent aggregation of the composite tungsten oxide fine particles, and have an effect of uniformly dispersing the fine particles even in the heat ray shielding film. Specific examples include acrylic-styrene copolymer dispersants having a carboxyl group as a functional group and acrylic dispersants having an amine-containing group as a functional group. The dispersant having an amine-containing group as a functional group preferably has a molecular weight Mw of 2000 to 200,000 and an amine value of 5 to 100 mgKOH / g. The dispersant having a carboxyl group preferably has a molecular weight of Mw 2000 to 200000 and an acid value of 1 to 50 mgKOH / g.

The amount of the dispersant added is desirably in the range of 10 to 1000 parts by weight, more preferably in the range of 30 to 400 parts by weight with respect to 100 parts by weight of the composite tungsten oxide fine particles. This is because if the added amount of the dispersant is in the above range, the composite tungsten oxide fine particles are uniformly dispersed in the polyvinyl acetal resin, and the physical properties of the obtained heat ray shielding film are not adversely affected.

(3) Selected Wavelength Absorbing Material The selected wavelength absorbing material according to the present invention is a material that selectively and strongly absorbs only light in a certain wavelength region.
As described above, the present inventors have considered the wavelength distribution of the weight coefficient used in the visible light transmittance calculation described in JIS R 3106, and further described in JIS Z 8701 and JIS K 7373. The YI calculation method for plastics was examined. As a result of the examination, the light near the wavelength of 420 nm that cannot be sufficiently shielded by the composite tungsten oxide fine particles alone is strongly absorbed, and near the wavelength of 550 nm, which is a wavelength region that greatly contributes to the visible light transmittance calculation. The inventors have conceived a configuration in which a selective wavelength absorbing material that does not absorb light and does not absorb light having a wavelength of about 460 nm that greatly affects YI is used in combination with the composite tungsten oxide fine particles. Then, by using a configuration in which a selective wavelength absorbing material that strongly absorbs light in the vicinity of the wavelength of 420 nm and has no absorption in the vicinity of the wavelength of 460 nm and the wavelength of about 550 nm is used in combination with the composite tungsten oxide fine particles, the composite tungsten oxide fine particles Compared with the case of using alone, the lower solar transmittance could be obtained without increasing the YI of the laminated transparent base material.

In addition, for example, when a heat ray shielding laminated transparent base material is used as a member that requires high visibility, such as an automobile windshield, strong light such as direct sunlight, headlamps, etc. When this is irradiated, fine particles such as composite tungsten oxide fine particles contained are strongly scattered in the short wavelength region of visible light, and the phenomenon that the transparent substrate for heat ray shielding becomes cloudy white may be a problem.
Here, the present inventors have made the above-mentioned selective wavelength absorbing material absorb the scattered light in the short wavelength region of visible light generated by being scattered by fine particles such as composite tungsten oxide fine particles, thereby generating the bluish and cloudy color. It was conceived that the effect of improving the transparency of the heat ray shielding film according to the present invention and the heat ray shielding laminated transparent base material can be exhibited.

As the optical characteristics of the selective wavelength absorbing material according to the present invention, the selective wavelength absorbing material itself excluding the absorption of the medium and the substrate has a light transmittance of 90% or more and a light transmittance of 460 nm. When it is 90% or more, the transmittance of light having a wavelength of 420 nm is preferably 40% or less. Further, when the transmittance of light having a wavelength of 550 nm is 90% or more and the transmittance of light having a wavelength of 460 nm is 90% or more, the transmittance of light having a wavelength of 420 nm is more preferably 15% or less.
This is because when the selected wavelength absorbing material itself has a light transmittance of 90% or more at a wavelength of 550 nm and a light transmittance of 90% or more at a wavelength of 460 nm, the light transmittance at a wavelength of 420 nm is 40% or less. If it has a profile, when the selected wavelength absorbing material and the composite tungsten oxide fine particles are used in combination, the visible light transmittance does not decrease, the YI of the substrate does not significantly increase, and the wavelength This is because sufficient absorption of light near 420 nm can be obtained. As a result, compared with the case where the composite tungsten oxide fine particles are used alone, there is no significant change in color tone, and the solar transmittance is lowered, so that the heat shielding characteristics are improved.

Specific examples of the wavelength-absorbing material used in the present invention include benzotriazole compounds, benzophenone compounds, hydroxyphenyltriazine compounds, indole compounds, azomethine compounds, benzotriazolyl compounds, benzoyl compounds, and the like. Among them, it is preferable to use an indole compound or an azomethine compound that has a high absorption coefficient of light having a wavelength of 420 nm and can obtain sufficient absorption at a concentration that does not affect the strength of the heat ray shielding film. In particular, the effect of the indole compound is clear even when added in a small amount.

When an indole compound is used as the selective wavelength absorption material according to the present invention, it is preferable to use a compound represented by (Chemical Formula 1). Here, R in the formula is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a butyl group, and 2-ethylhexyl group, and examples of the aralkyl group having 7 to 10 carbon atoms include a phenylmethyl group. Among them, among the indole compounds represented by (Chemical Formula 1), a compound in which R is a methyl group is particularly preferable as the selective wavelength absorption material according to the present invention.
However, even if it is not the indole compound represented by (Chemical Formula 1), it has an indole skeleton, the indole compound itself excluding the absorption of the medium and the substrate has a light transmittance of 90% or more at a wavelength of 550 nm and a wavelength of 460 nm. When the light transmittance is 90% or more, any indole compound having a light transmittance of 40% or less at a wavelength of 420 nm can be suitably used as the selective wavelength absorbing material according to the present invention.

The mixing ratio of the composite tungsten oxide fine particles and the selective wavelength absorbing material is preferably such that the value of the weight ratio (composite tungsten oxide fine particles / selective wavelength absorbing material) is in the range of 100/2 to 100/800. More preferably, it is 100/5 to 100/800, and more preferably 100/10 to 100/400. When the mixing ratio of the addition amount of the selective wavelength absorbing material is 100/800 or less, the visible wavelength region is not excessively absorbed by the selective wavelength absorbing material, and the visible light transmittance is maintained. As a result, the solar radiation transmittance is maintained as compared with the case where the composite tungsten oxide fine particles are used alone, and the heat shielding characteristics are maintained. Further, when the mixing ratio of the addition amount of the selective wavelength absorbing material is 100/800 or less, the absorption in the visible light short wavelength region, which has a great influence on YI, is not increased, and the heat ray shielding film does not increase significantly without increasing YI. This is because the color tone is maintained.

In particular, when an absorption coefficient of light having a wavelength of 420 nm is high as the selective wavelength absorption material, for example, an indole compound or an azomethine compound is used, the mixing ratio of the addition amount of the selective wavelength absorption material is 100 / weight ratio. Even if it is 100 or less and 100/2 or more, compared with the case where the composite tungsten oxide fine particles are used alone, the color tone is not greatly changed, and the solar radiation transmittance is lowered, so that the heat shielding property is improved. .

When the heat ray shielding laminated transparent base material according to the present invention is used as a window material in an automobile or a building, it is preferable to have a natural color tone (transparent or achromatic color). In particular, assuming that the heat-shielding transparent base material according to the present invention is used for an automobile windshield or the like, it is preferable that the color of the fluoroscopic image can be normally identified in order to ensure safety during driving.
From this viewpoint, for the heat ray-shielding laminated transparent substrate according to the present invention, for example, in the color discrimination test based on JIS R 3211 and JIS R 3212 that define the performance required for laminated glass for automobiles, the color of the fluoroscopic image Is preferably identifiable.
Here, when the YI of the heat ray shielding laminated transparent base material according to the present invention is -20 or more and 10 or less, the color of the fluoroscopic image can be normally identified. Then, by adopting the composition of the mixing ratio of the composite tungsten oxide fine particles and the selective wavelength absorbing material according to the present invention described above, the YI value of the heat ray shielding laminated transparent base material according to the present invention is set to -20 or more and 10 or less. I can do it. In addition, it is more preferable that the YI of the laminated transparent base material is −20 or more and 5 or less because the color of the fluoroscopic image can be further easily identified.

Any method can be selected as a method of adding the selective wavelength absorbing material to the heat ray shielding film. For example, the selected wavelength absorbing material can simply be added directly to the polyvinyl acetal resin and plasticizer. Alternatively, a selective wavelength absorbing material can be added to the plasticizer in which the composite tungsten oxide fine particles are dispersed, and this can be mixed with the polyvinyl acetal resin and the plasticizer at an appropriate ratio. Alternatively, the selective wavelength absorbing material can be dispersed or dissolved in a plasticizer and added to the polyville acetal resin. Alternatively, the selective wavelength absorbing material can be dispersed in a solid dispersant and added to the polyvinyl acetal resin and the plasticizer.

In any case, it is sufficient that the selective wavelength absorbing material is uniformly dispersed in the heat ray shielding film, and any method that does not impair the transparency of the obtained heat ray shielding film is preferably used.

(4) Ultraviolet absorber In the heat ray shielding film according to the present invention, when an absorption coefficient of light having a wavelength of 420 nm is high as the selective wavelength absorbing material, for example, an indole compound or an azomethine compound is added, an ultraviolet absorber is further added. Is a preferable configuration.
The first reason why it is preferable to further add an ultraviolet absorber to the heat ray shielding film according to the present invention is that indole compounds and azomethine compounds efficiently absorb visible light having a short wavelength, but an ultraviolet absorber is added. This is because effective absorption can be obtained even in the ultraviolet region.
By sufficiently cutting light in the ultraviolet region, a higher temperature rise deterrence effect can be obtained. In addition, it is possible to sufficiently prevent the influence of ultraviolet rays on people and interiors in automobiles and buildings, sunburns, furniture, and deterioration of interiors, in which the heat ray shielding laminated transparent base material according to the present invention is mounted.
The second reason is that by adding an ultraviolet absorber, the photodegradation of the selective wavelength absorbing material due to sunlight or the like can be suppressed.
As a result, even when the heat ray shielding laminated transparent base material according to the present invention is actually used for a long time as a window material for automobiles and buildings, an ultraviolet absorber is further added to the heat ray shielding film according to the present invention. By doing so, it is possible to suppress light degradation of the selected wavelength absorbing material due to sunlight or the like.

Examples of the ultraviolet shielding agent include organic ultraviolet absorbers such as benzophenone compounds, salicylic acid compounds, HALS compounds, benzotriazole compounds, triazine compounds, benzotriazolyl compounds, and benzoyl compounds, and inorganic substances such as zinc oxide, titanium oxide, and cerium oxide. Examples include ultraviolet absorbers, and among them, benzotriazole compounds and benzophenone compounds are particularly preferable. This is because the benzotriazole compound and the benzophenone compound have very high visible light transmittance and high durability against long-term exposure to strong ultraviolet rays even when a concentration sufficient to absorb ultraviolet rays is added.

The content of the ultraviolet absorber in the heat ray shielding film is preferably 0.1% by weight or more and 5.0% by weight or less. If the content is 0.1% by weight or more, it is possible to sufficiently absorb ultraviolet light that cannot be absorbed by the selective wavelength absorbing material, and to sufficiently prevent photodegradation of the selective wavelength absorbing material. Because. In addition, when the content is 5.0% by weight or less, the ultraviolet absorber does not precipitate in the heat ray shielding film, and does not significantly affect the strength, adhesive force, and penetration resistance of the film.

On the other hand, compounds such as benzotriazole compounds, benzophenone compounds, triazine compounds, benzotriazolyl compounds, and benzoyl compounds have a light absorption coefficient at a wavelength of 420 nm, although they are lower than indole compounds and azomethine compounds. Therefore, by adding a considerable amount of these compounds to the heat ray shielding film, when the transmittance of light having a wavelength of 550 nm is 90% or more and the transmittance of light having a wavelength of 460 nm is 90% or more, a wavelength of 420 nm The effect that the light transmittance is 40% or less can also be exhibited. According to the said structure, these compounds will serve as the effect of a selective wavelength absorption material and a ultraviolet absorber.

(5) Infrared-absorbing organic compound In the present invention, an infrared-absorbing organic compound having strong absorption in the near-infrared region may be further added to the heat ray shielding film as desired.
Examples of infrared absorbing organic compounds used for this purpose include phthalocyanine compounds, naphthalocyanine compounds, imonium compounds, diimonium compounds, polymethine compounds, diphenylmethane compounds, triphenylmethane compounds, quinone compounds, azo compounds, pentadiene compounds, azomethine compounds, squarylium. Compounds, organometallic complexes, cyanine compounds and the like can be used.
As the infrared absorbing organic compound, it is preferable to select one that dissolves in the plasticizer constituting the heat ray shielding film described above, because the transparency of the obtained heat ray shielding film is not impaired.

The infrared-absorbing organic compound is more preferably a material that strongly absorbs light in the range from the visible long wavelength region to the near infrared region having a wavelength of 650 nm to 1000 nm. This is because there is a large synergistic effect when the infrared absorbing organic compound having the optical characteristics and the composite tungsten oxide fine particles having strong absorption in the wavelength region of 800 nm or more are used in combination. This is because a higher heat shielding performance can be obtained as compared with the case of using in the above.
From this viewpoint, as the infrared absorbing organic compound used in the present invention, a diimonium compound and a phthalocyanine compound are particularly preferable.
The weight ratio of the infrared absorbing organic compound and the composite tungsten oxide fine particles is preferably in the range of [composite tungsten oxide fine particles / infrared absorbing organic compound] = 100/5 to 100/100.
If the mixing ratio of the addition amount of the infrared absorbing organic compound is more than 100/5 by the above-mentioned weight ratio, the infrared absorbing organic compound strongly increases the light in the visible light long wavelength region from the wavelength range of 650 nm to 1000 nm to the near infrared region. The effect to absorb is acquired and it is preferable. Further, if the mixing ratio of the addition amount of the infrared absorbing organic compound is 100/100 or less in the above-mentioned weight ratio, the wavelength region near 550 nm, which is a wavelength region that greatly contributes to the visible light transmittance calculation by the infrared absorbing organic compound. Therefore, it is possible to avoid a decrease in visible light transmittance. For this reason, even if the visible light transmittance is combined, the heat shielding property is secured, which is preferable.

(6) Polyvinyl acetal resin As the polyvinyl acetal resin used for the heat ray shielding film according to the present invention, a polyvinyl butyral resin is preferable. Further, in consideration of the physical properties of the heat ray shielding film, a plurality of types of polyvinyl acetal resins having different degrees of acetalization may be used in combination. Furthermore, a copolyvinyl acetal resin obtained by reacting a plurality of types of aldehydes in combination during acetalization can also be preferably used.
From this viewpoint, the preferable lower limit of the degree of acetalization of the polyvinyl acetal resin is 60%, and the upper limit is 75%.

The polyvinyl acetal resin can be prepared by acetalizing polyvinyl alcohol with an aldehyde.
The polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate. Generally, polyvinyl alcohol having a saponification degree of 80 to 99.8 mol% is used.
Moreover, the preferable minimum of the polymerization degree of the said polyvinyl alcohol is 200, and an upper limit is 3000. When the degree of polymerization is 200 or more, resistance to penetration of the manufactured heat ray shielding laminated transparent base material is maintained, and safety is maintained. On the other hand, if it is 3000 or less, the moldability of the resin film is maintained, the rigidity of the resin film is also maintained in a preferable range, and the workability is maintained.

The aldehyde is not particularly limited, and in general, aldehydes having 1 to 10 carbon atoms such as n-butyraldehyde, isobutyraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, acetaldehyde and the like are used. It is done. Of these, n-butyraldehyde, n-hexylaldehyde, and n-valeraldehyde are preferable, and butyraldehyde having 4 carbon atoms is more preferable.

(7) Plasticizer The plasticizer used for the heat ray shielding film mainly composed of the polyvinyl acetal resin according to the present invention includes a plasticizer that is a compound of a monohydric alcohol and an organic acid ester, and a polyhydric alcohol organic acid ester. Examples include ester plasticizers such as compounds, and phosphoric acid plasticizers such as organic phosphate plasticizers. Any plasticizer is preferably liquid at room temperature. In particular, a plasticizer that is an ester compound synthesized from a polyhydric alcohol and a fatty acid is preferred.

The ester compound synthesized from the polyhydric alcohol and fatty acid is not particularly limited. For example, glycol such as triethylene glycol, tetraethylene glycol, tripropylene glycol, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptyl Examples thereof include glycol ester compounds obtained by reaction with monobasic organic acids such as acids, n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonyl acid), and decyl acid. In addition, ester compounds of tetraethylene glycol, tripropylene glycol, and the above-mentioned monobasic organic are also included.
Of these, fatty acid esters of triethylene glycol such as triethylene glycol dihexanate, triethylene glycol di-2-ethylbutyrate, triethylene glycol dioctanoate, and triethylene glycol di-2-ethylhexanate are suitable. is there. The fatty acid ester of triethylene glycol has various properties such as compatibility with polyvinyl acetal and cold resistance in a well-balanced manner, and is excellent in processability and economy.

When choosing a plasticizer, keep in mind that it has low hydrolyzability. From this viewpoint, triethylene glycol di-2-ethylhexanate, triethylene glycol di-2-ethylbutyrate, and tetraethylene glycol di-2-ethylhexanate are preferable.

(8) Adhesive strength adjusting agent It is also preferable to add an optional adhesive strength adjusting agent to the heat ray shielding film according to the present invention.
Although the said adhesive force regulator is not specifically limited, An alkali metal salt and / or an alkaline-earth metal salt are used suitably. The acid which comprises the said metal salt is not specifically limited, For example, inorganic acids, such as carboxylic acids, such as octyl acid, hexyl acid, butyric acid, acetic acid, formic acid, or hydrochloric acid, nitric acid, are mentioned. Among the alkali metal salts and / or alkaline earth metal salts, a carboxylic acid magnesium salt having 2 to 16 carbon atoms and a potassium carboxylate salt having 2 to 16 carbon atoms are preferable.
The carboxylic acid magnesium salt or potassium salt of the organic acid having 2 to 16 carbon atoms is not particularly limited, and examples thereof include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutanoate, and 2-ethylbutane. Potassium acid, magnesium 2-ethylhexanoate, potassium 2-ethylhexanoate and the like are preferably used.

These adhesive strength modifiers may be used alone or in combination of two or more.
In addition, when sodium, potassium, magnesium, calcium, or cerium carboxylate is used as an adhesive strength modifier, the action as an original adhesive strength modifier and the above-described improved weather resistance of the composite tungsten oxide fine particles are improved. It can also have an effect.

(9) Other additives The heat-ray shielding film according to the present invention may further contain general additives as desired. For example, azo dyes, cyanine dyes, quinoline dyes, perylene dyes, carbon black, etc., which are generally used for coloring thermoplastic resins to give an arbitrary color tone as desired. It may be added. Particularly in the present invention, since the light on the short wavelength side of visible light is absorbed, the transmitted light color is slightly yellowish. Therefore, it is preferable to adjust the color tone of the heat ray shielding film by adding a compound such as a dye or a pigment.
As other additives, a coupling agent, a surfactant, an antistatic agent, and the like can be added.

[2] Heat ray shielding film In order to produce the heat ray shielding film according to the present invention,
(I) The composite tungsten oxide fine particles and the dispersant described above are dispersed in a part of the plasticizer added to the polyvinyl acetal resin to produce a composite tungsten oxide fine particle dispersion.
Or
(Ii) After obtaining a dispersion in which the composite tungsten oxide fine particles and the dispersant are dispersed in a general organic solvent, the composite tungsten oxide fine particles are dispersed in the solid dispersant by removing the organic solvent. What is necessary is just to manufacture the composite tungsten oxide fine particle dispersion in a state.

And the produced composite tungsten oxide fine particle plasticizer dispersion, or the produced composite tungsten oxide fine particle dispersion, the selective wavelength absorbing material, the polyvinyl acetal resin, the plasticizer, and preferably the ultraviolet absorber. If desired, it can be produced by, for example, forming into a film by a known method such as an extrusion molding method or a calender molding method after mixing and kneading other additives and an adhesive strength adjusting agent. Further, if an infrared absorbing organic compound is added to the heat ray shielding film as desired, higher heat ray shielding characteristics can be obtained.

Hereinafter, a method for producing a composite tungsten oxide fine particle plasticizer dispersion and a method for producing a composite tungsten oxide fine particle dispersion will be described.

(1) Manufacturing method of plasticizer dispersion liquid of composite tungsten oxide fine particles The composite tungsten oxide fine particles and the dispersant are added to and mixed with the plasticizer, and the composite tungsten oxide fine particles are plasticized using a general dispersion method. An agent dispersion can be obtained. Specifically, a dispersion method such as a bead mill, a ball mill, a sand mill, or ultrasonic dispersion can be used.

In addition, when the composite tungsten oxide fine particles are dispersed in the plasticizer, an organic solvent having a boiling point of 120 ° C. or lower may be added as desired.
As the organic solvent, those having a boiling point of 120 ° C. or less are preferably used. If the boiling point is 120 ° C. or lower, it is easy to remove by a drying step, which is a subsequent step, particularly by drying under reduced pressure. As a result, removal in the reduced-pressure drying step proceeds rapidly, contributing to the productivity of the composite tungsten oxide fine particle-containing composition. Furthermore, since the vacuum drying process proceeds easily and sufficiently, it can be avoided that an excess organic solvent remains in the composite tungsten oxide fine particle-containing composition according to the present invention. As a result, it is possible to avoid the occurrence of problems such as the generation of bubbles when forming the heat ray shielding film. Specific examples include toluene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, isopropyl alcohol, and ethanol. Any boiling point can be used as long as it has a boiling point of 120 ° C. or lower and can uniformly disperse the composite tungsten oxide fine particles. Can be selected.

The method of uniformly dispersing the composite tungsten oxide fine particles in the organic solvent can be arbitrarily selected from general methods. As specific examples, methods such as a bead mill, a ball mill, a sand mill, and ultrasonic dispersion can be used.

Further, as a method for removing the organic solvent from the composite tungsten oxide fine particle-containing dispersion, a method of drying under reduced pressure is preferable. Specifically, the composite tungsten oxide fine particle-containing dispersion is dried under reduced pressure while stirring to separate the composite tungsten oxide fine particle-containing composition and the organic solvent component. Examples of the apparatus used for drying under reduced pressure include a vacuum stirring type dryer, but any apparatus having the above functions may be used, and the apparatus is not particularly limited. Moreover, the pressure of the pressure reduction of a drying process is selected suitably.

By using the reduced-pressure drying method, the removal efficiency of the solvent is improved, and the composite tungsten oxide fine particle-containing composition is not exposed to high temperature for a long time, so that aggregation of dispersed fine particles does not occur. preferable. Furthermore, productivity is increased, and it is easy to collect the evaporated organic solvent, which is preferable from the environmental consideration.

(2) Manufacturing method of composite tungsten oxide fine particle dispersion The plasticizer dispersion liquid of the composite tungsten oxide fine particles described above, or the composite tungsten oxide fine particles, the dispersant, and the plasticizer have a boiling point of 120 ° C. or less. A composite tungsten oxide fine particle dispersion in which the concentration of the composite tungsten oxide fine particles is 50% by mass or less is produced using a general dispersion method.

The concentration of the composite tungsten oxide fine particles in the plasticizer is preferably 50% by mass or less. If the concentration of the composite tungsten oxide fine particles in the plasticizer is 50% by mass or less, the fine particles are hardly aggregated, easily dispersed, a sudden increase in viscosity can be avoided, and handling is easy.
A method of uniformly dispersing the composite tungsten oxide fine particles in the plasticizer can be arbitrarily selected from general methods. As a specific example, after obtaining a dispersion containing composite tungsten oxide fine particles, the organic solvent is removed by a known method, so that the composite tungsten oxide fine particles are dispersed in a solid dispersant. A dispersion can also be obtained.

[3] Heat ray shielding laminated transparent base material The heat ray shielding laminated transparent base material using the heat ray shielding film according to the present invention has various forms.
For example, a heat ray shielding laminated inorganic glass using inorganic glass as a transparent substrate is obtained by laminating and integrating a plurality of opposing inorganic glasses that are sandwiched by the heat ray shielding film according to the present invention by a known method. can get. The obtained heat-shielding laminated inorganic glass can be used mainly as an inorganic glass for the front of an automobile or a window of a building.

Furthermore, the structure which uses the heat ray shielding film concerning this invention and the infrared rays reflective film mentioned later together as a heat ray shielding film, and makes it a heat ray shielding laminated transparent base material is also preferable. In the case of adopting this configuration, the infrared reflective film is sandwiched between a heat ray shielding film and a transparent PVB resin film to be integrated into a multilayer film. The obtained multilayer film is sandwiched between a plurality of opposing inorganic glasses and laminated and integrated by a known method to obtain a heat-shielding laminated inorganic glass.
Here, considering that the heat ray shielding laminated inorganic glass is used in an automobile, the structure in which the infrared reflection film is present outside the heat ray shielding film according to the present invention in consideration of the temperature rise suppressing effect in the automobile. preferable.

The heat shielding characteristics of the heat-shielding laminated transparent base material according to the present invention are indicated by the solar radiation transmittance with respect to the visible light transmittance. The lower the solar radiation transmittance relative to the visible light transmittance, the more the heat ray shielding laminated transparent base material has better heat shielding properties. Specifically, when the visible light transmittance is 70%, the solar radiation transmittance is preferably 32.5% or less, more preferably 31% or less, and further preferably 30% or less.

In particular, when the heat ray shielding laminated transparent base material according to the present invention is used for a window material such as a windshield of an automobile, a high heat ray shielding ability is required while satisfying the transmittance of 70% or more stipulated by the Road Transport Vehicle Law. It is because it is said. Incidentally, if the solar radiation transmittance of the heat-shielding laminated transparent base material is 32.5% or less, the power consumption of the air conditioner when the outside air temperature is 30 ° C or higher is compared with the case where ordinary laminated glass is installed. Reduced by more than 5%. As a result, particularly in an automobile using a battery such as a hybrid car or an electric car, consumption of the battery can be suppressed, so that a significant effect is seen in extending the cruising distance. Therefore, it can be expected to contribute to improving the fuel efficiency of automobiles and reducing greenhouse gas emissions, and in the future, it is expected to become an essential member in the design of automobiles.

A transparent resin is used as a transparent substrate, and it is used in the same manner as the above inorganic glass, or in combination with the above inorganic glass, and a heat ray shielding film is sandwiched between opposing transparent substrates, so that the heat ray shielding transparent A substrate can be obtained. The application of the heat ray shielding laminated transparent base material is the same as that of the heat ray shielding laminated inorganic glass described above.
In addition, if desired, the heat ray shielding film according to the present invention can be used alone, or the heat ray shielding film according to the present invention can be used on one side or both sides of a transparent substrate such as inorganic glass or transparent resin. Is possible.

Here, the infrared reflective film used together with the heat ray shielding film according to the present invention described above will be described.
In consideration of optical characteristics when the infrared reflective film according to the present invention described above is used in combination with the heat ray shielding film according to the present invention, the visible light region hardly absorbs sunlight, and from the long wavelength region of visible light. It is preferable from the viewpoint of the heat ray shielding function to reflect only the near infrared region, specifically, the wavelength range of 700 nm to 1200 nm.
Specifically, the optical properties of the infrared film are preferably a visible light transmittance of 85% or more and a solar reflectance of 18% or more, and a visible light transmittance of 88% or more and a solar reflectance of 21% or more. More preferred.
Furthermore, in consideration of the use of a heat ray shielding laminated transparent base material for automobile windshields and building windows, the infrared reflective film according to the present invention transmits electromagnetic waves in the wavelength region used for mobile phones and ETC. Those are preferred. Accordingly, a film with a resin multilayer film that transmits electromagnetic waves and a film that has the property of reflecting infrared rays with cholesteric liquid crystal are preferable to the film with metal film that has conductivity and does not transmit electromagnetic waves.

[4] Summary As described above in detail, the plasticizer dispersion of the composite tungsten oxide according to the present invention, or the composite tungsten oxide dispersion according to the present invention, the selective wavelength absorbing material, and the polyvinyl acetal resin. And a plasticizer were kneaded and further formed into a film by a known method, whereby the heat ray shielding film according to the present invention can be produced.
And by presenting the heat ray shielding film according to the present invention so as to be sandwiched between a plurality of opposed transparent substrates, it exhibits a low solar transmittance while maintaining high transparency in the visible light region, The production of a heat-shielded transparent base material according to the present invention has become possible.
And the selective wavelength absorption material which has the transmission profile whose wavelength 420nm transmittance is 40% or less when the wavelength 550nm transmittance is 90% or more and the wavelength 460nm transmittance is 90% or more with the composite tungsten oxide fine particles By using together at a predetermined ratio, it becomes possible to exhibit higher heat ray shielding characteristics as compared with the case where the composite tungsten oxide fine particles are used alone.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
In addition, the transmittance of light having a wavelength of 420 nm, a wavelength of 460 nm, and a wavelength of 550 nm of the selective wavelength absorbing material in each example is a quartz glass cell having an optical path length of 1 cm obtained by dissolving a liquid in which the selective wavelength absorbing material is dissolved at an appropriate concentration. The spectrophotometer U-4000 manufactured by Hitachi, Ltd. was used for measurement. The baseline was drawn with only the organic solvent used for dissolution in the same cell. As the organic solvent for dissolving the selected wavelength absorbing material, one kind arbitrarily selected from toluene, methyl isobutyl ketone, and N-methyl-2-pyrrolidinone according to the solvent solubility of the selected wavelength absorbing material was used.
The visible light transmittance and solar radiation transmittance of the transparent substrate with heat ray shielding were similarly measured using a spectrophotometer U-4000. In addition, the said solar transmittance is an parameter | index which shows the heat ray shielding performance of a heat ray shielding matching transparent base material. YI of the heat ray shielding laminated transparent base material was calculated based on JIS Z 8701 and JIS K 7373 from the transmittance of light having a wavelength of 380 to 780 nm measured using a spectrophotometer U-4000.

[Example 1]
20% by mass of composite tungsten oxide fine particles Cs _0.33 WO ₃ (hereinafter referred to as fine particles a) and an acrylic dispersant having an amine-containing group as a functional group (amine value 48 mgKOH / g, decomposition temperature 250 ° C.) 10% by mass of acrylic dispersant (hereinafter referred to as “dispersant a”) and 70% by mass of triethylene glycol di-2-ethylhexanonate (hereinafter referred to as “plasticizer a”) were weighed. These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads, and pulverized and dispersed for 10 hours to obtain a plasticizer dispersion of fine particles a (hereinafter referred to as fine particle dispersion A).
Here, the dispersion average particle diameter of the tungsten oxide fine particles in the fine particle dispersion A was measured with a Nikkiso Microtrac particle size distribution meter and found to be 24 nm.

A predetermined amount of fine particle dispersion A and BONASORB UA-3911 (CAS No. 142676-93 manufactured by Orient Chemical Co., Ltd.), which is an indole compound as a selective wavelength absorbing material, are added to a mixture obtained by mixing 38% by weight of a plasticizer with respect to polyvinyl butyral resin. -5, an indole compound represented by (Chemical formula 1), wherein R is a methyl group, the transmittance at 420 nm when the transmittance of light at a wavelength of 550 nm is 99% and the transmittance of light at a wavelength of 460 nm is 90%. 0%, hereinafter referred to as indole compound A), the weight ratio of the composite tungsten oxide fine particles to the selective wavelength absorbing material [composite tungsten oxide fine particles / selective wavelength absorbing material] is 100/20, and Add a visible light transmittance of 70% or more when used as a transparent substrate to prepare a composition for manufacturing a heat ray shielding film. It was.
The composition for producing this heat ray shielding film was kneaded at 200 ° C. by a twin screw extruder, and the heat ray shielding film according to Example 1 was obtained as a sheet having a thickness of 0.7 mm by extrusion calendering from a T die.

The obtained heat ray shielding film according to Example 1 was sandwiched between two opposing inorganic glasses and bonded and integrated by a known method to obtain a heat ray shielding laminated transparent base material according to Example 1.

The optical characteristics of the heat-shielding transparent base material according to Example 1 were as follows: the solar radiation transmittance was 31.3% and the YI was −2.6 when the visible light transmittance was 70.4%. The results are shown in Table 1.

[Examples 2 to 9]
The kind of the selective wavelength absorbing material and the weight ratio of the composite tungsten oxide fine particles to the selective wavelength absorbing material in the composition for producing a heat ray shielding film described in Example 1 [Composite tungsten oxide fine particles / selected wavelength absorbing material] The heat-shielding laminated transparent base materials according to Examples 2 to 9 were obtained in the same manner as in Example 1 except that Table 1 was changed as shown in Table 1. Then, the optical characteristics of the heat ray shielding laminated transparent base materials according to Examples 2 to 9 were measured in the same manner as in Example 1. Table 1 shows the measurement results of optical characteristics of the heat-shielding transparent substrates according to Examples 2 to 9.
As the selective wavelength absorbing material, the above-mentioned indole compound A is used in Examples 2 to 4, and in Examples 5 to 6, BONASORB UA-3701 (CAS No. 55567-) manufactured by Orient Chemical Industry, which is an azomethine compound. 59-4, and the transmittance at 420 nm is 0% when the transmittance of light at a wavelength of 550 nm is 98% and the transmittance of light at a wavelength of 460 nm is 90%, hereinafter referred to as azomethine compound B Was used). In Example 7, the benzotriazole compound TINUVIN 109 (CAS No. 83044-89-7, manufactured by BASF) is represented by 99%, and the transmittance of light having a wavelength of 550 nm is 99% and the transmission of light having a wavelength of 460 nm is used. When the rate was 90%, the transmittance at 420 nm was 0%, and hereinafter referred to as benzotriazole compound C). In Example 8, TINUVIN 479 (CAS No. 204848-45-3 manufactured by BASF), which is a hydroxyphenyl triazine compound, is represented by 99% transmittance of light having a wavelength of 550 nm and light having a wavelength of 460 nm. When the transmittance is 90%, the transmittance at 420 nm is 15%, which is hereinafter referred to as hydroxyphenyltriazine compound D). In Example 9, DAINSORB P-6 (CAS No. 131-55-4 manufactured by Daiwa Kasei Co., Ltd.), which is a benzophenone compound, is represented by 97% transmittance of light having a wavelength of 550 nm and light having a wavelength of 460 nm. The transmittance at 420 nm was 25% when the transmittance was 92%, hereinafter referred to as benzophenone compound E).

[Comparative Example 1]
A heat ray shielding laminated transparent base material according to Comparative Example 1 was obtained in the same manner as Example 1 except that the selective wavelength absorbing material was not added. And the optical characteristic of the heat ray shielding laminated transparent base material which concerns on the said comparative example 1 was measured similarly to Example 1. FIG. Table 1 shows the optical property measurement results of the heat-shielding laminated transparent base material according to Comparative Example 1.

[Comparative Examples 2 to 4]
The kind of the selective wavelength absorbing material and the weight ratio of the composite tungsten oxide fine particles to the selective wavelength absorbing material in the composition for producing a heat ray shielding film described in Example 1 [Composite tungsten oxide fine particles / selected wavelength absorbing material] ] Were changed as shown in Table 1, and heat-shielded laminated transparent base materials according to Comparative Examples 2 to 4 were obtained in the same manner as in Example 1. Then, the optical characteristics of the heat ray shielding laminated transparent base materials according to Comparative Examples 2 to 4 were measured in the same manner as in Example 1. The results are shown in Table 1.
As the selective wavelength absorbing material, the above-mentioned indole compound A is used in Comparative Examples 2 and 3, and in Comparative Example 4, the quinophthalone compound C.I. I. Solvent yellow 33 (CAS No. 8003-22-3) (Chemical formula 6), the transmittance of 420 nm when the transmittance of light having a wavelength of 550 nm is 99% and the transmittance of light having a wavelength of 460 nm is 90% 55%, hereinafter referred to as quinophthalone compound H).

[Example 10]
20 wt% of composite tungsten oxide fine particles Rb _0.33 WO ₃ (hereinafter referred to as fine particles b), 10 wt% of dispersant a, and 70 wt% of plasticizer a were weighed. These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads and pulverized and dispersed for 10 hours to obtain a plasticizer dispersion of fine particles b (hereinafter referred to as fine particle dispersion B).
Here, the dispersion average particle diameter of the tungsten oxide fine particles in the fine particle dispersion B was measured with a Nikkiso Microtrac particle size distribution meter to be 27 nm.
A heat ray shielding laminated transparent base material according to Example 10 was obtained in the same manner as in Example 1 except that the fine particle dispersion B was used as an alternative to the fine particle dispersion A. And the optical characteristic of the heat ray shielding laminated transparent base material which concerns on the said Example 10 was measured similarly to Example 1. FIG.
The type of composite tungsten oxide fine particles in Example 10, the type of selective wavelength absorbing material, and the weight ratio of the composite tungsten oxide fine particles to the selective wavelength absorbing material in the composition for producing a heat ray shielding film [composite tungsten oxide Fine particles / selective wavelength absorbing material] are shown in Table 1. Furthermore, the optical characteristic measurement result of the heat ray shielding laminated transparent base material concerning Example 10 was shown in Table 1.

[Example 11]
A predetermined amount of the fine particle dispersion A, the indole compound A, and a diimonium compound manufactured by Nippon Carlit Co., Ltd. as an infrared-absorbing organic compound to the composition obtained by mixing 38% by mass of the plasticizer a with 100% by mass of the polyvinyl butyral resin described in Example 1. CIR-RL (hereinafter referred to as diimonium compound F) is added, and the weight ratio of the composite tungsten oxide fine particles to the selected wavelength absorbing material [composite tungsten oxide fine particles / selected wavelength absorbing material] is 100/20. The weight ratio of the composite tungsten oxide fine particles to the infrared absorbing organic compound [composite tungsten oxide fine particles / infrared absorbing organic compound] is 100/5, and the visible light transmittance when the laminated transparent base material is used. Was added so that it might become 70% or more, and the composition for manufacture of a heat ray shielding film was prepared.
The composition for producing this heat ray shielding film was kneaded at 200 ° C. with a twin-screw extruder, extruded from a T die, and a heat ray shielding film according to Example 11 was obtained as a sheet having a thickness of 0.7 mm by a calender roll method. The obtained heat ray shielding film was sandwiched between two opposing inorganic glasses and laminated together by a known method to obtain a heat ray shielding laminated transparent base material according to Example 11. And the optical characteristic of the heat ray shielding laminated transparent base material concerning the said Example 11 was measured similarly to Example 1. FIG. The type of composite tungsten oxide fine particles, the type of selective wavelength absorbing material in Example 11 and the weight ratio of the composite tungsten oxide fine particles to the selective wavelength absorbing material in the composition for producing a heat ray shielding film [composite tungsten oxide Fine particle / selective wavelength absorbing material], type of infrared absorbing organic compound, and weight ratio of the composite tungsten oxide fine particle to the infrared absorbing organic compound in the composition for producing a heat ray shielding film [composite tungsten oxide fine particle / infrared ray Absorbable organic compounds] are shown in Table 1. Furthermore, Table 1 shows the optical property measurement results of the heat ray shielding laminated transparent base material according to Example 11.

[Example 12]
The heat ray shielding laminated transparent base material which concerns on Example 12 was obtained like Example 11 except having used the phthalocyanine type compound as an infrared absorptive organic compound. And the optical characteristic of the heat ray shielding laminated transparent base material which concerns on the said Example 12 was measured similarly to Example 1. FIG. The type of composite tungsten oxide fine particles in Example 12, the type of selective wavelength absorbing material, and the weight ratio of the composite tungsten oxide fine particles to the selective wavelength absorbing material in the composition for producing a heat ray shielding film [composite tungsten oxide Fine particle / selective wavelength absorbing material], type of infrared absorbing organic compound, and weight ratio of the composite tungsten oxide fine particle to the infrared absorbing organic compound in the composition for producing a heat ray shielding film [composite tungsten oxide fine particle / infrared ray Absorbable organic compounds] are shown in Table 1. Furthermore, Table 1 shows the optical property measurement results of the heat ray shielding laminated transparent base material according to Example 12.

[Example 13]
The infrared ray reflective film (Scotch Tint Nano 90S manufactured by Sumitomo 3M Co., Ltd .: visible light transmittance 89%, solar reflectance 22%, hereinafter referred to as infrared reflective film Z) is transparent to the heat ray shielding film obtained in Example 1. Was sandwiched between two PVB interlayer films, and sandwiched between two opposing inorganic glasses, and bonded together by a known method to obtain a heat ray shielding laminated transparent base material according to Example 13.
And the optical characteristic of the heat ray shielding laminated transparent base material which concerns on the said Example 13 was measured similarly to Example 1. FIG. During the measurement, optical characteristics were measured from the glass surface in contact with the transparent PVB intermediate film.
The type of composite tungsten oxide fine particles in Example 13, the type of selective wavelength absorbing material, and the weight ratio of the composite tungsten oxide fine particles to the selective wavelength absorbing material in the composition for producing a heat ray shielding film [composite tungsten oxide Fine particles / selective wavelength absorbing material] and the infrared reflection film used are shown in Table 1. Furthermore, Table 1 shows the optical property measurement results of the heat ray shielding laminated transparent base material according to Example 13.

[Example 14]
A predetermined amount of fine particle dispersion A, indole compound A, and benzotriazole compound C as an ultraviolet absorber are added to a composition in which plasticizer a 38% by mass is mixed with 100% by mass of polyvinyl butyral resin described in Example 1. The weight ratio of the composite tungsten oxide fine particles to the selective wavelength absorbing material [composite tungsten oxide fine particles / selective wavelength absorbing material] is 100/20, and the content of the ultraviolet absorber in the composition is 1.0. A composition for producing a heat ray shielding film was prepared by adding so that the visible light transmittance was 70% or more when the laminated transparent substrate was used.
The composition for producing this heat ray shielding film was kneaded at 200 ° C. with a twin-screw extruder, extruded from a T die, and a heat ray shielding film according to Example 14 was obtained as a sheet having a thickness of 0.7 mm by a calender roll method. The obtained heat ray shielding film was sandwiched between two opposing inorganic glasses and laminated together by a known method to obtain a heat ray shielding laminated transparent base material according to Example 14. And the optical characteristic of the heat ray shielding laminated transparent base material which concerns on the said Example 14 was measured similarly to Example 1. FIG. The type of composite tungsten oxide fine particles in Example 14, the type of selective wavelength absorbing material, and the weight ratio of the composite tungsten oxide fine particles to the selective wavelength absorbing material in the composition for producing a heat ray shielding film [composite tungsten oxide Table 1 shows the fine particle / selective wavelength absorbing material], the type of the ultraviolet absorber, and the content of the ultraviolet absorber in the composition for producing the heat ray shielding film. Furthermore, Table 1 shows the optical property measurement results of the heat ray shielding laminated transparent base material according to Example 14.

[Examples 15 to 17]
The heat rays according to Examples 15 to 17 were the same as Example 14 except that the type of the UV absorber and the content of the UV absorber in the heat ray shielding film described in Example 14 were changed as shown in Table 1. A shielded laminated transparent substrate was obtained. Then, the optical characteristics of the heat ray shielding laminated transparent base materials according to Examples 15 to 17 were measured in the same manner as in Example 1. The results are shown in Table 1.
As the ultraviolet absorber, the above-mentioned benzotriazole compound C is used in Example 15, and in Example 16, it is a benzotriazole compound and is TINUVIN 326 (CAS No. 3896-11) manufactured by BASF represented by (Chemical Formula 7). -5.) (Hereinafter referred to as benzotriazole compound I), and in Example 17, the above-mentioned benzophenone compound E was used.

透過率＊１：550nmおよび460nmの透過率が90%以上のときの420nmの透過率
配合比＊２：[複合タングステン酸化物微粒子]／[選択波長吸収材料]
含有率＊３：熱線遮蔽膜中の含有率
配合比＊４：[複合タングステン酸化物微粒子]／[赤外線吸収性有機化合物]

Transmittance * 1: Transmission ratio of 420 nm when the transmittance at 550 nm and 460 nm is 90% or more * 2: [Composite tungsten oxide fine particles] / [Selected wavelength absorbing material]
Content ratio * 3: Content ratio in heat ray shielding film * 4: [Composite tungsten oxide fine particles] / [Infrared absorbing organic compound]

[Evaluation of Examples 1 to 10, Examples 14 to 17 and Comparative Examples 1 to 4]
In Examples 1 to 10 and Examples 14 to 17, the selected wavelength absorbing material was used in combination with the composite tungsten oxide fine particles in an appropriate ratio, so that the solar radiation transmission was lower than that of Comparative Example 1 in which the selected wavelength absorbing material was not used together. The rate was obtained. Further, the YI of the laminated transparent substrate did not exceed 10, and there was little change in color tone due to the combined use of the selective wavelength absorbing material. On the other hand, in Comparative Example 2, the absorption amount of the selective wavelength absorbing material was small, so that sufficient absorption could not be obtained, and only solar radiation transmittance comparable to that of Comparative Example 1 in which the selective wavelength absorbing material was not used together was obtained. In Comparative Example 3, since the amount of the selective wavelength absorbing material added was too large, the yellowness YI increased to 10 or more, and the color tone of the combined transparent base material changed greatly. In Comparative Example 4, since the quinophthalone compound H having a weak absorption of 420 nm with respect to the transmittance of light having a wavelength of 550 nm and a wavelength of 460 nm was used as the selective wavelength absorbing material, the YI increased to 10 or more. The color has changed greatly.

[Evaluation of Examples 11 to 13]
In Examples 11 to 13, in addition to the use of the selective wavelength absorbing material in combination with the composite tungsten oxide fine particles, the absorption of a wavelength of about 800 to 1100 nm, which is not sufficiently absorbed by the composite tungsten oxide fine particles or the selective wavelength absorbing material, or By using a reflective infrared absorbing organic compound or an infrared reflective film in combination, a very low solar transmittance was obtained.

Claims (23)

Formula M _y WO _Z (where, M is, Cs, Rb, K, Tl , In, Ba, Li, Ca, Sr, 1 or more elements selected Fe, Sn, Al, from Cu, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) and a composite tungsten oxide fine particle having a hexagonal crystal structure, a selective wavelength absorbing material, a polyvinyl acetal resin, a plasticizer, A heat ray shielding film containing
The selective wavelength absorbing material in the first period has a transmittance of light having a wavelength of 550 nm of 90% or more, and a transmittance of light having a wavelength of 420 nm when the transmittance of light having a wavelength of 460 nm is 90% or more. Have a profile,
A heat ray shielding film, wherein a weight ratio of the composite tungsten oxide fine particles to the selective wavelength absorbing material is in a range of (composite tungsten oxide fine particles / selective wavelength absorbing material) = 100/2 to 100/800. 2. The heat ray shielding film according to claim 1, wherein the composite tungsten oxide fine particles are at least one selected from Cs _0.33 WO ₃ and Rb _0.33 WO ₃ . 3. The heat ray shielding film according to claim 1, wherein the composite tungsten oxide fine particles are fine particles having a dispersed particle diameter of 40 nm or less. 2. The selective wavelength absorbing material is at least one selected from a benzotriazole compound, a benzophenone compound, a hydroxyphenyltriazine compound, an indole compound, an azomethine compound, a benzotriazolyl compound, and a benzoyl compound. To 4. The heat ray shielding film according to any one of items 1 to 3. 4. The heat ray shielding film according to claim 1, wherein the selective wavelength absorbing material is an indole compound. The selective wavelength absorbing material is an indole compound represented by (Chemical Formula 1), wherein R is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. The heat ray shielding film according to any one of claims 1 to 3.

4. The heat ray shielding film according to claim 1, wherein the selective wavelength absorbing material is a compound in which R in the formula is a methyl group among the indole compounds represented by (Chemical Formula 1).

The heat ray shielding film according to any one of claims 1 to 7, wherein the heat ray shielding film further contains an ultraviolet absorber. The heat ray shielding film according to claim 8, wherein the ultraviolet absorber is at least one selected from a benzotriazole compound and a benzophenone compound. The heat ray shielding film according to claim 8 or 9, wherein the content of the ultraviolet absorber in the heat ray shielding film is 0.1 wt% or more and 5.0 wt% or less. When the transmittance of the light of wavelength 550 nm is 90% or more and the transmittance of light of wavelength 460 nm is 90% or more, the selective wavelength absorbing material in the previous period has a transmission profile of 15% or less of light of wavelength 420 nm. The heat ray shielding film according to claim 1, wherein the heat ray shielding film is provided. The heat ray shielding film according to any one of claims 1 to 11, wherein the heat ray shielding film further contains an infrared absorbing organic compound. The infrared absorbing organic compound is a phthalocyanine compound, naphthalocyanine compound, imonium compound, diimonium compound, polymethine compound, diphenylmethane compound, triphenylmethane compound, quinone compound, azo compound, pentadiene compound, azomethine compound, squarylium compound, organometallic complex The heat ray shielding film according to claim 12, which is at least one selected from cyanine compounds. The heat ray shielding film according to claim 12, wherein the infrared absorbing organic compound is at least one selected from a phthalocyanine compound and a diimonium compound. The weight ratio between the infrared absorbing organic compound and the composite tungsten oxide fine particles is in the range of (composite tungsten oxide fine particles / infrared absorbing organic compound) = 100/5 to 100/100. The heat ray shielding film according to any one of 12 to 14. A heat ray shielding laminated transparent substrate, wherein the heat ray shielding film according to any one of claims 1 to 15 is present between a plurality of transparent substrates. The heat ray shielding laminated transparent base material according to claim 16, wherein the yellowness degree (YI) calculated by JIS K 7373 is -20.0 or more and 10.0 or less. The heat ray shielding laminated transparent base material according to claim 16, wherein the yellowness degree (YI) calculated by JIS K 7373 is -20.0 or more and 5.0 or less. The infrared reflective film having a visible light transmittance of 88% or more and a solar reflectance of 21% or more is further present between the plurality of transparent substrates. The heat ray shielding laminated transparent base material of description. 20. The heat ray shielding laminated transparent base material according to any one of claims 16 to 19, wherein at least one of the transparent base materials is glass. The visible light transmittance calculated by JIS R 3106 is 70% or more, and the solar radiation transmittance is 32.5% or less when the visible light transmittance is 70%. The heat ray shielding laminated transparent base material in any one of. An automobile characterized in that the heat ray shielding laminated transparent base material according to any one of claims 16 to 21 is mounted as a window material. A building characterized in that the heat-shielding transparent base material according to any one of claims 16 to 21 is used as a window material.